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Sample records for asphaltene

  1. Asphaltene characterization : sensitivity of asphaltene properties to extraction techniques

    Energy Technology Data Exchange (ETDEWEB)

    Alboudwarej, H.; Svrcek, W.; Yarranton, H. [Calgary Univ., AB (Canada); Akbarzadeh, K. [Shiraz Univ., Shiraz (Iran, Islamic Republic of)

    2001-06-01

    A study was conducted in which asphaltenes from three source oils (Athabasca, Cold Lake and Lloydminster) were examined and washed to remove the trapped resinous material. The effect of different degrees of washing on asphaltene properties was then examined, with particular emphasis on properties that are used in the modeling and measurement of asphaltene phase behaviour, such as yield, molar mass, density and solubility. It was determined that the degree of washing is an important consideration in the extraction of asphaltenes because in all cases, as the degree of washing increased, density and molar mass also increased but the solubility of the extracted asphaltenes decreased significantly. This paper presented a new washing method using a soxhlet apparatus. It was found to remove the largest amount of resinous material and yielded asphaltenes with very different properties from conventionally washed asphaltenes, which made it possible to conduct sensitive comparisons of the asphaltenes. 10 refs., 1 tab., 7 figs.

  2. Progress in modeling asphaltene precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Yarranton, H.W.; Satyro, M.A. [Department of Chemical and Petroleum Engineering, University of Calgary (Canada); Taylor, S.D. [DBR Technology Center, Schlumberger (Canada)

    2011-07-01

    In the oil industry, asphaltene precipitation may happen when heavy oils are in contact with a solvent, crude oils are blended or when light oils containing asphaltenes are depressurized. Asphaltene precipitation has proven challenging to predict and the aim of this paper is to evaluate 2 different approaches for asphaltene precipitation modeling: regular solution and equation of state. Two case were studied: an Athabasca bitumen diluted with n-alkane and a depressurized Gulf of Mexico crude oil and both models were applied to each case. Results showed that both thermodynamic models are, to a limited extend, suitable for asphaltene precipitation prediction but they do not offer a correct prediction at low asphaltene concentrations and the equation of state cannot predict asphaltene precipitation from depressurized crude oils. This study showed the limits of current models in predicting precipitation of asphaltene and provided a trick to overcome these deficiencies; further work should be undertaken to develop a consistent approach.

  3. Raman spectrum of asphaltene

    KAUST Repository

    Abdallah, Wael A.

    2012-11-05

    Asphaltenes extracted from seven different crude oils representing different geological formations from around the globe were analyzed using the Raman spectroscopic technique. Each spectrum is fitted with four main peaks using the Gaussian function. On the basis of D1 and G bands of the Raman spectrum, asphaltene indicated an ordered structure with the presence of boundary defected edges. The average aromatic sheet size of the asphaltene molecules is estimated within the range of 1.52-1.88 nm, which represents approximately seven to eight aromatic fused rings. This estimation is based on the integrated intensity of D1 and G bands, as proposed by Tunistra and Koenig. The results here are in perfect agreement with so many other used techniques and indicate the potential applicability of Raman measurements to determine the average aromatic ring size and its boundary. © 2012 American Chemical Society.

  4. Control of asphaltene deposition laboratory screening and evaluation of asphaltene inhibitors

    Energy Technology Data Exchange (ETDEWEB)

    Allenson, S. [Nalco/Exxon Energy Chemicals, Sugar Land, TX (United States)

    2000-08-01

    A systematic experimental program was developed to critically assess and control the potential for asphaltene deposition from reservoir fluids. By following the methodology, the GOM crude oil was successfully evaluated for its tendency to precipitate and deposit asphaltenes under typical production conditions. An asphaltene inhibitor that stabilizes the asphaltenes was also successfully evaluated. (au)

  5. Methods of making carbon fiber from asphaltenes

    Energy Technology Data Exchange (ETDEWEB)

    Bohnert, George; Bowen, III, Daniel E.

    2017-02-28

    Making carbon fiber from asphaltenes obtained through heavy oil upgrading. In more detail, carbon fiber is made from asphaltenes obtained from heavy oil feedstocks undergoing upgrading in a continuous coking reactor.

  6. Sans study of asphaltene aggregation

    Energy Technology Data Exchange (ETDEWEB)

    Overfield, R.E.; Sheu, E.Y.; Sinha, S.K.; Liang, K.S. (Esso Resources Canada Ltd., 339-50 Avenue S.E., Calgary, Alberta T2G 2B3 (CA))

    1988-06-01

    The colloidal properties of asphaltenes have long been recognized from peculiarities in their solubility and colligative properties. A layered micellar model or asphaltenes was proposed by others in which a highly condensed alkyl aromatic formed the central part, and molecules of decreasingly aromatic character (resins) clustered around them. Numerous studies, based on a variety of techniques such as ultracentrifugation and electron microscopy indicated a particulate nature for asphaltenes with size 20-40 A diameter. Others have proposed a refined model based on x-ray diffraction and small angle scattering. In this model, interactions between flat sheets of condensed aromatic rings form the central ''crystallite'' part of a spherical particle with the outer part being comprised of the aliphatic positions of the same molecules. These particles are bunched together with some degree of entanglement into ''micelles''. Concentration and solvent dependent radii of gyration, ranging from 30-50 A were reported. The aggregation creates a good deal of uncertainty as to the true molecular size or weight of asphaltenes. Neutron scattering offers novel contrast relative to light scattering (refractive index) and x-ray scattering (electron density). This is because the scattering length of proton is negative, whereas that from deuterium and other nuclei such as C, S, O, and N are positive. Thus by replacing hydrogen with deuterium in either the solvent or the scatterer the contrast can be varied, and different parts of the molecule can be highlighted.

  7. Sans study of asphaltene aggregration

    Energy Technology Data Exchange (ETDEWEB)

    Overfield, R.E.; (Esso Resources Canada Ltd., Alberta); Sheu, E.Y.; Sinha, S.K.; Liang, K.S. (Exxon Research and Engineering Co., Annandale, NJ (USA))

    1988-06-01

    The colloidal properties of asphaltenes have long been recognized from peculiarities in their solubility and colligative properties. A layered micellar model for asphaltenes was proposed by Pfeiffer and Saal in 1940, in which a highly condensed alkyl aromatic formed the central part, and molecules of decreasingly aromatic character (resins) clustered around them. Numerous studies, based on a variety of techniques such as ultracentrifugation and electron microscopy indicated a particulate nature for asphaltenes with size 20-40 {angstrom} diameter. T.F. Yen and co-workers proposed a refined model based on x-ray diffraction and small angle scattering. In this model, interactions between flat sheets of condensed aromatic rings form the central crystallite part of a spherical particle with the outer part being comprised of the aliphatic positions of the same molecules. These particles are bunched together with some degree of entanglement into micelles. Concentration and solvent dependent radii of gyration, ranging from 30-50 {angstrom} were reported. The aggregation creates a good deal of uncertainty as to the true molecular size of weight of asphaltenes. Neutron scattering offers novel contrast relative to light scattering (refractive index) and x-ray scattering (electron density). This is because the scattering length of proton is negative, whereas that from deuterium and other nuclei such as C, S, O, and N are positive. Thus by replacing hydrogen with deuterium in either the solvent or the scatterer the contrast can be varied, and different parts of the molecule can be highlighted.

  8. Ozonation of Canadian Athabasca asphaltene

    Science.gov (United States)

    Cha, Zhixiong

    Application of ozonation in the petrochemical industry for heavy hydrocarbon upgrading has not been sufficiently explored. Among heavy hydrocarbons, asphaltenes are the heaviest and the most difficult fractions for analysis and treatment. Therefore, ozonation of asphaltenes presents an interesting application in the petrochemical industry. Commercial application of ozonation in the petrochemical industry has three obstacles: availability of an ozone-resistant and environmentally friendly solvent, the precipitation of ozonation intermediates during reaction, and recovery of the solvent and separation of the ozonation products. Preliminary ozonation of Athabasca oil sands asphaltene in nonparticipating solvents encountered serious precipitation of the ozonation intermediates. The precipitated intermediates could be polymeric ozonides and intermolecular ozonides or polymeric peroxides. Because the inhomogeneous reaction medium caused low ozone efficiency, various participating solvents such as methanol and acetic acid were added to form more soluble hydroperoxides. The mass balance results showed that on average, one asphaltene molecule reacted with 12 ozone molecules through the electrophilic reaction and the subsequent decomposition of ozonation intermediates generated acetone extractable products. GC/MS analysis of these compounds indicated that the free radical reactions could be important for generation of volatile products. The extensively ozonated asphaltene in the presence of participating solvents were refluxed with methanol to generate more volatile products. GC/MS analysis of the methanol-esterified ozonation products indicated that most volatile products were aliphatic carboxylic acid esters generated through cleavage of substituents. Reaction kinetics study showed that asphaltene ozonation was initially a diffusion rate-controlled reaction and later developed to a chemical reaction rate-controlled reaction after depletion of the reactive aromatic sites

  9. Kinetics of asphaltene precipitation from crude oils

    Energy Technology Data Exchange (ETDEWEB)

    Maqbool, T.; Hussein, I.A.; Fogler, H.S. [Michigan Univ., Ann Arbor (United States). Dept. of Chemical Engineering

    2008-07-01

    The kinetics of asphaltene precipitation from crude oils was investigated using n-alkane precipitants. Recent studies have shown that there is a kinetic phenomenon associated with asphaltene precipitation. This study showed that the time needed to precipitate the asphaltenes can vary from a few minutes to several months, depending on the amount of n-alkane precipitant added. As such, the onset of asphaltene precipitation is a function of the concentration of precipitant and time. A technique to quantify the amount of asphaltenes precipitated as a function of time and precipitant concentration was presented. This study also investigated the kinetic effects caused by various precipitants. Optical microscopy was used to monitor the growth of asphaltene aggregates with time. Refractive index measurements provided further insight into the kinetics of asphaltene precipitation. Polarity based fractionation and dielectric constant measurements were used to compare the nature of asphaltenes precipitated early in the precipitation process with the asphaltenes precipitated at later times. It was concluded that asphaltenes precipitating at different times from the same crude oil-precipitant mixture are different from one another. 3 refs.

  10. Revisiting the flocculation kinetics of destabilized asphaltenes.

    Science.gov (United States)

    Vilas Bôas Fávero, Cláudio; Maqbool, Tabish; Hoepfner, Michael; Haji-Akbari, Nasim; Fogler, H Scott

    2017-06-01

    A comprehensive review of the recently published work on asphaltene destabilization and flocculation kinetics is presented. Four different experimental techniques were used to study asphaltenes undergoing flocculation process in crude oils and model oils. The asphaltenes were destabilized by different n-alkanes and a geometric population balance with the Smoluchowski collision kernel was used to model the asphaltene aggregation process. Additionally, by postulating a relation between the aggregation collision efficiency and the solubility parameter of asphaltenes and the solution, a unified model of asphaltene aggregation model was developed. When the aggregation model is applied to the experimental data obtained from several different crude oil and model oils, the detection time curves collapsed onto a universal single line, indicating that the model successfully captures the underlying physics of the observed process. Copyright © 2016 Elsevier B.V. All rights reserved.

  11. Electrodeposition of Asphaltenes. 2. Effect of Resins and Additives

    DEFF Research Database (Denmark)

    Khvostichenko, Daria S; Andersen, Simon Ivar

    2010-01-01

    Electrodeposition of asphaltenes from oil/heptane, asphaltene/heptane, and asphaltene/heptane/additive mixtures has been investigated. Toluene, native petroleum resins, and a synthetic asphaltene dispersant, p-nonylphenol, were used as additives. The addition of these components led to partial...... of preparation of the mixture and the toluene content. Introduction of petroleum resins into asphaltene/heptane mixtures resulted in neutralization of the asphaltene particle charge. The addition of p-nonylphenol to asphaltene suspensions in heptane did not alter the charge of asphaltene particles. Current...

  12. Thermogravimetric assessment of thermal degradation in asphaltenes

    Energy Technology Data Exchange (ETDEWEB)

    Barneto, Agustín García, E-mail: agustin.garcia@diq.uhu.es [Department of Chemical Engineering, Physical Chemistry and Organic Chemistry, University of Huelva, Huelva (Spain); Carmona, José Ariza [Department of Chemical Engineering, Physical Chemistry and Organic Chemistry, University of Huelva, Huelva (Spain); Garrido, María José Franco [CEPSA, RDI Centre, Madrid (Spain)

    2016-03-20

    Graphical abstract: - Highlights: • Asphaltenes content of visbreaking streams in oil refinery can be measured by using TGA. • Deconvoluting TGA curves allows the thermal-based composition of asphaltenes to be elucidated. • Asphaltenes cracking involves acceleratory stages compatible with autocatalytic kinetic. • Activation energy during asphaltenes pyrolysis increased with increasing temperature. • Activation energy remained almost constant at 200–225 kJ/mol during oxidative cracking. - Abstract: Monitoring asphaltenes is very important with a view to optimizing visbreaking units in oil refineries. Current analyses based on selective dissolution in different solvents are slow, so new, more expeditious methods for measuring asphaltenes are required to facilitate fuel-oil production. In this work, we studied the thermal degradation of asphaltenes as the potential basis for a thermogravimetric method for their monitoring in visbreaking streams. The thermal degradation of asphaltenes occurs largely from 400 to 500 °C; the process is quite smooth in an inert environment but involves several fast mass loss events in the air. Kinetic parameters for characterizing the process were determined by using two model-free methods and the modified Prout–Tompkins kinetic equation to examine asphaltene thermolysis. Both types of methods showed the activation energy to increase during pyrolysis but to remain almost constant during cracking in the presence of oxygen or even diminish during char oxidation. Deconvoluting the thermogravimetric profiles revealed that asphaltene thermolysis in the air cannot be accurately described in terms of an nth order kinetic model because it involves some acceleratory phases. Also, thermogravimetric analyses of visbreaking streams revealed that char production in them is proportional to their asphaltene content. This relationship enables the thermogravimetric measurement of asphaltenes.

  13. On the Mass Balance of Asphaltene Precipitation

    DEFF Research Database (Denmark)

    Andersen, Simon Ivar; Lira-Galeana, C.; Stenby, Erling Halfdan

    2001-01-01

    are performed in order to check the consistency of mass balances within asphaltene precipitation. Asphaltenes are precipitated in two step processes either by changing temperature or by changes in precipitant with increasing precipitation power. This has been performed for three different oils. The data...

  14. Study of asphaltene precipitation by Calorimetry

    DEFF Research Database (Denmark)

    Verdier, Sylvain Charles Roland; Plantier, Frédéric; Bessières, David

    2007-01-01

    Can calorimetry bring new input to the Current understanding of asphaltene precipitation? In this work, two types of precipitation were studied by means of calorimetry: addition of n-heptane into asphaltene solutions and temperature/pressure variations on a recombined live oil. The first series...

  15. Hydrodynamic perspective on asphaltene agglomeration and deposition

    NARCIS (Netherlands)

    Schutte, K.C.J.; Portela, L.M.; Twerda, A.; Henkes, R.A.W.M.

    2015-01-01

    In this work, we propose a detailed numerical model for asphaltene agglomeration and deposition, as induced by a resolved turbulent liquid carrier phase flow, in which transport, breakup, and re-entrainment are also taken into account. Asphaltene phase separation is represented by the appearance of

  16. Molecular thermodynamics for prevention of asphaltene precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Wu, Jianzhong; Prausnitz, J.M.

    1996-06-01

    Crude petroleum is a complex mixture of compounds with different chemical structures and molecular weights. Asphaltenes, the heaviest and most polar fraction of crude oil, are insoluble in normal alkanes such as n-heptane, but they are soluble in aromatic solvents such as toluene. The molecular nature of asphaltenes and their role in production and processing of crude oils have been the topic of numerous studies. Under some conditions, asphaltenes precipitate from a petroleum fluid, causing severe problems in production and transportation Our research objective is to develop a theoretically based, but engineering-oriented, molecular-thermodynamic model which can describe the phase behavior of asphaltene precipitation in petroleum fluids, to provide guidance for petroleum-engineering design and production. In this progress report, particular attention is given to the potential of mean force between asphaltene molecules in a medium of asphaltene-free solvent. This potential of mean force is derived using the principles of colloid science. It depends on the properties of asphaltene and those of the solvent as well as on temperature and pressure. The effect of a solvent on interactions between asphaltenes is taken into account through its density and through its molecular dispersion properties.

  17. Modeling of asphaltene and wax precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Chung, F.; Sarathi, P.; Jones, R.

    1991-01-01

    This research project was designed to focus on the development of a predictive technique for organic deposition during gas injection for petroleum EOR. A thermodynamic model has been developed to describe the effects of temperature, pressure, and composition on asphaltene precipitation. The proposed model combines regular solution theory with Flory-Huggins polymer solutions theory to predict maximum volume fractions of asphaltene dissolved in oil. The model requires evaluation of vapor-liquid equilibria, first using an equation of state followed by calculations of asphaltene solubility in the liquid-phase. A state-of-the-art technique for C{sub 7+} fraction characterization was employed in developing this model. The preliminary model developed in this work was able to predict qualitatively the trends of the effects of temperature, pressure, and composition. Since the mechanism of paraffinic wax deposition is different from that of asphaltene deposition, another thermodynamic model based on the solid-liquid solution theory was developed to predict the wax formation. This model is simple and can predict the wax appearance temperature with reasonable accuracy. Accompanying the modeling work, experimental studies were conducted to investigate the solubility of asphaltene in oil land solvents and to examine the effects of oil composition, CO{sub 2}, and solvent on asphaltene precipitation and its properties. This research focused on the solubility reversibility of asphaltene in oil and the precipitation caused by CO{sub 2} injection at simulated reservoir temperature and pressure conditions. These experiments have provided many observations about the properties of asphaltenes for further improvement of the model, but more detailed information about the properties of asphaltenes in solution is needed for the development of more reliable asphaltene characterization techniques. 50 refs., 8 figs., 7 tabs.

  18. Asphaltenes as new objects for nanoelectronics

    Science.gov (United States)

    Dolomatov, M. Yu; Petrov, A. M.; Bakhtizin, R. Z.; Dolomatova, M. M.; Khairudinov, I. R.; Shutkova, S. A.; Kovaleva, E. A.; Paymurzina, N. Kh

    2017-05-01

    Abstract. Modern carbon nanomaterials (carbon nanotubes, graphenes, fullerenes, polycyclic molecules) are products of rather complicated technologies. Therefore development of new not expensive materials on the basis of natural substances, in particular high-molecular compounds of oil - asphaltenes, is actual for nanoelectronics. Asphaltenes are complex materials that are found in crude oil, bitumen and high-boiling hydrocarbons distillates. Usually asphaltenes are composed mainly of polyaromatic carbon with a small amount of vanadium and nickel, which are in porphyrin structures. Molecules of asphaltenes may contain 5-10-member benzene and naphthenic rings in their structure and also have paramagnetic centers. A variety of techniques: electronic phenomenological spectroscopy (EPS), atomic force microscopy (AFM) and quantum chemistry calculations were used to define the structure of oil asphaltenes. It was supposed that asphaltene fraction is a strong donor (ionization potential 4.10-6.70 eV) and an acceptor (electron affinity 1.80-2.50 eV). The structures of asphaltenes fragments were calculated by RHF-6-31G** methods. AFM images of asphaltenes obtained from crude oil showed the presence of structure fragments ranged from 3 to 10 nm, disposed to strong intermolecular interactions. We used doped compounds for formation of wide band gap amorphous semiconductors from a concentrates of asphaltens. Changes of conductivity in dispersed petroleum systems (DPS) were studied during a pyrolysis at 500 K. The numerous experiments defined of conductivity testify about phase transitions dielectric - semiconductor in DPS for range of 360 - 400 K. The main conclusion is paramagnetic phase of asphaltenes is organic amorphous wide band gap semiconductor. Besides this substance can be consider as an organic spin glasses.

  19. Separation and characterization of asphaltenic subfractions

    Directory of Open Access Journals (Sweden)

    Siller O. Honse

    2012-01-01

    Full Text Available The structure of the various asphaltenic subfractions found in crude oil was evaluated. For this purpose, C5 asphaltenes were extracted from an asphaltic residue using n-pentane as the flocculant solvent. The different subfractions were isolated from the C5 asphaltenes by the difference in solubility in different solvents. These were characterized by infrared spectroscopy, nuclear magnetic resonance, X-ray fluorescence, elementary analysis and mass spectrometry. The results confirmed that the subfractions extracted with higher alkanes had greater aromaticity and molar mass. However, small solubility variations between the subfractions were attributed mainly to the variation in the concentrations of cyclical hydrocarbon compounds and metals.

  20. Separation and characterization of asphaltenic subfractions

    Energy Technology Data Exchange (ETDEWEB)

    Honse, Siller O.; Ferreira, Silas R.; Mansur, Claudia R. E.; Lucas, Elizabete F. [Universidade Federal do Rio de Janeiro (IMA/UFRJ), RJ (Brazil). Inst. de Macromoleculas Professora Eloisa Mano; Gonzalez, Gaspar, E-mail: elucas@ima.ufrj.br [Centro de Pesquisas da PETROBRAS (CENPES), Rio de Janeiro, RJ (Brazil)

    2012-07-01

    The structure of the various asphaltenic subfractions found in crude oil was evaluated. For this purpose, C5 asphaltenes were extracted from an asphaltic residue using n-pentane as the flocculant solvent. The different subfractions were isolated from the C5 asphaltenes by the difference in solubility in different solvents. These were characterized by infrared spectroscopy, nuclear magnetic resonance, X-ray fluorescence, elementary analysis and mass spectrometry. The results confirmed that the subfractions extracted with higher alkanes had greater aromaticity and molar mass. However, small solubility variations between the subfractions were attributed mainly to the variation in the concentrations of cyclical hydrocarbon compounds and metals (author)

  1. Interactions between Asphaltenes and Water in Solutions in Toluene

    DEFF Research Database (Denmark)

    Khvostichenko, Daria; Andersen, Simon Ivar

    2008-01-01

    Binding of water by asphaltenes dissolved in toluene was investigated for two asphaltene samples, OMV1 and OMV2, from the same reservoir deposit. Solubility of water in asphaltene solutions in toluene was found to increase with an increasing asphaltene concentration, indicative of solubilization...... of water by asphaltenes. Fourier transform infrared (FTIR) spectroscopy of stretching modes of OH groups in the region of 3800-3100 cm(-1) was used to obtain insight into the state of water in water-unsaturated asphaltene solutions in toluene. The number of water molecules bound to one asphaltene molecule...... was determined for water-saturated solutions (OMV1 and OMV2) and for water-unsaturated solutions (OMV1 only). These numbers were found to decrease from several water molecules per asphaltene molecule to below unity upon an increase of the asphaltene concentration in toluene from 0.1 to 20 g/L, suggesting...

  2. Characterization of asphaltenes by nonaqueous capillary electrophoresis

    NARCIS (Netherlands)

    Kok, W.T.; Tüdös, A.J.; Grutters, M.; Shepherd, A.G.

    2011-01-01

    Nonaqueous capillary electrophoresis was used for the separation and characterization of asphaltene samples from different sources. For the separation medium (background electrolyte), mixtures of tetrahydrofuran and a high-permittivity organic solvent could be used. The best results were obtained

  3. Asphaltenes-based polymer nano-composites

    Science.gov (United States)

    Bowen, III, Daniel E

    2013-12-17

    Inventive composite materials are provided. The composite is preferably a nano-composite, and comprises an asphaltene, or a mixture of asphaltenes, blended with a polymer. The polymer can be any polymer in need of altered properties, including those selected from the group consisting of epoxies, acrylics, urethanes, silicones, cyanoacrylates, vulcanized rubber, phenol-formaldehyde, melamine-formaldehyde, urea-formaldehyde, imides, esters, cyanate esters, allyl resins.

  4. A molecular-thermodynamic framework for asphaltene-oil equilibria

    Energy Technology Data Exchange (ETDEWEB)

    Wu, J.; Prausnitz, J.M. [Univ. of California, Berkeley, CA (United States). Dept. of Chemical Engineering]|[Lawrence Berkeley National Lab., CA (United States). Chemical Sciences Div.; Firoozabadi, A. [Reservoir Engineering Research Inst., Palo Alto, CA (United States)

    1997-02-01

    Asphaltene precipitation is a perennial problem in production and refinery of crude oils. To avoid precipitation, it is useful to predict the solubility of asphaltenes in petroleum liquids as a function of temperature, pressure and liquid-phase composition. In the molecular-thermodynamic model presented here, both asphaltenes and resins are represented by pseudo-pure components, and all other components in the solution are represented by a continuous medium which affects interactions among asphaltene and resin particles. The effect of the medium on asphaltene-asphaltene, resin-asphaltene, resin-resin pair interactions is taken into account through its density and molecular-dispersion properties. To obtain expressions for the chemical potential of asphaltene and for the osmotic pressure of an asphaltene-containing solution, the authors use the integral theory of fluids coupled with the SAFT model to allow for asphaltene aggregation and for adsorption of resin on asphaltene particles. With these expressions, a variety of experimental observations can be explained including the effects of temperature, pressure and composition on the phase behavior of asphaltene-containing fluids. For engineering application, the molecular parameters in this model must be correlated to some macroproperties of oil such as density and molecular weight. When such correlations are established, it will be possible to calculate asphaltene-precipitation equilibria at a variety of conditions for realistic systems.

  5. Effects of resins on asphaltene self-association and solubility

    Energy Technology Data Exchange (ETDEWEB)

    Yarranton, H.W.; Fox, W.A.; Svrcek, W.Y. [Calgary Univ., AB (Canada). Dept. of Chemical and Petroleum Engineering

    2007-10-15

    This paper described a method of modelling the self-association and precipitation of asphaltenes and resins. Self-association was assessed using vapor pressure osmometry (VPO) measurements of asphaltene and resin mixtures. A modified asphaltene self-association model was used to fit and interpret data. The molar mass distribution of the asphaltene-resin aggregates was characterized. Precipitation data were obtained by measuring asphaltenes and resins in solutions of asphaltenes, resins, toluene, and heptane. The molar mass distribution was then used as an input to the regular solution model. Results of the study suggested that resins participate in asphaltene self-association. It was concluded that both asphaltenes and resins are best characterized as a combined pseudo-component with a single molar mass distribution of the aggregated species. 30 refs., 4 tabs., 5 figs.

  6. Asphaltene nanoparticle aggregation in mixtures of incompatible crude oils

    International Nuclear Information System (INIS)

    Mason, T.G.; Lin, M.Y.

    2003-01-01

    We study the structure and phase behavior of asphaltenes comprised of large polyaromatic molecules in blends of naturally occurring crude oils using small angle neutron scattering (SANS). When two compatible oils are blended together, the asphaltenes remain dispersed as colloidal nanoparticles; however, when two incompatible oils are blended together, these asphaltene nanoparticles can aggregate to form microscale structures. We show that SANS directly probes asphaltene aggregation in unmodified (i.e., nondeuterated) crude oil mixtures due to a significant neutron scattering length density difference between the hydrogen-poor asphaltenes and the surrounding oil. Moreover, the small length scales probed by SANS are ideally suited for studying asphaltene aggregation: SANS simultaneously provides the average size and concentration of nanoscale asphaltene particles and also the volume fraction of microscale asphaltene aggregates. These discoveries yield a practical means for directly assessing the compatibility of crude oils and for diagnosing refinery fouling problems resulting from blending incompatible oils

  7. Carbonized asphaltene-based carbon-carbon fiber composites

    Energy Technology Data Exchange (ETDEWEB)

    Bohnert, George; Lula, James; Bowen, III, Daniel E.

    2016-12-27

    A method of making a carbon binder-reinforced carbon fiber composite is provided using carbonized asphaltenes as the carbon binder. Combinations of carbon fiber and asphaltenes are also provided, along with the resulting composites and articles of manufacture.

  8. Investigating Asphaltenes Composition in Crude Oil Samples using ...

    African Journals Online (AJOL)

    This research was carried out to investigate the percentage composition of asphaltenes by Iatroscan analysis using Thin Layer Chromatography-Flame Ion Detection method (Iatroscan TLC-FID) The percentage composition of asphaltenes by Iatroscan TLC-FID method was compared with the weight% of asphaltenes ...

  9. Asphaltene precipitates in oil production wells

    DEFF Research Database (Denmark)

    Kleinitz, W,; Andersen, Simon Ivar

    1998-01-01

    At the beginning of production in a southern German oil field, flow blockage was observed during file initial stage of production from the oil wells. The hindrance was caused by the precipitation of asphaltenes in the proximity of the borehole and in the tubings. The precipitates were of solid......, "dry" consistency and resulted in total damage to flow. On the basis of residue samples from the wells, a number of physical and chemical analyses were performed, and the results were compared with those from studies on other asphaltenic precipitates. Among other items, the fraction of aromatic...... samples are described and discussed in detail. The laboratory results were subsequently applied in preparing a stimulation concept which takes into account the specific asphaltene problems in this field. The stimulation measures were implemented several times in two wells. Eruptive production...

  10. The Critical Micelle Concentration of Asphaltenes as Measured by Calorimetry

    DEFF Research Database (Denmark)

    Andersen, Simon Ivar; Christensen, S. D.

    2000-01-01

    Micellization of asphaltenes in solution has been investigated using a micro calorimetric titration procedure (Andersen, S. I.; Birdi, K. S. J Colloid Interface Sci. 1991, 142, 497). The method uses the analysis of heat of dissociation and dilution of asphaltene micelles when a pure solvent (or...... solvent mixture) is titrated with a solution of asphaltene in the same solvent. The asphaltene concentration of the injected solution is at a level above the critical micelle concentration (CMC). In the present paper the procedure is applied in investigation of asphaltenes as well as subfractions...

  11. Investigation of Asphaltene Precipitation at Elevated Temperature

    DEFF Research Database (Denmark)

    Andersen, Simon Ivar; Lindeloff, Niels; Stenby, Erling Halfdan

    1998-01-01

    In order to obtain quantitative data on the asphaltene precipitation induced by the addition of n-alkane (heptane) at temperatures above the normal boiling point of the precipitant, a high temperature/high pressure filtration apparatus has been constructed. Oil and alkane are mixed at the appropr......In order to obtain quantitative data on the asphaltene precipitation induced by the addition of n-alkane (heptane) at temperatures above the normal boiling point of the precipitant, a high temperature/high pressure filtration apparatus has been constructed. Oil and alkane are mixed...... in the extracted fraction, hence there is no room for stirring. The equipment as well as solutions to some of the problems are presented along with precipitation data from 40 to 200 degrees C. The asphaltenes separated are analyzed using FT-ir. The filtrate containing the maltenes was cooled to room temperature...... and the asphaltenes separating upon cooling was collected and analyzed. The oil and selected maltene fractions and extraction/cleaning solvents were analyzed using GC....

  12. Investigation of Asphaltene Precipitation at Elevated Temperature

    DEFF Research Database (Denmark)

    Andersen, Simon Ivar; Lindeloff, Niels; Stenby, Erling Halfdan

    1998-01-01

    In order to obtain quantitative data on the asphaltene precipitation induced by the addition of n-alkane (heptane) at temperatures above the normal boiling point of the precipitant, a high temperature/high pressure filtration apparatus has been constructed. Oil and alkane are mixed at the appropr...

  13. Isolation of Asphaltene-Degrading Bacteria from Sludge Oil

    Directory of Open Access Journals (Sweden)

    Pingkan Aditiawati

    2015-03-01

    Full Text Available Sludge oil contains 30%–50% hydrocarbon fractions that comprise saturated fractions, aromatics, resins, and asphaltene. Asphaltene fraction is the most persistent fraction. In this research, the indigenous bacteria that can degrade asphaltene fractions from a sludge oil sample from Balikpapan that was isolated using BHMS medium (Bushnell-Hass Mineral Salt with 0.01% (w/v yeast extract, 2% (w/v asphaltene extract, and 2% (w/v sludge oil. The ability of the four isolates to degrade asphaltene fractions was conducted by the biodegradation asphaltene fractions test using liquid cultures in a BHMS medium with 0.01% (w/v yeast extract and 2% (w/v asphaltene extract as a carbon source. The parameters measured during the process of biodegradation of asphaltene fractions include the quantification of Total Petroleum Hydrocarbon (g, log total number of bacteria (CFU/ml, and pH. There are four bacteria (isolates 1, 2, 3, and 4 that have been characterized to degrade asphaltic fraction and have been identified as Bacillus sp. Lysinibacillus fusiformes, Acinetobacter sp., and Mycobacterium sp., respectively. The results showed that the highest ability to degrade asphaltene fractions is that of Bacillus sp. (isolate 1 and Lysinibacillus fusiformes (Isolate 2, with biodegradation percentages of asphaltene fractions being 50% and 55%, respectively, and growth rate at the exponential phase is 7.17x107 CFU/mL.days and 4.21x107 CFU/mL.days, respectively.

  14. Examining Asphaltene Solubility on Deposition in Model Porous Media.

    Science.gov (United States)

    Lin, Yu-Jiun; He, Peng; Tavakkoli, Mohammad; Mathew, Nevin Thunduvila; Fatt, Yap Yit; Chai, John C; Goharzadeh, Afshin; Vargas, Francisco M; Biswal, Sibani Lisa

    2016-08-30

    Asphaltenes are known to cause severe flow assurance problems in the near-wellbore region of oil reservoirs. Understanding the mechanism of asphaltene deposition in porous media is of great significance for the development of accurate numerical simulators and effective chemical remediation treatments. Here, we present a study of the dynamics of asphaltene deposition in porous media using microfluidic devices. A model oil containing 5 wt % dissolved asphaltenes was mixed with n-heptane, a known asphaltene precipitant, and flowed through a representative porous media microfluidic chip. Asphaltene deposition was recorded and analyzed as a function of solubility, which was directly correlated to particle size and Péclet number. In particular, pore-scale visualization and velocity profiles, as well as three stages of deposition, were identified and examined to determine the important convection-diffusion effects on deposition.

  15. Separation of Asphaltenes by Polarity using Liquid-Liquid Extraction

    DEFF Research Database (Denmark)

    Andersen, Simon Ivar

    1997-01-01

    with increasing content of toluene. Although large fractions of the crude oil (Alaska ´93) was extracted in the higher polarity solvents (high concentration of methanol), the asphaltene content of the dissolved material was low. As the toluene content increased more asphaltenes were transferred to the solvent......In order to investigate the nature of petroleum asphaltenes in terms of polarity a process was developed using initial liquid-liquid extraction of the oil phase followed by precipitation of the asphaltenes using n-heptane. The liquid-liquid extraction was performed using toluene-methanol mixtures...... of the maltene phase also increase while H/C decreases. The content of heteroatoms in the asphaltenes are relatively higher and apparently increase with the polarity of the solvent. It is concluded that these asphaltenes are indeed dominated by high molecular weight substances that cannot be extracted...

  16. Monitoring of large diesel engines through asphaltene content

    Energy Technology Data Exchange (ETDEWEB)

    Declerck, R. [Texaco Technology Ghent (Belgium)

    1997-12-31

    Lubricants in large diesel engines, for marine and power plant application, are open contaminated with heavy fuel. This type of contamination results in blackening of the engines and deposit formation because of the coagulation of asphaltene particles. Monitoring of the asphaltene content presents the operator with important information on the condition of the engine and the lubricant. This technique was an important asset in developing a new range of lubricants highly capable of tackling the presence of asphaltenes. (orig.)

  17. Separation of Asphaltenes by Polarity using Liquid-Liquid Extraction

    DEFF Research Database (Denmark)

    Andersen, Simon Ivar

    1997-01-01

    In order to investigate the nature of petroleum asphaltenes in terms of polarity a process was developed using initial liquid-liquid extraction of the oil phase followed by precipitation of the asphaltenes using n-heptane. The liquid-liquid extraction was performed using toluene-methanol mixtures...... phase. The asphaltenes were analysed using FTir, Elemental analysis, and HPLC-SEC with a diode array detector. With increasing content of toluene in the methanol the molecular weight distribution of the asphaltenes significantly move to higher molecular weights. The content of nitrogen and sulfur...

  18. Modelling asphaltene deposition in turbulent pipeline flows

    Energy Technology Data Exchange (ETDEWEB)

    Eskin, D.; Ratulowski, J.; Akbarzadeh, K.; Pan, S. [Schlumberg DBR Technology Center (Canada)

    2011-06-15

    Asphaltene deposition is one of the important problems of oil production that requires accurate predictive modeling. A model of asphaltene deposition in a turbulent pipe flow is introduced in this paper. A Couette device is employed to perform experiments. There are two major modules in this model. (1) A model of particle size distribution evolution along a pipe - the concept of 'critical particle size' is introduced. Only particles smaller than the critical particle size may deposit. (2) A model of particle transport to the wall. The major mechanism of particle transport to the wall is the Brownian motion. The model developed contains three major tuning parameters that are determined experimentally using a Couette device: particle-particle collision efficiency, particle-wall sticking efficiency, and particle critical size. Performance of the deposition model for a pipeline with the coefficients obtained using a laboratory Couette device is also illustrated in this paper.

  19. Asphaltene precipitates in oil production wells

    DEFF Research Database (Denmark)

    Kleinitz, W,; Andersen, Simon Ivar

    1998-01-01

    , "dry" consistency and resulted in total damage to flow. On the basis of residue samples from the wells, a number of physical and chemical analyses were performed, and the results were compared with those from studies on other asphaltenic precipitates. Among other items, the fraction of aromatic...... compounds in the organic scales from operations definitely differed from the data published in the literature. In order to dissolve the precipitates and thus eliminate the damage, various organic solvents and industrial solvent mixtures were examined. The kinetics of the dissolution process in operational...... samples are described and discussed in detail. The laboratory results were subsequently applied in preparing a stimulation concept which takes into account the specific asphaltene problems in this field. The stimulation measures were implemented several times in two wells. Eruptive production...

  20. Investigating Asphaltenes Composition in Crude Oil Samples using ...

    African Journals Online (AJOL)

    MBI

    2015-12-22

    Dec 22, 2015 ... ABSTRACT. This research was carried out to investigate the percentage composition of asphaltenes by Iatroscan analysis using Thin Layer Chromatography-Flame Ion Detection method (Iatroscan TLC-FID) The percentage composition of asphaltenes by Iatroscan TLC-FID method was compared with the ...

  1. Effect of asphaltenes on crude oil wax crystallization

    DEFF Research Database (Denmark)

    Kriz, Pavel; Andersen, Simon Ivar

    2005-01-01

    The paper summarizes the experimental work done on asphaltene influenced wax crystallization. Three different asphaltenes (from stable oil, instable oil, and deposit) were mixed at several concentrations or dispersions into the waxy crude oil. These blends were evaluated by viscometry and yield s...

  2. Pyrolysis of petroleum asphaltenes from different geological origins ...

    Indian Academy of Sciences (India)

    Home; Journals; Bulletin of Materials Science; Volume 33; Issue 4. Pyrolysis of petroleum asphaltenes from different geological origins and use of methylnaphthalenes and methylphenanthrenes as maturity indicators for asphaltenes. Manoj Kumar Sarmah Arun Borthakur Aradhana Dutta. Fuel Cells Volume 33 Issue 4 ...

  3. Pyrolysis of petroleum asphaltenes from different geological origins

    Indian Academy of Sciences (India)

    Home; Journals; Bulletin of Materials Science; Volume 36; Issue 2. Pyrolysis of petroleum asphaltenes from different geological origins and use of methylnaphthalenes and methylphenanthrenes as maturity indicators for asphaltenes. Manoj Kumar Sarmah Arun Borthakur Aradhana Dutta. Volume 36 Issue 2 April 2013 pp ...

  4. Pyrolysis of petroleum asphaltenes from different geological origins ...

    Indian Academy of Sciences (India)

    Home; Journals; Bulletin of Materials Science; Volume 36; Issue 2. Pyrolysis of petroleum asphaltenes from different geological origins and use of methylnaphthalenes and methylphenanthrenes as maturity indicators for asphaltenes. Manoj Kumar Sarmah Arun Borthakur Aradhana Dutta. Volume 36 Issue 2 April 2013 pp ...

  5. Study on the polarity, solubility, and stacking characteristics of asphaltenes

    KAUST Repository

    Zhang, Long-li

    2014-07-01

    The structure and transformation of fused aromatic ring system in asphaltenes play an important role in the character of asphaltenes, and in step affect the properties of heavy oils. Polarity, solubility and structural characteristics of asphaltenes derived from Tahe atmospheric residue (THAR) and Tuo-826 heavy crude oil (Tuo-826) were analyzed for study of their internal relationship. A fractionation method was used to separate the asphaltenes into four sub-fractions, based on their solubility in the mixed solvent, for the study of different structural and physical-chemical properties, such as polarity, solubility, morphology, stacking characteristics, and mean structural parameters. Transmission electron microscope (TEM) observation can present the intuitive morphology of asphaltene molecules, and shows that the structure of asphaltenes is in local order as well as long range disorder. The analysis results showed that n-heptane asphaltenes of THAR and Tuo-826 had larger dipole moment values, larger fused aromatic ring systems, larger mean number of stacking layers, and less interlayer spacing between stacking layers than the corresponding n-pentane asphaltenes. The sub-fractions that were inclined to precipitate from the mixture of n-heptane and tetrahydrofuran had larger polarity and less solubility. From the first sub-fraction to the fourth sub-fraction, polarity, mean stacking numbers, and average layer size from the TEM images follow a gradual decrease. The structural parameters derived from TEM images could reflect the largest fused aromatic ring system in asphaltene molecule, yet the parameters derived from 1H NMR data reflected the mean message of poly-aromatic ring systems. The structural parameters derived from TEM images were more consistent with the polarity variation of sub-fractions than those derived from 1H NMR data, which indicates that the largest fused aromatic ring system will play a more important role in the stacking characteristics of

  6. Structural Study of Asphaltenes from Iranian Heavy Crude Oil

    Directory of Open Access Journals (Sweden)

    Davarpanah L.

    2015-11-01

    Full Text Available In the present study, asphaltene precipitation from Iranian heavy crude oil (Persian Gulf off-shore was performed using n-pentane (n-C5 and n-heptane (n-C7 as light alkane precipitants. Several analytical techniques, each following different principles, were then used to structurally characterize the precipitated asphaltenes. The yield of asphaltene obtained using n-pentane precipitant was higher than asphaltene precipitated with the use of n-heptane. The asphaltene removal affected the n-C5 and n-C7 maltene fractions at temperatures below 204°C, as shown by the data obtained through the simulated distillation technique. Viscosity of heavy oil is influenced by the asphaltene content and behavior. The viscosity dependence of the test heavy oil on the shear rate applied was determined and the flow was low at y. above 25 s-1 . The reconstituted heavy oil samples were prepared by adding different amounts of asphaltenes to the maltenes (deasphalted heavy oil and asphaltene effects were more pronounced at the low temperature of 25°C as compared with those at the higher temperatures. According to the power law model used in this study the flowability of the test heavy oil exhibited a pseudoplastic character. Structural results obtained from Fourier Transform InfraRed (FTIR spectroscopy showed the presence of the different functional groups in the precipitated asphaltenes. For instance, the presence of different hydrocarbons (aliphatic, aromatic and alicyclic based on their characteristics in the FTIR spectra was confirmed. Resins are effective dispersants, and removal of this fraction from the crude oil is disturbing to the colloidal nature of heavy oil; asphaltene flocculation and precipitation eventually occur. Appearance of pores in the Scanning Electron Microscopy (SEM images was used as an indicator of the resin detachment. With the use of 1H and 13C Nuclear Magnetic Resonance (NMR spectroscopy, two important structural parameters of the

  7. A new approach in modelling asphaltene precipitation in heavy oil

    Energy Technology Data Exchange (ETDEWEB)

    Nikooker, M.; Pazuki, G.H.; Masoudi, R. [Society of Petroleum Engineers, Dubai (United Arab Emirates)]|[National Iranian Oil Co., Tehran (Iran, Islamic Republic of)

    2005-11-01

    Asphaltene precipitation in oil reservoirs can cause flow assurance problems and undermine the economy and safety of operations by causing diffusivity reduction and wettability alteration in reservoirs. A thermodynamic model was proposed for the prediction of asphaltene precipitation in n-alkenes. The Soave-Redlich-Kwong equation of state was modified based on perturbation theory in order to improve phase behaviour predictions. Parameters for 40 pure hydrocarbon and non-hydrocarbon compounds with absolute average deviation percentages of 0.814, 2.614 and 5.814 were determined using 3 phase behaviour calculations for saturated vapour pressure, vapour volume, and saturated liquid density. The modifications were applied to a Flory-Huggins model. Adjustable parameters were defined based on solubility parameters of asphaltene in heavy oil. The predicted asphaltene precipitation quantity in the modified Flory-Huggins model correlated with available experimental data. Results of the simulation indicate that the parameters of asphaltene-oil solubility have a significant effect on the amount of asphaltene precipitation. It was concluded that the modified Flory-Huggins model was successful in accurately predicting the amount of asphaltene precipitation in different proportions of the solvents. 11 refs., 2 tabs., 6 figs.

  8. Composition of asphaltenes and resins of west Siberian petroleums

    Energy Technology Data Exchange (ETDEWEB)

    Goncharov, I.V.; Babicheva, T.A.; Bodak, A.N.; Nemirovskaya, G.B.; Mashigorov, A.A.

    1985-01-01

    ESR and X-ray diffraction analysis was used to examine asphaltene and resin samples of West Siberia. Experiments were carried out to simulate the effect of catagenesis on resin and asphaltene composition. Processes of thermocatalytic transformations of crude oil in the deposit were found to have no marked effect on asphaltene and resin composition. Transformation of the organic input at sedimentation was assumed to be the main factor determining the qualitative and quantitative composition of crude oil resins and asphaltenes of West Siberia. Petroleums formed from organic matter, accumulating under reducing conditions, contain more asphaltenes and resins, they include much tetravalent vanadium and the asphaltenes have abundant paramagnetic centres. Petroleums formed from oxidized organic matter contain very little asphaltene low concentrations of paramagnetic centers, and little tetravalent vanadium. Resins of these petroleums are rich in oxygen. High levels of asphalt-resin matter in petroleums is related to the presence in the initial organic progenitors of polyunsaturated fatty acids and various nitrogen- and sulfur-containing compounds.

  9. Cooee bitumen. II. Stability of linear asphaltene nanoaggregates

    DEFF Research Database (Denmark)

    Lemarchand, Claire; Schrøder, Thomas; Dyre, J. C.

    2014-01-01

    Asphaltene and smaller aromatic molecules tend to form linear nanoaggregates in bitumen. Over the years bitumen undergoes chemical aging and during this process, the size of the nanoaggregate increases. This increase is associated with an increase in viscosity and brittleness of the bitumen...... chose first to consider the simple case where only asphaltene molecules are counted in a nanoaggregate. We used a master equation approach and a related statistical mechanics model. The linear asphaltene nanoaggregates behave as a rigid linear chain. The most complicated case where all aromatic...

  10. Analysis of Asphaltenes Subfractionated by N-Methyl-2-pyrrolidone

    DEFF Research Database (Denmark)

    Ascanius, Birgit Elkjær; Garcia, Daniel Merino; Andersen, Simon Ivar

    2004-01-01

    -pyrrolidone (NMP) as a mobile phase. However, an NMP-insoluble asphaltene fraction of 9-53 wt % was observed for different petroleum n-heptane asphaltenes. Further analysis of the insoluble fraction surprisingly has shown that this fraction hardly exhibits any ultraviolet-visible light absorption......When petroleum asphaltenes are analyzed using size exclusion chromatography (SEC), it is desirable to use a mobile phase that allows elevated temperatures and suppresses effects that are not related to size. Recent developments in the analysis of tars and pitch have tried to use N-methyl-2...

  11. A theory of phase separation in asphaltene-micellar solutions

    Energy Technology Data Exchange (ETDEWEB)

    Pacheco Sanchez, Juan H. [Instituto Mexicano del Petroleo, Mexico D.F. (Mexico)

    2001-08-01

    A theory of phase separation in micellar solutions of asphaltene in aromatic hydrocarbons was reported in this paper, based on both the approach of the phase behavior of amphiphile/water micelles, and the self-association of asphaltene in aromatic core. Several experimental techniques have been used by different investigators showing the existence of some kind of critical micellar concentration (CMC) on asphaltenes in aromatic solutions. So, at least asphaltene-monomer and asphaltene-micellar phases are experimentally demonstrated facts. These two phases are the main purpose in this report on a theoretical model. Some results show the temperature versus asphaltene concentration phase diagram. The phase diagram is examined against the limited critical micelle concentration data for asphaltenes-in-toluene systems. Such phase diagram is also qualitatively examined against an experimental demonstration of phase separation. The asphaltene-micelle growth depends on the parameter K responsible for the shape and size of it. At the same time, parameter K depends on both the number of asphaltene-monomer associated in the asphaltene-micelle, and the chemical potentials in the interior and in the periphery of the micelle. An expression for getting the number of asphaltene-monomers self-associated in the asphaltene-micelle was obtained. [Spanish] Se reporta una teoria de separacion de fases en soluciones micelares de asfalteno en hidrocarburos aromaticos, basada tanto en la conducta de fase de micelas formadas por anififilos en agua como en la autoasociacion de asfaltenos en nucleos aromaticos. Se han usado diversas tecnicas experimentales por diferentes investigadores que demuestran la existancia de algun tipo de concentracion micelar critica (CMC) de soluciones de asfaltenos en aromaticos. Entonces, al menos las fases de asfalteno-monomerico y de asfalteno-micelar son hechos experimentalmente demostrados. Esta dos fases son el principal proposito de este reporte en un modelo

  12. Comparisons Between Asphaltenes from the Dead and Live-Oil Samples of the Same Crude Oils

    DEFF Research Database (Denmark)

    Aquino-Olivos, M.A.; Andersen, Simon Ivar; Lira-Galeana, C.

    2003-01-01

    extracted and analyzed. These pressure-driven asphaltenes found on the filter were found to make up in the range between 50 and 100 ppm of the whole crude oil. Opening of the cell did not reveal asphaltenes retained due to wall adhesion. Size exclusion chromatography tests performed on both the live......-oil-derived asphaltenes and the standard asphaltenes as precipitated by atmospheric titration on the same crude oil, revealed that the live-oil asphaltenes had apparent smaller hydrodynamic volume and narrower distributions than the standard asphaltenes for two oils. Further FTIR tests also showed large differences...

  13. Modelling the effect of gas injections on the stability of asphaltene-containing crude oils

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, X.; Moorwood, T. [Infochem, Munich (Germany); Merino Garcia, D.; Pena Diez, J.L. [Repsol YPF, Madrid (Spain)

    2008-07-01

    In oil fields where asphaltene deposits occur, they present major remediation problems and can halt production due to flow blockage. Crude oils which precipitate asphaltenes generally contain both asphaltene molecules and lighter resin molecules. Resins are thought to solvate the asphaltene molecules, thus stabilizing the solution, while light gases have the opposite effect. In order to model asphaltene phase behaviour, it is important to understand the impact of adding gas to asphaltene-containing crudes. This study presented several experimental investigations of gas injection into asphaltene-containing crudes. The trends of asphaltene destabilization were discussed. The injection gases ranged from pure gases to a gas condensate. The data were modelled using a conventional equation of state together with an extra term that considered the association between asphaltene molecules and their solvation by resins. Since the model could simultaneously described the gas, oil and asphaltene phases, it was possible to calculate phase stability and phase equilibria. However, a different model had to be used to obtain the gas-oil equilibrium because the use of solubility parameters only allows the stability of the asphaltene phase to be calculated. The model correctly predicted that the gases will promote asphaltene precipitation. In its original form, the model tended to over-predict the trend. The optimal parameter values needed to represent all the available experimental data were determined. The extent to which the effect of gas injection on asphaltenes can be predicted was then discussed.

  14. Synthesis and evaluation of copolymer based on cardanol and styrene on the stability of asphaltenes

    International Nuclear Information System (INIS)

    Loureiro, Tatiana S.; Spinelli, Luciana S.

    2015-01-01

    The destabilization of asphaltenes in crude oil mainly happens due to variations in pressure, temperature and oil composition, causing significant losses. Polymers containing specific groups can be used as asphaltenes stabilizers and thus, avoid your precipitation, or as asphaltenes flocculants to assist the removal of suspended particles in a particular oil. The monitoring of asphaltenes precipitation is usually evaluated by tests with variation in stability of asphaltenes in function of adding a flocculant solvent. In this work, it was evaluated the influence of a synthesized copolymer based on cardanol and styrene on the stability of asphaltenes. The stability of asphaltenes was monitored by precipitation tests induced by a flocculant agent (n-heptane), using an ultraviolet-visible (UV-Vis) spectrometer. The structural characterization of copolymer was performed by FTIR and 1 H NMR. The results showed that copolymer can act as asphaltene flocculant. (author)

  15. Chemical composition of asphaltenes of crude oil from Baradero field in Cuba

    Energy Technology Data Exchange (ETDEWEB)

    Platonov, V.V.; Proskuryakov, V.A.; Klyavina, O.A.; Kolyabina, N.A. [L.N. Tolstoi Tula State Pedagogical Institute (Russian Federation)

    1994-09-10

    Asphaltenes of crude oil from Baradero field in Cuba have been studied by physical and physicochemical methods. Dynamics of distribution of nitrogen, sulfur, and oxygen and also various functional groups in asphaltenes has been described. These data can be used for the proper deasphalting of crude oil and further treatment of asphaltenes.

  16. Waxes in asphaltenes of crude oils and wax deposits

    Directory of Open Access Journals (Sweden)

    Yulia M. Ganeeva

    2016-07-01

    Full Text Available Abstract Composition and molecular mass distribution of n-alkanes in asphaltenes of crude oils of different ages and in wax deposits formed in the borehole equipment were studied. In asphaltenes, n-alkanes from C12 to C60 were detected. The high molecular weight paraffins in asphaltenes would form a crystalline phase with a melting point of 80–90 °C. The peculiarities of the redistribution of high molecular paraffin hydrocarbons between oil and the corresponding wax deposit were detected. In the oils, the high molecular weight paraffinic hydrocarbons C50–C60 were found, which were not practically detected in the corresponding wax deposits.

  17. A Thermodynamic Mixed-Solid Asphaltene Precipitation Model

    DEFF Research Database (Denmark)

    Lindeloff, Niels; Heidemann, R.A.; Andersen, Simon Ivar

    1998-01-01

    A simple model for the prediction of asphaltene precipitation is proposed. The model is based on an equation of state and uses standard thermodynamics, thus assuming that the precipitation phenomenon is a reversible process. The solid phase is treated as an ideal multicomponent mixture. An activity......, that out of the total PNA composition of a crude, the asphaltenes and resins are mainly aromatic-naphtenic in their nature. The predictions shows the correct qualitative behavior with respect to temperature and pressure, but due to lack of data the model was not evaluated quantitatively with respect...

  18. Aluminum Oxide Nanoparticles for Highly Efficient Asphaltene Separation from Crude Oil Using Ceramic Membrane Technology

    Directory of Open Access Journals (Sweden)

    Rezakazemi Mashallah

    2017-11-01

    Full Text Available The effects of aluminum oxide nanoparticles on the removal of asphaltenes from an Iranian crude oil (Soroush using a ceramic membrane with pore size of 0.2 µm were investigated. In order to achieve superior asphaltene separation by ultrafiltration, it is essential to make some changes for destabilizing asphaltene in crude oil. The asphaltene destabilization was done using crude oil contact with an acid containing dissolved metal ions. Metal oxide nanoparticles adsorbed asphaltene molecules and increased their molecular size. The nanoparticle of aluminum oxide was applied to alter precipitation and peptization properties of asphaltenes. Dynamic Light Scattering (DLS was used to measurement of the asphaltene molecular size dissolved in toluene. Raman spectroscopy and the Tuinstra equation were used to determine the aromatic sheet diameter (La via the integrated intensities of the G and D1 modes. This revealed that the asphaltene particles react with nano aluminum oxide and the average molecular size of asphaltene was raised from 512.754 to 2949.557 nm and La from 5.482 to 13.787. The obtained results showed that using nano aluminum oxides, asphaltene separation increased from 60–85 wt% to 90–97 wt% based on the asphaltene content of crude oil.

  19. Methods for estimating properties of hydrocarbons comprising asphaltenes based on their solubility

    Science.gov (United States)

    Schabron, John F.; Rovani, Jr., Joseph F.

    2016-10-04

    Disclosed herein is a method of estimating a property of a hydrocarbon comprising the steps of: preparing a liquid sample of a hydrocarbon, the hydrocarbon having asphaltene fractions therein; precipitating at least some of the asphaltenes of a hydrocarbon from the liquid sample with one or more precipitants in a chromatographic column; dissolving at least two of the different asphaltene fractions from the precipitated asphaltenes during a successive dissolution protocol; eluting the at least two different dissolved asphaltene fractions from the chromatographic column; monitoring the amount of the fractions eluted from the chromatographic column; using detected signals to calculate a percentage of a peak area for a first of the asphaltene fractions and a peak area for a second of the asphaltene fractions relative to the total peak areas, to determine a parameter that relates to the property of the hydrocarbon; and estimating the property of the hydrocarbon.

  20. Enhanced Oil Recovery (EOR by Miscible CO2 and Water Flooding of Asphaltenic and Non-Asphaltenic Oils

    Directory of Open Access Journals (Sweden)

    Edwin A. Chukwudeme

    2009-09-01

    Full Text Available An EOR study has been performed applying miscible CO2 flooding and compared with that for water flooding. Three different oils are used, reference oil (n-decane, model oil (n-C10, SA, toluene and 0.35 wt % asphaltene and crude oil (10 wt % asphaltene obtained from the Middle East. Stearic acid (SA is added representing a natural surfactant in oil. For the non-asphaltenic oil, miscible CO2 flooding is shown to be more favourable than that by water. However, it is interesting to see that for first years after the start of the injection (< 3 years it is shown that there is almost no difference between the recovered oils by water and CO2, after which (> 3 years oil recovery by gas injection showed a significant increase. This may be due to the enhanced performance at the increased reservoir pressure during the first period. Maximum oil recovery is shown by miscible CO2 flooding of asphaltenic oil at combined temperatures and pressures of 50 °C/90 bar and 70 °C/120 bar (no significant difference between the two cases, about 1% compared to 80 °C/140 bar. This may support the positive influence of the high combined temperatures and pressures for the miscible CO2 flooding; however beyond a certain limit the oil recovery declined due to increased asphaltene deposition. Another interesting finding in this work is that for single phase oil, an almost linear relationship is observed between the pressure drop and the asphaltene deposition regardless of the flowing fluid pressure.

  1. Pyrolysis of petroleum asphaltenes from different geological origins ...

    Indian Academy of Sciences (India)

    Administrator

    classical definition of asphaltenes is based on the solution properties. ... from which the petroleum is derived and may be expelled as part of it. In addition to their geological significance they are indispensable in either demonstrated or proven applications in ..... Yasar M, Trauth D M and Klein M T 2001 Energy Fuels 15 504.

  2. Pyrolysis of petroleum asphaltenes from different geological origins ...

    Indian Academy of Sciences (India)

    The classical definition of asphaltenes is based on the solu-. ∗ ... Later it was demonstrated that the elemental composition of asphal- tene fractions precipitated by different solvents from various sources of petroleum varies considerably (Kawanalca et al ..... Yasar M, Trauth D M and Klein M T 2001 Energy Fuels 15 504.

  3. Pyrolysis of petroleum asphaltenes from different geological origins ...

    Indian Academy of Sciences (India)

    Administrator

    alteration effects. They represent a major class of petro- leum components that have no analogous counterpart in the biological systems. This suggests that they are secon- ... present communication, asphaltenes from two crude oils of different sources ..... national meeting American Chemical Society, Chicago IL, p. 700.

  4. Pyrolysis of petroleum asphaltenes from different geological origins ...

    Indian Academy of Sciences (India)

    ing of their role in petroleum generation, migration and ma- turation. Asphaltenes are emerging as frontier molecules in geochemical research as they provide important clues about nature and source of organics, maturation, migration and se- condary ..... Radke M 1987 Advances in petroleum geochemistry (London:.

  5. Asphaltene detection using surface enhanced Raman scattering (SERS).

    Science.gov (United States)

    Alabi, O O; Edilbi, A N F; Brolly, C; Muirhead, D; Parnell, J; Stacey, R; Bowden, S A

    2015-04-28

    Surface enhanced Raman spectroscopy using a gold substrate and excitation at 514 nm can detect sub parts per million quantities of asphaltene and thereby petroleum. This simple format and sensitivity make it transformative for applications including sample triage, flow assurance, environmental protection and analysis of unique one of a kind materials.

  6. Extraction and characterization of crude oil asphaltenes sub fractions

    International Nuclear Information System (INIS)

    Ferreira, Silas R.; Calado, Lucas S.; Honse, Siller O.; Mansur, Claudia R.E.; Lucas, Elizabete F.

    2011-01-01

    Asphaltenes from crude oil have been studied for a long time. However, until today their chemical structures and physical-chemical properties are not well established. Nowadays, it is accepted that asphaltenes are dispersed in the crude oil as macro structures, which are mainly constituted of some condensed aromatic rings (about 6-20), containing aliphatic or naphthenic groups. The asphaltenes are also defined as the crude oil fraction that is insoluble in low molar mass n-alkanes and soluble in aromatic solvents, like benzene and toluene In order to investigate the molecular structure, in this work the asphaltenes were separated by using a different procedure as that normally described in the literature and characterized by infrared spectrometry, nuclear magnetic resonance, x-ray fluorescence, elemental analyses and particle size and size distribution. The difference in subfractions polarity can be attributed not only to the aromaticity changes but also to the content of elements, such as N, O, Fe, V, Si e Ni. (author)

  7. A Thermodynamic Mixed-Solid Asphaltene Precipitation Model

    DEFF Research Database (Denmark)

    Lindeloff, Niels; Heidemann, R.A.; Andersen, Simon Ivar

    1998-01-01

    A simple model for the prediction of asphaltene precipitation is proposed. The model is based on an equation of state and uses standard thermodynamics, thus assuming that the precipitation phenomenon is a reversible process. The solid phase is treated as an ideal multicomponent mixture. An activity...

  8. Modelling of asphaltene precipitation in well column of Iranian crudes : Kuapl case study

    Energy Technology Data Exchange (ETDEWEB)

    Soulgani, B.S.; Rashtchian, D. [Sharif Univ. of Technology, Tehran, (Iran, Islamic Republic of); Tohidi, B. [Heriot-Watt Univ., Edinburgh, (United Kingdom). Inst. of Petroleum Engineering; Jamialahmadi, M. [Petroleum Univ. of Technology, Abadan (Iran, Islamic Republic of)

    2008-07-01

    Asphaltene precipitation and deposition can result in the partial or total blockage of wellbores during heavy oil recovery processes. This paper provided details of a thermodynamic model of asphaltene precipitation. The model was combined with temperature and pressure models of wellbores at an oilfield in Iran and used to predict the depth of asphaltene precipitation in the wellbores in several oilfields. Bottom hole samples were taken in order to analyze asphaltene levels. The heaviest fractions were split into components with different interaction coefficients. Peng-Robinson equation of state (EOS) was used to determine critical pressures, temperatures, molecular weights, and volume shift parameters for the heavy fractions. The asphaltene precipitation model was matched to results obtained during the experimental tests. A general kinetic deposition model was developed to calculate asphaltene deposition rates within a wellstring. Sensitivity analyses were then conducted to examine the influence of flow rates, wellhead pressure, and tubing diameter. The study showed that asphaltene precipitation in the wellstring occurs in windows limited by asphaltene flocculation onset pressures and cross points of hydrodynamic and thermodynamic conditions. It was concluded that asphaltene precipitation can be controlled by changing the operational conditions to reduce the amounts and intervals of asphaltene precipitation. 23 refs., 2 tabs., 10 figs.

  9. A combined QCM and XPS investigation of asphaltene adsorption on metal surfaces.

    Science.gov (United States)

    Rudrake, Amit; Karan, Kunal; Horton, J Hugh

    2009-04-01

    To investigate asphaltene-metal interactions, a combined quartz crystal microbalance (QCM) and X-ray photoelectron spectroscopy (XPS) study of asphaltene adsorption on a gold surface was conducted. Adsorption experiments were conducted at 25 degrees C with solutions of asphaltenes in toluene at concentrations ranging from 50 to 1500 ppm. QCM measurements yielded information on the kinetics of adsorption and further assessment of the data allowed the estimation of equilibrium adsorption levels. XPS analysis of adsorbed and bulk asphaltene demonstrated the presence of carboxylic, thiophenic, sulfide, pyridinic and pyrrolic type functional groups. The intensity of the main carbon (C-H) peak was related to surface coverage of adsorbed asphaltene as a function of asphaltene concentration by a simple mathematical model. The mass adsorption data from the QCM experiments also allowed estimation of the surface coverage, which was compared to those from XPS analyses. Surface coverage estimates as a function of asphaltene concentration could be described by a Langmuir (type-I) isotherm. The free energy of asphaltene adsorption was estimated to be -26.8+/-0.1 and -27.3+/-0.1 kJ/mol from QCM and XPS data, respectively assuming asphaltene molar mass of 750 g/gmol. QCM and XPS data was also analyzed to estimate adsorbed layer thickness after accounting for surface coverage. The thickness of the adsorbed asphaltene estimated from both XPS and QCM data analyses ranged from 6-8 nm over the entire range of adsorption concentrations investigated.

  10. Modeling and Scaling of the Viscosity of Suspensions of Asphaltene Nanoaggregates

    Directory of Open Access Journals (Sweden)

    Rajinder Pal

    2017-06-01

    Full Text Available The scaling and modeling of the viscosity of suspensions of asphaltene nanoaggregates is carried out successfully taking into consideration the solvation and clustering of nanoaggragates, and the jamming of the suspension at the glass transition volume fraction of asphaltene nanoaggregates. The nanoaggregates of asphaltenes are modeled as solvated disk-shaped “core–shell” particles taking into account the most recent small-angle neutron scattering (SANS, small-angle X-ray scattering (SAXS, and solid-state 1H NMR studies available on the size and structure of asphaltene nanoaggregates. This work is an extension of our earlier studies on modeling of asphaltene suspensions where solvation of asphaltene nanoaggregates was not considered. A new mathematical model is developed for estimating the aspect ratio (ratio of thickness to diameter of particle and the corresponding intrinsic viscosity of suspension of solvated disk-shaped asphaltene nanoaggregates using the experimental relative viscosity data of suspensions at low asphaltene concentrations. The solvation of asphaltene nanoaggregates is found to be significant. The intrinsic viscosity increases with the increase in the degree of solvation of nanoaggregates. At high concentrations of asphaltenes, clustering of solvated nanoaggregates dominates resulting in large viscosities. A new scaling law is discovered to scale the viscosity data of different asphaltene suspensions. According to the new scaling law, a unique correlation is obtained, independent of the type of asphaltene system, when the data are plotted as ( η r − 1 / [ η ] S versus ϕ S where η r is the relative viscosity of suspension, [ η ] S is the intrinsic viscosity of suspension of solvated nanoaggregates, and ϕ S is the volume fraction of solvated nanoaggregates. Twenty sets of experimental viscosity data on asphaltene suspensions gathered from different sources are used to verify and confirm the scaling law and the

  11. Method for determining asphaltene stability of a hydrocarbon-containing material

    Energy Technology Data Exchange (ETDEWEB)

    Schabron, John F; Rovani, Jr., Joseph F

    2013-02-05

    A method for determining asphaltene stability in a hydrocarbon-containing material having solvated asphaltenes therein is disclosed. In at least one embodiment, it involves the steps of: (a) precipitating an amount of the asphaltenes from a liquid sample of the hydrocarbon-containing material with an alkane mobile phase solvent in a column; (b) dissolving a first amount and a second amount of the precipitated asphaltenes by changing the alkane mobile phase solvent to a final mobile phase solvent having a solubility parameter that is higher than the alkane mobile phase solvent; (c) monitoring the concentration of eluted fractions from the column; (d) creating a solubility profile of the dissolved asphaltenes in the hydrocarbon-containing material; and (e) determining one or more asphaltene stability parameters of the hydrocarbon-containing material.

  12. The importance of asphaltene origin on its behaviour in production systems

    Energy Technology Data Exchange (ETDEWEB)

    Grutters, M.; Stankiewicz, A.; Cornelisse, P.; Utech, N. [Shell Global Solutions, The Hague (Netherlands)

    2008-07-01

    Despite much progress in characterizing asphaltenes, little is known about the relation between the size and shape of asphaltenes and their impact on flow assurance. This lack of understanding is related primarily to the fact that the asphaltenes structure found in crudes depends on many geochemical processes that are generally not included as input for flow assurance studies. The geochemical processes that are important to asphaltenes are type of source rock and deposited organic matter, maturity, migration history, and processes in the reservoir as hybridization and biodegradation. A careful examination of geochemical processes can reveal the relationship between asphaltene behaviour in fields that are seemingly very different or distant. This paper provided some examples of these relationships. Understanding the structure of asphaltenes is critical and warrants the further development of methods for more accurate characterization.

  13. Chemical structure of asphaltenes of tar semicoked from Kansk-Achinsk lignite

    Energy Technology Data Exchange (ETDEWEB)

    Platanov, V.V.; Proskuryakov, V.A.; Klyavina, O.A. [Ln Tolstoi Tula State Pedagogical Institute, Tula (Russian Federation)

    1994-03-01

    The chemical structure has been studied of asphaltenes of tar semicoked from Kansk-Achinsk lignite and recovered at a temperature less than or equal to 350{degree}C. Asphaltenes have been found to be a complete mixture of aromatic, alicyclic, hydroaromatic, and heterocyclic compounds substituted by alkyl chains and various functional groups. A number of asphaltene compounds originate from steroids and triterpanes, which widely occur in lipid and tar fractions of plants and in the metabolites of microbes. A procedure based on adsorptive liquid chromatography has been developed to separate asphaltenes into a great number of eluates with considerably differing structural parameters and functional compositions.

  14. COMPARISON BETWEEN ASPHALTENES (SUBFRACTIONS EXTRACTED FROM TWO DIFFERENT ASPHALTIC RESIDUES: CHEMICAL CHARACTERIZATION AND PHASE BEHAVIOR

    Directory of Open Access Journals (Sweden)

    Silas R. Ferreira

    2016-01-01

    Full Text Available Asphaltenes are blamed for various problems in the petroleum industry, especially formation of solid deposits and stabilization of water-in-oil emulsions. Many studies have been conducted to characterize chemical structures of asphaltenes and assess their phase behavior in crude oil or in model-systems of asphaltenes extracted from oil or asphaltic residues from refineries. However, due to the diversity and complexity of these structures, there is still much to be investigated. In this study, asphaltene (subfractions were extracted from an asphaltic residue (AR02, characterized by NMR, elemental analysis, X-ray fluorescence and MS-TOF, and compared to asphaltene subfractions obtained from another asphaltic residue (AR01 described in a previous article. The (subfractions obtained from the two residues were used to prepare model-systems containing 1 wt% of asphaltenes in toluene and their phase behavior was evaluated by measuring asphaltene precipitation onset using optical microscopy. The results obtained indicated minor differences between the asphaltene fractions obtained from the asphaltic residues of distinct origins, with respect to aromaticity, elemental composition (CHN, presence and content of heteroelements and average molar mass. Regarding stability, minor differences in molecule polarity appear to promote major differences in the phase behavior of each of the asphaltene fractions isolated.

  15. Asphaltenes in Mexican fuel oils; Asfaltenos en combustoleos mexicanos

    Energy Technology Data Exchange (ETDEWEB)

    Longoria Ramirez, Rigoberto [Instituto de Investigaciones Electricas, Cuernavaca (Mexico)

    1996-12-31

    In this article the main aspects in which the Instituto de Investigaciones Electricas (IIE) has worked to contribute to the solution of problems due to the presence of asphaltenes in national fuel oils, are emphasized. The increment of these compounds, that concentrate harmful elements, in the last ten years has reached 22% by weight of the fuel oil. It is demonstrated that the quantification of asphaltenes depends on the type of solvent employed. [Espanol] En este articulo se subrayan los principales aspectos en los que el Instituto de Investigaciones Electricas (IIE) ha trabajado para contribuir a la solucion de problemas debidos a la presencia de asfaltenos en combustoleos nacionales. El incremento de estos compuestos, que concentran elementos nocivos, en los ultimos diez anos ha llegado hasta un 22% del peso del combustoleo. Se demuestra que la cuantificacion de los asfaltenos depende del tipo de solvente utilizado.

  16. Behavior of asphaltene model compounds at w/o interfaces.

    Science.gov (United States)

    Nordgård, Erland L; Sørland, Geir; Sjöblom, Johan

    2010-02-16

    Asphaltenes, present in significant amounts in heavy crude oil, contains subfractions capable of stabilizing water-in-oil emulsions. Still, the composition of these subfractions is not known in detail, and the actual mechanism behind emulsion stability is dependent on perceived interfacial concentrations and compositions. This study aims at utilizing polyaromatic surfactants which contains an acidic moiety as model compounds for the surface-active subfraction of asphaltenes. A modified pulse-field gradient (PFG) NMR method has been used to study droplet sizes and stability of emulsions prepared with asphaltene model compounds. The method has been compared to the standard microscopy droplet counting method. Arithmetic and volumetric mean droplet sizes as a function of surfactant concentration and water content clearly showed that the interfacial area was dependent on the available surfactant at the emulsion interface. Adsorption of the model compounds onto hydrophilic silica has been investigated by UV depletion, and minor differences in the chemical structure of the model compounds caused significant differences in the affinity toward this highly polar surface. The cross-sectional areas obtained have been compared to areas from the surface-to-volume ratio found by NMR and gave similar results for one of the two model compounds. The mean molecular area for this compound suggested a tilted geometry of the aromatic core with respect to the interface, which has also been proposed for real asphaltenic samples. The film behavior was further investigated using a liquid-liquid Langmuir trough supporting the ability to form stable interfacial films. This study supports that acidic, or strong hydrogen-bonding fractions, can promote stable water-in-oil emulsion. The use of model compounds opens up for studying emulsion behavior and demulsifier efficiency based on true interfacial concentrations rather than perceived interfaces.

  17. Metaphysics, science and the asphaltene phase behavior problem

    Energy Technology Data Exchange (ETDEWEB)

    Lockhart, T.P. [Eniricerche SpA, Milanese (Italy)

    1996-12-31

    Spontaneous phase separation and deposition of the asphaltenic component of crude oils is the source of costly problems in the petroleum industry. Over the past several decades so-called {open_quotes}colloid stabilization{close_quotes} model has dominated attempts to account for the phase behavior of the asphaltene fraction of the crude oil. We will argue that this model is not {open_quotes}scientific{close_quotes} in the sense that is has been applied only for the post-hoc rationalization of experimental results; absent have been serious attempts to experimentally test specific predictions deduced from the model. A critical examination of the colloid stabilization model brings to light several fundamental shortcomings. An alternative thermodynamic, or {open_quotes}solvation{close_quotes} model is shown to make predictions in far better agreement with experiment, and has been the key to developing an analytical model that accurately predicts the conditions under which crude oils become unstable to asphaltene deposition. This example will be used to argue that the defining elements of (good) scientific research - the formulation of explicit hypotheses of high predictive content and their critical evaluation, above all by experimental attempts at falsification - are also effective, indeed necessary, for analyzing the complex problems offered by the {open_quotes}real{close_quotes} world and for achieving technological advancement.

  18. Influence of asphaltene aggregation and pressure on crude oil emulsion stability

    Energy Technology Data Exchange (ETDEWEB)

    Auflem, Inge Harald

    2002-07-01

    Water-in-crude oil emulsions stabilised by various surface-active components are one of the major problems in relation to petroleum production. This thesis presents results from high-pressure separation experiments on ''live'' crude oil and model oil emulsions, as well as studies of Interactions between various indigenous stabilising materials in crude oil. A high-pressure separation rig was used to study the influence of gas and gas bubbles on the separation of water-in-crude oil emulsions. The results were interpreted as a flotation effect from rising gas bubbles, which led to increased separation efficiency. The separation properties of a ''live'' crude oil were compared to crude oil samples recombined with various gases. The results showed that water-in-oil emulsions produced from the ''live'' crude oil samples, generally separated faster and more complete, than emulsions based on recombined samples of the same crude oil. Adsorption of asphaltenes and resins onto a hydrophilic surface from solutions with varying aromatic/aliphatic character was investigated by a quarts crystal microbalance. The results showed that asphaltenes adsorbed to a larger degree than the resins. The resins were unable to desorb pre-adsorbed asphaltenes from the surface, and neither did they adsorb onto the asphaltene-coated surface. In solutions of both of resins and asphaltenes the two constituents associated in bulk liquid and adsorbed to the surface in the form of mixed aggregates. Near infrared spectroscopy and pulsed field gradient spin echo nuclear magnetic resonance were used to study asphaltene aggregation and the influence of various amphiphiles on the asphaltene aggregate size. The results showed Interactions between the asphaltenes and various chemicals, which were proposed to be due to acid-base interactions. Among the chemicals used were various naphthenic acids. Synthesised monodisperse acids gave a reduction of

  19. Modeling of Asphaltene Precipitation from Crude Oil with the Cubic Plus Association Equation of State

    DEFF Research Database (Denmark)

    Arya, Alay; Liang, Xiaodong; von Solms, Nicolas

    2017-01-01

    In this study, different modeling approaches using the Cubic Plus Association (CPA) equation of state (EoS) are developed to calculate the asphaltene precipitation onset condition and asphaltene yield from degassed crude oil during the addition of n-paraffin. A single model parameter is fitted...

  20. Enhancing the Effectiveness of Carbon Dioxide Flooding by Managing Asphaltene Precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Deo, Milind D.

    2002-02-21

    This project was undertaken to understand fundamental aspects of carbon dioxide (CO2) induced asphaltene precipitation. Oil and asphaltene samples from the Rangely field in Colorado were used for most of the project. The project consisted of pure component and high-pressure, thermodynamic experiments, thermodynamic modeling, kinetic experiments and modeling, targeted corefloods and compositional modeling.

  1. Real-time monitoring of asphaltene deposition for solvent job cycle optimization

    NARCIS (Netherlands)

    Boer, J.P. de; Linden, R.J.P. van der; Renes, W.A.

    2015-01-01

    Asphaltene agglomeration and deposition is a complex process, leading to progressive production losses without mitigative actions. Injection of asphaltenes inhibitors (solvents) in the tubing is a common practice to avoid deposition in production tubing. This does however not avoid deposition in the

  2. Impact of maltene and asphaltene fraction on mechanical behavior and microstructure of bitumen

    NARCIS (Netherlands)

    Hofko, B.; Eberhardsteiner, L.; Fussl, J.; Grothe, H.; Handle, F.; Hospodka, M.; Grossegger, D.; Nahar, S.N.; Schmets, A.J.M.; Scarpas, A.

    2015-01-01

    As a widely accepted concept, bitumen consists of four fractions that can be distinguished by their polarity. Highly polar asphaltene micelles are dispersed in a viscous phase of saturates, aromatics and resins (maltene phase). Different concentrations of asphaltenes in the bitumen result in a range

  3. Phase Behavior Modeling of Asphaltene Precipitation for Heavy Crudes: A Promising Tool Along with Experimental Data

    Science.gov (United States)

    Tavakkoli, M.; Kharrat, R.; Masihi, M.; Ghazanfari, M. H.; Fadaei, S.

    2012-12-01

    Thermodynamic modeling is known as a promising tool for phase behavior modeling of asphaltene precipitation under different conditions such as pressure depletion and CO2 injection. In this work, a thermodynamic approach is used for modeling the phase behavior of asphaltene precipitation. The precipitated asphaltene phase is represented by an improved solid model, while the oil and gas phases are modeled with an equation of state. The PR-EOS was used to perform flash calculations. Then, the onset point and the amount of precipitated asphaltene were predicted. A computer code based on an improved solid model has been developed and used for predicting asphaltene precipitation data for one of Iranian heavy crudes, under pressure depletion and CO2 injection conditions. A significant improvement has been observed in predicting the asphaltene precipitation data under gas injection conditions. Especially for the maximum value of asphaltene precipitation and for the trend of the curve after the peak point, good agreement was observed. For gas injection conditions, comparison of the thermodynamic micellization model and the improved solid model showed that the thermodynamic micellization model cannot predict the maximum of precipitation as well as the improved solid model. The non-isothermal improved solid model has been used for predicting asphaltene precipitation data under pressure depletion conditions. The pressure depletion tests were done at different levels of temperature and pressure, and the parameters of a non-isothermal model were tuned using three onset pressures at three different temperatures for the considered crude. The results showed that the model is highly sensitive to the amount of solid molar volume along with the interaction coefficient parameter between the asphaltene component and light hydrocarbon components. Using a non-isothermal improved solid model, the asphaltene phase envelope was developed. It has been revealed that at high temperatures, an

  4. An experimental study of asphaltene particle sizes in n-heptane-toluene mixtures by light scattering

    Directory of Open Access Journals (Sweden)

    Rajagopal K.

    2004-01-01

    Full Text Available The particle size of asphaltene flocculates has been the subject of many recent studies because of its importance in the control of deposition in petroleum production and processing. We measured the size of asphaltene flocculates in toluene and toluene - n-heptane mixtures, using the light-scattering technique. The asphaltenes had been extracted from Brazilian oil from the Campos Basin, according to British Standards Method IP-143/82. The asphaltene concentration in solution ranged between 10-6 g/ml and 10-7 g/ml. Sizes was measured for a period of about 10000 minutes at a constant temperature of 20°C. We found that the average size of the particles remained constant with time and increase with an increase in amount of n-heptane. The correlation obtained for size with concentration will be useful in asphaltene precipitation models.

  5. Chemical modification of cobalt ferrite nanoparticles with possible application as asphaltene flocculant agent

    Directory of Open Access Journals (Sweden)

    G. E. Oliveira

    2013-06-01

    Full Text Available Asphaltenes can cause enormous losses in the oil industry, because they are soluble only in aromatic solvents. Therefore, they must be removed from the petroleum before it is refined, using flocculant agents. Aiming to find new materials that can work as flocculant agents to asphaltenes, cobalt ferrite nanoparticles were chemically modified through acid-base reactions using dodecylbenzene sulfonic acid (DBSA to increase their lipophilicity. Nanoparticle synthesis was performed using the co-precipitation method followed by annealing of these nanoparticles, aiming to change the structural phase. Modified and unmodified nanoparticles were tested by FTIR-ATR, XRD and TGA/DTA. In addition, precipitation onset of the asphaltenes was performed using modified and unmodified nanoparticles. These tests showed that modified nanoparticles have a potential application as flocculant agents used to remove asphaltenes before oil refining, since the presence of nanoparticles promotes the asphaltene precipitation onset with the addition of a small amount of non-solvent.

  6. Chemical modification of cobalt ferrite nanoparticles with possible application as asphaltene flocculant agent

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, G.E.; Clarindo, J.E.S.; Santo, K.S.E., E-mail: geiza.oliveira@ufes.br [Universidade Federal do Espirito Santo (CCE/DQUI/UFES), Vitoria, ES (Brazil). Centro de Ciencias Exatas. Dept. de Quimica; Souza Junior, F.G. [Universidade Federal do Rio de Janeiro (IMA/UFRJ), Rio de Janeiro, RJ (Brazil). Instituto de Macromoleculas

    2013-11-01

    Asphaltenes can cause enormous losses in the oil industry, because they are soluble only in aromatic solvents. Therefore, they must be removed from the petroleum before it is refined, using flocculant agents. Aiming to find new materials that can work as flocculant agents to asphaltenes, cobalt ferrite nanoparticles were chemically modified through acid-base reactions using dodecylbenzene sulfonic acid (DBSA) to increase their lipophilicity. Nanoparticle synthesis was performed using the co-precipitation method followed by annealing of these nanoparticles, aiming to change the structural phase. Modified and unmodified nanoparticles were tested by FTIR-ATR, XRD and TGA/DTA. In addition, precipitation onset of the asphaltenes was performed using modified and unmodified nanoparticles. These tests showed that modified nanoparticles have a potential application as flocculant agents used to remove asphaltenes before oil refining, since the presence of nanoparticles promotes the asphaltene precipitation onset with the addition of a small amount of non-solvent (author)

  7. Solving asphaltene precipitation issue in vertical wells via redesigning of production facilities

    Directory of Open Access Journals (Sweden)

    Mahdi Zeinali Hasanvand

    2015-06-01

    Full Text Available Precipitation of heavy hydrocarbon components such as Wax and Asphaltenes are one of the most challenging issues in oil production processes. The associated complications extend from the reservoir to refineries and petrochemical plants. Precipitation is most destructive when the affected areas are hard to reach, for example the wellbore of producing wells. This work demonstrates the effect of adjusting choke valve sizes on thermodynamic parameters of fluid flowing in a vertical well. Our simulation results revealed optimum choke valve sizes that could keep producing vertical wells away from Asphaltene precipitation. The results of this study were implemented on a well in Darquin Reservoir that had been experiencing asphaltene precipitation. Experimental analysis of reservoir fluid, Asphaltene tests and thermodynamic simulations of well column were carried out and the most appropriate size of choke valve was determined. After replacing the well's original choke valve with the suggested choke valve, the Asphaltene precipitation problem diminished.

  8. Modeling of Asphaltene Precipitation from Crude Oil with the Cubic Plus Association Equation of State

    DEFF Research Database (Denmark)

    Arya, Alay; Liang, Xiaodong; von Solms, Nicolas

    2017-01-01

    In this study, different modeling approaches using the Cubic Plus Association (CPA) equation of state (EoS) are developed to calculate the asphaltene precipitation onset condition and asphaltene yield from degassed crude oil during the addition of n-paraffin. A single model parameter is fitted...... to calculate the asphaltene onset condition during the addition of different n-paraffin precipitants (n-pentane to n-hexadecane). Three parameters per precipitant are fitted to calculate the asphaltene yield during the addition of the precipitant. The results obtained from the model are compared...... with the experimental data for eight different crude oils. Results were also obtained for seven crudes using the Perturbed Chain Statistical Associating Fluid Theory (PC-SAFT) EoS based approach described in the literature. The CPA EoS based approaches treat the asphaltene fraction as an associating component whereas...

  9. Mesoscale Simulation and Machine Learning of Asphaltene Aggregation Phase Behavior and Molecular Assembly Landscapes.

    Science.gov (United States)

    Wang, Jiang; Gayatri, Mohit A; Ferguson, Andrew L

    2017-05-11

    Asphaltenes constitute the heaviest fraction of the aromatic group in crude oil. Aggregation and precipitation of asphaltenes during petroleum processing costs the petroleum industry billions of dollars each year due to downtime and production inefficiencies. Asphaltene aggregation proceeds via a hierarchical self-assembly process that is well-described by the Yen-Mullins model. Nevertheless, the microscopic details of the emergent cluster morphologies and their relative stability under different processing conditions remain poorly understood. We perform coarse-grained molecular dynamics simulations of a prototypical asphaltene molecule to establish a phase diagram mapping the self-assembled morphologies as a function of temperature, pressure, and n-heptane:toluene solvent ratio informing how to control asphaltene aggregation by regulating external processing conditions. We then combine our simulations with graph matching and nonlinear manifold learning to determine low-dimensional free energy surfaces governing asphaltene self-assembly. In doing so, we introduce a variant of diffusion maps designed to handle data sets with large local density variations, and report the first application of many-body diffusion maps to molecular self-assembly to recover a pseudo-1D free energy landscape. Increasing pressure only weakly affects the landscape, serving only to destabilize the largest aggregates. Increasing temperature and toluene solvent fraction stabilizes small cluster sizes and loose bonding arrangements. Although the underlying molecular mechanisms differ, the strikingly similar effect of these variables on the free energy landscape suggests that toluene acts upon asphaltene self-assembly as an effective temperature.

  10. Characterization of Physically and Chemically Separated Athabasca Asphaltenes Using Small-Angle X-ray Scattering

    Energy Technology Data Exchange (ETDEWEB)

    Amundaraín Hurtado, Jesús Leonardo; Chodakowski, Martin; Long, Bingwen; Shaw, John M. (Alberta)

    2012-02-07

    Athabasca asphaltenes were characterized using small-angle X-ray scattering (SAXS). Two methods were used to separate asphaltenes from the Athabasca bitumen: namely, chemical separation by precipitation with n-pentane and physical separation by nanofiltration using a zirconia membrane with a 20 nm average pore size. The permeate and chemically separated samples were diluted in 1-methylnaphtalene and n-dodecane prior to SAXS measurements. The temperature and asphaltene concentration ranges were 50-310 C and 1-10.4 wt %, respectively. Model-independent analysis of SAXS data provided the radius of gyration and the scattering coefficients. Model-dependent fits provided size distributions for asphaltenes assuming that they are dense and spherical. Model-independent analysis for physically and chemically separated asphaltenes showed significant differences in nominal size and structure, and the temperature dependence of structural properties. The results challenge the merits of using chemically separated asphaltene properties as a basis for asphaltene property prediction in hydrocarbon resources. While the residuals for model-dependent fits are small, the results are inconsistent with the structural parameters obtained from model-independent analysis.

  11. Study on the dipole moment of asphaltene molecules through dielectric measuring

    KAUST Repository

    Zhang, Long Li

    2015-01-01

    The polarity of asphaltenes influences production, transportation, and refining of heavy oils. However, the dipole moment of asphaltene molecules is difficult to measure due to their complex composition and electromagnetic opaqueness. In this work, we present a convenient and efficient way to determine the dipole moment of asphaltene in solution by dielectric measurements alone without measurement of the refractive index. The dipole moment of n-heptane asphaltenes of Middle East atmospheric residue (MEAR) and Ta-He atmospheric residue (THAR) are measured within the temperature range of -60°C to 20°C. There is one dielectric loss peak in the measured solutions of the two types of asphaltene at the temperatures of -60°C or -40°C, indicating there is one type of dipole in the solution. Furthermore, there are two dielectric loss peaks in the measured solutions of the two kinds of asphaltene when the temperature rises above -5°C, indicating there are two types of dipoles corresponding to the two peaks. This phenomenon indicates that as the temperature increases above -5°C, the asphaltene molecules aggregate and present larger dipole moment values. The dipole moments of MEAR C7-asphaltene aggregates are up to 5 times larger than those before aggregation. On the other hand, the dipole moments of the THAR C7-asphaltene aggregates are only 3 times larger than those before aggregation. It will be demonstrated that this method is capable of simultaneously measuring multi dipoles in one solution, instead of obtaining only the mean dipole moment. In addition, this method can be used with a wide range of concentrations and temperatures.

  12. Synthesis and characterization of the polystyrene - asphaltene graft copolymer BY FT-IR spectroscopy

    International Nuclear Information System (INIS)

    Leo, Adan Yovani; Salazar Ramiro

    2008-01-01

    The creation of new polymer compounds to be added to asphalt has drawn considerable attention because these substances have succeeded in modifying the asphalt rheological characteristics and physical properties for the enhancement of its behavior during the time of use. This work explains the synthesis of a new graft copolymer based on an asphalt fraction called asphaltene, modified with maleic anhydride. Polystyrene functionalization is conducted in a parallel fashion in order to obtain polybenzylamine resin with an amine - NH2 free group that reacts with the anhydride graft groups in the asphaltene, thus obtaining the new Polystyrene/Asphaltene graft copolymer

  13. Asphaltene self-association: Modeling and effect of fractionation with a polar solvent

    DEFF Research Database (Denmark)

    Garcia, Daniel Merino; Murgich, J; Andersen, Simon Ivar

    2004-01-01

    because it does not self-associate or because the dilution effect is not strong enough to break the aggregates. Fluorescence and IR spectroscopy experiments confirm there is self-association in INS fraction, leading to the conclusion that asphaltene aggregates are formed by bonds of different strengths......The self-association of asphaltenes in toluene is believed to occur step-wise, rather than by the formation of micelles. A number of step-wise models have been used to fit the calorimetric titration of asphaltenes in dried toluene solutions, with excellent results. All the models are based...... on chemical reactions equivalent to the ones found in polymerization. The study shows that the choice of the average properties of asphaltenes, such as the molecular weight, is critical in the final value of the parameter of interest, namely the average heat of self-association DeltaH(a). The low values...

  14. Dispersing of Petroleum Asphaltenes by Acidic Ionic Liquid and Determination by UV-Visible Spectroscopy

    Directory of Open Access Journals (Sweden)

    Eshagh Rezaee Nezhad

    2013-01-01

    Full Text Available Nowadays, constructing a mechanism to prevent the aggregation petroleum asphaltenes by the use of new acidic ionic liquids has become of fundamental importance. In this research, 3-(2-carboxybenzoyl-1-methyl-1H-imidazol-3-ium chloride ([CbMIM] [Cl] and other ionic liquids such as [CbMIM]BF4, [HMIM]Cl, [BMIM]Br, and [HMIM]HSO4 were tested. It should be noted that during the experiment the presence of the acidic ionic liquid moiety enhanced interactions between asphaltenes and acidic ionic liquids and it greatly limited asphaltene aggregation. We considered parameters such as temperature, amount of dispersant, effect of water: toluene ratio, the stirring time and effects of other ionic liquids, and determination of concentration of petroleum asphaltenes after dispersing by acidic ionic liquid under various parameters using UV-Visible spectroscopy.

  15. Studies of water-in-oil emulsions: the role of asphaltenes and resins

    International Nuclear Information System (INIS)

    Fingas, M.F.; Fieldhouse, B.

    1996-01-01

    Experiments were conducted to study the role of asphaltenes in water-in-oil emulsions. Asphaltenes are the agents that act like surfactants and are responsible for the formation and stability of these emulsions. Experiments were conducted on an emulsion that had been standing for three months, and on a salt water-oil emulsion. A series of tests were performed to study how asphaltenes would migrate in the absence of a strong gravity effect. All the experiments showed that asphaltenes migrate to the oil-water interface from the oil. This explains why an emulsion which sits for a long time can become more viscous and more stable as time progresses. Future work will determine whether resins will behave in the same manner. 36 refs., 2 tabs

  16. Modelling asphaltene precipitation equilibrium : influence of the experimental contact time and temperature

    Energy Technology Data Exchange (ETDEWEB)

    Dufour, J.; Marugan, J.; Calles, J.A.; Gimenez-Aguirre, R. [Rey Juan Carlos Univ., Madrid (Spain). Dept. of Chemical and Environmental Technology, Repsol-YPF Flow Assurance Laboratory; Pena, J.L. [Rey Juan Carlos Univ., Madrid (Spain). Dept. of Chemical and Environmental Technology, Repsol-YPF Flow Assurance Laboratory; Centro Tecnologico Repsol-YPF, Madrid (Spain); Merino-Garcia, D. [Centro Tecnologico Repsol-YPF, Madrid (Spain)

    2008-07-01

    Asphaltene deposition creates flow assurance problems and economic losses for petroleum companies. Predictive models are therefore needed to prevent these problems. Most models found in the literature are based on equilibrium calculations and must be checked against experimental data of both onset and amount of asphaltenes separated. However, the samples must be equilibrated for a long time since the kinetics of asphaltene aggregation and precipitation are slow. This paper discussed the kinetics of asphaltene precipitation, based on results obtained from a problematic South American crude and its residue. The influence of temperature, chain length of the n-alkane solvent and n-alkane/oil mass ratio was evaluated. The solids were characterized by 1H NMR, elemental analysis and Fourier transform infrared (FTIR) spectroscopy to determine their chemical structure. Metal contents (mainly Fe, V and Ni) have been measured by atomic emission spectroscopy. The true equilibrium data will be used to validate equilibrium models from the literature.

  17. Distribution of metals in vacuum residuums, asphaltenes and maltenes by PIXE

    International Nuclear Information System (INIS)

    Romero G, E.T.; Camacho M, V.; Sanchez B, A.C.; Lopez M, J.; Ramirez T, J.J.; Villasenor S, P.; Aspiazu F, J.A.

    2001-01-01

    The PIXE technique for determining directly the distribution and abundance of trace metals in vacuum residuum, asphaltenes and maltenes separated with n-alkanes (C 5 -C 8 ) is used. The metal content of petroleum derivatives revealed that the vacuum residuum contains iron, aluminium, vanadium and nickel mainly, while that the asphaltenes and maltenes maintain inside of their composition only preferably the vanadium and nickel as majority elements. (Author)

  18. Analysis of metals in asphaltenes of KU-46 by PIXE analysis

    International Nuclear Information System (INIS)

    Navidad G, P.; Pina L, L.I.; Lopez M, J.; Ramirez T, J.J.; Aspiazu F, J.A.; Romero G, E.T.

    2002-01-01

    The content of metals of the asphaltenes obtained from the KU-46 mexican crude with n-heptane was evaluated. The found metals in higher concentration are transition metals as well as the vanadium, nickel, copper and zinc. Moreover the sulfur in high concentrations was quantified. The metallic content of the asphaltenes revealed that the crude contains a lower quantity of metals unlike the vacuum residue previously analysed. (Author)

  19. Prediction of the Gas Injection Effect on the Asphaltene Phase Envelope

    Directory of Open Access Journals (Sweden)

    Bahrami Peyman

    2015-11-01

    Full Text Available Asphaltene instability may occur when pressure, temperature and compositional variations affect the reservoir oil. Permeability reduction, wettability alteration, and plugging of wells and flow lines are the consequences of this phenomenon. Therefore, it is crucial to investigate the asphaltene behavior in different thermodynamic conditions by knowing the Asphaltene Precipitation Envelope (APE in a preventive way rather than the costly clean-up procedures. The selected reservoir oil has faced a remarkable decline in production due to several years of extraction, and Enhanced Oil Recovery (EOR has been considered as a solution. Therefore, in this paper, a comprehensive study was carried out to predict the effects of different injected gases on asphaltene onset and to prevent future asphaltene precipitation based on the laboratory data. The Advanced Redlich-Kwong-Soave (RKSA equation of state was considered to develop APE using Multiflash (Infochem Co.. For the selected reservoir oil, with temperature reduction at low temperatures, asphaltene precipitation weakened and made the onset pressure decrease, so this behavior is different from the results obtained in other published reports. On the basis of this model, several sensitivity analyses were performed with different gases (i.e., methane, CO2, N2 and associated gases to compare the risk of each gas for future EOR strategies. APE tend to expand as the amount of injected gases increases, except for CO2 gas injection, that showed another unconventional behavior for this crude oil. It was observed that for CO2 gas injection below a certain temperature, asphaltene stability increased, which can be considered as a good inhibitor of asphaltene precipitation.

  20. Multi-scale simulation of asphaltene aggregation and deposition in capillary flow.

    Science.gov (United States)

    Boek, Edo S; Headen, Thomas F; Padding, Johan T

    2010-01-01

    Asphaltenes are known as the 'cholesterol' of crude oil. They form nano-aggregates, precipitate, adhere to surfaces, block rock pores and may alter the wetting characteristics of mineral surfaces within the reservoir, hindering oil recovery efficiency. Despite a significant research effort, the structure, aggregation and deposition of asphaltenes under flowing conditions remain poorly understood. For this reason, we have investigated asphaltenes, their aggregation and their deposition in capillary flow using multi-scale simulations and experiments. At the colloid scale, we use a hybrid simulation approach: for the solvent, we used the stochastic rotation dynamics (also known as multi particle collision dynamics) simulation method, which provides both hydrodynamics and Brownian motion. This is coupled to a coarse-grained MD approach for the asphaltene colloids. The colloids interact through a screened Coulomb potential with varying well depth epsilon. We tune the flow rate to obtain Pe(flow) > 1 (hydrodynamic interactions dominate) and Re force (PMF) between pairs of asphaltene molecules in an explicit solvent. We obtain a reasonable fit using a -1/r2 attraction for the attractive tail of the PMF at intermediate distances. We speculate that this is due to the two-dimensional nature of the asphaltene molecules. Finally, we discuss how we can relate this interaction to the mesoscopic colloid aggregate interaction. We assume that the colloidal aggregates consist of nano-aggregates. Taking into account observed solvent entrainment effects, we deduct the presence of lubrication layers between the nano-aggregates, which leads to a significant screening of the direct asphaltene-asphaltene interactions.

  1. Upgrading fuzzy logic by GA-PS to determine asphaltene stability in crude oil

    Directory of Open Access Journals (Sweden)

    Saeid Ahmadi

    2017-06-01

    Full Text Available Precipitation and deposition of asphaltene are undesirable phenomena that arise during petroleum production which give rise to a pronounced rate of increase in operational cost and adversely affect production rates as well. Hence, it is imperative to develop a mathematical model for the assessment of asphaltene stability in crude oil. In the present study, delta RI which constitutes the difference between refractive index of crude oil (RI and refractive index of crude oil at the onset of asphaltene precipitation (PRI is employed as the principal factor for determining the asphaltene stability of the region. Fuzzy logic is a potent tool capable of extracting the underlying dependency between SARA fractions (saturate, aromatic, resin, and asphaltene data and delta RI for the inexpensive and rapid diagnosis of asphaltene stability. In this study a novel strategy known as hybrid genetic algorithm-pattern search (GA-PS is suggested for the development of an optimal fuzzy logic model as a reliable alternative for the widely-applied subtractive clustering (SC method. While SC solely optimizes mean of input Gaussian membership functions (GMFs, GA-PS tool optimizes both mean and variance of input GMFs. Comparison between GA-PS and SC methods confirmed the capability of GA-PS for developing an optimal fuzzy logic model.

  2. Chemistry and structure of coal derived asphaltenes and preasphaltenes. Interim report

    Energy Technology Data Exchange (ETDEWEB)

    Yen, T. F.

    1979-01-01

    It is the objective of this project to isolate the asphaltene and preasphaltene fractions from coal liquids from a number of liquefaction processes. These processes consist of in general: catalytic hydrogenation, staged pyrolysis and solvent refining. The asphaltene fractions may be further separated by both gradient elution through column chromatography, and molecular size distribution through gel permeation chromatography. These coal-derived asphaltene and preashpaltene fractions will then be investigated by various chemical and physical methods for characterization of their structures. After the parameters are obtained, these parameters will be correlated with the refining and conversion variables which control a given type of liquefaction process. The effects of asphaltene in catalysis, ash or metal removal, desulfurization and denitrification will also be correlated. It is anticipated that understanding the role of asphaltenes in liquefaction processes will enable engineers to both improve existing processes, and to make recommendations for operational changes in planned liquefaction units. The objective of Phase 1 was to complete the isolation and separation of coal liquid fractions and to initiate their characterization. The objective of Phase 2 is to continue the characterization of coal asphaltenes and other coal liquid fractions by use of physical and instrumental methods. The structural parameters obtained will be used to postulate hypothetical average structures for coal liquid fractions.The objective of Phase 3 is to concentrate on the characterization of the preasphaltene (benzene insoluble fraction) of coal liquid fraction by the available physical and chemical methods to obtain a number of structural parameters.

  3. Structural Characterisation of Asphaltenes during Residue Hydrotreatment with Light Cycle Oil as an Additive

    Directory of Open Access Journals (Sweden)

    Yong-Jun Liu

    2015-01-01

    Full Text Available Several atmospheric residues (AR of Kuwaiti crude, in the absence, or in the presence, of light cycle oil (LCO as an aromatic additive, were hydrotreated in an experimental plant. Asphaltenes (precipitated from Kuwaiti AR, a hydrotreated AR, and a hydrotreated blend of AR and LCO were characterised by chemical structure and changes during residue hydrotreatment. The average structural parameters of these asphaltenes, obtained from a combined method of element analysis, average molecular weight, X-ray diffraction, and NMR, demonstrate that, after hydrotreatment, the aromatic cores of the asphaltenes become more compact and smaller whereas the peripheral alkyl branches are decreased in number and shortened. The influence of LCO on residue hydrotreating is also studied in terms of structural changes in the asphaltenes. The findings imply that LCO added to AR during hydrotreating improves the degree of aromatic substitution, the total hydrogen/carbon atomic ratio per average molecule, the distance between aromatic sheets and aliphatic chains, and so forth, by modifying the colloidal nature and microstructure of asphaltene: this is beneficial for the further hydroprocessing of AR. Three hypothetical average molecules are proposed to represent the changes undergone by such asphaltenes during hydrotreatment as well as the effects of additive LCO.

  4. A stochastic method for asphaltene structure formulation from experimental data: avoidance of implausible structures.

    Science.gov (United States)

    De León, Jennifer; Velásquez, Ana M; Hoyos, Bibian A

    2017-04-12

    This work presents a stochastic procedure designed to formulate a discrete set of molecular structures that, as a whole, adjust properly to experimental asphaltene data. This algorithm incorporates the pentane effect concept and Clar's sextet rule to the formulation process. The set of viable structures was constructed based on probability distribution functions obtained from experimental information and an isomer database containing all plausible configurations for a given number of rings, avoiding high-energy structures. This procedure was applied to a collection of experimental data from the literature. Ten sets, consisting of 5000 structures each, were obtained. Each set was then optimized. For the most accurate representation, four molecules were sufficient to properly reproduce the experimental input. The asphaltene system obtained is consistent with the reported molecular weight, number of aromatic rings and heteroatom content. Molecular dynamic simulations showed that the asphaltene representation adequately reproduced asphaltene aggregation behavior in toluene and n-heptane. In toluene, a single three-molecule aggregate was observed, and the majority of asphaltene molecules remained in a monomeric state. In n-heptane, aggregates containing up to four molecules were observed; both porous and compact aggregates were found. The asphaltene molecular representation obtained, which allows researchers to avoid inappropriate torsions in the molecule, is able to reproduce interplanar distances between aromatic cores of 4 Å or less for the aggregation state, as supported by experimental results.

  5. Determination of the zone of maximum probability of asphaltenes precipitation utilizing experimental data in an Iranian carbonate reservoir

    Energy Technology Data Exchange (ETDEWEB)

    Hamid, K.; Jamshidnezhad, M. [National Iranian South Oil Co. (Iran, Islamic Republic of)

    2005-07-01

    In the south Iranian Bangestan carbonate reservoirs, asphaltene precipitation within deep well tubing has been increasing. This is a major operational problem affecting oil production from these oil fields. Asphaltene precipitation can negatively impact the economics of oil production due to a reduction in well productivity or clogging of production facilities. This paper described the efforts to monitor this asphaltene flocculation and precipitation in oil well tubing. The monitoring technique to estimate the zone of maximum probability of asphaltene precipitation is based on the interpretation of the well flowing pressure data. Nodal analysis was used to determine pressure versus depth behavior at the well for different operational conditions. The most probable range of depth at which asphaltenes precipitation will occur was determined upon knowing the saturation pressure and the flocculation onset pressure. The purpose of this methodology is to determine the optimum operational conditions that maximize production at minimum risk of asphaltenes precipitation, and to select better preventive measures for each particular case to maintain control of the asphaltenes plugging problem. Field applications of the methodology were presented. Hydraulic fracturing is recommended to control asphaltene precipitation, depending on the depth range of asphaltenes precipitation. 6 refs., 2 tabs., 4 figs.

  6. Hindered diffusion of asphaltenes at elevated temperature and pressure. Semiannual report, March 20 - September 20, 1996

    Energy Technology Data Exchange (ETDEWEB)

    Guin, J.A.; Geelen, R.; Gregory, C.; Yang, X.

    1996-11-01

    The objectives are to: investigate the hindered diffusion of coal and petroleum asphaltenes in the pores of catalyst particles at elevated temperature and pressures; and examine the effects of concentration, temperature, solvent type, and pressure on the intraparticle diffusivity of asphaltenes. Progress was made in several areas during this time period. The high temperature/high pressure autoclave has been received from Parr Instrument Company and is in the process of being set up and checked out. During this time period we mainly worked in two areas. In the first area, we performed some measurements on the adsorption isotherms of the model compound quinoline in cyclohexane onto a Criterion 324 catalyst at three temperatures. We are looking at the effect of temperature on the adsorption isotherms of several model compounds. This area is important since the adsorptive uptake of asphaltenes is being studied and the model compound systems lend insight as to how we may expect the more complex asphaltene systems to behave during adsorption on the surface of the porous particles. We found that even for the simple model compound quinoline, the adsorption behavior vs. temperature was quite 0563 complex. The second area explored during this time period was the application of a mathematical model to adsorptive uptake data for asphaltenes on Criterion 324 catalyst particles. This adsorptive uptake data was obtained during the previous time period and was analyzed by mathematical modeling during the current time period. The detailed findings in both of these areas are presented in this report.

  7. A new thermodynamic model for the prediction of asphaltene precipitation in crude oil

    Directory of Open Access Journals (Sweden)

    Alireza Fazlali

    2010-01-01

    Full Text Available It has been proved that asphaltene precipitation is a difficult problem to define and study. Precipitation of these complex and heavy organic compounds can cause serious problems in crude oil production and transportation, residual oil processing and heavy oil combustion. Several theories have been proposed to explain the mechanism of asphaltenes precipitation. The Flory-Huggins (F-H is one of the famous models, which are used to describe the asphaltene precipitation mechanisms in the same ways as polymeric solutions. In this research, the F-H model has been modified to predict the phasebehavior of asphaltene precipitation process during adding non-polar (normal alkane solvents. The adjustable parameters of this model are computed by using a least-square approach between the modeling results and experimental data. Then, the results of these models are compared with the obtained results of the original F-H and the experimental data at different conditions. According to the interaction parameter as an adjustable parameter, four new functionalities have been used for this target. According to the obtained results, the modified model with a second order equation can predict the amount of asphaltene precipitation better than the others with a minimum error. The calculation shows good agreement between theexperimental data and the results of the modified model.

  8. Microstructural study of asphaltene precipitated with methylene chloride and n-hexane

    Energy Technology Data Exchange (ETDEWEB)

    R. Perez-Hernandez; D. Mendoza-Anaya; G. Mondragon-Galicia; M.E. Espinosa; V. Rodriguez-Lugo; M. Lozada; J. Arenas-Alatorre [Instituto Nacional de Investigaciones Nucleares, Mexico-Toluca (Mexico)

    2003-05-01

    This work presents a study of the microstructure, molecular structure and elemental composition of asphaltene precipitated from vacuum residue using a solvent mixture. The infrared spectroscopy (FTIR) results show vibration bands of functional groups such as aromatic C H (4 adj H and 1 adj H) and sulfoxide (C{sub 2}S=O). Low vacuum scanning electron microscopy (LV-SEM) reveals a highly porous and a smooth surface asphaltene. C, S and V are the main elements identified by energy dispersive X-ray spectroscopy (EDS) analysis, though some variations in concentration were observed between the porous and the smooth surface asphaltene. Transmission electron microscopy (TEM) analysis shows that asphaltenes are constituted by nanometric particles (micelles) of {approx} 50 nm in diameter. These particles conform agglomerates (flocs) from 350 to 550 nm in size, some of them in layer arrangement with a tendency to graphitize. These results reveal important information about flocculation processes of the asphaltene. 21 refs., 8 figs., 3 tabs.

  9. An investigation of heat effects in N-alkanes and asphaltenes systems

    Energy Technology Data Exchange (ETDEWEB)

    Stachowiak, C.; Grolier, J.P.E.; Randzio, S.L. [Univ. Blaise Pascal, Lab. de Thermodynamiqueet Genie Chimique, Aubiere (France); Achard, C.; Rogalski, M.; Voguie, J.R. [Univ. de Metz, Lab. de Thermodynamique et d' Analyse Chimique, Metz (France)

    2000-08-01

    We report results of studies carried out on the heat effects observed during the dilution of asphaltenic crude oil by n-alkanes. The dilution process induces aspheltene flocculation. However, the flocculation is not a first order phase transition and no strong heat effect is expected. The experimental results show that significant endo- and exo-thermic effects occur in this case. Titration calorimetry and inverse chromatography were used to elucidate the nature and the intensity of these thermal phenomena. The calorimetric titration of two crude oils by n-heptane was performed at ambient temperature. Then, the two oils were stabilised with behenic and titrated by n-heptane. Behenic acid, CH{sub 3}(CH{sub 2}){sub 20} CO{sub 2}H, has dispersing effect on asphaltenes and influences the flocculation onset. The chromatographic study was performed using columns coated with asphaltenes or with mixtures containing asphaltenes, in the temperature range between 340 and 520 K. Indirect enthalpic data obtained by this method over wide temperature ranges complete the direct calorimetric measurements. It can be hypothesised that observed heat effects are mainly due to the modifications of the asphaltenes structure. The objective of this work is to evaluate the possibility of using calorimetric methods to controlling flocculation processes in crude oils. (ln)

  10. Chemical structure of asphaltenes from tar produced in semicoking of lignite from the Kansk-Achinsk fields (Berezovka deposit)

    Energy Technology Data Exchange (ETDEWEB)

    Platonov, V.V.; Proskuryakov, V.A.; Ryltsova, S.V.; Klyavina, O.A. [Lev Tolstoi State Pedagogical University, Tula (Russian Federation)

    1998-10-01

    The chemical composition of asphaltenes from semicoking tar recovered at 450-600{degree}C from Kansk-Achinsk lignite was studied by a set of physicochemical methods. A liquid adsorption chromatographic scheme was developed for separation of asphaltenes into a large number of subfractions significantly differing in the structural parameters and in the nature and content of functional groups.

  11. Removal of asphaltene and paraffin deposits using micellar solutions and fused reactions. Final report, 1995--1997

    Energy Technology Data Exchange (ETDEWEB)

    Chang, C.L.; Nalwaya, V.; Singh, P.; Fogler, H.S.

    1998-05-01

    Chemical treatments of paraffin and asphaltene deposition by means of cleaning fluids were carried out in this research project. Research focused on the characterization of asphaltene and paraffin materials and dissolution of asphaltene and paraffin deposits using surfactant/micellar fluids developed early in the project. The key parameters controlling the dissolution rate were identified and the process of asphaltene/paraffin dissolution were examined using microscopic apparatus. Numerical modeling was also carried out to understand the dissolution of paraffin deposits. The results show that fused chemical reaction systems are a promising way of removing paraffin deposits in subsea pipelines. The fused system may be in the form of alternate pulses, emulsions systems or encapsulated catalyst systems. Fused reaction systems, in fact, are extremely cost-effective--less than 10% of the cost of replacing entire sections of the blocked pipeline. The results presented in this report can have a real impact on the petroleum industry and the National Oil Program, if it is realized that the remediation technologies developed here can substantially delay abandonment (due to asphaltene/paraffin plugging) of domestic petroleum resources. The report also sheds new light on the nature and properties of asphaltenes and paraffin deposits which will ultimately help the scientific and research community to develop effective methods in eliminating asphaltene/paraffin deposition problems. It must also be realized that asphaltene remediation technologies developed and presented in this report are a real alternative to aromatic cleaning fluids currently used by the petroleum industry.

  12. Characterization of the onset asphaltenes by focused-beam laser reflectance : a tool for chemical additives screening

    Energy Technology Data Exchange (ETDEWEB)

    Marugan, J.; Calles, J.A.; Dufour, J.; Gimenez-Aguirre, R. [Univ. Rey Juan Carlos, Madrid (Spain). URJC-Repsol-YPF Flow Assurance Laboratory, Dept. of Chemical and Environmental Technology; Pena, J.L. [Univ. Rey Juan Carlos, Madrid (Spain). URJC-Repsol-YPF Flow Assurance Laboratory, Dept. of Chemical and Environmental Technology; Centro Tecnologico Repsol-YPF, Madrid (Spain); Merino-Garcia, D. [Centro Tecnologico Repsol-YPF, Madrid (Spain)

    2008-07-01

    The deposition of asphaltenes in crude oil can cause flow assurance problems. In this study, a laser reflectance technique known as Focused-Beam Reflectance Measurement (FBRM) was used to study the kinetics of asphaltenes aggregation near onset. The FBRM tool provides a very sensitive way of determining the onset n-alkane/oil mass ratio. The influence of the n-alkane solvent and temperature on the solvent/oil threshold ratio of 2 South American crude oils with 21 and 27 API were investigated. The FBRM technique provided kinetic information about the evolution with time of the size distribution of asphaltenes flocs. Additional FBRM experiments of asphaltene redissolution and reprecipitation were also performed for a comparative evaluation, beginning with the solids recovered following the IP- 143 standard, which were fractionated into 4 different polarity groups using n-pentane - chloroform mixtures. The objective was to find correlations between polarity of the asphaltenes and its instability near the onset. Metal content was determined through atomic emission spectroscopy. The solids were characterized by 1H NMR, FT-IR spectroscopy, and vapour-pressure osmometry in order to determine the chemical and structural features of the most unstable asphaltenes. The FBRM probe was used to screen commercial chemical additives to prevent asphaltenes deposits. This technique was shown to be a very powerful tool for examining the influence of additives on the aggregation kinetics and the particle size distribution of the first asphaltene solids.

  13. Estimation of particle size and initial growth kinetics of asphaltene particles using spectral analysis of reservoir fluid

    Energy Technology Data Exchange (ETDEWEB)

    Jamaluddin, A.; Joshi, N.; Mullins, O. [Schlumberger Canada Ltd., Calgary, AB (Canada); Creek, J. [Chevron Canada Resources, Calgary, AB (Canada); McFadden, J. [BHD Petroleum, Calgary, AB (Canada)

    2002-06-01

    One of the challenges facing heavy oil reservoir management and production operations is to minimize the impact of asphaltene deposition, the most aromatic and heaviest fraction of a crude oil. A study was conducted in which both fixed wavelength near infrared (NIR) and variable wavelength spectral analysis methods were applied to two individual crude oil samples obtained from one reservoir. The objective was to assess asphaltene properties. The samples were collected using 2 different sampling chambers and techniques. Both were homogenized and treated identically. The macroscopic properties of both samples were similar, but the microscopic asphaltene particle properties varied significantly in the asphaltene particle size, as did the formation kinetics between the 2 samples. The paper also presented estimates of asphaltene particle size and initial growth kinetics from the acquired data. The properties were used to determine the basic differences between fluid samples collected using different techniques. 14 refs., 1 tab., 9 figs.

  14. Prediction of Gas Injection Effect on Asphaltene Precipitation Onset Using the Cubic and Cubic-Plus-Association Equations of State

    DEFF Research Database (Denmark)

    Arya, Alay; Liang, Xiaodong; von Solms, Nicolas

    2017-01-01

    Gas injection is a proven enhanced oil recovery technique. The gas injection changes the reservoir oil composition, temperature, and pressure conditions, which may result in asphaltene precipitation. In this work, we have used a modeling approach from the literature in order to predict asphaltene...... precipitation onset condition during gas injection. The modeling approach is used with the Soave Redlich Kwong, Soave Redlich Kwong-Plus-Huron Vidal mixing rule and cubic-plus-association (CPA) equations of state (EoS). Six different reservoir fluids are studied with respect to asphaltene onset precipitation...... on asphaltene onset conditions. The CPA EoS is more reliable than the other two models, which are sensitive to asphaltene molecular weight and sometimes predict highly nonlinear behavior outside the experimental temperature range used for fitting the model parameters....

  15. Influence of containing of asphaltenes and naphthenic acids over organic deposition inhibitor performance

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Geiza E.; Mansur, Claudia R.E.; Pires, Renata V.; Passos, Leonardo B.; Lucas, Elizabete F. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Inst. de Macromoleculas; Alvares, Dellyo R.S.; Gonzalez, Gaspar [PETROBRAS, Rio de Janeiro, RJ (Brazil). Centro de Pesquisas (CENPES)

    2004-07-01

    Organic deposition is a serious problem confronted by the petroleum industry in Brazil and worldwide. Among the main petroleum components that may cause deposition problems are waxes and asphaltenes. This work aims at evaluating the influence of petroleum fractions (asphaltenes and naphthenic acids) on the organic deposition phenomenon as well as on organic deposition inhibitors performance. The influence of the organic fractions was evaluated by their ability to change wax crystals, to lower the pour point and to alter the initial wax appearance temperature. The efficiency of the additives was tested by pour point measurements. The results show that asphaltenes seem to act as organic deposition inhibitors, while naphthenic acids do not significantly change the system. Moreover, employing both of them produces no synergic effect. Among polymeric inhibitors, all of the chemically modified EVA copolymer presented better results than the non-modified commercial EVA copolymer. The best result was observed for EVA28C{sub 16}. (author)

  16. High temperature transformation of tar-asphaltene components of oil sand bitumen

    Directory of Open Access Journals (Sweden)

    Imanbayev Yerzhan

    2017-01-01

    Full Text Available Transformations of high-molecular-weight compounds of oil sand natural bitumen under the heat treatment were studied in this work. For that purpose the natural bitumen isolated from oil sand taken from the Beke field (Kazakhstan was used as a substrate. Thermal processing of natural bitumen leads to a general change in the chemical composition of components and to an increase in the output of certain fractions. The contents of oil, tar and asphaltenes were determined and the elemental composition of tar-asphaltene compounds was evaluated. Molecular structures of the tar and asphaltene components of natural bitumen before and after cracking have been defined from the data of elemental analysis, NMR spectroscopy and molecular weight. The high molecular compounds were presented as giant molecules containing small aromatic islands some of which were linked by aliphatic chains, that was proved by infrared spectroscopy.

  17. Effect on molecular interactions of chemical alteration of petroleum asphaltenes. I

    DEFF Research Database (Denmark)

    Juyal, Priyanka; Garcia, Daniel Merino; Andersen, Simon Ivar

    2005-01-01

    Asphaltenes are naturally occurring components of crude oil and have been the subject of many studies that have involved a variety of methods to determine their complex structure, their association in crude oil with resins, and their agglomeration phenomena. Yet, the molecular structures of aspha......Asphaltenes are naturally occurring components of crude oil and have been the subject of many studies that have involved a variety of methods to determine their complex structure, their association in crude oil with resins, and their agglomeration phenomena. Yet, the molecular structures...... these fractions. Experimental data from isothermal titration calorimetry has been used in assessing the role of polar hydrogen bonding functionalities in self-association of these complex molecules. Stability characteristics of these altered asphaltenes have further been studied by onset flocculation titration...

  18. A study of some asphaltenes solutions structure and of a Safaniya vacuum residue

    Energy Technology Data Exchange (ETDEWEB)

    Guille, V.

    1996-05-20

    A lot of problems in the petroleum industry are due to the presence of asphaltenes compounds in petroleum products. A good knowledge of the chemical composition and the different properties of asphaltenes in solution are necessary to cope with these difficulties. We have then examined a Safaniya Vacuum Residue (VR) and its fractions (asphaltenes, resins, aromatics and saturates). In order to describe the macro-structure of these complex colloidal systems, we used different characterisation techniques: small angle X-ray and neutron scattering (SAXS and SANS), rheology and electron microscopy. Scattering techniques allows us to precise the model for asphaltenes and resins in solution. These macromolecules are poly-dispersed disk-like particles with thickness and diameter which are respectively close to 1 to 10 nm. The average molecular weight is equal to 106 000 for asphaltenes and 3 300 for resins. We have shown that SAXS is more sensitive to the scattering of the aromatic part of the molecule. Adding n-heptane induces first a de-solvation of the molecules and then an aggregation up to flocculation. These solutions present large heterogeneities due to concentration fluctuations. A huge difference in the chemical composition of the different asphaltenes molecules can explain these fluctuations. These heterogeneities are stable as a function of temperature; this means that exist strong molecular interactions. Ultracentrifugation gives two different fractions which contain different chemical structures, more or less aromatic. Solutions, in good solvent, of these two fractions are homogeneous but a mixture of these two fractions exhibits, heterogeneities. SAXS gives information about the structure of VR. We have observed the presence of large density fluctuations up to 300 deg. C. Rheological measurements confirm three-dimensional organisation. (author). 11 refs., 11 figs., 49 tabs.

  19. Transitiometric investigation of asphaltenic fluids under real conditions of temperature and pressure

    Energy Technology Data Exchange (ETDEWEB)

    Stachowiak, C.; Grolier, J.P.E. [Univ. Blaise Pascal, Lab. de Thermodynamique et Genie Chimique, Aubiere (France); Randzio, S. [Polish Academy of Sciences, Inst. of Physical Chemistry, Warsaw (Poland)

    2000-08-01

    Flocculation of asphaltenes is a major concern in the petroleum industry in such activities as production, extraction and transport. With the aim of characterising flocculation phenomena and primarily the flocculation threshold, titration calorimetry has already been used to study the effect of solvents on asphaltenic fluids; the precipitation of asphaltenes is in that case induced by the addition of solvent (usually n-alkanes, according to the definition of asphaltenes). We have recently developed a new experimental technique, scanning transitiometry which appears typically suitable to investigate phase changes in asphaltenic fluids. This technique which makes use of a calorimetric detector allows to scan one of the three independent variables p, V or T, while one is maintained constant. From the recording of the variation of the dependent variable and of the associated heat effect, thermomechanical coefficients of the bulk phase can be computed and phase changes detected very accurately. The scanning rates as well as the operating ranges of T and p permit to rigorously monitor the thermodynamic behaviour of the system loaded in the transitiometric cell. Moreover, a full thermodynamic study is possible over an extended p, V, T-surface and fluids under real high T-high p in-well conditions can be treated. This means also that the possible reversibility of phase transitions can be investigated with this technique. We report here a preliminary investigation on real petroleum fluids under in-well conditions of temperature and pressure. Fluids containing asphaltenes have been used to illustrate the advantages of scanning transitiometry to investigate such systems. Of particular importance is the transferring of the fluid system into the measuring cell under isobaric condition. (au)

  20. Experimental Study and Mathematical Modeling of Asphaltene Deposition Mechanism in Core Samples

    Directory of Open Access Journals (Sweden)

    Jafari Behbahani T.

    2015-11-01

    Full Text Available In this work, experimental studies were conducted to determine the effect of asphaltene deposition on the permeability reduction and porosity reduction of carbonate, sandstone and dolomite rock samples using an Iranian bottom hole live oil sample which is close to reservoir conditions, whereas in the majority of previous work, a mixture of recombined oil (a mixture of dead oil and associated gas was injected into a core sample which is far from reservoir conditions. The effect of the oil injection rate on asphaltene deposition and permeability reduction was studied. The experimental results showed that an increase in the oil injection flow rate can result in an increase in asphaltene deposition and permeability reduction. Also, it can be observed that at lower injection flow rates, a monotonic decrease in permeability of the rock samples can be attained upon increasing the injection flow rate, while at higher injection rates, after a decrease in rock permeability, an increasing trend is observed before a steady-state condition can be reached. The experimental results also showed that the rock type can affect the amount of asphaltene deposition, and the asphaltene deposition has different mechanisms in sandstone and carbonate core samples. It can be seen that the adsorption and plugging mechanisms have a more important role in asphaltene deposition in carbonate core samples than sandstone core samples. From the results, it can be observed that the pore volumes of the injected crude oil are higher for sandstone cores compared with the carbonate cores. Also, it can be inferred that three depositional types may take place during the crude oil injection, i.e., continuous deposition for low-permeability cores, slow, steady plugging for high-permeability cores and steady deposition for medium-permeability cores. It can be seen from the experimental results that damage to the core samples was found to increase when the production pressures were

  1. Fractal characteristics of an asphaltene deposited heterogeneous surface

    International Nuclear Information System (INIS)

    Amin, J. Sayyad; Ayatollahi, Sh.; Alamdari, A.

    2009-01-01

    Several methods have been employed in recent years to investigate homogeneous surface topography based on image analysis, such as AFM (atomic force microscopy) and SEM (scanning electron microscopy). Fractal analysis of the images provides fractal dimension of the surface which is used as one of the most common surface indices. Surface topography has generally been considered to be mono-fractal. On the other hand, precipitation of organic materials on a rough surface and its irregular growth result in morphology alteration and converts a homogeneous surface to a heterogeneous one. In this case a mono-fractal description of the surface does not completely describe the nature of the altered surface. This work aims to investigate the topography alteration of a glass surface as a result of asphaltene precipitation and its growth at various pressures using a bi-fractal approach. The experimental results of the deposited surfaces were clearly indicating two regions of micro- and macro-asperities namely, surface types I and II, respectively. The fractal plots were indicative of bi-fractal behavior and for each surface type one fractal dimension was calculated. The topography information of the surfaces was obtained by two image analyses, AFM and SEM imaging techniques. Results of the bi-fractal analysis demonstrated that topography alteration in surface type II (macro-asperities) is more evident than that in surface type I (micro-asperities). Compared to surface type II, a better correlation was observed between the fractal dimensions inferred from the AFM images (D A ) and those of the SEM images (D S ) in surface type I.

  2. Modeling of asphaltene particle deposition from turbulent oil flow in tubing: Model validation and a parametric study

    Directory of Open Access Journals (Sweden)

    Peyman Kor

    2016-12-01

    Full Text Available The deposition of asphaltenes on the inner wall of oil wells and pipelines causes flow blockage and significant production loss in these conduits. The major underlying mechanism(s for the deposition of asphaltene particles from the oil stream are still under investigation as an active research topic in the literature. In this work, a new deposition model considering both diffusional and inertial transport of asphaltene toward the tubing surface was developed. Model predictions were compared and verified with two sound experimental data available in the literature to evaluate the model's performance. A parametric study was done using the validated model in order to investigate the effect of the asphaltene particle size, flow velocity and oil viscosity on the magnitude of asphaltene deposition rate. Results of the study revealed that increasing the oil velocity causes more drag force on wall's inner surface; consequently, particles tend to transport away from the surface and the rate of asphaltene deposition is decreased. In addition, the developed model predicts that at low fluid velocity (∼0.7 m/s, the less viscous oil is more prone to asphaltene deposition problem.

  3. Chemistry and structure of coal-derived asphaltenes, Phase III. Quarterly progress report, July--September 1978

    Energy Technology Data Exchange (ETDEWEB)

    Yen, T. F.

    1978-01-01

    Preparative scale GPC separation of Synthoil asphaltene was carried out on styrene-divinyl benzene packing (Bio-Beads S-X8). The elution took place in the order of high to low molecular weight. Analyses indicate that aromatic ring systems with large saturated substituents elute first followed by more aromatic molecules with less saturated substituents. Infrared measurements on coal-derived asphaltenes were carried out with a large path cell (1 cm) in order to measure absorbance as a function of concentration in dilute solution down to 0.3 g/l where association between asphaltenes is not significant. VPO molecular weight studies indicate that coal-derived oils and resins undergo very little association in the solvent THF in the range 4 to 30 g/l in contrast to coal-derived asphaltenes and benzene insolubles. Thermal treatment of a Synthoil Coal liquid solvent fraction (oil + resin), in tetralin (1:2 wt. ratio) at 232/sup 0/C for 20 h resulted in the transformation of 3 to 10% of the oil + resin into asphaltene. These results support the proposed reversibility of coal liquefaction steps. Pryolysis of coal-derived asphaltenes has been shown to produce residues that are characteristic of coalesced mesophase. Asphaltenes from three liquefaction processes, Catalytic Incorporatd SRC, Synthoil, and FMC-COED, were pyrolyzed under a nitrogen atmosphere at 20/sup 0/C/h to 360/sup 0/C and at 5/sup 0/C/h to 420/sup 0/C. Crossed polarized light reflection micrographs showed a coarse deformed structure for Synthoil asphaltene, a course, but not deformed structure for Catalytic Inc. asphaltne, and a fine isotropic structure for FMC-COED asphaltene.

  4. Determination of asphaltene onset conditions using the cubic plus association equation of state

    DEFF Research Database (Denmark)

    Arya, Alay; von Solms, Nicolas; Kontogeorgis, Georgios M.

    2015-01-01

    The cubic-plus-association (CPA) equation of state (EoS) has already been proven to be a successful model for phase equilibrium calculations for systems containing associating components and has already been applied for asphaltene modeling by few researchers. In the present work, we apply the CPA...

  5. Calorimetric Evidence about the Application of the Concept of CMC to Asphaltene Self-Association

    DEFF Research Database (Denmark)

    Garcia, Daniel Merino; Andersen, Simon Ivar

    2005-01-01

    For many years, the concept of critical micellar concentration (CMC) has been projected from surfactant science into asphaltene science. There are several similarities between these two species, such as the stabilization of water-in-oil emulsions and surface activity, which suggested...

  6. Diagnosis of asphaltene stability in crude oil through “two parameters” SVM model

    DEFF Research Database (Denmark)

    Chamkalani, Ali; Mohammadi, Amir H.; Eslamimanesh, Ali

    2012-01-01

    is determined using the existing SARA fractions experimental data for this purpose. The powerful Least-Square modification of Support Vector Machine (LSSVM) strategy is applied to develop a computer program, by which the asphaltene stability region can be determined for various crudes. The developed two...

  7. Molecular mechanics and microcalorimetric investigations of the effects of molecular water on the aggregation of asphaltenes in solutions

    DEFF Research Database (Denmark)

    Murgich, J.; Lira-Galeana, C.; Garcia, Daniel Merino

    2002-01-01

    by titration calorimetry. A simple dimer dissociation model was used to derive the information about the heat and the constant of dissociation from asphaltenes of Mexico and Alaska obtained from the calorimetric data. The association enthalpies calculated were found to be in excellent agreement with those...... bond mechanism depends on the heteroatoms involved, the extension of the aromatic regions, and the steric interference present in the asphaltene molecules. The simulation results have been compared with experimental values of enthalpy of association of two different petroleum asphaltenes obtained...... measured, although the simulation only employed the interaction between averaged molecular structures....

  8. Asphaltene adsorption onto acidic/basic metal oxide nanoparticles toward in situ upgrading of reservoir oils by nanotechnology.

    Science.gov (United States)

    Hosseinpour, Negahdar; Khodadadi, Abbas Ali; Bahramian, Alireza; Mortazavi, Yadollah

    2013-11-19

    The effects of surface acidity and basicity of metal oxide nanoparticles on the thermodynamics of asphaltene adsorption were studied. Three different categories of metal oxides/salts with acidic (WO3 and NiO), amphoteric (Fe2O3 and ZrO2), and basic (MgO and CaCO3) surfaces were synthesized, and their textural, structural, and acid-base properties were characterized. Asphaltenes were extracted from a dead oil sample and characterized by X-ray powder diffraction and Fourier transform infrared spectroscopy. The acid and base numbers of the asphaltenes were measured. The nanoparticles were added to the asphaltene-toluene solutions, and the amount of adsorbed asphaltene was obtained through centrifugation followed by UV-vis spectroscopy of the supernatant liquid and temperature-programmed oxidation analysis of the precipitated solid. The concentrations of organic acid and base groups in the asphaltenes are 2.75 and 12.34 mg of KOH/g, respectively, indicating that the asphaltenes are more basic in nature. Isotherms of the asphaltene adsorption onto the six metal oxides/salts fit the Langmuir model closely. The asphaltene adsorption capacity of the nanoparticles is 1.23-3.67 mg/m(2) and decreases in the order of NiO > Fe2O3 > WO3 > MgO > CaCO3 > ZrO2, concomitant with the synergetic effects of acidity and the net charge of the surfaces. High-resolution transmission electron microscopy illustrates that the asphaltenes are spread out over the surfaces with no short-range/long-range order. The adsorption of the asphaltenes onto the six samples is exothermic and spontaneous with the Gibbs energy change of -27.80 to -28.79 kJ/mol at 25 °C. The absolute value of the enthalpy change of the adsorption is calculated to be within the range of 5-20 kJ/mol. Acid-base interaction and electrostatic attraction seem to be the dominant forces contributing to the adsorption of the asphaltenes onto the metal oxide/salt surfaces.

  9. Separation and characterization of resins and asphaltenes coming from Castilla crude Evaluation of their molecular interaction

    International Nuclear Information System (INIS)

    Navarro, Lina; Alvarez, Mario; Grosso, Jorge Luis; Navarro, Uriel

    2004-01-01

    The study of resins and asphaltenes, the heaviest fractions of oil, has become an area of interest due to the abundance of heavy crude oils in Colombia and Latin America. We studied the chemical composition of the heavy fractions of Castilla crude oil, evaluated some of its molecular parameters and found evidence of the interaction between the resins extracted from the crude with the asphaltenes of the original crude. With this objective, we carried out at the pilot plant level precipitation of the resin-asphaltene (R-A) aggregate by adding and mixing under controlled conditions, a paraffin solvent, from the Apiay refinery, called Apiasol. By extracting Soxhlet with the same solvent, resin 1 of aggregate R-A was separated. Resin ll defined as the soluble fraction that is part of the maltenes, was separated from the deasphalted crude by open column chromatography, using alumina as support, according to the SAR method (Saturated, Aromatics, Resins). The fractions of resins and the asphaltenes obtained, were characterized by: Nuclear Magnetic Resonance (NMR), FT-lR, DRX, elementary analysis (C, H, N, S), metal content (Ni and V), distribution of molecular weight by GPC, and average molecular weight by VPO. The results obtained show evidence that resin l which is part of the aggregate has less average molecular weight than resin ll which is present in the fraction of maltenes. In addition, some changes were found in the elementary analysis of among the resins. On the one hand, and taking into account the existing theories of molecular interactions among these fractions, it was found that the resins l separated from the R-A aggregate, when added to the crude, they stabilize their asphaltenes. This evaluation was carried out by analyzing the flocculation point of the crude and its mixtures with 1,9% and 3,8% of resin l, when they are titrated with a precipitating agent in an NIR cell that works with high pressure and temperature

  10. Compositional thermodynamic model of asphaltenes flocculation out of crudes; Modelisation thermodynamique compositionnelle de la floculation des bruts asphalteniques

    Energy Technology Data Exchange (ETDEWEB)

    Szewczyk, V.

    1997-12-02

    The aim of this work is to propose to the oil industry a compositional thermodynamic model able to predict the operating conditions which induce asphaltenes flocculation out of crudes. In this study, various analytical methods (calorimetry, elemental analysis, {sup 13}C nuclear magnetic resonance, neutron diffusion,...) have been used in order to get a better description of the asphaltene fraction to infer its flocculation mechanism. The proposed model describes this flocculation as a thermodynamic transition inducing the formation of a new liquid phase with a high asphaltene content and formed by all the components initially in the crude: the asphaltene deposit. Asphaltenes are represented as a pseudo-component essentially made of carbon and hydrogen. The analytical modelling of the F11-F20 light fraction is the one proposed by Jaubert (1993). The F20+ heavy fraction is represented by four pseudo-components, their physical properties are calculated using the group contribution methods of Avaullee (1995) and of Rogalski and Neau (1990). The Peng-Robinson equation of state (1976) combined with the Abdoul and Peneloux group contribution mixing rules (1989) is used in order to restitute the gas-liquid-asphaltene deposit phase equilibria. This model not being able to compute flocculation conditions on a predictive manner, the method consists in fitting some physical properties of the pseudo-components introduced in the analytical representation of the asphaltene crudes. he obtained results show results show that the proposed flocculation model is then well adapted to the description of the thermodynamic properties (saturation pressures, relative volumes, flocculation curves) of asphaltene crudes within a relatively large range of temperature (30-150 deg C) and pressure (0.1-50 MPa), covering the majority of conditions met in oil production. (author) 109 refs.

  11. The influence of petroleum asphaltenic sub fractions on the demulsifiers performance; Influencia de subfracoes asfaltenicas de petroleo sobre a acao de desemulsificantes

    Energy Technology Data Exchange (ETDEWEB)

    Honse, Siller O.; Mansur, Claudia R.E.; Lucas, Elizabete F. [Universidade Federal do Rio de Janeiro (IMA/UFRJ), RJ (Brazil). Inst. de Macromoleculas. Lab. de Macromoleculas e Coloides na Industria de Petroleo], e-mail: celias@ima.ufrj.br

    2011-07-01

    The aim of this work is to evaluate the influence of asphaltene fractions and subfractions on the stabilization of petroleum emulsions, as well as on the efficiency of demulsifiers based on poly(ethylene oxide-b-propylene oxide) (PEO-PPO). Asphaltenes were extracted from an asphaltic residue using n-heptane (C5 asphaltenes) and n-decane (asphaltenes C10). Intermediate subfractions were also obtained. Model emulsions, consisted of water and dispersions of the asphaltene in toluene were prepared, with and without adding demulsifier. The stability of the emulsions was higher when adding more polar fractions. However, asphaltenes presenting a broad distribution of polarity cause higher emulsion stability than that presenting very narrow distribution of intermediate polarity. The efficiency of PEO-PPO copolymer on emulsions separation is related to the original stability of the emulsions. In this work, it was confirmed that branched surfactant presents higher efficiency than the linear. (author)

  12. Molecular Dynamics Simulation: The Behavior of Asphaltene in Crude Oil and at the Oil/Water Interface

    KAUST Repository

    Gao, Fengfeng

    2014-12-18

    Carboxyl asphaltene is commonly discussed in the petroleum industry. In most conditions, electroneutral carboxyl asphaltene molecules can be deprotonated to become carboxylate asphaltenes. Both in crude oil and at the oil/water interface, the characteristics of anionic carboxylate asphaltenes are different than those of the carboxyl asphaltenes. In this paper, molecular dynamics (MD) simulations are utilized to study the structural features of different asphaltene molecules, namely, C5 Pe and anionic C5 Pe, at the molecular level. In crude oil, the electroneutral C5 Pe molecules prefer to form a steady face-to-face stacking, while the anionic C5 Pe molecules are inclined to form face-to-face stacking and T-shaped II stacking because of the repulsion of the anionic headgroups. Anionic C5 Pe has a distinct affinity to the oil/water interface during the simulation, while the C5 Pe molecules persist in the crude oil domain. A three-stage model of anionic C5 Pe molecules adsorbed at the oil/water interface is finally developed.

  13. Source of 1,2,3,4-tetramethylbenzene in asphaltenes from the Tarim Basin

    Science.gov (United States)

    Wanglu, Jia; Ping'an, Peng; Chiling, Yu; Zhongyao, Xiao

    2007-07-01

    1-Alkyl-2,3,6-trimethylbenzenes and a high relative amount of 1,2,3,4-tetramethylbenzene (TTMB) have been previously detected in the marine oils and asphaltenes in the oils from the Tarim Basin. In the present study, the stable carbon isotopic compositions of TTMB and n-alkanes in the pyrolysates of asphaltenes in the marine oils from the northern Tarim Basin and Silurian tar sands from the Tarim Basin were determined. TTMB has stable carbon isotopic compositions in the range from -23‰ to -24‰ and are about 12‰ more enriched in 13C than concomitant n-alkanes (-35‰ to -37‰) in the pyrolysates. The results indicate a contribution from green sulfur bacteria ( Chlorobiaceae) to TTMB. Thus, the depositional environments of the source rocks for the marine oils and the bitumen in tar sands from the Tarim Basin are characterized by periods of euxinic conditions within the photic zone.

  14. The vanadium isotopic constitution of petroleum asphaltenes: La Luna Formation (Venezuela

    Directory of Open Access Journals (Sweden)

    OLIVERA M. NESKOVIC

    2000-08-01

    Full Text Available High resolution mass spectrometry indicates that the isotopic abundance of 50vanadium (V of the Late Cretaceous La Luna petroleum asphaltenes and related source kerogen of marine origin (both highly enriched with V >> 2000 ppm is higher by about 3,5 % than that of an inorganic vanadium source (VOSO4 > 5H2O, Merck. It is proposed that the difference in the 50V/51V values between the La Luna source kerogen/the associated petroleum asphaltenes and the inorganic source can be best ascribed to the biological processing of seawater V. The fact that the isotopic compositions of V vary over a very narrow range (2.46-2.50 suggest an essentially same (or similar and fixed bilogical source of V.

  15. Synthesis and evaluation of copolymer based on cardanol and styrene on the stability of asphaltenes; Sintese e avaliacao de copolimero a base de cardanol e estireno sobre a estabilidade dos asfaltenos

    Energy Technology Data Exchange (ETDEWEB)

    Loureiro, Tatiana S.; Spinelli, Luciana S., E-mail: tatianaloureiro@ima.ufrj.br [Universidade Federal do Rio de Janeiro (UFRJ), Rio de Janeiro, RJ (Brazil). Instituto de Macromoleculas

    2015-07-01

    The destabilization of asphaltenes in crude oil mainly happens due to variations in pressure, temperature and oil composition, causing significant losses. Polymers containing specific groups can be used as asphaltenes stabilizers and thus, avoid your precipitation, or as asphaltenes flocculants to assist the removal of suspended particles in a particular oil. The monitoring of asphaltenes precipitation is usually evaluated by tests with variation in stability of asphaltenes in function of adding a flocculant solvent. In this work, it was evaluated the influence of a synthesized copolymer based on cardanol and styrene on the stability of asphaltenes. The stability of asphaltenes was monitored by precipitation tests induced by a flocculant agent (n-heptane), using an ultraviolet-visible (UV-Vis) spectrometer. The structural characterization of copolymer was performed by FTIR and {sup 1}H NMR. The results showed that copolymer can act as asphaltene flocculant. (author)

  16. Impact of Asphaltenes and Resins on the Wetting Characteristics of Tars at Former Manufactured Gas Plants

    Science.gov (United States)

    Hauswirth, S. C.; Birak, P. S.; Rylander, S.; Pedit, J. A.; Miller, C. T.

    2008-12-01

    Tars produced as a byproduct of coal and oil gasification at manufactured gas plants (MGPs) during the 19th and early 20th centuries were often released into the environment through poor disposal practices or leaks in holding tanks and piping. These tars are persistent contaminants, leaching polycyclic aromatic hydrocarbons (PAHs) into groundwater and posing a significant risk to human and ecological health. MGP tars also have several properties that make them notoriously difficult to remediate. They are denser than water, so they can migrate to depths which make direct removal difficult or impossible, and their relatively high viscosities and ability to alter the wetting characteristics of porous media result in inefficient removal by traditional pump-and-treat methods. In this study, we investigate the last of these properties. Previous studies have linked wetting changes to asphaltenes---polar, high molecular weight compounds present in the tars. However, we have conducted qualitative bottle tests for tar samples collected from two former MGPs which indicate that there is no direct correlation between asphaltene concentration and the tendency to alter wetting characteristics of porous media. To better understand the factors controlling wetting behavior, we isolate asphaltenes and resins, another class of polar compounds, from a tar sample and recombine them with the remaining PAH mixture to create a series of tars of varying composition. We assess the relative impact of each of the fractions on wettability through contact angle measurements conducted at three different pHs.

  17. Syngas obtainment from the gasification of asphaltenes of the San Fernando crude oil

    International Nuclear Information System (INIS)

    Moreno A, Laura; Rodriguez C, Fabio; Afanador R, Luz E; Grosso V, Jorge

    2010-01-01

    In this work, we developed the first study in Colombia to obtain and evaluate syngas compositions derived from asphaltenes gasification. These asphaltenes came from the implementation of a Deasphalting process to San Fernando crude oil, with the purpose of looking for technological options for their utilization. We performed the design, installation and commissioning of facilities for the gasification of asphaltenes at laboratory scale, it following an experimental methodology, performing nine tests and considering temperature and agent gasification quantity (oxygen) as independent variables. The syngas derived from gasification was analyzed by two chromatographic techniques, which reported the presence of refinery gases and sulfur. We evidenced a growth tendency of CO, H 2 and sulfur composition and a decrease in CH 4 and CO 2 composition with temperature. The composition of the syngas was evaluated with different quantities of gasification agent (33%, 40% and 47% the amount of oxygen theoretically required for complete combustion) at each temperature levels operated. It was established that when using a 40% of gasification agent, you get greater average content of CO and H 2 , which are the interest gases in the gasification process.

  18. Estimation of the size of asphaltene aggregates produced by shear of crude oil

    Energy Technology Data Exchange (ETDEWEB)

    Gmachowski, L.; Paczuski, M. [Warsaw Univ. of Technology, Plock (Poland). Inst. of Chemistry

    2008-07-01

    This study investigated asphaltene aggregation in Russian Export Blend Crude Oil (REBCO) using a Couette device over a range of shear rates similar to that in pipelines transporting the crude oil. After each experiment an amount of n-heptane was added to a crude oil sample. A turbidimeter was used to observe the sedimentation behaviour of the obtained suspension. The behaviour was found to be highly dependent on the concentration of the crude oil in the mixture. The fractal dimension was determined upon analyzing the sedimentation velocity of asphaltene aggregates. The mutual dependence between the sedimentation velocity and the turbidity for different concentrations was also determined. The fractal dimension was shown to be very close to that of the diffusion limited process, suggesting that aggregates were formed during a secondary process induced by the addition of n-heptane. The earlier aggregates produced by shear of crude oil were monomers for the secondary aggregates. The affect of the shear rate on the settling velocity-turbidity relation was very weak, indicating that the size of asphaltene aggregates produced by crude oil shear does not change much with the shear rate.

  19. Air oxidation of the kerogen/asphaltene vanadyl porphyrins: an electron spin resonance study

    Directory of Open Access Journals (Sweden)

    MIRJANA S. PAVLOVIC

    2000-02-01

    Full Text Available The thermal behavior of vanadyl porphyrins was studied by electron spin resonance during heating of kerogens, isolated from the La Luna (Venezuela and Serpiano (Switzerland bituminous rocks, at 25°C for 1 to 20 days in the presence of air. During the thermal treatment of the kerogens, the vanadyl porphyrins resonance signals decrease monotonically and become quite small after 6 days of heating. Concomitantly, new vanadyl signals appear and, at longer heating times, dominate the spectrum. It is suggested that the secondary vanadyl species must have been formed from vanadyl porphyrins. Similar conversions of vanadyl porphyrins are observed under the same experimental conditions for asphaltenes extracted from the La Luna and Serpiano rocks, and floating asphalt from the Dead Sea (Israel. A comparison of the spin-Hamiltonian parameters for vanadyl porphyrins and the vanadyl compounds obtained during pyrolysis of the kerogens/asphaltenes suggests that the latter are of a non-porphyrin type. For comparison a study was conducted on Western Kentucky No. 9 coal enriched with vanadium (>>400 ppm from six mines. All the coal samples show only the presence of predominant by non-porphyrin vanadyl compounds, similar to those generated through laboratory heating of the kerogens/asphaltenes in air. In addition, some samples also contain a minor amount of vanadyl porphyrins.

  20. The Removal of Phenol and Its Derivatives from Aqueous Solutions by Adsorption on Petroleum Asphaltene

    Directory of Open Access Journals (Sweden)

    Omer El-Amin Ahmed Adam

    2013-01-01

    Full Text Available This research describes the adsorption of phenol and o-substituted phenols and xylenol isomers on petroleum asphaltenes from aqueous solution. The results revealed that the adsorption equilibrium data were best fitted with the generalized and Freundlich isotherms. For o-substituted phenols, it was found that electron-withdrawing groups increase the adsorption capacity. The uptake of these phenols decreases in the order: o-nitrophenol > o-chlorophenol > o-aminophenol > o-cresol > phenol, while the adsorption of xylenol isomers decreases in the order: 2,6-xylenol > 2,5-xylenol > 3,5-xylenol > 3,4-xylenol. Batch equilibrium results at different temperatures suggest that the adsorption of 2,6-xylenol and 3,5-xylenol onto asphaltene is an endothermic process, values obtained were positive indicating a nonspontaneous process with increasing randomness at the solid-solution interface. The influence of solution pH on the adsorption of 3,5-xylenol on asphaltenes was also investigated. The adsorption process was found to be independent on the solution pH. The adsorption capacity of 3,5-xylenol was found to increase with the decrease in particle size of the adsorbent.

  1. Biotransformation of petroleum asphaltenes and high molecular weight polycyclic aromatic hydrocarbons by Neosartorya fischeri.

    Science.gov (United States)

    Hernández-López, E Lorena; Perezgasga, Lucia; Huerta-Saquero, Alejandro; Mouriño-Pérez, Rosa; Vazquez-Duhalt, Rafael

    2016-06-01

    Neosartorya fischeri, an Aspergillaceae fungus, was evaluated in its capacity to transform high molecular weight polycyclic aromatics hydrocarbons (HMW-PAHs) and the recalcitrant fraction of petroleum, the asphaltenes. N. fischeri was able to grow in these compounds as sole carbon source. Coronene, benzo(g,h,i)perylene, and indeno(1,2,3-c,d)pyrene, together with the asphaltenes, were assayed for fungal biotransformation. The transformation of the asphaltenes and HMW-PAHs was confirmed by reverse-phase high-performance liquid chromatography (HPLC), nano-LC mass spectrometry, and IR spectrometry. The formation of hydroxy and ketones groups on the PAH molecules suggest a biotransformation mediated by monooxygenases such as cytochrome P450 system (CYP). A comparative microarray with the complete genome from N. fischeri showed three CYP monooxygenases and one flavin monooxygenase genes upregulated. These findings, together with the internalization of aromatic substrates into fungal cells and the microsomal transformation of HMW-PAHs, strongly support the role of CYPs in the oxidation of these recalcitrant compounds.

  2. Developing grey-box model to diagnose asphaltene stability in crude oils: Application of refractive index

    Directory of Open Access Journals (Sweden)

    Mahdi Zeinali Hasanvand

    2016-12-01

    Full Text Available Asphaltene precipitation can cause serious problems in petroleum industry while diagnosing the asphaltene stability conditions in crude oil system is still a challenge and has been subject of many investigations. To monitor and diagnose asphaltene stability, high performance intelligent approaches based bio-inspired science like artificial neural network which have been optimized by various optimization techniques have been carried out. The main purpose of the implemented optimization algorithms is to decide high accurate interconnected weights of proposed neural network model. The proposed intelligent approaches are examined by using extensive experimental data reported in open literature. Moreover, to highlight robustness and precision of the addressed approaches, two different regression models have been developed and results obtained from the aforementioned intelligent models and regression approaches are compared with the corresponding refractive index data measured in laboratory. Based on the results, hybrid of genetic algorithm and particle swarm optimization have high performance and average relative absolute deviation between the model outputs and the relevant experimental data was found to be less than 0.2%. Routs from this work indicate that implication of HGAPSO-ANN in monitoring refractive index can lead to more reliable estimation of addressed issue which can lead to design of more reliable phase behavior simulation and further plans of oil production.

  3. Characterisation of crude oil components, asphaltene aggregation and emulsion stability by means of near infrared spectroscopy and multivariate analysis

    Energy Technology Data Exchange (ETDEWEB)

    Aske, Narve

    2002-06-01

    Effective separation of water-in-crude oil emulsions is a central challenge for the oil industry on the Norwegian Continental Shelf, especially with the future increase in subsea and even down-hole processing of well fluids. The mechanisms and properties governing emulsion stability are far from fully understood but the indigenous surface active crude oil components are believed to play a major role. In this work a thorough physico-chemical characterisation of a set of crude oils originating from a variety of production fields has been performed. Crude oil properties responsible for emulsion stability were identified by use of multivariate analysis techniques like partial least squares regression (PLS) and principal component analysis (PCA). Interfacial elasticity along with both asphaltene content and asphaltene aggregation state were found to be main contributors to emulsion stability. Information on a crude oils ability to form elastic crude oil-water interfaces was found to be especially crucial when discussing emulsion stability. However, measured values of interfacial elasticity were highly dependent on asphaltene aggregation state. Several experimental techniques was utilised and partly developed for the crude oil characterisation. A high-pressure liquid chromatography (HPLC) scheme was developed for SARA-fractionation of crude oils and an oscillating pendant drop tensiometer was used for characterisation of interfacial rheological properties. For emulsion stability a cell for determining the stability as a function of applied electric fields was used. In addition, near infrared spectroscopy (NIR) was used throughout the work both for chemical and physical characterisation of crude oils and model systems. High pressure NIR was used to study the aggregation of asphaltenes by pressure depletion. A new technique for detection of asphaltene aggregation onset pressures based on NIR combined with PCA was developed. It was also found that asphaltene aggregation is

  4. Chemical derivatization of Athabasca oil sand asphaltene for analysis of hydroxyl and carboxyl groups via nuclear magnetic resonance spectroscopy

    Energy Technology Data Exchange (ETDEWEB)

    Desando, M.A.; Ripmeester, J.A. [National Research Council of Canada, Ottawa, ON (Canada). Division of Chemistry

    2002-07-01

    Athabasca oil sand asphaltene was methylated with different base catalyst/solvent combinations in order to find an optimum procedure for analysis of the number and types of hydroxyl and carboxyl functional groups. High resolution carbon-13, fluorine-19, and silicon-29 NMR spectra were used to monitor the degree of methylation, trifluoroacetylation, trimethylsilylation, and aromaticity of asphaltenes. Tetra-n-butylammonium hydroxide as phase transfer base catalyst and tetrahydrofuran or dichloromethane as solvent result in enhanced O-methylation of asphaltene. At least two types of acidic oxygen containing functionality have been detected, namely, hydroxyl and carboxyl (aliphatic and aryl). On average there are few, {<=} 4-8, hydroxyl containing groups (including COOH) per asphaltene molecule. {sup 13}C NMR lineshapes suggest a broad asymmetric distribution of acidic sites. The NMR and elemental analyses allow for oxygen containing functionalities to be included in an average molecular structure. A sludge phase collected from aqueous and hydrochloric acid extractions of asphaltene has also been analyzed. A correlation is observed between the degree of O-methylation and the dielectric permittivity of the solvent and the acidity of the substrate reaction site. 62 refs., 9 figs., 2 tabs.

  5. Modeling of Asphaltene Onset Precipitation Conditions with Cubic Plus Association (CPA) and Perturbed Chain Statistical Associating Fluid Theory (PC-SAFT) Equations of State

    DEFF Research Database (Denmark)

    Arya, Alay; Liang, Xiaodong; von Solms, Nicolas

    2016-01-01

    using various equations of state and empirical models. In the past few years, association models based on CPA and SAFT equations of state have been found to be promising models for studies of asphaltene precipitation. In this work, we compare asphaltene precipitation results obtained from different...

  6. Influence of pH on Oil-Water Interfacial Tension and Mass Transfer for Asphaltenes Model Oils. Comparison with Crude Oil Behavior

    Directory of Open Access Journals (Sweden)

    Hutin Anthony

    2016-07-01

    Full Text Available Asphaltenes are shown to be amphoteric, containing acidic and basic species that can ionize at low and high pH respectively when they come in contact with water. We have used a mass transfer model in order to determine the partition coefficients of asphaltenes between oil and water. We have compared the influence of type of asphaltenes on interfacial tension and on mass transfer between oil and water and analysed the influence of an added surfactant. We have also compared the behavior of asphaltenes dissolved in model solvents with that of diluted heavy crude oils. Although asphaltenes qualitatively reproduce the behavior of crude oil components at the oil-water interface, differences were observed, either in interfacial tensions at low pH, or in partition coefficients at high pH. These differences are due to other molecules present in crude oil, which are either more interfacially active or more soluble in water.

  7. Properties of the Langmuir films made by petroleum asphaltenes. Model systems of crude oil-water emulsions; Proprietes des films de Langmuir formes par des asphaltenes du petrole. Systemes modeles des emulsions eau - petrole brut

    Energy Technology Data Exchange (ETDEWEB)

    Deghais, S.; Solimando, R. [Institut National Polytechnique de Lorraine, Ecole Nationale Superieure des Industries Chimiques, Lab. de Thermodynamique des Separations, 54 - Nancy (France); Zywocinski, A.; Rogalska, E. [Universite Henri Poincare, Lab. de Physco-Chimie des Colloides, UMR CNRS 7565, 54 - Vandoeuvre les Nancy (France); Rogalski, M.; Rogalska, E. [Metz Univ., Lab. de Thermodynamique et d' Analyse Chimique, 57 (France)

    2001-07-01

    This work deals with the analysis of the properties of the water-petroleum fluid interfaces using the Langmuir films technique. The stability of the water-petroleum emulsions is ensured by complex interactions which exist at the interface between paraffins and heavy petroleum compounds like asphaltenes and resins. The experiments performed have shown that the stabilizing properties of the asphaltene films depend on the dielectric constant of the fluid, on the presence or not of resins, and on the presence of possible paraffinic depositions. (J.S.)

  8. Isothermal Titration Calorimetry and Fluorescence Spectroscopy Study Of Asphaltene Self-Association In Toluene And Interaction With A Model Resin

    DEFF Research Database (Denmark)

    Garcia, Daniel Merino; Andersen, Simon Ivar

    2002-01-01

    This article collects the work performed by Isothermal Titration Caloritnetry (ITC) in the study of the self-association of asphaltenes in toluene solutions. Calorimetric experiments show that asphaltenes, start self-associating at very low concentrations and that the existence of a Critical...... with the results of the titration of three model molecules: nonylphenol, which associates by means of hydrogen bond formation, and coronene and pyrene, which associates by stacking. The results obtained leave open the question about the model-stacking molecules, as it was not possible to elucidate whether they do...

  9. Comparative studies on compounds occluded inside asphaltenes hierarchically released by increasing amounts of H{sub 2}O{sub 2}/CH{sub 3}COOH

    Energy Technology Data Exchange (ETDEWEB)

    Zhao Jing [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China)] [Laboratoire des Fluides Complexes, UMR 5150 TOTAL-CNRS-UPPA, BP 1155, 64013 Pau Cedex (France); Liao Zewen, E-mail: liaozw@gig.ac.cn [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Zhang Luehui [State Key Laboratory of Organic Geochemistry, Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou 510640 (China); Creux, Patrice [Laboratoire des Fluides Complexes, UMR 5150 TOTAL-CNRS-UPPA, BP 1155, 64013 Pau Cedex (France); Yang Chupeng [Guangzhou Marine Geological Survey, Ministry of Land and Resources, Guangzhou 510760 (China); Chrostowska, Anna [Institut Pluridisciplinaire de Recherche sur l' Environnement et les Materiaux, UMR CNRS 5254, Universite de Pau et des Pays de l' Adour, Av. de l' Universite, BP 1155, 64013 Pau Cedex (France); Zhang Haizu [Institute of Petroleum Exploration and Development, Tarim Oilfield Company, Korla 841000 (China); Graciaa, Alain [Laboratoire des Fluides Complexes, UMR 5150 TOTAL-CNRS-UPPA, BP 1155, 64013 Pau Cedex (France)

    2010-09-15

    Research highlights: {yields} Some other molecules are occluded inside asphaltenes {yields} These occluded molecules can be released from asphaltenes by H{sub 2}O{sub 2}/CH{sub 3}COOH oxidation {yields} These occluded molecules are representatives of the original oils from kerogens - Abstract: Being the heaviest fraction of crude oils, asphaltenes are liable to aggregate, and other molecules in the oils can be steadily adsorbed onto, and even occluded inside the macromolecular structures of the asphaltenes. These occluded compounds inside the asphaltenes can survive over geological time in oil reservoirs owing to effective protection by the macromolecular structures of the asphaltenes. The asphaltenes of a crude oil (ZG31) from the central Tarim Basin, NW China, were hierarchically degraded by increasing the amount of H{sub 2}O{sub 2}/CH{sub 3}COOH to release the occluded compounds. Besides the common components, series of even numbered n-alk-1-enes and 3-ethylalkanes were detected among the occluded compounds. Comparison of the biomarker distributions and the compound-specific C isotopic results between the compounds from the maltenes and those from the occluded fraction, the ZG31 reservoir was suggested to have been charged multiple times, with different charges being derived from different strata of source rocks.

  10. Study of flow properties of asphaltenic oils in a porous medium; Etude des proprietes d`ecoulement des bruts asphalteniques en milieu poreux

    Energy Technology Data Exchange (ETDEWEB)

    Petrova-Bensalem, R.

    1998-06-30

    Deposits of asphaltenes during production can adversely affect the exploitation of certain fields, that of Hassi Messaoud is a known example. The objective of this study is essentially focused on the damage aspects due to formation of this deposits. A methodology has been developed which makes it possible to determine the flow properties of asphaltenic oils in a porous medium under conditions close to those of a reservoir and to detect the formation of organic deposits in situ. Several types of rocks with different morphology were selected along with a number of asphaltenic oils having varied geographic origins. It was shown with these that it was possible to evaluate, in laboratory, the reduction in permeability to the oil resulting from an asphaltene deposit during the circulation of crude oil in the samples. It was observed that the variation in blocking the cores as a function of the volume of injected fluid is similar to the blocking kinetics ascertained for the retention of solid suspended particles in injection water. This similarity in the phenomena led to using particle damage models developed for the latter case. Several experiments involving blocking by asphaltenes could thus be satisfactory simulated, showing that this approach is worth developing despite the differences between the two types of colloidal suspension. The method using injection or `squeeze` of co- solvents was studied with the same systems (rock/crude oil) as a possible remedy for asphaltene deposition. To select suitable solvents and additives. A methodology was established based on application of Hansen`s theory for adjusting the polarity of solvent to the chemical properties of the asphaltene to be eliminated. This was combined with a series of in vitro tests with separated asphaltenes and the minerals of the reservoir rock. The efficiency of the co-solvents thus selected was verified by slug injection in to cores which has been damaged by asphaltenes. This approach may well help the

  11. Prediction of Gas Injection Effect on Asphaltene Precipitation Onset Using the Cubic and Cubic-Plus-Association Equations of State

    DEFF Research Database (Denmark)

    Arya, Alay; Liang, Xiaodong; von Solms, Nicolas

    2017-01-01

    precipitation onset condition during gas injection. The modeling approach is used with the Soave Redlich Kwong, Soave Redlich Kwong-Plus-Huron Vidal mixing rule and cubic-plus-association (CPA) equations of state (EoS). Six different reservoir fluids are studied with respect to asphaltene onset precipitation...

  12. Investigation of the Gas Injection Effect on Asphaltene Onset Precipitation Using the Cubic-Plus-Association Equation of State

    DEFF Research Database (Denmark)

    Arya, Alay; von Solms, Nicolas; Kontogeorgis, Georgios M.

    2016-01-01

    problem. Therefore, it is imperative to investigate beforehand the effect of gas injection into the reservoir from the modeling results. The cubic-plus-association (CPA) equation of state (EoS) has previously been applied to model the asphaltene onset precipitation condition. In this work, we adopt...

  13. Time-resolved small angle neutron scattering measurements of asphaltene nanoparticle aggregation kinetics in incompatible crude oil mixtures

    International Nuclear Information System (INIS)

    Mason, Thomas G.; Lin, Min Y.

    2003-01-01

    We use time-resolved-small angle neutron scattering to study the kinetics of asphaltene nanoparticle aggregation in incompatible crude oil mixtures. We induce asphaltene aggregation by mixing asphaltene-rich Syrian crude oil (SACO) with a paraffinic British crude oil and observe the scattered neutron intensity, I, as a function of wave number, q, over times, t, ranging from twenty minutes to about a week. We observe a growth in I at low q as the nanoscale asphaltenes agglomerate into microscale aggregates and interpret this growth as an increase in surface scattering from the aggregates. We fit I(q,t) to an empirical model and measure the growth in the power-law exponent, α, associated with the low-q logarithmic slope of I(q). We define a time, τ α , associated with the first appearance of the aggregates when α>3; τ α increases as a function of the volume fraction, φ m , of SACO in the mixture. The surface scattering intensity initially increases and then saturates at long times when the aggregate structures no longer evolve at the length scales we probe. Based on this saturation, we define a time scale, τ I , which is larger than τ α but has essentially the same dependence on φ m . We interpret τ α (φ m ) and τ I (φ m ) in terms of a simple aggregation model based on diffusion-limited kinetics and a repulsive potential barrier that models the effective solvent quality

  14. Extraction and characterization of crude oil asphaltenes sub fractions; Extracao e caracterizacao de subfracoes de asfaltenos de petroleo

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Silas R.; Calado, Lucas S.; Honse, Siller O.; Mansur, Claudia R.E.; Lucas, Elizabete F., E-mail: silas@ima.ufrj.br [Universidade Federal do Rio de Janeiro, Instituto de Macromoleculas, Laboratorio de Macromoleculas e Coloides na Industria de Petroleo, Rio de Janeiro, RJ (Brazil)

    2011-07-01

    Asphaltenes from crude oil have been studied for a long time. However, until today their chemical structures and physical-chemical properties are not well established. Nowadays, it is accepted that asphaltenes are dispersed in the crude oil as macro structures, which are mainly constituted of some condensed aromatic rings (about 6-20), containing aliphatic or naphthenic groups. The asphaltenes are also defined as the crude oil fraction that is insoluble in low molar mass n-alkanes and soluble in aromatic solvents, like benzene and toluene In order to investigate the molecular structure, in this work the asphaltenes were separated by using a different procedure as that normally described in the literature and characterized by infrared spectrometry, nuclear magnetic resonance, x-ray fluorescence, elemental analyses and particle size and size distribution. The difference in subfractions polarity can be attributed not only to the aromaticity changes but also to the content of elements, such as N, O, Fe, V, Si e Ni. (author)

  15. Organic sulphur in macromolecular sedimentary organic matter : I. Structure and origin of sulphur-containing moieties in kerogen, asphaltene and coal as revealed by flash pyrolysis

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Eglinton, T.I.; Leeuw, J.W. de; Schenk, P.A.

    1989-01-01

    The distributions of sulphur-containing compounds generated by flash pyrolysis of macromolecular sedimentary organic matter (kerogen, coal, asphaltenes) were studied by gas chromatography in combination with S-selective flame photometric detection or mass spectrometry. The abundance of

  16. A Practical Approach for Formation Damage Control in Both Miscible and Immiscible CO2 Gas Flooding in Asphaltenic Crude Systems Using Water Slugs and Injection Parameters

    Science.gov (United States)

    David, Sergio Z.

    CO2 flooding has proven to be an effective technique for enhanced oil recovery. However, the application of CO2 flooding in the recovery process of asphaltenic crude systems is often avoided, as high asphaltene precipitation rates may occur. While the effects of asphaltene concetration and CO2 injection pressure on asphaltene precipitation rate have been the focus of many studies, asphaltene precipitation rate is not a reliable factor to predict the magnitude of asphaltene-induced formation damage. Wettability alteration is only caused by the immobile asphaltene deposits on the rock surface. The enternmaint of flocs may occur at high fluid velocity. Morover, the effective permeability reduction is only caused by the flocs, which have become large enough to block the pore throats. The dissociation of the flocs may occur under certain flow conditions. In this study, a compositional reservoir simulation was conducted using Eclipse 300 to investigate the injection practice, which avoids asphaltene-induced formation damage during both immiscible and miscible CO2 flooding in asphaltenic crude system. Without injection, at pressure above bubble point, slight precipitation occurred in the zone of the lowest pressure near the producing well. As pressure approached the bubble point, precipitation increased due to the change in the hydrocarbon composition, which suggested that the potential of asphaltene-induced formation damage is determined by the overall fluid composition. At very low pressure, precipitation decreased due to the increase in the density. As CO2 was injected below the minimum miscibility pressure, a slight precipitation occurred in the transition zone at the gas-oil interface due to the microscopic diffusion of the volatile hydrocarbon components caused by the local concentration gradients. The increase in CO2 injection rate did not significantly increase the precipitation rate. As CO2 was injected at pressure above the minimum miscibility pressure

  17. Analysis of metals in asphaltenes of KU-46 by PIXE analysis; Analisis de metales en asfaltenos de crudo mexicano KU-46 por PIXE

    Energy Technology Data Exchange (ETDEWEB)

    Navidad G, P.; Pina L, L.I.; Lopez M, J.; Ramirez T, J.J.; Aspiazu F, J.A.; Romero G, E.T. [Gerencia de Ciencias Basicas, Instituto Nacional de Investigaciones Nucleares, A.P. 18-1027, 11801 Mexico D.F. (Mexico)

    2002-07-01

    The content of metals of the asphaltenes obtained from the KU-46 mexican crude with n-heptane was evaluated. The found metals in higher concentration are transition metals as well as the vanadium, nickel, copper and zinc. Moreover the sulfur in high concentrations was quantified. The metallic content of the asphaltenes revealed that the crude contains a lower quantity of metals unlike the vacuum residue previously analysed. (Author)

  18. Configurational diffusion of asphaltenes in fresh and aged catalyst extrudates. Final technical report, September 20, 1991--September 30, 1996

    Energy Technology Data Exchange (ETDEWEB)

    Guin, J.A.

    1998-12-31

    The overall objective of this project was to investigate the diffusion of coal and petroleum asphaltenes in the pores of a supported catalyst. Experimental measurements together with mathematical modeling was conducted to determine how the diffusion rate of asphaltenes, as well as some model compounds, depended on molecule sizes and shapes. The process of diffusion in the pores of a porous medium may occur by several mechanisms. Hindered diffusion occurs when the sizes of the diffusion molecules are comparable to those of the porous pores through which they are diffusing. Hindered diffusion phenomena have been widely observed in catalytic hydrotreatment of asphaltenes, heavy oils, coal derived liquids, etc. Pore diffusion limitations can be greater in spent catalysts due to the deposition of coke and metals in the pores. In this work, a general mathematical model was developed for the hindered diffusion-adsorption of solute in a solvent onto porous materials, e. g. catalysts, from a surrounding bath. This diffusion model incorporated the nonuniformities of pore structures in the porous media. A numerical method called the Method of Lines was used to solve the nonlinear partial differential equations resulting from the mathematical model. The accuracy of the numerical solution was verified by both a mass balance in the diffusion system and satisfactory agreement with known solutions in several special cases.

  19. Modeling of asphaltene precipitation due to steam and n-alkane co-injection in the ES-SAGD process

    Energy Technology Data Exchange (ETDEWEB)

    Badamchizadeh, A.; Kohse, Bruce F.; Kumar, A. [Computer Modelling Group Ltd (Canada)

    2011-07-01

    This paper provides an insight into the SAGD process in general, and the formation of asphaltene participates in the hybrid ES-SAGD process in particular. The objective of this work was to build an EoS model able to calculate the physical and chemical properties of the bitumen and n-alkane mixture, develop a model to quantify asphaltene participates in bitumen due to n-alkane injection, and investigate their effect on the ES-SAGD process. Athabasca bitumen properties identified under various test conditions and from the results of previous efforts, mainly the SimDist experimental data, were illustrated. These data were used to develop the EoS model, which in turn was used to generate the STARS thermal simulator. Overall, the EoS model was successfully developed and hence was able to predict bitumen and n-heptane properties. Moreover, asphaltene deposition in the ES-SAGD process was modeled in the thermal simulator its effect in causing oil blockage and restrictions in the steam chamber over a long run of the process was demonstrated.

  20. Sorption and distribution of asphaltene, resin, aromatic and saturate fractions of heavy crude oil on quartz surface: molecular dynamic simulation.

    Science.gov (United States)

    Wu, Guozhong; He, Lin; Chen, Daoyi

    2013-09-01

    The molecular scale sorption, diffusion and distribution of asphaltene, resin, aromatic and saturate fractions of heavy crude oil on quartz surface were studied using molecular dynamic simulation. Sorption of saturates on quartz decreased by 31% when temperature increased from 298 to 398K while opposite trend was observed for resins, but insignificant changes were found in asphaltenes and aromatics. Despite of this variety, the main contribution of interactions was van der Waals energy (>90%) irrespective of molecular components and temperatures. The diffusion coefficient of saturates was predicted as 10.8×10(-10)m(2)s(-1) while that of the remaining fractions was about 4×10(-10)m(2)s(-1) at 298K. The most likely oil distribution on quartz surface was that aromatics and saturates transported randomly into and out of the complex consisting of asphaltenes surrounded by resins, which was influenced by temperature. Overall, the knowledge on quartz-oil and oil-oil interactions gained in this study is essential for future risk assessment and remediation activities as previous studies on soil remediation either limited to light oil fractions with <40 carbons or treated the heavy crude oil as a single pseudo entity ignoring the interactions between oil fractions. Copyright © 2013 Elsevier Ltd. All rights reserved.

  1. Mise en évidence de la polydispersité physico-chimique des asphaltènes Evidence of the Physicochemical Polydispersity of Asphaltenes

    Directory of Open Access Journals (Sweden)

    Szewczyk V.

    2006-11-01

    Full Text Available Afin d'élaborer un modèle thermodynamique capable de décrire la floculation des asphaltènes en s'appuyant au maximum sur la réalité physicochimique, nous nous sommes efforc In order to develop a thermodynamic model able to describe the flocculation of asphaltenes according to their physicochemical properties, we have tried to give a better definition of the asphaltenes chemical structure and to show its influence on the mechanism of aggregation in solution. This work consisted in :- putting in evidence the physical and chemical polydispersity of asphaltenes;- studying simultaneously the nature and the localization of the chemical functions in the asphaltene oligomers (elemental analysis, analysis of the pyrolysed products, etc. and their capacity to aggregate in solution (X-ray diffusion to better understand the aggregation mechanims and to identify the functions responsible of this aggregation;- establishing a relation between the proportion of these functions and the size of the aggregates in order to take it in account in the thermodynamic model.The fractionation of a sample of asphaltenes with increasing quantities of n-heptane has allowed to separate different classes of aggregates. For each added quantity of n-heptane, the sample of asphaltenes has been separated in an insoluble fraction and a soluble one. The insoluble fraction contains the aggregates which firstly floculate. The elemental composition of each fraction has been determined by elemetal analysis. The pyrolysis in an open medium has allowed to break the aggregates in elementary patterns, the nature of the different patterns has been determined by liquid and gazeous chromatography. The size of the aggregates has been observed by X-ray diffusion.The results of this chemical characterization have shown that the initial sample of asphaltenes is formed by a group of oligomers having different elemental compositions and different chemical structures. The aggregates which

  2. Asphaltenes analysis arising of non conventional oils; Analise de asfaltenos oriundos de petroleos nao convencionais

    Energy Technology Data Exchange (ETDEWEB)

    Silva, Fernanda B. da; Fiorio, Paula G.P.; Guimaraes, Maria Jose O.C.; Seidl, Peter R. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Escola de Quimica

    2012-07-01

    The need to use heavy fractions in an efficient way in the production of nobler fractions has motivated the search for ways of separating the asphaltenes, since these molecules increase the viscosity of the fractions submitted to distillation, contribute to the formation of coke and to poisoning and deactivation of catalysts used in process such as cracking, reform, etc, besides provoking cloggings and blockages caused by its deposition, generating losses on the productivity and increases of the operational costs. This paper evaluates the influence of solvent blends (EQ-NP) in the selective extraction of constituents of three samples from Brazilian heavy crude. For the extraction process was used two solvent blends (N1P1 and N1P2). The solvent blend composed of N1P1 showed a higher selectivity in the extraction of aggregates than N1P2. The extracted fraction was characterized by Hydrogen Nuclear Magnetic Resonance ({sup 1}H-NMR) and revealed that the chemical species extracted from different blends exhibit very small differences. (author)

  3. Study of the colloidal structure of crude oils - Characterisation of asphaltene suspensions. Relationships between microscopic description and macroscopic properties under different conditions

    International Nuclear Information System (INIS)

    Guille, Veronique; Espinat, Didier; Ravey, Jean-Claude

    1994-04-01

    The authors report the use of techniques of X-ray and neutron scattering, and of rheological measurements to characterise the macrostructure of asphaltenes in solution. They confirm the relevance of a lamellar model for asphaltene particles. They also show that the addition of resin particles results in a decrease of asphaltene size, and hides solvent effects. They also performed a characterisation of the residue of a vacuum distillation. Rheological measurements showed that this residue behaves like a Newtonian liquid above 100 C. Scattering spectra reveal a structure modification between 20 and 90 C. No significant change of the scattering spectrum is then noticed, even up to 300 C. It appears that the scattering technique does not allow an observation of structure modifications to be performed on a large size range [fr

  4. Chemical modification of a bitumen and its non-fuel uses. [Reactions of tar sand asphaltenes in synthesis of non-fuel products

    Energy Technology Data Exchange (ETDEWEB)

    Moschopedis, S.E.; Speight, J.G.

    1974-01-01

    Simple reactions are described whereby tar sand bitumen can be converted to a whole range of materials. Examples are given to illustrate the non-fuel uses of the products. The following reactions of Athabasca asphaltenes are considered: oxidation, halogenation, sulfonation and sulfomethylation, phosphorylation, hydrogenation, reactions with S and O, reactions with metal salts, and miscellaneous chemical conversions. (JGB)

  5. MULTIPLE REGRESSION ANALYSIS OF THE INFLUENCE OF CATALYST CHARACTERS SUPPORTED ON γ-Al2O3 TOWARDS THEIR HYDROCRACKING CONVERSION OF ASPHALTENE

    Directory of Open Access Journals (Sweden)

    Wega Trisunaryanti

    2010-06-01

    Full Text Available Multiple regression study of the influence of catalyst's characters with γ-Al2O3 as a support, including acidity, specific area, average pore volume, average pore radius, Ni content, and Mo content the hydrocracking conversion of asphaltene has been conducted. A multivariable regression analysis method, including regression analysis and correlation analysis, was applied on this study. Using multivariable regression, the characters of catalyst was correlated together with the data of the asphaltene conversions. Furthermore, using this method, the characters of catalyst, which have the greatest influence on conversion, may be evaluated. The results showed that there was a high correlation between catalyst characters and hydrocracking conversion of asphalten (r = 0.983. It means that the conversion was 98.3% correlated with the catalyst characters. The value of the multivariable determination coefficient was 0.966, indicating that at least 96.6% variation on the conversions was determined by combination of catalyst characters on this research. From the parameter value of regression equation, it could also be known that average pore radius and specific surface area were the two characters that have the greatest influence on the hydrocracking conversion of asphalten.   Keywords: multivariable regression, catalyst's characters, high correlation degree, determination coefficient

  6. Combustion of drops of Mexican fuel oils with high asphaltenes content; Combustion de gotas de combustoleos mexicanos con alto contenido de asfaltenos

    Energy Technology Data Exchange (ETDEWEB)

    Garcia Rodriguez, Jose Francisco [Instituto de Investigaciones Electricas, Cuernavaca (Mexico)

    1998-09-01

    In this work the combustion of fuel drops with a content of 18% of asphaltenes has been studied . The results obtained for this fuel were compared with the ones obtained for another with a content of 12% asphaltenes. The drops were suspended in a platinum filament and burned in an spherical radiant furnace. The drop size varied between 600 and 800 microns. The fuel drops with 12% asphaltenes showed shorter combustion times, a smaller diameter increment of the smaller diameter during the combustion stages and also a shorter burning time of the carbonaceous residue than the fuel drops with a content of 18% asphaltenes. [Espanol] En el presente trabajo se ha estudiado la combustion de gotas de combustible con 18% de contenido de asfaltenos. Los resultados obtenidos para este combustible se compararon con los obtenidos para otro con 12% de contenido de asfaltenos. Las gotas fueron suspendidas en un filamento de platino y quemadas en un horno radiante esferico. El tamano de las gotas vario entre 600 y 800 micras. Las gotas de combustible con 12% de asfaltenos mostraron tiempos de combustion mas cortos, un incremento del diametro menor durante las etapas de combustion y un tiempo de quemado del residuo carbonoso tambien mas corto que las gotas del combustible con 18% de contenido de asfaltenos.

  7. Comparison between asphaltenes fractions extracted from different asphaltic residue; Comparacao de fracoes de asfaltenos obtidas a partir de residuos asfalticos distintos

    Energy Technology Data Exchange (ETDEWEB)

    Barreira, Fabio R.; Lucas, Elizabete F., E-mail: fabiorbarreira@yahoo.com.br [Universidade Federal do Rio de Janeiro (UFRJ), Rio de Janeiro, RJ (Brazil); Ferreira, Silas R. [Clariant S/A, Rio de Janeiro, RJ (brazil)

    2015-07-01

    Asphaltenes are blamed for various problems in the petroleum industry, especially formation of solid deposits and stabilization of water-in-oil emulsions. Due to the diversity and complexity of these structures, there is still much to be investigated in terms of characterization and stability. In this study, asphaltene subfractions were extracted from an asphaltic residue (AR02), characterized by nuclear magnetic resonance (NMR), elemental analysis (CHN), X-ray fluorescence and time-of-flight mass spectrometry (MS-TOF), and compared to previous results obtained for another asphaltic residue. The precipitation onset of (sub)fractions was assessed by optical microscopy. The results obtained indicate there are more differences than similarities between the asphaltene fractions obtained from the asphaltic residues of distinct origins, with respect to aromaticity, elemental composition (CHN), presence and content of hetero elements and average molar mass. On the matter of stability, it seems that small differences in molecules polarity provoke great differences on phase behavior of every isolated asphaltenes fractions. (author)

  8. Probing the Carbonyl Functionality of a Petroleum Resin and Asphaltene through Oximation and Schiff Base Formation in Conjunction with N-15 NMR.

    Directory of Open Access Journals (Sweden)

    Kevin A Thorn

    Full Text Available Despite recent advances in spectroscopic techniques, there is uncertainty regarding the nature of the carbonyl groups in the asphaltene and resin fractions of crude oil, information necessary for an understanding of the physical properties and environmental fate of these materials. Carbonyl and hydroxyl group functionalities are not observed in natural abundance 13C nuclear magnetic resonance (NMR spectra of asphaltenes and resins and therefore require spin labeling techniques for detection. In this study, the carbonyl functionalities of the resin and asphaltene fractions from a light aliphatic crude oil that is the source of groundwater contamination at the long term USGS study site near Bemidji, Minnesota, have been examined through reaction with 15N-labeled hydroxylamine and aniline in conjunction with analysis by solid and liquid state 15N NMR. Ketone groups were revealed through 15N NMR detection of their oxime and Schiff base derivatives, and esters through their hydroxamic acid derivatives. Anilinohydroquinone adducts provided evidence for quinones. Some possible configurations of the ketone groups in the resin and asphaltene fractions can be inferred from a consideration of the likely reactions that lead to heterocyclic condensation products with aniline and to the Beckmann reaction products from the initially formed oximes. These include aromatic ketones and ketones adjacent to quaternary carbon centers, β-hydroxyketones, β-diketones, and β-ketoesters. In a solid state cross polarization/magic angle spinning (CP/MAS 15N NMR spectrum recorded on the underivatized asphaltene as a control, carbazole and pyrrole-like nitrogens were the major naturally abundant nitrogens detected.

  9. Rheological properties of hydrate suspensions in asphaltenic crude oils; Proprietes rheologiques de suspensions d'hydrate dans des bruts asphalteniques

    Energy Technology Data Exchange (ETDEWEB)

    Marques de Toledo Camargo, R.

    2001-03-01

    The development of offshore oil exploitation under increasing water depths has forced oil companies to increase their understanding of gas hydrate formation and transportation in multiphase flow lines in which a liquid hydrocarbon phase is present. This work deals with the flow behaviour of hydrate suspensions in which a liquid hydrocarbon is the continuous phase. Three different liquid hydrocarbons are used: an asphaltenic crude oil, a condensate completely free of asphaltenes and a mixture between the asphaltenic oil and heptane. The rheological characterisation of hydrate suspensions is the main tool employed. Two original experimental devices are used: a PVT cell adapted to operate as a Couette type rheometer and a semi-industrial flow loop. Hydrate suspensions using the asphaltenic oil showed shear-thinning behaviour and thixotropy. This behaviour is typically found in flocculated systems, in which the particles attract each other forming flocs of aggregated particles at low shear rates. The suspensions using the condensate showed Newtonian behaviour. Their relative viscosities were high, which suggests that an aggregation process between hydrate particles takes. place during hydrate formation. Finally, hydrate suspensions using the mixture asphaltenic oil-heptane showed shear-thinning behaviour, thixotropy and high relative viscosity. From these results it can be inferred that, after the achievement of the hydrate formation process, the attractive forces between hydrate particles are weak. making unlikely pipeline obstruction by an aggregation process. Nevertheless, during the hydrate formation, these attractive forces can be sufficiently high. It seems that the hydrate surface wettability is an important parameter in this phenomena. (author)

  10. Probing the carbonyl functionality of a petroleum resin and asphaltene through oximation and schiff base formation in conjunction with N-15 NMR

    Science.gov (United States)

    Thorn, Kevin A.; Cox, Larry G.

    2015-01-01

    Despite recent advances in spectroscopic techniques, there is uncertainty regarding the nature of the carbonyl groups in the asphaltene and resin fractions of crude oil, information necessary for an understanding of the physical properties and environmental fate of these materials. Carbonyl and hydroxyl group functionalities are not observed in natural abundance 13C nuclear magnetic resonance (NMR) spectra of asphaltenes and resins and therefore require spin labeling techniques for detection. In this study, the carbonyl functionalities of the resin and asphaltene fractions from a light aliphatic crude oil that is the source of groundwater contamination at the long term USGS study site near Bemidji, Minnesota, have been examined through reaction with 15N-labeled hydroxylamine and aniline in conjunction with analysis by solid and liquid state 15N NMR. Ketone groups were revealed through 15N NMR detection of their oxime and Schiff base derivatives, and esters through their hydroxamic acid derivatives. Anilinohydroquinone adducts provided evidence for quinones. Some possible configurations of the ketone groups in the resin and asphaltene fractions can be inferred from a consideration of the likely reactions that lead to heterocyclic condensation products with aniline and to the Beckmann reaction products from the initially formed oximes. These include aromatic ketones and ketones adjacent to quaternary carbon centers, β-hydroxyketones, β-diketones, and β-ketoesters. In a solid state cross polarization/magic angle spinning (CP/MAS) 15N NMR spectrum recorded on the underivatized asphaltene as a control, carbazole and pyrrole-like nitrogens were the major naturally abundant nitrogens detected.

  11. Effect of asphaltene and resin oils on the viscosity of bituminous petroleum materials to be used as asphalt primers

    Directory of Open Access Journals (Sweden)

    Bencomo, M. R.

    2006-03-01

    Full Text Available The bituminous crude from the Machete, Venezuela, area, which has such a fluid consistency that it falls outside the normal scope of the A5TM D-5 (1 penetration test exceeding the 3D-mm ceiling specified in that standard and can be used as an asphalt primer: Like other asphalt products, these materials are -chemically speaking- a mix of numerous naphthenic, paraffinic and aromatic hydrocarbons and heterocyclic compounds containing sulphur, nitrogen, oxygen and so on. They have a dense and a malthene oil phase which, along with the natural hydrocarbons additives used in these products acts as a volatile fluidizer. The former is described as a mix of asphaltenes: complex high molecular weight substances that are insoluble in paraffinic hydrocarbons and soluble in aromatic compounds such as benzene. The malthene oil phase, in turn, consists in a mix of resins and hydrocarbons and together the two constitute a colloidal system. The experiments discussed in the present paper were conducted to determine the effect of the proportion of asphaltenes and resin oils on the viscosity of such bituminous crude emulsions/ with a view to their use as primers. These experiments were run in a Parr batch reactor in a nitrogen atmosphere using n-heptane as a solvent. The resins were separated after the asphaltenes precipitated from the samples and subsequently from the malthene fraction obtained. The results showed that the asphaltenes account for the structural characteristics and consistency of the medium and the resin oils for its cohesive properties/,the malthene oils act as solvents.Los crudos extrapesados procedentes del área Machete (Venezuela son materiales de consistencia blanda o fluida, por lo que se salen del campo en el que normalmente se aplica el ensayo de penetración a productos asfálticos según el método ASTM D-5 (1, cuyo límite máximo es 30 mm, y pueden ser utilizados como pinturas asfálticas de imprimación. Al igual que otros productos

  12. Géochimie des résines et asphaltènes Geochernistry of Resins and Asphaltenes

    Directory of Open Access Journals (Sweden)

    Tissot B.

    2006-11-01

    Full Text Available Les produits lourds des huiles brutes (résines et asphaltènes jouent un rôle important dans la genèse et l'accumulation du pétrole, ainsi que dans la mise en production par des méthodes conventionnelles ou par récupération assistée. Les asphaltènes et résines sont considérés ici comme des fragments de kérogène, avec une structure d'ensemble comparable : ils peuvent constituer des intermédiaires dans la genèse de l'huile brute par dégradation thermique du kérogène. De plus, la pyrolyse des asphaltènes séparés à partir d'un pétrole biodégradé peut produire de nouveaux hydrocarbures saturés qui reproduisent la fraction saturée primitive, détruite par la dégradation ; on peut ainsi disposer d'un nouvel outil pour corréler ce type d'huiles brutes. Les produits lourds semblent défavorisés par rapport aux hydrocarbures, dans la migration de la roche-mère vers le réservoir, où les résines et asphaltènes sont proportionnellement moins abondants. La structure physique des asphaltènes et résines dans les pétroles, et en particulier l'existence d'une macrostructure du type micelles ou agrégats, est probablement responsable de la viscosité élevée des huiles lourdes. Une meilleure connaissance de cette macrostructure pourrait suggérer de nouvelles méthodes pour diminuer la viscosité et améliorer la récupération des huiles lourdes. The heavy constituents of crude oil (resins and asphaltenes play an important role in generation and accumulation of petroleum, and also in production by conventional and enhanced oil recovery processes. Asphaltenes and resins are considered here as small fragments of kerogen, with a comparable overall structure: they may act as intermediate compounds in oil generation by thermal breakdown of kerogen. Furthermore, pyrolysis of asphaltenes separated from a degraded crude oil is able to generate a new saturated hydrocarbon fraction which duplicates the original one, now degraded

  13. Atomistic modeling of oil shale kerogens and asphaltenes along with their interactions with the inorganic mineral matrix

    Energy Technology Data Exchange (ETDEWEB)

    Facelli, Julio [Univ. of Utah, Salt Lake City, UT (United States); Pugmire, Ronald [Univ. of Utah, Salt Lake City, UT (United States); Pimienta, Ian [Univ. of Utah, Salt Lake City, UT (United States)

    2011-03-31

    The goal of this project is to obtain and validate three dimensional atomistic models for the organic matter in both oil shales and oil sands. In the case of oil shales the modeling was completed for kerogen, the insoluble portion of the organic matter; for oil sands it was for asphaltenes, a class of molecules found in crude oil. The three dimensional models discussed in this report were developed starting from existing literature two dimensional models. The models developed included one kerogen, based on experimental data on a kerogen isolated from a Green River oil shale, and a set of six representative asphaltenes. Subsequently, the interactions between these organic models and an inorganic matrix was explored in order to gain insight into the chemical nature of this interaction, which could provide vital information in developing efficient methods to remove the organic material from inorganic mineral substrate. The inorganic substrate used to model the interaction was illite, an aluminum silicate oxide clay. In order to obtain the feedback necessary to validate the models, it is necessary to be able to calculate different observable quantities and to show that these observables both reproduce the results of experimental measurements on actual samples as well as that the observables are sensitive to structural differences between models. The observables that were calculated using the models include 13C NMR spectra, the IR vibrational spectra, and the atomic pair wise distribution function; these were chosen as they are among the methods for which both experimental and calculated values can be readily obtained. Where available, comparison was made to experiment results. Finally, molecular dynamic simulations of pyrolysis were completed on the models to gain an understanding into the nature of the decomposition of these materials when heated.

  14. Avaliação geoquímica de biomarcadores ocluídos em estruturas asfaltênicas Geochemical evaluation of occluded biomarkers in asphaltenic structures

    Directory of Open Access Journals (Sweden)

    Débora de Almeida Azevedo

    2009-01-01

    Full Text Available Asphaltenes from two Brazilian crude oils were submitted to mild oxidation to disrupt their structure, releasing the occluded oil. The released hydrocarbons were compared with those from the original crude oil, and used to evaluate the alteration of the oils, especially as a result of biodegradation, but also thermal maturity. The crude oils used are depleted in n-alkanes, which are usually related to biodegradation. However, the released products from the corresponding asphaltenes have n-alkane distributions from nC10 to nC40, suggesting a protection effect from biodegradation. The m/z 191 mass chromatograms showed higher relative intensities for tricyclic terpanes than the hopanes in the crude in comparison with the released ones.

  15. Study of Asphaltene Solutions by Electrical Conductivity Measurements Conductivité électrique des solutions d'asphaltènes

    Directory of Open Access Journals (Sweden)

    Behar E.

    2006-11-01

    Full Text Available The asphaltene interactions in model solutions were studied using a technique based on the electrical conductivity measurement. Interactions with n-heptane, resins, surfactants, water, phenol and NaCI were investigated. The conclusions drawn from this study confirmed previous opinions on aggregation mechanism of asphaltenes in solutions. They confirmed also the interpretation of asphaltene behaviour in terms of colloidal solution theories. Les interactions des asphaltènes avec leur environnement moléculaire dans des solutions modèles ont été étudiées par la mesure de la conductivité électrique de ces solutions. Les interactions avec le n-heptane, des résines, des tensioactifs, l'eau, le phénol et le chlorure de sodium ont été explorées. Les conclusions tirées de cette étude ont confirmé certaines hypothèses faites sur les mécanismes d'agrégation des asphaltènes en solution, en particulier dans le cadre de la théorie des solutions colloïdales.

  16. Molecular Weight and Association of Asphaltenes: a Critical Review Masse moléculaire et association des asphaltènes : une revue critique

    Directory of Open Access Journals (Sweden)

    Speight J. G.

    2006-11-01

    Full Text Available The determination of asphaltene molecular weights is complicated by the tendency of asphaltene molecules to associate with each other and with other petroleum constituents, and reported molecular weights vary from 900 to 300 000. This paper reviews the methods (vapor pressure osmometry, size exclusion chromatography, ultrafiltration, ultracentrifugation, viscosity, small angle X-ray scattering, infrared spectroscopy, solubilization, and interfacial tension that have been used to estimate asphaltene molecular weights and to probe association phenomena. It is concluded that asphaltene fractions from typical crudes have a number average molecular weight of 1 200-2 700 and a molecular weight range of 1,000-10,000 or higher. Intermolecular association phenomena are primarily responsible for observed molecular weights up to and in excess of 100,000 but detailed mechanisms of the intermolecular associations are not well understood. Certain observations suggest that asphaltene molecules are associated in reversedmicelles and that asphaltenes interact selectively with resins although the evidence on these points is subject to alternate interpretations. H-bond interactions between asphaltenes and resins have been demonstrated. La détermination de la masse moléculaire des asphaltènes est difficile à cause de la tendance qu'ont les molécules d'asphaltènes à s'associer les unes aux autres et avec d'autres constituants des pétroles. Ces masses moléculaires varient de 900 à 300 000. Cet article passe en revue les méthodes (osmométrie par tension de vapeur, chromatographie d'exclusion stérique, ultrafiltration, ultracentrifugation, viscosité, diffusion centrale des rayons X, spectroscopie infra-rouge, solubilisation et tension interfaciale qui ont été utilisées pour estimer les masses moléculaires des asphaltènes et pour étudier les phénomènes d'association. On conclut que les asphaltènes extraits de bruts types ont des masses mol

  17. The low temperature oxidation of Athabasca oil sand asphaltene observed from {sup 13}C, {sup 19}F, and pulsed field gradient spin-echo proton n.m.r. spectra

    Energy Technology Data Exchange (ETDEWEB)

    Desando, M.A.; Lahanjar, G.; Ripmeester, J.A.; Zupancic, I. [National Research Council of Canada, Ottawa, ON (Canada). Division of Chemistry

    1999-01-01

    Carbon-13 and fluorine-19 nuclear magnetic resonance spectra of chemically derivatized, by phase transfer methylation and trifluoroacetylation, Athabasca oil sand asphaltene, reveal a broad site distribution of different types of hydroxyl-containing functional groups, viz., carboxylic acids, phenols, and alcohols. The low temperature air oxidation of asphaltene, at ca. 130{degree}C for 3 days, generates a few additional carboxyl and phenolic groups. These results are consistent with a mechanism in which diaryl methylene and ether moieties react with oxygen. Self-diffusion coefficients, from the pulsed field gradient spin-echo proton magnetic resonance technique, suggest that low temperature oxidation does not appreciably alter the average particle size and diffusion properties of asphaltene in deuterochloroform. 55 refs., 9 figs., 3 tabs.

  18. Far infrared (terahertz) spectroscopy of a series of polycyclic aromatic hydrocarbons and application to structure interpretation of asphaltenes and related compounds

    Science.gov (United States)

    Cataldo, Franco; Angelini, Giancarlo; García-Hernández, D. A.; Manchado, Arturo

    2013-07-01

    A series of 33 different polycyclic aromatic hydrocarbons (PAHs) were studied by far infrared spectroscopy (terahertz spectroscopy) in the spectral range comprised between 600 and 50 cm-1. In addition to common PAHs like naphthalene, anthracene, phenanthrene, fluoranthene, picene, pyrene, benzo[α]pyrene, and perylene, also quite unusual PAHs were studied like tetracene, pentacene, acenaphtene, acenaphtylene, triphenylene, and decacyclene. A series of alkylated naphthalenes and anthracenes were studied as well as methypyrene. Partially or totally hydrogenated PAHs were also object of the present investigation, ranging from tetrahydronaphthalene (tetralin) to decahydronaphthalene (decalin), 9,10-dihydroanthracene, 9,10-dihydrophenanthrene, hexahydropyrene, and dodecahydrotriphenylene. Finally, the large and quite rare PAHs coronene, quaterrylene, hexabenzocoronene, and dicoronylene were studied by far infrared spectroscopy. The resulting reference spectra were used in the interpretation of the chemical structure of asphaltenes (as extracted from a heavy petroleum fraction and from bitumen), the chemical structures of other petroleum fractions known as DAE (distillate aromatic extract) and RAE (residual aromatic extract), and a possible interpretation of components of the chemical structure of anthracite coal. Asphaltenes, heavy petroleum fractions, and coal were proposed as model compounds for the interpretation of the emission spectra of certain proto-planetary nebulae (PPNe) with a good matching in the mid infrared between the band pattern of the PPNe emission spectra and the spectra of these oil fractions or coal. Although this study was finalized in an astrochemical context, it may find application also in the petroleum and coal chemistry.

  19. Adsorption Isotherms of Phenol and 4-Chlorophenol on Petroleum Asphaltenes Adsorption du phénol et du 4-chlorophénol sur les asphaltènes pétroliers

    Directory of Open Access Journals (Sweden)

    Jaoui M.

    2006-11-01

    Full Text Available The adsorption isotherms for phenol and 4-chlorophenol from water onto asphaltenes flocculated in bulk and asphaltenes deposited on silica were established by frontal analysis chromatography at 293, 298, 303, and 308 K. The adsorption was more important with asphaltenes flocculated in bulk and corresponded to a Freundlich isotherm mechanism. The high adsorbed amount of phenols suggests possible migration of phenols through the loose asphaltene structure. Isotherms observed with the silica coated by asphaltenes showed that adsorption occurs in two stages corresponding probably to two different organizations of solute molecules at the surface. Les isothermes d'adsorption du phénol et du 4-chlorophénol en solution dans l'eau sur des asphaltènes floculés en masse et sur des asphaltènes déposés sur de la silice ont été déterminés par analyse chromatographique frontale à 293, 298, 303 et 308 K. L'adsorption sur des asphaltènes floculés en masse était la plus importante avec des isothermes correspondant à un mécanisme de Freundlich. La quantité élevée de phénols adsorbés suggère une migration possible des molécules du phénol à travers la structure peu compacte des asphaltènes. Les isothermes observés dans le cas de silice tapissée d'asphaltènes ont montré que l'adsorption se produit en deux étapes correspondant probablement à deux organisations différentes des molécules de soluté à la surface.

  20. Colloidal Structure of Heavy Crudes and Asphaltene Soltutions Structure colloïdale des bruts lourds et des suspensions d'asphaltènes

    Directory of Open Access Journals (Sweden)

    Barre L.

    2006-12-01

    Full Text Available Many industrial problems that arise during petroleum processing are related to the high concentration of asphaltenes. A good knowledge of the chemical composition of these macromolecules and a detailed understanding of the evolution of the colloïdal structures present in oil and its derivatives can play a decisive role in improving processing facilities. Asphaltenes are defined by their insolubility in n-heptane. Soluble molecules are called maltenes which can be fractionated by liquid chromatography in so-called resins, aromatic and saturated fractions. The major part of the research carried out on these complex molecules concerned the chemical composition determination from powerful techniques measurements as for instance IR or NMR methods. Nevertheless, very little information on the colloïdal structure of asphaltenes or resins in pure solvent or in real systems is accessible.The molecular weight determination was the first objective; several techniques, as vapour pressure osmometry (VPO, were used. The main conclusion of these determinations was the huge variation of the molecular weight measured by different methods. We used X-ray and neutron small angle scattering techniques in order to deduce the size polydispersity and the weight average molecular weight. Different systems as (i asphaltenes or resins in solution with different solvents, or (ii asphaltene and resin mixtures in suspension with good or bad solvents were investigated as a function of temperature increase. We have exhibited that the aggregation number, i.e. the number of smaller entities , can strongly vary with solvent composition and temperature. Resins appear as very good solvent for asphaltene molecules. Scattering measurements often exhibit strong scattered intensity at small scattering vector, showing the presence in the suspension of large heterogeneities in diluted solutions of asphaltenes and resins. We can suggest that these heterogeneities are due to

  1. Impact of Liquid-Vapor to Liquid-Liquid-Vapor Phase Transitions on Asphaltene-Rich Nanoaggregate Behavior in Athabasca Vacuum Residue + Pentane Mixtures

    Energy Technology Data Exchange (ETDEWEB)

    Long, Bingwen; Chodakowski, Martin; Shaw, John M. [Alberta; (Beijing U)

    2013-06-05

    The bulk phase behavior of heavy oil + alkane mixtures and the behavior of the asphaltenes that they contain are topics of importance for the design and optimization of processes for petroleum production, transport, and refining and for performing routine saturates, aromatics, resins, and asphaltenes (SARA) analyses. In prior studies, partial phase diagrams and phase behavior models for Athabasca vacuum residue (AVR) comprising 32 wt % pentane asphaltenes + n-alkanes were reported. For mixtures with pentane, observed phase behaviors included single-phase liquid as well as liquid–liquid, liquid–liquid–vapor, and liquid–liquid–liquid–vapor regions. Dispersed solids were detected under some conditions as well but not quantified. In this work, small-angle X-ray scattering (SAXS) is used to study nanostructured materials in liquid phases present in AVR + n-pentane mixtures from 50 to 170 °C at mixture bubble pressure. The investigation focuses on the impact of the transition from a single AVR-rich liquid to co-existing pentane-rich and AVR-rich liquids on the nanostructure and the nanostructures most resistant to aggregation as the pentane composition axis is approached. Background scattering subtraction was performed using global mixture composition. The robustness of this assumption with respect to values obtained for coefficients appearing in a two level Beaucage unified equation fit is demonstrated. The nanostructured material is shown to arise at two length scales from 1 to 100 wt % AVR. Smaller nanostructures possess mean radii less than 50 Å, while the larger nanostructures possess mean radii greater than 250 Å. The addition of pentane to the AVR causes an increasingly large fraction of the large and small nanostructures to grow in size. Only nanostructures resistant to aggregation remain in the pentane-rich phase as the 0 wt % AVR axis is approached. Step changes in aggregation identified from changes in average radius of gyration, scattering

  2. Evaluation of nano emulsion containing asphaltenes dispersant additive in dehydration of oil; Avaliacao de nanoemulsoes contendo aditivo dispersante de asfaltenos na desidratacao de petroleo

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Priscila F. de; Rodrigues, Jessica S.; Mansur, Claudia R.E. [Universidade Federal do Rio de Janeiro/ Instituto de Macromoleculas/ Laboratorio de Macromoleculas e Coloides na Industria de Petroleo, Rio de Janeiro, RJ (Brazil)], e-mail: prisfrias@hotmail.com

    2011-07-01

    Due to the problem of the formation of emulsions type water-oil during oil production, new alternatives of the breakdown of these emulsions have been proposed over the years. Several polymers have been used to destabilize these emulsions and among them are those based on polyphenylene ether. The aim of this study was to develop nanoemulsions type oil / water, where an asphaltenes dispersant additive was dissolved in dispersed phase in order to evaluate them as a new alternative in the breakdown of oil emulsions. The nanoemulsions were prepared in the presence of surfactant based on polyoxide using a high pressure homogenizer (HPH). We obtained stable nanoemulsions for more than 30 days in the presence or absence of additive. These nanoemulsions were effective in water /oil phase separation, and the nanoemulsion containing the dispersant additive provided a faster separation of these phases. (author)

  3. Far infrared (terahertz) spectroscopy of a series of polycyclic aromatic hydrocarbons and application to structure interpretation of asphaltenes and related compounds.

    Science.gov (United States)

    Cataldo, Franco; Angelini, Giancarlo; García-Hernández, D Aníbal; Manchado, Arturo

    2013-07-01

    A series of 33 different polycyclic aromatic hydrocarbons (PAHs) were studied by far infrared spectroscopy (terahertz spectroscopy) in the spectral range comprised between 600 and 50 cm(-1). In addition to common PAHs like naphthalene, anthracene, phenanthrene, fluoranthene, picene, pyrene, benzo[α]pyrene, and perylene, also quite unusual PAHs were studied like tetracene, pentacene, acenaphtene, acenaphtylene, triphenylene, and decacyclene. A series of alkylated naphthalenes and anthracenes were studied as well as methypyrene. Partially or totally hydrogenated PAHs were also object of the present investigation, ranging from tetrahydronaphthalene (tetralin) to decahydronaphthalene (decalin), 9,10-dihydroanthracene, 9,10-dihydrophenanthrene, hexahydropyrene, and dodecahydrotriphenylene. Finally, the large and quite rare PAHs coronene, quaterrylene, hexabenzocoronene, and dicoronylene were studied by far infrared spectroscopy. The resulting reference spectra were used in the interpretation of the chemical structure of asphaltenes (as extracted from a heavy petroleum fraction and from bitumen), the chemical structures of other petroleum fractions known as DAE (distillate aromatic extract) and RAE (residual aromatic extract), and a possible interpretation of components of the chemical structure of anthracite coal. Asphaltenes, heavy petroleum fractions, and coal were proposed as model compounds for the interpretation of the emission spectra of certain proto-planetary nebulae (PPNe) with a good matching in the mid infrared between the band pattern of the PPNe emission spectra and the spectra of these oil fractions or coal. Although this study was finalized in an astrochemical context, it may find application also in the petroleum and coal chemistry. Copyright © 2013 Elsevier B.V. All rights reserved.

  4. Planar limit-assisted structural interpretation of saturates/aromatics/resins/asphaltenes fractionated crude oil compounds observed by Fourier transform ion cyclotron resonance mass spectrometry.

    Science.gov (United States)

    Cho, Yunju; Kim, Young Hwan; Kim, Sunghwan

    2011-08-01

    Planar limits, defined as lines generated by connecting maximum double-bond equivalence (DBE) values at given carbon numbers, are proposed as a means of predicting and understanding the molecular structure of compounds in crude oil. The slopes and y-intercepts of the lines are determined by the DBE/carbon number ratios of functional groups defining the planar limits. For example, the planar limit generated by a serial addition of saturated cyclic rings has a slope of 0.25. The planar limit formed by the linear and nonlinear addition of benzene rings yields lines with slopes of 0.75 and 1, respectively. The y-intercepts of these lines were determined by additional functional groups added within a series of molecules. Plots of DBE versus carbon number for S(1) class compounds observed by Fourier transform ion cyclotron resonance mass spectrometry (FTICR MS) showed that saturates/aromatics/resins/asphaltenes (SARA) fractions exhibited unique slopes and y-intercepts. The slope of the planar limit observed from a saturates fraction matched well with the slope of a planar limit generated by the serial addition of saturated cyclic rings. The slopes of planar limits of aromatics and resins fractions were very similar to that obtained from the linear addition of benzene rings. Finally, the slope of the asphaltenes fraction was almost identical to the slope obtained from the nonlinear addition of benzene rings. Simulated and experimental data show that SARA fractions exhibit different molecular structure characteristics. On the basis of the slope and y-intercept of the planar limit, the structures of molecules in SARA fractions were predicted and suggested. The use of planar limits for structural interpretation is not limited to crude oil compounds but can also be used to study other organic mixtures such as humic substances or metabolites.

  5. Estudo da interatividade entre macromoléculas asfaltênicas e compostos estabilizantes: LCC e Cardanol Study of the interactivity between asphaltenic macromolecules and stabilizing compounds: cashew-nut Shell liquid and Cardanol

    Directory of Open Access Journals (Sweden)

    Luiz Fernando B. Moreira

    1998-01-01

    Full Text Available O asfalteno contido no petróleo pode se depositar gerando inúmeros problemas que podem afetar não só a produção, mas também todas as etapas que envolvem o transporte, armazenamento e processamento do óleo cru. Este trabalho apresenta uma adaptação matemática de modelos de interatividade para o sistema asfalteno/estabilizante capaz de prever o desempenho do estabilizante em evitar a precipitação de asfalteno. A capacidade do líquido da casca da castanha de caju (LCC e de um dos seus derivados, o cardanol, foi estudada empregando-se o teste de peptização. Tanto o LCC quanto o cardanol apresentaram propriedades estabilizadoras de asfaltenos e exibiram interatividade positiva em ambos os casos.Asphaltenes deposition may cause serious problems for crude oil production, treatment and refining. Additives that disperse or peptisize asphaltenes particles may prevent this deposition process, avoiding serious technological problems. The results presented in this paper show that the oil extracted from cashew nut shell and cardanol, one of its components, may be used as peptizing agent for asphaltenes. Furthermore, it is shown that dispersants display binding isotherms presenting typical co-operative association.

  6. Optimization of asphaltenes decantation equipment used in deasphalting process using computational fluid dynamics; Otimizacao de um equipamento para a decantacao de asfaltenos no processo de desasfaltacao usando fluidodinamica computacional

    Energy Technology Data Exchange (ETDEWEB)

    Arenales, Carlos Gregorio Dallos [Cooperativa de Trabajadores Profesionales Ltda (CTP), Santander (Colombia); Pimiento, Carlos Eduardo Lizcano; Quintero, Lina Constanza Navarro; Bueno, Jhon Ivan Penaloza [Empresa Colombiana de Petroleos S.A. (ICP/ECOPETROL), Santander (Colombia). Instituto Colombiano del Petroleo

    2012-07-01

    Heavy crude oil is a complex mixture of compounds that include saturates, aromatics, resins and asphaltenes. In this mixture, the asphaltenes are the heaviest components and can be unstable and precipitate. This kind of components causes troubles in transportation and processing. One way to reduce this problem is through technologies that use solvents, which under adequate operating conditions, separate the heavy fraction, improving the properties and conditions for transporting and refining of heavy crude oil. One of the processes used in the petroleum industry to improve the properties of heavy and residue oil is the solvent deasphalting. These processes have the disadvantage of work at elevated pressure and temperature. The Colombian Petroleum Company, ECOPETROL S.A. has developed its own process of upgrading heavy oils, ECODESF, a process that is designed to work at moderate conditions of pressure and temperature and that by using a paraffinic solvent, significantly improves the quality of heavy oil, reducing its viscosity and increasing API gravity. The present work develops a model of computational fluid dynamics (CFD) for asphaltene settler, using microscopic balance. The response of this model allowed determine: the solids flow pattern distribution and accumulation points of heavy phase. This information is useful for understanding the fluid-dynamic behavior of the system. The model was validated using data from a pilot plant with capacity for treatment 1.25 BPD of heavy crude oil. This pilot plant is located in the Colombian Petroleum Institute of ECOPETROL (ICP), Piedecuesta city, Santander, Colombia. (author)

  7. Wetting Alteration of Solid Surfaces by Crude Oils and Their Asphaltenes Modification de la mouillabilité des surfaces solides par les pétroles bruts et leurs asphaltènes

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    Buckley J. S.

    2006-12-01

    Full Text Available Crude oils contain a variety of components - including asphaltenes - that can adsorb onto mineral surfaces and alter wetting. What distinguishes the asphaltenes from other constituents of an oil is their tendency to aggregate and even separate from the oil in response to changes in oil solvency. Because they change in size, asphaltenes can be viewed as both macromolecules and colloids. Their influence on wettability can change with this shift from molecular to colloidal regimes. As macromolecules, asphaltenes and other crude oil components with polar functionality can adsorb on mineral surfaces. Many different crude oils have been shown to have similar effects on wetting of dry silicate surfaces. When water is present, however, the results of exposing surfaces to different oils can be quite complex, depending on the distribution of water, the compositions of oil and brine, and mineralogy of rock surfaces. Acid and base numbers and the relationship between them provide a measure of the potential for a particular oil to alter wetting through ionic interactions. As colloids, asphaltenes can alter wetting by an additional mechanism. Near the onset of precipitation, wetting alteration occurs by surface precipitation because of the interfacial aggregation of the colloidal asphaltenes, which can precede flocculation in bulk. The influence of asphaltenes on wetting is thus strongly dependent on the environment in which they are found. Mixture refractive index is a useful measure for quantifying the stability of asphaltenes in a crude oil and thus in differentiating between macromolecular and colloidal contributions of asphaltenes to wetting alteration. Les pétroles bruts contiennent de nombreux constituants - dont les asphaltènes - qui peuvent être adsorbés sur les surfaces minérales et modifier leurs caractéristiques de mouillage. Ce qui distingue les asphaltènes des autres constituants de l'huile est leur tendance à s'agréger et même à se s

  8. Laser Desorption/Ionization-Time of Flight (LDI-TOF and Matrix-Assisted Laser Desorption/Ionization - Time of Flight (MALDI – TOF mass spectrometry of an Algerian asphaltene

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    T. Fergoug

    2017-09-01

    Full Text Available Both LDI-TOF and MALDI-TOF Mass spectroscopy experiments of an Algerian asphaltene derived from a deposit were performed. LDI mass experiments were conducted for both linear and reflectron modes under laser wavelength/attenuation variation. The different LDI-Mass spectra show that mass distribution depends on experimental condition for masses below 1000 amu and that the average molecular weight is around 650 for the polar fraction and beyond 1000 amu for non-polar ones. The use of different matrices as CHCA, HABA and Dithranol changes slightly the aspect of the spectra.

  9. The determination of maturity levels in source rocks of the La Luna Formation, Maracaibo Basin, Venezuela, based on convention geochemical parameters and asphaltenes; Determinacao do grau de maturacao em rochas geradoras de petroleo, formacao La Luna, Bacia de Maracaibo, Venezuela: parametros geoquimicos convencionais e asfaltenos

    Energy Technology Data Exchange (ETDEWEB)

    Castro, L.P. de [Pontificia Universidade Catolica (PUC-RS), Porto Alegre, RS (Brazil). Centro de Excelencia em Pesquisas sobre o Armazenamento de Carbono; Franco, N. [Universidade Federal do Rio de Janeiro (UFRJ), Rio de Janeiro, RJ (Brazil). Dept. de Geologia; Lopez, L.; Lo Monaco, S.; Escobar, G. [Universidad Central de Venezuela (UCV), Caracas (Venezuela); Kalkreuth, W. [Universidade Federal do Rio Grande do Sul (UFRGS), Porto Alegre, RS (Brazil). Centro de Excelencia em Analises de Carvao e Rochas Geradoras de Petroleo

    2008-07-01

    The La Luna Formation, main source rock of the Maracaibo Basin was studied by conventional geochemical parameters, used to determine the maturity, and they were compared with the physic-chemical and molecular properties of the asphaltenes present in the bitumen of the rocks. Three wells were studied (A, B and C) with a total of 13 samples. Based on Rock-Eval results the organic matter in well A (455 deg C Tmax) shows a relatively high level of maturation (top of the oil window), whereas the organic matter in well B (435 - 436 deg C Tmax) is in the beginning of the oil window. Tmax values in well C (438 - 446 deg C) and well C suggest an intermediate maturity level. The biomarkers identified in well B and C show ratios indicating an equilibrium state in the maturity level. A good correlation was found comparing the conventional analytical data with the determination of maturity level obtained from the asphaltenes precipitated from the bitumen of the samples. With increased maturity levels the H1 NMR analysis showed enrichment in aromatic molecules in relation to aliphatic, due to the bitumen aromatization process. Similarly, the asphaltenes molecular weight has higher values in samples characterized by elevated maturity levels. This confirms earlier studies that showed that asphaltenes may be utilized as maturity parameter of organic matter. (author)

  10. Prediction of Volumetric Properties and (Multi- Phase Behaviour of Asphaltenic Crudes Prédiction des propriétés volumétriques et des équilibres de phases des bruts asphalténiques

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    Szewczyk V.

    2006-11-01

    Full Text Available Asphaltenes flocculation is described as a thermodynamic transition inducing the formation of a new liquid phase with a high asphaltenic content; this phase being the asphaltenic deposit. The thermodynamic model selected is the Peng-Robinson Equation of State associated with the Abdoul and Péneloux group contribution mixing rules. The oil is modeled by 33 pseudocomponents. Mainly, the heavy F(11+ residue is represented as one pseudocomponent for the F11 - F20 cut and as 4 pseudocomponents for the F(20+ cut : Sat F(20+ , Aro F(20+ , Resinsand Asphaltenes . The physical properties of the Sat F(20+ , Aro F(20+and Resinspseudocomponents are calculated using the group contribution methods of Avaullée, and of Rogalski and Neau, based on the knowledge of their molecular structure. The physical properties of the F11 - F20and Asphaltenespseudocomponents are fitted in order to reproduce correctly the bubble pressure, the relative volumes and the flocculated quantities at 303 K. The model gives the proportion and the composition of asphaltene deposits in the oil at different temperatures (303 - 403 K within a relatively large pressure range (0. 1 - 50 MPa including the bubble pressure of the considered crude. La floculation des asphaltènes est décrite comme une transition thermodynamique conduisant à la formation d'une nouvelle phase liquide riche en asphaltènes : le dépôt asphalténique. Le modèle thermodynamique choisi est l'équation d'état de Peng-Robinson associée aux règles de mélange d'Abdoul et Péneloux fondées sur les contributions de groupes. Le brut est représenté par 33 pseudo-constituants. La fraction lourde F(11+ est représentée par un pseudo-constituant pour la coupe F11 - F20 et 4 pseudo-constituants pour la coupe F(20+ : Sat F(20+ , Aro F(20+ , Résines , Asphaltènes . Les propriétés physiques des pseudo-constituants Sat F(20+, Aro F(20+et Résinessont calculées à l'aide des méthodes de contribution de groupes

  11. Obtenção da massa molar de asfaltenos através de osmometria de pressão de vapor Determination of the molar mass of asphaltenes using vapor pressure osmometry

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    Lyzette G. M. de Moura

    2009-01-01

    Full Text Available A massa molar é uma propriedade essencial na caracterização de asfaltenos e um dos principais parâmetros de entrada nos modelos para a predição da precipitação. Na literatura são relatadas massas molares entre 1000 e 10000 g.mol-1 para os asfaltenos, variando em função da técnica, natureza do petróleo, tipo de solvente e temperatura. Neste trabalho foi determinada a massa molar média numérica para dois asfaltenos em tolueno, o C7I (insolúveis em heptano e o C5I (insolúveis em pentano através da osmometria de pressão de vapor. Os dados experimentais foram avaliados levando em consideração efeitos da agregação dos asfaltenos em solução e sua maior dispersão em baixas concentrações. Foram feitos ainda ajustes matemáticos respeitando a tendência das curvas para diluições infinitas buscando produzir melhores resultados no valor da massa molar. Os valores obtidos foram comparados com os métodos convencionais aplicados à análise da osmometria de pressão de vapor, e situaram-se entre 3200 e 5200 g.mol-1 para o asfaltenos C5I e entre 4100 e 5400 g.mol-1 para o C7I.Molar mass is an essential property for the characterization of asphaltenes and one of the main input parameters in the models for the prediction of the precipitation. In the literature molar masses between 1,000 and 10,000 g.mol-1 for the asphaltenes are quoted, depending on the technique, petroleum origin, solvent nature and temperature. In this work the numerical average molar mass for two asphaltenes in toluene, the C7I (insoluble in heptane and the C5I (insoluble in pentane, was determined by vapor pressure osmometry. The experimental data were evaluated taking into account effects of asphaltenes aggregation in solution and its larger dispersion at low concentrations. Mathematical fittings were also made to comply with the curve bias for infinite dilutions, which was aimed at finding more accurate values for the molar mass. The results found were

  12. Study of the interface solid/solutions containing PEO-PPO block copolymers and asphaltenes by FTIR/ATR; Estudo de solucoes de copolimeros em bloco de PEO-PPO contendo asfaltenos por FTIR/DTA

    Energy Technology Data Exchange (ETDEWEB)

    Aguiar, Janaina I.S.; Neto, Jessica S.G.; Mansur, Claudia R.E. [Universidade Federal do Rio de Janeiro, Instituto de Macromoleculas, Laboratorio de Macromoleculas e Coloides na Industria de Petroleo, Rio de Janeiro, RJ (Brazil)], E-mails: janaina_333@hotmail.com, kinha_dac_dm@hotmail.com; celias@ima.ufrj.br

    2011-07-01

    The formation of water/oil emulsions can cause problems in various stages of production, processing and refining of petroleum. In this study, the technique of Fourier transform infrared spectroscopy (FTIR) using the method of attenuated total reflectance (ATR) was applied to study the solid-solutions of block copolymers based on poly(ethylene oxide)-poly(propylene oxide) (PEO-PPO) interface and its interaction in this interface with asphaltenic fractions of petroleum. The solid is the crystal of the ATR. Initially, we determined the critical micelle concentration values of the copolymers, which were consistent those obtained by a tensiometer. Bottle Test was also performed to correlate the efficiency of PEO-PPO copolymers in the breaking of water/oil emulsions with its adsorption at the interfaces solutions. (author)

  13. Modélisation de la combustion de fuels lourds prenant en compte la dispersion des asphaltènes Modeling Heavy Fuel-Oil Combustion (While Considering Or Including Asphaltene Dispersion

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    Audibert F.

    2006-11-01

    difficultés relevant du mode d'exploration et de la non adéquation entre les structures asphalténiques et fractales. On a finalement opté pour une détermination visuelle s'appuyant sur les clichés sur lesquels les agglomérats d'asphaltènes sont clairement visualisés tels qu'ils sont dans le fuel. Ce mode d'exploration laborieux a cependant permis de déterminer un modèle construit sur une série de 25 fuels dont 10 ont été brûlés sur une chaudière de 2 MW, et 15 sur un four de 100 kW. Ce modèle fait intervenir les teneurs en carbone Conradson et en métaux, ainsi que le taux de dispersion des asphaltènes. Le perfectionnement des moyens d'exploration aidant, on peut s'attendre à ce que soient disponibles des techniques d'évaluation de la dispersion sur les clichés. Ce paramètre pourra alors être pris en considération pour une meilleure prédiction de résultats de combustion insuffisamment expliqués avec les paramètres classiques. Various models aiming to predict the amount of unburned particles (solids during heavy fuel-oil combustion have been developed. The parameters taken into consideration are generally asphaltenes precipitated by normal heptane or pentane and Conradson carbon as well as the metals content having a known catalytic effect on cenosphere combustion in the combustion chamber. The Exxon and Shell models can be mentioned, which were developed respectively in 1979 and 1981 (Chapter II. Other models also give consideration to the fuel-oil composition, the way it is atomized and diffused in the chamber and the combustion kinetics (research done by the MIT Energy Laboratory published in 1986. However, the above parameters are not the only ones involved. For some fuel oils, experience has shown that the state of dispersion of asphaltenes may also play an important role particularly for combustion installations with mechanical injection for which the dispersion of fuel-oil droplets is not very great and does not affect the structures built

  14. Experimental Investigation of the Asphaltene Deposition Process during Different Production Schemes Étude expérimentale du processus de dépôt d’asphaltènes au cours de différents modes de production

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    Bagheri M.B.

    2011-02-01

    Full Text Available This paper presents the results of asphaltene precipitation and deposition during lean gas injection, CO2 injection and natural depletion in reservoir conditions. In addition, the effect of variations in operating pressure, injection gas concentration and production rate on asphaltene precipitation and deposition were investigated. The severity of asphaltene deposition was found to be more pronounced in lean gas injection in comparison with CO2 injection and natural depletion. Increasing the flow rate in natural depletion experiments showed a considerable increase in asphaltene deposition, and consequently permeability reduction in the core matrix. Moreover, more asphaltene deposition was observed along the porous media in the gas injection experiments when the gas mol percent of the mixture was increased. Cet article présente les résultats d’une étude de la précipitation et du dépôt d’asphaltènes qui peuvent se produire lors d’une injection de gaz pauvre, d’une injection de CO2 ou d’une déplétion naturelle en conditions de réservoir. En outre, les effets de la pression de fonctionnement, de la concentration en gaz injecté et du débit de production sur la précipitation et le dépôt d’asphaltènes ont été étudiés. Il a été constaté que l’importance du dépôt d’asphaltènes est plus prononcée dans le cas d’une injection de gaz pauvre comparativement à une injection de CO2 ou à une déplétion naturelle. Une augmentation du débit au cours d’expériences de déplétion naturelle a montré un accroissement considérable du dépôt d’asphaltènes et, en conséquence, une réduction de perméabilité au sein de la matrice poreuse. Par ailleurs, un dépôt d’asphaltènes plus important a été observé au cours des expériences d’injection de gaz lorsque la concentration molaire gazeuse dans le mélange était augmentée.

  15. Etude de l'état des asphaltènes dans les mélanges d'hydrocarbures : taille des amas moléculaires Research on the State of Asphaltenes in Hydrocarbon Mixtures: Size of Molecular Clusters

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    Briant J.

    2006-11-01

    Full Text Available On expose dans cet article les mesures, par différentes méthodes expérimentales (tonométrie, viscosimétrie, ultrafiltration, des poids et des tailles moléculaires des asphaltènes dans divers mélanges de diluants. Les variations des poids et des tailles moléculaires en fonction de la concentration en soluté et de la composition du mélange de diluants sont expliquées en relation avec le modèle de Yen et ses différentes structures et sous-structures. This article describes the different experimental methods (tonometry, viscosimetry, ultrafiltration used to measure the molecular weights and sizes of asphaltenes in different diluent mixtures. Variations in molecular weights and sizes as a function of the solute concentration and the composition of the diluent mixture are explained in relation to Yen's model and its different structures and substructures.

  16. The influence of asphaltenes of the petroleum on the rheology of O/W (Oil/Water) emulsions; Influencia de asfaltenos do petroleo sobre a reologia de emulsoes O/A (Oleo/Agua)

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Ronaldo Goncalves dos; Mohamed, Rahoma Sadeg; Loh, Watson; Bannwart, Antonio Carlos [Universidade Estadual de Campinas (UNICAMP), Campinas, SP (Brazil)

    2004-07-01

    Heavy oils represent a large fraction of the Brazilian petroleum reserves and display a great potential for application as substitute to the conventional oils, provided a suitable technology for their transportation is available. The high viscosity of these heavy oils leads to high flow resistance and increase in the recovery and transportation costs. Methodologies employed to reduce these problems involve application of heat of addition of diluents or lighter oils, but are associated with high costs. Formation of low viscosity oil-in-water emulsions has been proposed as an alternative for the transportation of heavy oils, as investigated in this work. Preliminary results indicate significant viscosity decreases upon emulsification of heavy oils (viscosities greater than 1,000 cP) forming o/w emulsions with high oil content (between 50-65 vol. %), which display viscosities within 4-25 cP. Additionally, the effect of different surfactants, methodology of preparation and oil asphaltene content on the emulsion stability was also evaluated. These results confirm the potential of emulsification as a viable methodology for heavy oil transportation. (author)

  17. Résines et asphaltènes : évolution en fonction des types de matière organique et de leur enfouissement Resins and Asphaltenes: Evolution As a Function of Organic-Matter Type and Burial

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    Castex H.

    2006-11-01

    Full Text Available 151 résines et 175 asphaltènes d'extraits de roche de plusieurs bassins ont été étudiés par analyse élémentaire. On montre que : - les résines ont des valeurs moyennes en carbone et en hydrogène plus élevées ainsi qu'un rapport C/H plus faible que celui des asphaltènes; elles présentent donc une structure plus aliphatique et/ou plus alicyclique. Par contre, les asphaltènes contiennent plus de soufre, d'oxygène et d'azote ; - le soufre et l'oxygène sont des paramètres permettant de différencier des bassins ; - différents types de matière organique sont mis en évidence sur un diagramme H/C, O/C ; leur évolution chimique avec l'enfouissement est caractérisée par une décroissance des teneurs en hydrogène, oxygène et soufre. La résonance magnétique nucléaire du proton et la spectroscopie infrarouge ont été utilisées pour suivre l'évolution structurale des résines et asphaltènes provenant de différents types de matière organique (algaire, marine et terrestre enfouie à des profondeurs croissantes. La résonance magnétique nucléaire permet de calculer plusieurs paramètres structuraux tels que l'aromaticité FA et le degré de substitution sigma du système aromatique. Le facteur FA semble augmenter en fonction de l'enfouissement et du type de matière organique tandis que sigma semble décroître. La spectroscopie infrarouge compléte ces informations. Les surfaces de bandes correspondant aux fonctions suivantes ont été calculées : - OH dans la région 3700-2700 cm-1 - C=O carbonyl vers 1700 cm-1 - C-H aliphatiques à 2900, 1455 et 1380 cm-1 - C=C aromatique à 1610 cm-1. Les variations d'intensité des bandes : - décroissance des C-H aliphatiques, des fonctions C=O ; - augmentation des C-H et C=C aromatiques sont en relation d'une part avec le type de matière organique, d'autre part avec sa catagénèse. Elemental analysis was used to investigate 151 resins and 175 asphaltenes extracted from rocks from

  18. Permeability Damage Due to Asphaltene Deposition : Experimental and Modeling Aspects Endommagement d'un milieu poreux par dépôts d'asphaltènes : expériences et modélisation

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    Minssieux L.

    2006-12-01

    Full Text Available The flow properties of several asphaltenic crudes were studied at reservoir temperature in rocks of different morphology and mineralogy. The experiments performed showed a progressive reduction in permeability to oil during injection, varying in rate according to the system considered. The existence of organic deposits was verified by Rock-Evalpyrolysis measurements made on sections of samples taken at the end of flow at different distances from the entry face. This technique enables the profile of the deposits to be quantified. The interpretation of the permeability damage experiments and their simulation are treated by comparing the asphaltenes in oil to colloidal particles in suspension, capable of being deposited at the surface of the pores and thus reducing the permeability of the porous medium. The first simulations were carried out using the PARISIFP particle damage model, which has recently been extended to the case of multi-layer deposition. A satisfactory qualitative agreement is observed with the experimental results. Les propriétés d'écoulement de plusieurs bruts asphalténiques ont été étudiées à la température du réservoir d'origine dans des roches de morphologie et minéralogie différentes. Les expériences réalisées mettent en évidence une réduction progressive de la perméabilité à l'huile au cours de l'injection, plus ou moins rapide selon les cas. L'existence de dépôts organiques a été vérifiée par des mesures de pyrolyse Rock-Evaleffectuées sur des sections d'échantillons prélevées en fin d'écoulement à différentes distances de la face d'entrée. Cette technique permet de quantifier le profil des dépôts. L'interprétation des expériences de colmatage et leur simulation sont traitées en assimilant les asphaltènes dans l'huile à des particules colloïdales en suspension, susceptibles de se déposer à la surface des pores et ainsi de réduire la perméabilité du milieu poreux. Les premi

  19. Représentation chimique de la structure des kérogènes et des asphaltènes en fonction de leur origine et de leur degré d'évolution Chemical Modeling of the Structure of Kerogens and Asphaltenes As a Function of Their Origin and Evolution Stage

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    Behar F.

    2006-11-01

    Full Text Available Dans cet article nous proposons des modèles de structures chimiques de kérogènes et d'asphaltènes de roche. Nous avons choisi de représenter les kérogènes appartenant aux trois types classiques de matières organiques aux stades d'évolution suivants : - début de la diagenèse sensu-stricto; - début de la catagenèse (formation de l'huile; - fin de la catagenèse (formation du gaz. Les asphaltènes représentés correspondent à la phase de formation de l'huile. Nous avons tenu compte des données d'analyse obtenues sur des échantillons naturels : analyse élémentaire, microscopie électronique, RMN 13C, thermogravimétrie, analyse fonctionnelle, dégradation par pyrolyse. Afin d'obtenir une représentation chimique ayant une valeur statistique suffisante, nous avons choisi une masse moléculaire de 25 000 environ, identique pour les trois kérogènes au début de la diagenèse, et une masse de 8000 environ pour les asphaltènes associés. Nous avons ensuite dessiné à l'échelle moléculaire les structures correspondantes. This paper proposes models for the chemical structures of kerogens and asphaltenes from rocks. The kerogens belonging to the three conventional types of organic matter are represented in the following stages of evolution: (1 beginning of diagenesis sensu stricto,(2 beginning of catagenesis (formation of oil, and (3 end of catagenesis (formation of gas. The asphaltenes represented here correspond to the phase of oil formation. Models are based on analytical data obtained on natural samples, i. e. elemental analysis, electron microscopy, 13C NMR, thermogravimetry, functional analysis and pyrolysis. To get enough statistical value for the chemical modelling, a same molecular mass of about 25 000 was chosen for the three kerogens at the beginning of diagenesis. A molecular mass of about 8000 was chosen for the related asphaltenes. The chemical structures were then constructed at the molecular scale.

  20. Action de divers diluants sur les produits pétroliers lourds : mesure, interprétation et prévision de la floculation des asphaltènes Action of Different Thinners on Heavy Petroleum Products: Measuring, Interpreting and Forecasting Asphaltene Flocculation

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    Hotier G.

    2006-11-01

    Full Text Available La mesure de la teneur normalisée en asphaltènes ne fournit pas de renseignements sur le moment d'apparition de la précipitation ni sur sa cinétique. Ces phénomènes ont une importance pratique indéniable et leur étude fait l'objet de ce travail. Dans cet article, on définit le seuil de floculation et l'on présente une méthode originale de mesure de ce dernier. On introduit ensuite la notion de potentiel de précipitation et l'on démontre ses propriétés d'additivité. Cette notion permet de prévoir, à partir d'un petit nombre d'essais, si la dilution d'un produit pétrolier lourd par une certaine quantité d'un diluant pur ou d'un mélange de diluants provoque ou non la floculation des asphaltènes. De plus, les potentiels de précipitation permettent de classer les différents diluants en fonction de leur aptitude à faire floculer ou à solubiliser les asphaltènes. A measurement of the standardized asphaltene content does not provide any information neither on the incipient flocculation moment nor on the precipitation kinetics. These phenomena are of undeniable practical importance, and they are examined in this article. Flocculation threshold is defined, and an original method of measuring it is described. Then the notion of precipitation potential is taken up, and its additivity properties are brought out. With only a small number of tests, this notion can be used to forecast whether the dilution of a heavy petroleum product by a given amount of pure thinner or by a mixture of thinners causes asphaltene flocculation or not. Furthermore, precipitation potentials can be used to classify different thinners as a function of their capacity to flocculate or solubilize asphaltenes.

  1. Mise en évidence d'associations par pont hydrogène dans les asphaltènes par chromatographie d'exclusion stérique Detection of Associations by Hydrogen Bridge in Asphaltenes by Steric Exclusion Chromatography

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    Monin J. C.

    2006-11-01

    Full Text Available Des asphaltènes de Batiraman ont été mis en solution dans différents solvants, chloroforme, pyridine, toluène, tétrahydrofuranne (THF, nitrobenzène. Des chromatographies d'exclusion stérique (SEC ont été effectuées à des temps variables après la dissolution des asphaltènes. Les masses moléculaires (MW calculées par rapport à des étalons polystyrènes varient de 3000 à 8000 et c'est dans la pyridine puis le nitrobenzène que l'on obtient les masses les plus petites. L'addition aux diverses solutions d'asphaltènes de composés susceptibles de donner lieu à formation de liaisons hydrogènes entraine des modifications des chromatogrammes. Ainsi un ajout de 1 % d'acide acétique entraine une diminution sensible des masses moléculaires. Le remplacement de l'acide acétique par l'acide formique entraine des résultats semblables. Par contre le phénol se révèle peu actif. Ce sont donc des liaisons hydrogènes qui sont, au moins partiellement, responsables des liaisons entre asphaltènes. L'utilisation de la SEC pour caractériser des asphaltènes n'est envisageable qu'en utilisant un mode opératoire rigoureux afin d'en rendre les résultats raisonnablement reproductibles et comparables. Batiraman asphaltenes were placed in solution in different solvents such as chloroform, pyridine, toluene, tetrahydrofuran (THF and nitrobenzene. Steric exclusion chromatography (SEC was performed at different times after asphaltene dissolution. The molecular weights (MW calculated in relation to polystyrene standards varied from 3000 to 8000, and the lowest weights were obtained in pyridine and then nitrobenzene. Compounds capable of causing the formation of hydrogen bonds were added to the different asphaltene solutions, causing modifications in the chromatograms. For example, the adding of 1% acetic acid created an appreciable decrease in molecular weights. Similar results were obtained by replacing acetic acid by formic acid. On the other

  2. An Evaluation of the Delayed-Coking Product Yield of Heavy Feedstocks Using Asphaltene Content and Carbon Residue Évaluation du rendement en produit de cokéfaction différée de pétrole lourd à l'aide de la teneur an asphaltènes et du résidu de coke

    Directory of Open Access Journals (Sweden)

    Schabron J. F.

    2006-11-01

    Full Text Available Six residua from different crude oils were evaluated for composition and carbon residue forming tendencies. The whole residua were evaluated for elemental composition, trace metals content, carbon residue, and specific gravity. Each residuum was deasphaltened in heptane, and the heptane-soluble materials were separated into saturate, aromatic, and polar fractions on activated silica gel. The asphaltenes were evaluated for elemental composition, trace metals content, molecular weight, and carbon residue. The relationship between carbon residues and features of the asphaltenes was studied, and a correlation of contributing features was developed. The asphaltenes were further separated into four fractions according to apparent molecular size by preparative size exclusion chromatography (SEC. The preparative size exclusion chromatographic fractions from the asphaltenes were evaluated for sulfur content, molecular weight, and trace metals content. Material balances showed that the data obtained on the fractions account for the data obtained on the original material. This indicates that the contributions of the properties of the fractions can be studied and related to properties of the whole material. La composition et le résidu de coke de six résidus de raffinage de différents pétroles lourds ont été évalués afin de déterminer des tendances. La composition élémentaire, la teneur en métaux-traces, le résidu de coke et la densité spécifique ont été déterminés sur le résidu complet. Chaque résidu a été désasphalténé dans l'heptane et les produits solubles dans l'heptane ont été séparés en fractions saturée, aromatique et polaire sur du gel de silice activée. La composition élémentaire, la teneur en métaux-traces, la masse moléculaire et le résidu de coke ont été déterminés sur les asphaltènes. La relation entre les résidus de coke et les caractéristiques des asphaltènes a été étudiée, ce qui a permis d

  3. Influence sur les imbrûlés solides de composés métalliques particuliers et du taux de dispersion des asphaltènes dans les fuels lourds Influence of Unburned Solids Made of Unusual Metal Compounds and of the Asphaltene Dispersion Rate in Heavy Fuel Oils

    Directory of Open Access Journals (Sweden)

    Audibert F.

    2006-11-01

    des asphaltes précipités au pentane dilués avec un gaz oil aromatique de raffinerie. Il a été notamment mis en évidence le rôle joué par les résines dans les dispersions des agglomérats d'asphaltènes et par voie de conséquence dans l'émission d'imbrûlés solides. L'ensemble des observations faites permet de mieux comprendre certains mécanismes intervenant en combustion de fuels lourds. Si l'on se situe sur le plan des émissions particulaires, celles-ci peuvent être largement réduites par l'utilisation de taux suffisants de vapeur auxiliaire au niveau de l'injection. The growing diversity of the origins of crude oils has led to giving consideration to the metal content in combustion models in addition of Conradson carbon or C7 asphaltenes in heavy fuel oils. Such models have been developed by Exxon (1979 and Shell (1981 in particular. Recent research done at Institut Français du Pétrole (IFP on a 2 MW package boiler has shown the influence of unusual metal compounds present in fuel oil in the form of sulfides impregnating porous carbon particles. These microparticles may be formed when severe operating conditions are applied to the visbreaking of residual fuel oils in the presence of hydrogen and a suitable catalyst. These microparticles have proved to be very active in combustion and have shown that the metal concentration is not the only factor to be taken into consideration but that the way in which it is combined may be preponderant. To widen the field of application of models, other parameters, such as the operating conditions of the boiler and the spraying of the fuel oil, have been taken into consideration together with the actual parameters of the influence of the fuel oil (research by the MIT Energy Laboratory, publications in 1986. Concerning the predicting of particulate emissions, a method in addition to tests for Conradson residue and n-heptane insolubility has been applied at IFP as part of a project to upgrade heavy oils in

  4. Insights of asphaltene aggregation mechanism from molecular dynamics simulation

    Directory of Open Access Journals (Sweden)

    Jennifer De León

    2015-01-01

    Full Text Available Se estudió el proceso de agregación de asfaltenos utilizando té cnicas de dinámica molecular. Se utilizaron cuatro estructuras diferentes. Las primeras tres moléculas tienen una estructura continental, con núcleos aromáticos condensador, mientras que la cuarta pose e una estructura tipo archipiélago, con pequeños grupos de anillos ar omáticos conectados con cadenas saturadas. Las moléculas fueron construidas de manera atomística, en la cual cada átomo se desc ribe individualmente. Se calcula ron las fuerzas de interacción a 300 K y 200 atm; las fuerzas de Van der W aals y las interacciones elect rostáticas fueron evaluadas separadamente. Se calculó el paráme tro de solubilidad para las cuatro molécu las. Se encontró que las inte racciones de Van der Waals asoc iadas a los anillos aromáticos y las fuerzas electrostáticas ocasionadas princ ipalmente por la presencia de heteroátomos como oxígeno, azufr e y nitrógeno, son igualmente r elevantes en la agregación de moléculas de asfalteno. Para todas las molé culas se encontró que los sistemas de asfaltenos tienen menor e nergía en estado de agregación que en estado monomérico. Para las estruct uras continentales, la presencia de largas cadenas obstruye el proceso de formación de agregados. Para las estructuras tipo archipiélago, la flexibilidad de las moléculas facilita la agregación con ot ras estructuras. La presencia de heteroátomos ocasiona una fuerza repulsiva que dificulta la agregación. El volumen molecular y la energía de c ohesión también son sensibles a la confi guración geométrica y la compos ición de las especies, lo cual afecta el parámetro de solubilidad.

  5. Aggregation study of asphaltenes from colombian Castilla crude oil using molecular simulation

    Directory of Open Access Journals (Sweden)

    Jennifer de León-Barreneche

    2015-01-01

    Full Text Available Se presenta un modelo de simulación molecular para estudiar el mecanismo de agregación de asfaltenos. Se seleccionaron cuatro especies, obtenidas a partir de análisis estructurales del petróleo extraído del campo Castilla, en Colombia. Se estudiaron las contribuciones energéticas al proceso de agregación y se calculó el parámetro de solubilidad para cada especie. Finalmente, se estudió el proceso de agregación entre las diferentes especies con el fi n de determinar la tendencia de las moléculas hacia la autoasociación. Los resultados muestran que para todas las especies, el estado de agregación es energéticamente favorable, y que tanto las fuerzas de Van der Waals como las fuerzas electrostáticas contribuyen en igual magnitud al proceso de agregación. Se encontró también que la estructura molecular de las moléculas tiene una gran infl uencia en la manera cómo se agregan los asfaltenos. Para las estructuras continentales, las ramifi caciones largas ocasionan un impedimento físico para la agregación. Por otro lado, la fl exibilidad asociada a las moléculas tipo archipiélago favorece la agregación con otras especies, pero de alguna manera entorpece la autoasociación. El parámetro de solubilidad para todas las especies se encontró dentro del rango establecido por la literatura.

  6. Asphaltenes and preasphaltenes from coal liquid extracts: feedstocks to obtain carbon mesophase

    Directory of Open Access Journals (Sweden)

    Juan Barraza

    2014-01-01

    Full Text Available El objetivo de este trabajo fue producir mesofase usando como materia prima asfáltenos y preasfáltenos de extractos líquidos de carbones obtenido en un proceso de Licuefacción de Carbón Directa (LCD. Los asfáltenos y preasfáltenos se carbonizaron en atmosfera inerte a las temperaturas de 350, 400 and 450 °C durante 180 min. La identificación y cuantificación de la mesofase se realizó por microscopía de luz polarizada. Los resultados mostraron que la mayor concentración de mesofase (79% v/v con rendimientos másicos de 12,4% p/p se obtuvo de los asfáltenos carbonizados a 400 °C. El mayor rendimiento global de mesofase obtenida respecto al carbón alimentado fue de 4,4 % p/p.

  7. Identification of C2-C4 alkylated benzenes in flash pyrolysates of kerogens, coals and asphaltenes

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Hartgers, W.A.; Leeuw, J.W. de

    1992-01-01

    Pseudo-Kováts indices were determined for all positional isomers of C2-C4 alkylated benzenes using a non-polar capillary column (CP Sil-5). These indices were applied in combination with mass spectral data to identify these compounds in complex mixtures of a relatively non-polar nature generated

  8. Concentration of paramagnetic centres at low-temperature thermal destruction of asphaltenes of heavy petroleum distillates

    Directory of Open Access Journals (Sweden)

    Dolomatov M.U., Rodionov A.A., Gafurov M.R., Petrov A.V., Biktagirov T.B., Bakhtizin R.Z., Makarchikov S.O., Khairudinov I.Z., Orlinskii S.B.

    2016-11-01

    Full Text Available Changes of paramagnetic centers (PC concentration in dispersed petroleum systems were studied in the process of low-temperature thermolysis. The kinetic model of PC concentration dynamics based on the processes of unpaired electrons formation during singlet-triplet transitions, weak chemical bonds dissociation and recombination of free radicals is proposed.

  9. Geochemical significance of alkylbenzene distributions in flash pyrolysates of kerogens, coals and asphaltenes

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Hartgers, W.A.; Leeuw, J.W. de

    1994-01-01

    The distribution of C0-C5 alkylbenzenes in flash pyrolysates of forty-seven immature kerogens and coals from different geographical locations and of different ages were studied using gas chromatography (GC) in combination with mass spectrometry (MS) in order to decipher the origin of aromatic

  10. Rapid estimation of the organic sulphur content of kerogens, coals and asphaltenes by pyrolysis-gas chromatography

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Eglinton, T.I.; Kohnen, M.E.L.; Leeuw, J.W. de

    1990-01-01

    A pyrolysis-gas Chromatographic (py-g.c.) method for estimation of the Sorg/C ratio in kerogens and other forms of sedimentary macromolecular organic matter is described. The method is based upon flash pyrolysis at 610 °C for 10s and areal integration of the FID peaks attributed to

  11. KINETIC AND THERMODYNAMIC EQUILIBRIUM OF ASPHALTENES SORPTION ONTO FORMATION ROCK: EVALUATION OF THE WASH IN THE ADSORPTIVE PROPERTIES

    Directory of Open Access Journals (Sweden)

    CAMILO A. FRANCO

    2012-01-01

    Full Text Available El principal objetivo del estudio fue obtener la cinética y el equilibrio termodinámico de la sorcion de asfaltenos en polvo de roca obtenida de la formación Guadalupe (lavada y sin lavar, a diferentes tiempos, temperaturas y concentraciones. Sin embargo, el efecto de temperatura en el equilibrio de sorción no era significativo. Los polvos de roca fueron caracterizados por sorción de N2 a -196°C. El equilibrio de sorcion de los asfaltenos en los polvos de roca, dentro de un rango de concentraciones desde 250 hasta 1500 ppm, fue determinado usando un método estático. Las curvas de sorcion muestran un comportamiento Tipo I, según la IUPAC. El modelo de Langmuir se usó para calcular los valores del contenido de asfaltenos monocapa para la sorcion a diferentes temperaturas, mostrando un buen ajuste con respecto a los datos experimentales. La cinética de sorcion de los asfaltenos en muestras de rocas es función de la concentración y para concentraciones de 1500 ppm el equilibrio es alcanzado alrededor de 90 min. Se aplicaron los modelos cinéticos de pseudo primer orden y pseudo segundo orden a los datos experimentales para las diferentes concentraciones para las dos muestras de rocas con un mejor resultado para el modelo cinético de pseudo-primer orden. El efecto de lavado en el equilibrio no fue significativo, sin embargo la capacidad adsortiva de la roca sin lavar fue ligeramente mayor que la roca lavada con n-heptano y tolueno.

  12. Configurational diffusion of asphaltenes in fresh and aged catalyst extrudates. Quarterly progress report, September 20, 1993--December 20, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Guin, J.A.; Tarrer, A.R.

    1993-12-31

    Objective is to determine the relation between the size and shape of coal and petroleum macromolecules and their diffusion rates in catalyst pore structures. During this past quarter, experiments using narrow molecular weight polystyrenes and alumina extrudates made in the lab were carried out (cyclohexane was used as solvent). Freundlich and Langmuir constants for the adsorption equilibrium isotherms were determined for these materials. A Langmuir isotherm was a slightly better fit for the data. Results follow the expected trend and may be used to predict the adsorption isotherm for any polystyrene and alumina combination. 8 figs, 19 refs, 4 tabs.

  13. Comparing ignitability for in situ burning of oil spills for an asphaltenic, a waxy and a light crude oil as a function of weathering conditions under arctic conditions

    DEFF Research Database (Denmark)

    Fritt-Rasmussen, Janne; Brandvik, Per Johan; Villumsen, Arne

    2012-01-01

    In situ burning of oil spills in the Arctic is a promising countermeasure. In spite of the research already conducted more knowledge is needed especially regarding burning of weathered oils. This paper uses a new laboratory burning cell (100 mL sample) to test three Norwegian crude oils, Grane...... (asphalthenic), Kobbe (light oil) and Norne (waxy), for ignitability as a function of ice conditions and weathering degree. The crude oils (9 L) were weathered in a laboratory basin (4.8 m3) under simulated arctic conditions (0, 50 and 90% ice cover). The laboratory burning tests show that the ignitability......-windows for the oil to be ignitable. The composition of the oils is important for the window of opportunity. The asphalthenic Grane crude oil had a limited timewindow for in situ burning (9 h or less), while the light Kobbe crude oil and the waxy Norne crude oil had the longest time-windows for in situ burning (from...

  14. Polymer science applied to petroleum production; Ciencia de polimeros aplicada a producao de petroleo

    Energy Technology Data Exchange (ETDEWEB)

    Lucas, Elizabete F.; Mansur, Claudia R.E.; Garreto, Maria S.E.; Honse, Siller O.; Mazzeo, Claudia P.P. [Universidade Federal do Rio de Janeiro/ Instituto de Macromoleculas/ Laboratorio de Macromoleculas e Coloides na Industria de Petroleo, Rio de Janeiro, RJ (Brazil)], e-mail: elucas@ima.ufrj.br

    2011-07-01

    The petroleum production comprises several operations, from well drilling to oil and water treatment, in which polymer science is applied. This work is focused in the phase behavior of asphaltenes that can be evaluated by precipitation tests and particle size determination. Recent researches show that the petroleum can be diluted with a specific model solvent, without causing any changes on asphaltenes phase behavior, and that a representative model system can be obtained if asphaltenes could be extracted using n-alkane as low as C1. The phase behavior of asphaltenes directly depends on the solubility parameter, which can be estimated for petroleum and asphaltenic fractions by microcalorimetry. More polar asphaltenes are not completely stabilized by less polar molecules, and this affects the stability of the A/O emulsions. There is a relationship between the amount of polar groups in the polymer chain and its capability in stabilizing/flocculating the asphaltenes, which interferes in the asphaltenes particle sizes. (author)

  15. Chemical modification of bitumen heavy ends and their non-fuel uses

    Energy Technology Data Exchange (ETDEWEB)

    Moschopedis, S.E.; Speight, J.G.

    1976-01-01

    Bitumen asphaltenes undergo a variety of simple chemical conversions. For example, asphaltenes can be oxidized, sulfonated, sulfomethylated, halogenated, and phosphorylated. The net result is the introduction of functional entities into the asphaltene structure which confers interesting properties on the products for which a variety of uses are proposed.

  16. Method for determining processability of a hydrocarbon containing feedstock

    Energy Technology Data Exchange (ETDEWEB)

    Schabron, John F.; Rovani, Jr., Joseph F.

    2013-09-10

    Disclosed herein is a method involving the steps of (a) precipitating an amount of asphaltenes from a liquid sample of a first hydrocarbon-containing feedstock having solvated asphaltenes therein with one or more first solvents in a column; (b) determining one or more solubility characteristics of the precipitated asphaltenes; (c) analyzing the one or more solubility characteristics of the precipitated asphaltenes; and (d) correlating a measurement of feedstock reactivity for the first hydrocarbon-containing feedstock sample with a mathematical parameter derived from the results of analyzing the one or more solubility characteristics of the precipitated asphaltenes.

  17. Method for predicting fouling tendency of a hydrocarbon-containing feedstock

    Energy Technology Data Exchange (ETDEWEB)

    Schabron, John F; Rovani, Jr., Joseph F

    2013-07-23

    Disclosed herein is a method involving the steps of (a) precipitating an amount of asphaltenes from a liquid sample of a first hydrocarbon-containing feedstock having solvated asphaltenes therein with one or more first solvents in a column; (b) determining one or more solubility characteristics of the precipitated asphaltenes; (c) analyzing the one or more solubility characteristics of the precipitated asphaltenes; and (d) correlating a measurement of feedstock fouling tendency for the first hydrocarbon-containing feedstock sample with a mathematical parameter derived from the results of analyzing the one or more solubility characteristics of the precipitated asphaltenes.

  18. Proceedings of the 8. Brazilian congress on polymers

    International Nuclear Information System (INIS)

    2005-01-01

    Theoretical and experimental papers are presented covering the following subjects: polymers, copolymers, nuclear magnetic resonance, small and wide angle X-ray scattering, polysaccharides, asphaltenes and rubbers

  19. Proceedings of the 6. Brazilian congress on polymers; 9. International macromolecular colloquium

    International Nuclear Information System (INIS)

    2001-01-01

    Theoretical and experimental papers are presented covering the following subjects: polymers, copolymers, nuclear magnetic resonance, small and wide angle X-ray scattering, polysaccharides, asphaltenes and rubbers

  20. Estudo da influência dos particulados no fenômeno de agregação dos asfaltenos por espectrometria de varredura óptica

    Directory of Open Access Journals (Sweden)

    Claudete Bernardo Henriques

    2011-01-01

    Full Text Available The processing of national petroleums causes many operational problems due to the asphaltene aggregation phenomena. To evaluate the behavior of these phenomena, a study based on optical scan technique was carried out to understand the behavior of pure oils and their mixtures. The evaluation according to criteria established by ASTM D7061-06¹ gives a result of asphaltene flocculation of according to the separability number. In this study, the aspects related to the existence of colloidal forms of peptized asphaltenes in distinct solvents present in petroleums can cause changes in the kinetics of asphaltene flocculation.

  1. Stabilization of Model Crude Oil Emulsion using Different ...

    African Journals Online (AJOL)

    As part of an ongoing research into the stability of oil-field emulsions, model oil samples have been utilized to probe the effects of asphaltene interactions on crude oil/water emulsion stability. Asphaltenes were precipitated from treated Ondo State oil sand bitumen with n-hexane in a 40:1 solvent to bitumen ratio which was ...

  2. Estimation of SARA fraction properties with the SRK EOS

    Energy Technology Data Exchange (ETDEWEB)

    Akbarzadeh, K.; Moshfeghian, M.; Ayatollahi, S. [Shiraz Univ., Shiraz (Iran, Islamic Republic of); Alboudwarej, H.; Yarranton, H. [Calgary Univ., AB (Canada)

    2001-06-01

    A newly developed form of the Soave-Redlich-Kwong (SRK) equation of state (EOS) with Peneloux correction was presented. The new EOS was developed to extend the SRK approach to crude oils. Consequently the proposed EOS can estimate the molar volumes and solubility parameters of the four solubility classes of bitumens and heavy oils. These included saturates, aromatics, resins and asphaltenes (SARA). In this study, asphaltenes were considered as polymer-like compounds of aggregates of monodisperse asphaltene monomers. Correlations were developed for the critical properties and acentric factor of each solubility class. The EOS predicted properties were tested against density measurements of SARA fractions from several bitumens. The objective was to determine the onset of asphaltene precipitation from bitumen when heptane is added. The agreement between the predicted and measured onsets was very good. It was concluded that asphaltenes have a low degree of association in bitumen and that the asphaltene monomer molar mass is about 1800 g/mol for asphaltenes from Western Canada sources. Future work will focus on predicting asphaltene precipitation for varying conditions. 35 refs., 7 tabs., 4 figs.

  3. Bulletin of Materials Science | News

    Indian Academy of Sciences (India)

    SEM/EDAX was used to characterize the compositions. pp 509-515 Fuel Cells. Pyrolysis of petroleum asphaltenes from different geological origins and use of methylnaphthalenes and methylphenanthrenes as maturity indicators for asphaltenes · Manoj Kumar Sarmah Arun Borthakur Aradhana Dutta · More Details Abstract ...

  4. Method for estimating processability of a hydrocarbon-containing feedstock for hydroprocessing

    Energy Technology Data Exchange (ETDEWEB)

    Schabron, John F; Rovani, Jr., Joseph F

    2014-01-14

    Disclosed herein is a method involving the steps of (a) precipitating an amount of asphaltenes from a liquid sample of a first hydrocarbon-containing feedstock having solvated asphaltenes therein with one or more first solvents in a column; (b) determining one or more solubility characteristics of the precipitated asphaltenes; (c) analyzing the one or more solubility characteristics of the precipitated asphaltenes; and (d) correlating a measurement of feedstock reactivity for the first hydrocarbon-containing feedstock sample with a mathematical parameter derived from the results of analyzing the one or more solubility characteristics of the precipitates asphaltenes. Determined parameters and processabilities for a plurality of feedstocks can be used to generate a mathematical relationship between parameter and processability; this relationship can be used to estimate the processability for hydroprocessing for a feedstock of unknown processability.

  5. Water-in-model oil emulsions studied by small-angle neutron scattering: interfacial film thickness and composition.

    Science.gov (United States)

    Verruto, Vincent J; Kilpatrick, Peter K

    2008-11-18

    The ever-increasing worldwide demand for energy has led to the upgrading of heavy crude oil and asphaltene-rich feedstocks becoming viable refining options for the petroleum industry. Traditional problems associated with these feedstocks, particularly stable water-in-petroleum emulsions, are drawing increasing attention. Despite considerable research on the interfacial assembly of asphaltenes, resins, and naphthenic acids, much about the resulting interfacial films is not well understood. Here, we describe the use of small-angle neutron scattering (SANS) to elucidate interfacial film properties from model emulsion systems. Modeling the SANS data with both a polydisperse core/shell form factor as well as a thin sheet approximation, we have deduced the film thickness and the asphaltenic composition within the stabilizing interfacial films of water-in-model oil emulsions prepared in toluene, decalin, and 1-methylnaphthalene. Film thicknesses were found to be 100-110 A with little deviation among the three solvents. By contrast, asphaltene composition in the film varied significantly, with decalin leading to the most asphaltene-rich films (30% by volume of the film), while emulsions made in toluene and methylnaphthalene resulted in lower asphaltenic contents (12-15%). Through centrifugation and dilatational rheology, we found that trends of decreasing water resolution (i.e., increasing emulsion stability) and increasing long-time dilatational elasticity corresponded with increasing asphaltene composition in the film. In addition to the asphaltenic composition of the films, here we also deduce the film solvent and water content. Our analyses indicate that 1:1 (O/W) emulsions prepared with 3% (w/w) asphaltenes in toluene and 1 wt % NaCl aqueous solutions at pH 7 and pH 10 resulted in 80-90 A thick films, interfacial areas around 2600-3100 cm (2)/mL, and films that were roughly 25% (v/v) asphaltenic, 60-70% toluene, and 8-12% water. The increased asphaltene and water film

  6. Mechanical Properties of the Blends of Recycled Polypropylene with Blown and Soft Bitumens

    Directory of Open Access Journals (Sweden)

    V. Hadadi

    2008-02-01

    Full Text Available In this investigation, the mechanical properties of the blends of blown bitumen110/10, heavy vacuum slops (H.V.S, bitumen 60/70 penetration grade and isotactic polypropylene (iPP were studied for the first time. Our results showed that modulus varies non-linearly and at certain asphaltenes contents a peak appears. Considering these phenomena it is revealed that in the absence of iPP, interactions between the asphaltenes control the modulus of the blends. These interactions are dependent on the H.V.S and soft bitumen contents. The asphaltenes establish strong interactions with other asphaltene groups during dissolution in H.V.S or bitumen 60/70 (called solubility limit. At low percentges of iPP and high concentrations of asphaltenes a segregated network of asphaltenes is formed.Formation of this network increases the modulus of blends. At higher percentages of iPP and low asphaltenes concentration an interdiffusion-coalescence network is established. This network creates transition structures and increases the blend modulus. Finally, it is found that incorporation of iPPimproves the modulus of bituminous blends.

  7. Hindered diffusion of coal liquids. Quarterly report number 11, March 18--June 17, 1995

    Energy Technology Data Exchange (ETDEWEB)

    Tsotsis, T.T.; Sahimi, M. [University of Southern California, Los Angeles, CA (United States). Dept. of Chemical Engineering; Webster, I.A. [UNOCAL Corp., Los Angeles, CA (United States)

    1995-12-31

    The design of industrial catalysts requires that the diffusivity of the reacting species within the catalyst be accurately known. Nowhere is this more important than in the area of coal liquefaction and upgrading of coal liquids. In this area one is faced with the task of processing a number of heavy oils, containing metals and other contaminants, in a variety of process dependent solvents. It is important, therefore, on the basis of predicting catalyst activity, selectivity, and optimizing reactor performance, that the diffusivities of these oil species be accurately known. Contrary to laboratory reactors, where most of the studies of asphaltene`s chemical structure have taken place, most industrial reactors are continuous systems. The state of the asphaltene molecule therefore does not only depend on the temperature, pressure and polarity of the solvent but also on the reactor`s residence time. It is, therefore, very important to have a correct concept of the asphaltene`s structure and through careful experimentation, one can then decide whether such a concept has any practical implications at realistic upgrading conditions. It is the purpose of the project described here to provide such a correct concept of coal asphaltenes by careful and detailed investigations of asphaltenes transport through porous systems under realistic process temperature and pressure conditions. The experimental studies will be coupled with detailed, in-depth statistical and molecular dynamics models intended to provide a fundamental understanding of the overall transport mechanisms. 60 refs.

  8. Residency of rhenium and osmium in a heavy crude oil

    Science.gov (United States)

    DiMarzio, Jenna M.; Georgiev, Svetoslav V.; Stein, Holly J.; Hannah, Judith L.

    2018-01-01

    Rhenium-osmium (Re-Os) isotope geochemistry is an emerging tool for the study of oil formation and migration processes, and a new technology for petroleum exploration. Little is known, however, about the residency of Re and Os within asphaltene and maltene sub-fractions of crude oil. This information is crucial for understanding the 187Re-187Os radiometric clock held in petroleum systems and for interpreting geochronology for key processes such as oil formation, migration, and biodegradation. In this study, a heavy crude oil was separated into soluble (maltene, MALT) and insoluble (asphaltene, ASPH) fractions using n-heptane as the asphaltene-precipitating agent. The asphaltenes were separated sequentially into sub-fractions using two different solvent pairs (heptane-dichloromethane and acetone-toluene), and the bulk maltenes were separated into saturate, aromatic, and resin (SAR) fractions using open column chromatography. Each asphaltene and maltene sub-fraction was analyzed for Re and Os. The asphaltene sub-fractions and the bulk ASPH, MALT, and crude oil were analyzed for a suite of trace metals by ICP-MS. Our results show that Re and Os concentrations co-vary between the asphaltene sub-fractions, and that both elements are found mostly in the more polar and aromatic sub-fractions. Significant Re and Os are also present in the aromatic and resin fractions of the maltenes. However, each asphaltene and maltene sub-fraction has a distinct isotopic composition, and sub-fractions are not isochronous. This suggests that asphaltene sub-fractionation separates Re-Os complexes to the point where the isotopic integrity of the geochronometer is compromised. The mobility of individual Re and Os isotopes and the decoupling possibilities between radiogenic 187Os produced from 187Re remain elusive, but their recognition in this study is a critical first step. Re and Os correlate strongly with Mo and Cd in the asphaltene sub-fractions, suggesting that these metals occupy

  9. Effect of the structure of commercial poly(ethylene oxide-b-propylene oxide) demulsifier bases on the demulsification of water-in-crude oil emulsions: elucidation of the demulsification mechanism

    Energy Technology Data Exchange (ETDEWEB)

    Ramalho, Joao Batista V.S. [PETROBRAS S.A., Rio de Janeiro, RJ (Brazil). Centro de Pesquisas; Lechuga, Fernanda C.; Lucas, Elizabete F., E-mail: elucas@ima.ufrj.b [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Inst. de Macromoleculas Profa. Eloisa Mano

    2010-07-01

    Water-in-crude oil emulsions are formed during petroleum production and asphaltenes play an important role in their stabilization. Demulsifiers are added to destabilize such emulsions,however the demulsification mechanism is not completely known. In this paper, the performances of commercial poly(ethylene oxide-b-propylene oxide) demulsifiers were studied using synthetic water-in-oil emulsions and model-systems (asphaltenes in organic solvent). No change in the asphaltene aggregate size induced by the demulsifier was observed. The demulsification performance decreased as the asphaltene aggregate size increased, so it can be suggested that the demulsification mechanism is correlated to the voids between the aggregates adsorbed on the water droplets surface. (author)

  10. Petroleum Processing Efficiency Improvement

    Energy Technology Data Exchange (ETDEWEB)

    John Schabron; Joseph Rovani; Mark Sanderson; Jenny Loveridge

    2012-09-01

    A series of volatile crude oils was characterized using the Asphaltene Determinator oncolumn precipitation and re-dissolution method developed at Western Research Institute (WRI). Gravimetric asphaltenes and polars fractions from silica gel chromatography separation of the oils were characterized also. A study to define the differences in composition of asphaltenes in refinery desalter rag layer emulsions and the corresponding feed and desalter oils was conducted. Results indicate that the most polar and pericondensed aromatic material in the asphaltenes is enriched in the emulsions. The wax types and carbon number distributions in the two heptaneeluting fractions from the Waxphaltene Determinator separation were characterized by repetitive collection of the fractions followed by high temperature gas chromatography (GC) and Fourier transform infrared spectroscopy (FTIR). High resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICRMS) was conducted by researchers at the Florida State University National High Magnetic Field laboratory in a no-cost collaboration with the study.

  11. Effect of the structure of commercial poly(ethylene oxide-b-propylene oxide demulsifier bases on the demulsification of water-in-crude oil emulsions: elucidation of the demulsification mechanism

    Directory of Open Access Journals (Sweden)

    João Batista V. S. Ramalho

    2010-01-01

    Full Text Available Water-in-crude oil emulsions are formed during petroleum production and asphaltenes play an important role in their stabilization. Demulsifiers are added to destabilize such emulsions,however the demulsification mechanism is not completely known. In this paper, the performances of commercial poly(ethylene oxide-b-propylene oxide demulsifiers were studied using synthetic water-in-oil emulsions and model-systems (asphaltenes in organic solvent. No change in the asphaltene aggregate size induced by the demulsifier was observed. The demulsification performance decreased as the asphaltene aggregate size increased, so it can be suggested that the demulsification mechanism is correlated to the voids between the aggregates adsorbed on the water droplets surface.

  12. The relationship between SARA fractions and crude oil stability

    Directory of Open Access Journals (Sweden)

    Siavash Ashoori

    2017-03-01

    Full Text Available Asphaltene precipitation and deposition are drastic issues in the petroleum industry. Monitoring the asphaltene stability in crude oil is still a serious problem and has been subject of many studies. To investigate crude oil stability by saturate, aromatic, resin and asphaltene (SARA analysis seven types of crudes with different components were used. The applied methods for SARA quantification are IP-143 and ASTM D893-69 and the colloidal instability index (CII is computed from the SARA values as well. In comparison between CII results, the values of oil compositions demonstrated that the stability of asphaltenes in crude oils is a phenomenon that is related to all these components and it cannot be associated only with one of them, individually.

  13. HINDERED DIFFUSION OF COAL LIQUIDS

    Energy Technology Data Exchange (ETDEWEB)

    Theodore T. Tsotsis; Muhammad Sahimi; Ian A. Webster

    1996-01-01

    It was the purpose of the project described here to carry out careful and detailed investigations of petroleum and coal asphaltene transport through model porous systems under a broad range of temperature conditions. The experimental studies were to be coupled with detailed, in-depth statistical and molecular dynamics models intended to provide a fundamental understanding of the overall transport mechanisms and a more accurate concept of the asphaltene structure. The following discussion describes some of our accomplishments.

  14. Determination of the streaming potential and the corresponding total charge in aqueous asphalthene containing suspensions; Bestimmung der Stroemungspotentiale und der korrespondierenden Gesamtladungen in waessrigen, asphaltenhaltigen Suspensionen

    Energy Technology Data Exchange (ETDEWEB)

    Edler, S. [Inst. fuer Erdoel- und Erdgasforschung, Clausthal-Zellerfeld (Germany); Rosenplaenter, A. [Inst. fuer Erdoel- und Erdgasforschung, Clausthal-Zellerfeld (Germany); Rahimian, I. [Inst. fuer Erdoel- und Erdgasforschung, Clausthal-Zellerfeld (Germany)

    1996-02-01

    The choice of demulgators for separating crude oil emulsions is still done empirically. The knowledge of the charge of crude oil compounds is essential for the amount of needed demulsifiers. By using the Particle Charge Detector of the Muetek Company the surface charges of these compounds could be determined. The suspension will be titrated with demulsifier. Surface active compounds ar enriched within the colloids of crude oil, i.e. the resins and the asphaltenes. The asphaltenes could be divided into the easy, medium and difficult soluble asphaltenes. The streaming potential of the colloids and their corresponding total charge could be determined successfully. With increasing quantity of asphaltenes the charge consumption increase almost linearly. The heavy soluble asphaltenes are needing the highest share of demulsifiers followed by the middle and the light soluble asphaltenes. The resins only show very small charge consumption. (orig.) [Deutsch] Die Auswahl von Spaltern zur Trennung von Rohoelemulsionen erfolgt zumeist empirisch. Bei Kenntnis der Ladung der rohoeleigenen Emulgatoren ist eine gezieltere Auswahl der Splater moeglich. Mit Hilfe eines Partikelladungsdetektors sollten die Oberflaechenladungen der rohoeleigenen Emulgatoren bestimmt werden. Dazu wurden Suspensionen der Rohoelkolloide mit Tensid titriert. Grenzflaechenaktive Stoffe sind in den Rohoelkolloiden, also den Erdoelharzen und den Asphaltenen, angereichert. Die Asphaltene lassen sich in leicht-, mittel- und schwerloesliche Komponenten einteilen. Es konnte das Stroemungspotential der Rohoelkolloide und die korrespondierende Gesamtladung erfolgreich bestimmt werden. Mit konstant steigendem Gehalt an Kolloiden steigt auch der Ladungsverbrauch annaehernd linear. Bei den Asphaltenfraktionen verbrauchen die schwerloeslichen Asphaltene mit Abstand den groessten Anteil der Ladung, gefolgt von den mittel- und den leichtloeslichen. Die Erdoelharze zeigen einen sehr geringen Ladungsverbrauch. (orig.)

  15. Relations between interfacial properties and heavy crude oil emulsions stability; Relations entre les proprietes interfaciales et la stabilite des emulsions de brut lourd

    Energy Technology Data Exchange (ETDEWEB)

    Hoebler-Poteau, S.

    2006-02-15

    Oil in water emulsions are currently being investigated to facilitate the transport of viscous heavy oils. The behavior of these emulsions is largely controlled by oil / water interfaces. The surface-active components of crude oil such as asphaltenes and naphthenic acids compete among themselves at these interfaces and also with possibly added synthetic surfactant emulsifier.Here, we present a study of dynamic interfacial tension and rheology of interfaces between water and a model oil (toluene) in which asphaltenes and other surface active molecules from crude oil are dissolved. We show that different parameters such as aging of the interface, asphaltenes concentration, the pH and salinity of the aqueous phase have a strong influence on interfacial properties of asphaltenes at the oil/water interface. Several micro-pipette experiments, in which micrometric drops have been manipulated, are described as well as small angle neutron scattering measurements. The influence of lower molecular weight surface-active species, such as the natural naphthenic acids contained in maltenes (crude oil without asphaltenes) has been investigated, and an interaction between asphaltenes and maltenes which facilitates molecular arrangement at the interface was detected. The microscopic properties of the different interfaces and the stability of the corresponding emulsions are determined to be correlated.The results obtained on model emulsions and model oil/water interfaces were found to be helpful in order to explain and predict the behavior of heavy crude oil emulsions. (author)

  16. Colloidal structure of heavy petroleum products; Structure colloidale des produits petroliers lourds

    Energy Technology Data Exchange (ETDEWEB)

    Fenistein, D.

    1998-12-11

    Asphaltenes, the heaviest components of petroleum products, are defined as insoluble in an alkane excess. Their aggregation state, which depends on the thermodynamic conditions (solvent composition, temperature) has been characterized using scattering techniques and viscosimetry. In a solvent (toluene) asphaltenes are stable aggregates. The shape of the scattering spectra, their sensitivity to concentration on the one hand the values of intrinsic viscosities on the other hand, are compatible with a structure of solvated fractal aggregates. The mass distribution of asphaltene aggregates has been evaluated using ultracentrifugation. An increasing addition of flocculant (heptane) induces the extension of asphaltene aggregation. When approaching the flocculation threshold, their structure can be compared to the predictions of the RLCA theoretical model. Crossing the flocculation threshold induces the two phase separation of the system. The flocculated phase of compact aggregates undergoes fast sedimentation if the medium viscosity allows it. The study of asphaltenes in their natural medium (the maltenes) enables to recognize the solvated structures of the non - flocculated asphaltenes in other fluids. (author) 140 refs.

  17. Amélioration des procédés de craquage thermique des résidus par optimisation de la transformation des résines et des asphaltènes Improving Heat Treatment Processes for Residues by Optimizing the Transformation of Resins and Asphaltenes

    Directory of Open Access Journals (Sweden)

    Decroocq D.

    2006-11-01

    Full Text Available L'amélioration de procédés de traitement thermiques de coupes lourdes de pétrole en présence d'additifs susceptibles d'augmenter à la fois la qualité et le degré de conversion en limite de formation de coke est décrit. L'hydroviscoréduction du RSV Safaniya en présence d'un diluant aromatique donneur d'hydrogène (tétraline associé à un composé sulfuré (thiol, disulfure ou sulfoxyde permet l'obtention de conversions élevées sans production notable de coke et de gaz, ceci aussi bien en réacteur statique qu'en régime dynamique. Ces résultats sont confirmés par l'étude du traitement thermique de charges lourdes de natures diverses. Des essais menés sur pilote industriel montrent l'influence d'un additif soufré associé à une coupe LCO ou HCO sur la qualité de bases pour fuels commerciaux produites à partir d'un résidu sous vide de Safaniya. La caractérisation analytique des recettes de pyrolyses ou de certaines de leur fraction, par pyroanalyse oxydante, chromatographies liquides (SARA, GPC, spectroscopies RMN 1H et 13C , diffraction des rayons X, microscopies optiques et électroniques, met en évidence de profondes transformations de la matière hydrocarbonée et confirme l'effet de synergie entre les deux types d'additifs dans le traitement thermique de ces coupes lourdes.

  18. Characterization of petroleum products by laser-induced acoustic desorption in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer

    Science.gov (United States)

    Pinkston, David S.

    Many petroleum products, in particular large nonpolar saturated hydrocarbons, have proven difficult to analyze via mass spectrometry due to their low volatility, lack of basic or acidic groups needed for most ionization methods, and low activation energies for fragmentation after ionization. The above limitation has been addressed by using laser-induced acoustic desorption (LIAD) to evaporate nonvolatile and thermally labile petroleum components for analysis in a Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometer. The gaseous neutral analytes were ionized by electron impact. Model compounds were studied first to test the viability of this method. After that, different types of asphaltenes were characterized successfully. For example, the molecular weight distribution of a North American asphaltene was determined. A comparison between asphaltene samples obtained from different geographical locations showed distinct molecular weight characteristics, possibly allowing for the determination of an unknown asphaltene sample's geographic origin. Asphaltenes were also characterized via electrospray ionization (ESI) in a linear quadrupole ion trap (LQIT). The observed molecular weight distribution had an extended tail past 2000 Da. Collision-activated dissociation (CAD) experiments on isolated ions revealed that water aggregation was present in this analysis. The observed molecular weight distribution of asphaltenes reduced dramatically when water was eliminated from the system. The usefulness of a new chemical ionization reagent, ClMn(H2O) +, is also discussed. This reagent has been shown to ionize hydrocarbons without fragmentation to yield [ClMnR]+, where R is the hydrocarbon, thus providing molecular weight information. CAD of the [ClMnR]+ ions is demonstrated to allow the differentiation of isomeric hydrocarbons. Finally, the LIAD/ClMn(H2O)+ mass spectrometric method was applied to the successful analysis of various petroleum fractions and asphaltene

  19. The stability of water-in-crude and model oil emulsions

    Energy Technology Data Exchange (ETDEWEB)

    Sullivan, A.P.; Zaki, N.N.; Kilpatrick, P.K. [North Carolina State Univ., Raleigh, NC (United States). Dept. of Chemical Engineering; Sjoblom, J. [Norwegian Univ. of Science and Technology, Trondheim (Norway). Dept. of Chemical Engineering, Ugelstad Laboratory

    2007-12-15

    Emulsions are among the most persistent problems faced by petroleum producers. Water is added at refineries to generate a large oil-water interfacial area to facilitate the extraction of salts from the crude oil. The produced emulsions do not readily resolve into neat crude and water phases, and some volume of the emulsion remains. This paper described the surface-active components in petroleum as well as methods of measuring emulsion stability. The stabilities of a variety of water-in-model oil and petroleum emulsions were measured using the critical electric field (CEF) technique. In this study, CEF was used to measure the stability of water-in-heptane-toluene-asphaltene emulsions. Results for emulsions with 60 and 30 per cent water were presented. The effect of interfacial film thickness was discussed and a kinetic model for interfacial film formation was presented. The importance of solvation of asphaltenes to emulsion stability was confirmed along with the importance of the state of asphaltene aggregation. It was shown that emulsion stability increased with the concentration of soluble asphaltenes near the point of precipitation. In order to calculate interfacial area and film thickness, optical microscopy was used to measure droplet size. Film thickness increased with asphaltene concentration up to the solubility limit. Increased concentration above that limit had little effect. CEF increased with interfacial film thickness up to a monolayer coverage of asphaltene aggregates, but film thickness had a much smaller effect above the monolayer. These results were used to develop correlations of the stability of water-in-crude oil emulsions. A strong correlation was found for CEF with the product of asphaltene concentration and the difference in hydrogen to carbon atomic ratios of the asphaltenes and petroleum solvent. The effects of asphaltene chemistry, solvency, and resin concentration on the adsorption and consolidation of emulsion stabilizing interfacial

  20. Simple statistical model for branched aggregates

    DEFF Research Database (Denmark)

    Lemarchand, Claire; Hansen, Jesper Schmidt

    2015-01-01

    We propose a statistical model that can reproduce the size distribution of any branched aggregate, including amylopectin, dendrimers, molecular clusters of monoalcohols, and asphaltene nanoaggregates. It is based on the conditional probability for one molecule to form a new bond with a molecule......, given that it already has bonds with others. The model is applied here to asphaltene nanoaggregates observed in molecular dynamics simulations of Cooee bitumen. The variation with temperature of the probabilities deduced from this model is discussed in terms of statistical mechanics arguments....... The relevance of the statistical model in the case of asphaltene nanoaggregates is checked by comparing the predicted value of the probability for one molecule to have exactly i bonds with the same probability directly measured in the molecular dynamics simulations. The agreement is satisfactory...

  1. Mechanical Property and Analysis of Asphalt Components Based on Molecular Dynamics Simulation

    Directory of Open Access Journals (Sweden)

    Rui Li

    2017-01-01

    Full Text Available The asphalt-aggregate interface interaction plays a significant role in the overall performances of asphalt mixture. In order to analyze the chemical constitution of asphalt effects on the asphalt-aggregate interaction, the average structure C64H52S2 is selected to represent the asphalt, and the colloid, saturated phenol, and asphaltene are selected to represent the major constitutions in asphalt. The molecular models are established for the three compositions, respectively, and the Molecular Dynamics (MD simulation was conducted for the three kinds of asphaltene-aggregate system at different presses. Comparing the E value of Young modulus of these three polymers, the maximum modulus value of asphaltene was 2.80 GPa, the modulus value of colloid was secondary, and the minimum modulus of saturated phenol was 0.52 GPa. This result corresponds to conventional understanding.

  2. About Coloured Cold Asphaltic Mixtures

    Directory of Open Access Journals (Sweden)

    Loredana Judele

    2008-01-01

    Full Text Available The first coloured bitumen was obtained by using bitumen from Peru and then bitumen from the Middle East, with a low content of asphaltenes, also called "colourable" bitumens. The colours obtained by adding iron oxides led nevertheless to dark colours, due to the presence of asphaltenes. Nowadays the coloured asphalt is obtained from synthesis binders with translucent aspect. The colours are obtained by adding inorganic pigments, mainly iron oxide for red, chromic oxide for green, titanic dioxide for white. The properties and behaviour of the coloured bitumen during its lifetime are comparable with the ones of classic bitumen, sometimes even better.

  3. Coal liquefaction with preasphaltene recycle

    Science.gov (United States)

    Weimer, Robert F.; Miller, Robert N.

    1986-01-01

    A coal liquefaction system is disclosed with a novel preasphaltene recycle from a supercritical extraction unit to the slurry mix tank wherein the recycle stream contains at least 90% preasphaltenes (benzene insoluble, pyridine soluble organics) with other residual materials such as unconverted coal and ash. This subject process results in the production of asphaltene materials which can be subjected to hydrotreating to acquire a substitute for No. 6 fuel oil. The preasphaltene-predominant recycle reduces the hydrogen consumption for a process where asphaltene material is being sought.

  4. Avaliação das incertezas associadas à determinação do parâmetro de solubilidade de Hildebrand de petróleos

    Directory of Open Access Journals (Sweden)

    Lyzette Gonçalves Moraes de Moura

    2011-01-01

    Full Text Available Asphaltenes are fractions of crude oils that can precipitate and one of the parameters used in the prediction of the conditions in which this phenomenon occurs is the Hildebrand solubility parameter. In this work, it was evaluated the uncertainty propagation in the experimental determination of the solubility parameter of different crude oils, calculated from data of the asphaltenes precipitation by the addition of n-heptane, identified by optical microscopy. It was verified that the solubility parameter of an oil and the associated uncertainty are specific, being recommended that, whenever viable, it is determined parallel both, conferring higher credibility to the results.

  5. Solid Organic Deposition During Gas Injection Studies

    DEFF Research Database (Denmark)

    Dandekar, Abhijit Y.; Andersen, Simon Ivar; Stenby, Erling Halfdan

    2000-01-01

    was also evident as oil fractions expelled from the top to bottom of the PVT cell were observed to vary in density, molecular weight, as well as darkness of color. The change in stability of the oil samples before and after the contact with gas was analyzed using flocculation threshold titration....... The asphaltene content of the different oil samples were determined by the TP 143 method. The standard asphaltenes and the solid organic deposit recovered from the swelling tests were analyzed using FTIR, HPLC-SEC and H-1 NMR. The aim of these analyses is to reveal the molecular nature of the deposits formed...

  6. Characterization of oil and gas reservoir heterogeneity

    Energy Technology Data Exchange (ETDEWEB)

    1991-01-01

    The objective of the cooperative research program is to characterize Alaskan reservoirs in terms of their reserves, physical and chemical properties, geologic configuration and structure, and the development potential. The tasks completed during this period include: (1) geologic reservoir description of Endicott Field; (2) petrographic characterization of core samples taken from selected stratigraphic horizons of the West Sak and Ugnu (Brookian) wells; (3) development of a polydispersed thermodynamic model for predicting asphaltene equilibria and asphaltene precipitation from crude oil-solvent mixtures, and (4) preliminary geologic description of the Milne Point Unit.

  7. Characterization of oil and gas reservoir heterogeneity. Annual report, November 1, 1990--October 31, 1991

    Energy Technology Data Exchange (ETDEWEB)

    1991-12-31

    The objective of the cooperative research program is to characterize Alaskan reservoirs in terms of their reserves, physical and chemical properties, geologic configuration and structure, and the development potential. The tasks completed during this period include: (1) geologic reservoir description of Endicott Field; (2) petrographic characterization of core samples taken from selected stratigraphic horizons of the West Sak and Ugnu (Brookian) wells; (3) development of a polydispersed thermodynamic model for predicting asphaltene equilibria and asphaltene precipitation from crude oil-solvent mixtures, and (4) preliminary geologic description of the Milne Point Unit.

  8. Quantitative analysis of properties of petroleum mixtures by near infrared spectroscopy; Analise quantitativa de propriedades de misturas de petroleos via espectrofotometria no infravermelho proximo

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Leila M.; Silva, Elisangela B.; Fortuny, Montserrat; Dariva, Claudio; Santos, Alexandre F. [Universidade Tiradentes (UNIT), Aracaju, SE (Brazil). Instituto de Tecnologia e Pesquisa (ITP); Araujo, Augusto M. [Siemens Brazil, Rio de Janeiro, RJ (Brazil); Coutinho, Raquel C.C. [PETROBRAS, Rio de Janeiro, RJ (Brazil). Centro de Pesquisas (CENPES)

    2008-07-01

    An experimental study is carried out aiming to develop a method of quantitative analysis of properties of petroleum mixtures, such as water and asphaltene contents, heavy oil concentration and viscosity based on the use of a NIR spectrophotometer. A strategy of generation of crude oil mixtures with known properties was developed to help calibrating the NIR spectrophotometer. Petroleum mixtures involving 2 or 3 oils under known ratios were prepared based on a set of different light and heavy Brazilian crude oil samples. Moreover, experimental data of 5 binary mixtures were also assembled into a data set named multi-compound. Results indicated that excellent calibration models can be obtained for binary mixtures with correlation coefficient (R{sup 2}) greater than 99% for water and asphaltene contents, viscosity and heavy oil concentration. For ternary systems, excellent correlations (R{sup 2}>99%) can be attained for asphaltene and heavy oil contents. Finally for the multi-compound data set, the asphaltene content was the only property that resulted in R{sup 2}>99%, which demonstrates the adequacy of the NIR technique for assessing this property. (author)

  9. Organic sulphur in macromolecular sedimentary organic matter. II. Analysis of distributions of sulphur-containing pyrolysis products using multivariate techniques

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Eglinton, T.I.; Pool, W.; Leeuw, J.W. de; Eijkel, G.; Boon, J.J.

    1992-01-01

    This study describes the analysis of sulphur-containing products from Curie-point pyrolysis (Py) of eighty-five samples (kerogens, bitumen, and petroleum asphaltenes and coals) using gas chromatography (GC) in combination with sulphur-selective detection. Peak areas of approximately forty individual

  10. Classes of organic molecules targeted by a methanogenic microbial consortium grown on sedimentary rocks of various maturities

    Directory of Open Access Journals (Sweden)

    Margaux eMesle

    2015-06-01

    Full Text Available Organic-rich shales are populated by methanogenic consortia that are able to degrade the fossilized organic matter into methane gas. To identify the organic fraction effectively degraded, we have sequentially depleted two types of organic-rich rocks, shales and coal, at two different maturities, by successive solvent extractions to remove the most soluble fractions (maltenes and asphaltenes and isolate kerogen. We show the ability of the consortia to produce methane from all rock samples, including those containing the most refractory organic matter, i.e. the kerogen. Shales yielded higher methane production than lignite and coal. Mature rocks yielded more methane than immature rocks. Surprisingly, the efficiency of the consortia was not influenced by the removal of the easily biodegradable fractions contained in the maltenes and asphaltenes. This suggests that one of the limitations of organic matter degradation in situ may be the accessibility of the carbon and energy source. Indeed, bitumen has a colloidal structure that may limit the accessibility to asphaltenes in the bulk rock. Solvent extractions might favor the access to asphaltenes and kerogen by modifying the spatial organization of the molecules in the rock matrix.

  11. Rheological properties of nanofiltered Athabasca bitumen and Maya crude oil

    Czech Academy of Sciences Publication Activity Database

    Hasan, M.D.A.; Fulem, Michal; Bazyleva, A.; Shaw, J.M.

    2009-01-01

    Roč. 23, - (2009), s. 5012-5021 ISSN 0887-0624 Institutional research plan: CEZ:AV0Z10100521 Keywords : viscosity * rheology * Athabasca bitumen * Maya crude oil * phase behavior * asphaltenes * nanofiltration Subject RIV: JJ - Other Materials Impact factor: 2.319, year: 2009

  12. Assessment of aromatics to saturate ratios in three Niger Delta crudes

    Directory of Open Access Journals (Sweden)

    Chukwuemeka A. Nwadinigwe

    2017-09-01

    Full Text Available This study was designed to determine the aromatics to saturate ratios in three Nigerian Niger Delta crude oils to ascertain the crude oil source with the highest asphaltene risk. Three crude oil samples were collected from different locations: Kokori, Afiesere and Nembe in the Niger Delta region, Nigeria. The physical properties of the crudes (viscosity, density, API gravity were determined. Saturates, aromatics, resins, asphaltenes (SARA fractionation method was employed to separate different components in the crude oil. The composition and concentration of the saturates and aromatics hydrocarbon fractions were determined using a gas chromatograph. Results showed that API gravities ranged from 34° to 39° indicating that the three crudes are light. n-Heptane precipitation showed that Kokori crude had the highest weight percent concentration of asphaltenes (2.33% and Afiesere crude, the least (1.91%. The gas chromatographic analysis of the saturates and aromatics showed that the total concentrations (mg/L of all the saturates in Kokori, Afiesere, and Nembe were 871.26, 885.56, and 780.21 respectively while the total concentration of all the aromatics in the crudes were 80.15, 89.73 and 75.11 respectively. The aromatics to saturate ratios were computed and the results showed that this ratio decreased in the order Kokori crude < Nembe crude < Afiesere crude. This implies that Kokori crude with the lowest ratio will cause most asphaltene deposition problems than the other crudes.

  13. Classes of organic molecules targeted by a methanogenic microbial consortium grown on sedimentary rocks of various maturities.

    Science.gov (United States)

    Meslé, Margaux; Dromart, Gilles; Haeseler, Frank; Oger, Philippe M

    2015-01-01

    Organic-rich shales are populated by methanogenic consortia that are able to degrade the fossilized organic matter into methane gas. To identify the organic fraction effectively degraded, we have sequentially depleted two types of organic-rich sedimentary rocks, shale, and coal, at two different maturities, by successive solvent extractions to remove the most soluble fractions (maltenes and asphaltenes) and isolate kerogen. We show the ability of the consortia to produce methane from all rock samples, including those containing the most refractory organic matter, i.e., the kerogen. Shales yielded higher methane production than lignite and coal. Mature rocks yielded more methane than immature rocks. Surprisingly, the efficiency of the consortia was not influenced by the removal of the easily biodegradable fractions contained in the maltenes and asphaltenes. This suggests that one of the limitations of organic matter degradation in situ may be the accessibility to the carbon and energy source. Indeed, bitumen has a colloidal structure that may prevent the microbial consortia from reaching the asphaltenes in the bulk rock. Solvent extractions might favor the access to asphaltenes and kerogen by modifying the spatial organization of the molecules in the rock matrix.

  14. NMR and Chemometric Characterization of Vacuum Residues and Vacuum Gas Oils from Crude Oils of Different Origin

    Directory of Open Access Journals (Sweden)

    Jelena Parlov Vuković

    2015-03-01

    Full Text Available NMR spectroscopy in combination with statistical methods was used to study vacuum residues and vacuum gas oils from 32 crude oils of different origin. Two chemometric metodes were applied. Firstly, principal component analysis on complete spectra was used to perform classification of samples and clear distinction between vacuum residues and vacuum light and heavy gas oils were obtained. To quantitatively predict the composition of asphaltenes, principal component regression models using areas of resonance signals spaned by 11 frequency bins of the 1H NMR spectra were build. The first 5 principal components accounted for more than 94 % of variations in the input data set and coefficient of determination for correlation between measured and predicted values was R2 = 0.7421. Although this value is not significant, it shows the underlying linear dependence in the data. Pseudo two-dimensional DOSY NMR experiments were used to assess the composition and structural properties of asphaltenes in a selected crude oil and its vacuum residue on the basis of their different hydrodynamic behavior and translational diffusion coefficients. DOSY spectra showed the presence of several asphaltene aggregates differing in size and interactions they formed. The obtained results have shown that NMR techniques in combination with chemometrics are very useful to analyze vacuum residues and vacuum gas oils. Furthermore, we expect that our ongoing investigation of asphaltenes from crude oils of different origin will elucidate in more details composition, structure and properties of these complex molecular systems.

  15. Results of real-time production optimization of a maturing North Sea gas asset with production constraints

    NARCIS (Netherlands)

    Linden, R.J.P. van der; Marck, J.W.; Boer, J.P. de

    2015-01-01

    Operating maturing assets poses increasingly complex challenges to operators. Meeting hourly or daily production targets becomes more difficult when wells are more often shut in for e.g. water washes (against salt deposition) or solvent jobs (at asphaltenes deposition). Declining reservoir pressure

  16. The effect of different solvent polarity on the precipitation of heavy ...

    African Journals Online (AJOL)

    The precipitation of heavy organics (Saturates, Aromatics, Resins and Asphaltenes) from the Niger delta (Atan crude oil residue) was studied. Two C4 organic polar solvents (ethyl acetate and butanone) were used to investigate the effect of polarity of the precipitating solvents. The heavy organics precipitated from Antan ...

  17. Author Details

    African Journals Online (AJOL)

    Vol 6, No 2 (2015) - Articles Stabilization of Model Crude Oil Emulsion using Different Concentrations of Asphaltene Abstract PDF. ISSN: 2384-6028. AJOL African Journals Online. HOW TO USE AJOL... for Researchers · for Librarians · for Authors · FAQ's · More about AJOL · AJOL's Partners · Terms and Conditions of Use ...

  18. Organically-bound sulphur in the geosphere : a molecular approach

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.

    1988-01-01

    In this thesis the results of molecular organic geochemical investigations into the structure and origin of organic sulphur compounds (OSC) and sulphur-containing moieties in macromolecular organic matter (i.e. kerogen, coal and asphaltenes) occurring in the geosphere are described. In the

  19. Microbial removal of weathered hydrocarbons by well adapted ...

    African Journals Online (AJOL)

    The effectiveness of bioremediation processes may be limited by the physical and chemical properties of the pollutant, such as availability, recalcitrance, concentration and weathering, among others. The aim of this work was to evaluate the removal of recalcitrant oil fractions (aliphatic-aromatic and asphaltenic fractions) ...

  20. Infilling Direction and Fluid Communication in the E2.0 Reservoir of ...

    African Journals Online (AJOL)

    The study reveals a close similarity in percentage contents of the saturates, aromatics, resins and asphaltenes in all the oils. The maturity gradient clearly shows a maturation trend in the Southwest-Northeast direction which indicates that subsequent charge from the oil kitchen were more mature than the initial charges.

  1. Surfactant-assisted liquefaction of particulate carbonaceous substances

    Science.gov (United States)

    Hsu, G. C. (Inventor)

    1978-01-01

    A slurry of carbonaceous particles such as coal containing an oil soluble polar substituted oleophilic surfactant, suitably an amine substituted long chain hydrocarbon, is liquefied at high temperature and high hydrogen presence. The pressure of surfactant results in an increase in yield and the conversion product contains a higher proportion of light and heavy oils and less asphaltene than products from other liquefaction processes.

  2. BANANA (MUSA SAPINTUM) LEAVES

    African Journals Online (AJOL)

    DR. AMINU

    to petroleum in terms of source and composition, Yaro. (2011) classified bioliquid on the basis of petroleum classification by Brame and King (1967) as follows: i. Paraffinic bioliquid, if the side chains are over. 75% ii. Naphthenic bioliquid, if the naphthenic rings are over 70%. iii. Asphaltic bioquid, if the asphaltenes contents.

  3. Petroleum Resins: Separation, Character, and Role in Petroleum

    DEFF Research Database (Denmark)

    Andersen, Simon Ivar; Speight, James

    2001-01-01

    In petroleum science, the term resin generally implies material that has been eluted from various solid adsorbents, whereas the term maltenes (or petrolenes) indicates a mixture of the resins and oils obtained as filtrates from the asphaltene precipitation. Thus, after the asphaltenes are precipi......In petroleum science, the term resin generally implies material that has been eluted from various solid adsorbents, whereas the term maltenes (or petrolenes) indicates a mixture of the resins and oils obtained as filtrates from the asphaltene precipitation. Thus, after the asphaltenes...... are precipitated, adsorbents are added to the n-pentane solutions of the resins and oils, by which process the resins are adsorbed and subsequently recovered by the use of a more polar solvent, and the oils remain in solution. The resin fraction plays an important role in the stability of petroleum and prevents...... of the fact that the resin fraction is extremely important to the stability of petroleum, there is surprisingly little work reported on the characteristics of the resins. This article summarizes the work that has been carried out in determining the character and properties of the resin constituents...

  4. Cooee bitumen:

    DEFF Research Database (Denmark)

    Lemarchand, Claire; Schrøder, Thomas; Dyre, J. C.

    2013-01-01

    different compositions. The aging reaction causes a significant dynamics slowdown, which is correlated to the aggregation of asphaltene molecules in larger and dynamically slower nanoaggregates. Finally, a detailed description of the role of each molecule types in the aggregation and aging processes...

  5. Characterization of the rheological behavior of heavy crude oils for the optimization of their transport; Caracterisation du comportement rheologique des bruts lourds en vue de l'optimisation de leur transport

    Energy Technology Data Exchange (ETDEWEB)

    Coustet Pierre, C.

    2003-10-01

    Despite their huge reserves, production of heavy crude oils remains weak, partially because of the high viscosity. This work aims to understand the origin of this viscosity in a view of diminishing In this context, we performed structural (SAXS) and rheological studies (under shearing and oscillatory regime) in order to link macroscopic and microscopic properties of heavy oils. investigated the effect of asphaltenes and resins which are the two most polar and the high molecular mass components of heavy oils. Most of the literature work performed measures organic solvents which are considered as model solvents in a first assumption. These media haw structure too simple compared to oils. That is why we decided to complete this work by experiments in the crude. We shed some light on asphaltenes described as colloidal particles with fractal dimension of 2. Their overlapping, due to numerous polar and hydrogen bonds, responsible for the high viscosity. The contribution of asphaltenes on viscosity is lowered by resins who are able to dissociate aggregates and to reduce the interactions, so to diminish the overlapping The kinetics of formation of bonds involved in asphaltenes overlapping are strongly slower at low temperatures, which implies a shear thinning behavior under sufficiently high shearing. This allow us to describe the crude as a transient network of fractal aggregates. (author)

  6. Author Details

    African Journals Online (AJOL)

    Environmental impacts of marine oil spill; a case study of Deepwater Horizon oil spill at the Gulf of Mexico United States of America 2010 (a review) Abstract PDF · Vol 6, No 2 (2015) - Articles Investigating Asphaltenes Composition in Crude Oil Samples using Iatroscan TLC-FID Method. Abstract PDF. ISSN: 2384-6028.

  7. Deasphalting solvents

    International Nuclear Information System (INIS)

    Carrillo, J. A; Caceres, J; Vela, G; Bueno, H

    1996-01-01

    This paper describes how the deasphalted oil (DMO) or demetalized oil (DMO) quality (CCR, Ni, V end asphaltenes contents) changes with: DAO or DMO yield, solvent/feed ratio, type of vacuum reside (from paraffinic to blends with vis breaking bottoms), extraction temperature and extraction solvent (propane, propylene, n-butane and I butane)

  8. 2. Home 3. Journals 4. Bulletin of Materials Science 5. Volume 33 6 ...

    Indian Academy of Sciences (India)

    Administrator

    Pyrolysis of petroleum asphaltenes from different geological origins and use ... solutions. 111. Catalytic property of TiO2/PS complex nanoparticles pre- ..... grown by plasma-assisted molecular beam epitaxy. 221. Nanomaterials. Rapid synthesis of CdSe nanocrystals in aqueous solution at room temperature. 543. Effects of ...

  9. Tar balls from Deep Water Horizon oil spill: environmentally persistent free radicals (EPFR) formation during crude weathering.

    Science.gov (United States)

    Kiruri, Lucy W; Dellinger, Barry; Lomnicki, Slawo

    2013-05-07

    Tar balls collected from the Gulf of Mexico shores of Louisiana and Florida after the BP oil spill have shown the presence of electron paramagnetic resonance (EPR) spectra characteristic of organic free radicals as well as transition metal ions, predominantly iron(III) and manganese(II). Two types of organic radicals were distinguished: an asphaltene radical species typically found in crude oil (g = 2.0035) and a new type of radical resulting from the environmental transformations of crude (g = 2.0041-47). Pure asphaltene radicals are resonance stabilized over a polyaromatic structure and are stable in air and unreactive. The new radicals were identified as products of partial oxidation of crude components and result from the interaction of the oxidized aromatics with metal ion centers. These radicals are similar to semiquinone-type, environmentally persistent free radicals (EPFRs) previously observed in combustion-generated particulate and contaminated soils.

  10. Analysis of the relationship between the coal properties and their liquefaction characteristics by using the coal data base; Tanshu data base ni yoru tanshitsu to ekika tokusei no kaiseki

    Energy Technology Data Exchange (ETDEWEB)

    Kanbayashi, Y.; Okada, K. [Coal Mining Research Center, Tokyo (Japan)

    1996-10-28

    The relationship between coal properties and liquefaction or gasification characteristics was analyzed by using the analysis and test results and liquefaction characteristics in the coal data base. On liquefaction reaction, the close relation between an oil yield and coal constituent composition or a coal rank is well-known. Various multivariable regression analyses were conducted by using 6 factors as variables such as calorific value, volatile component, O/C and H/C atomic ratios, exinite+vitrinite content and vitrinite reflectance, and liquefaction characteristics as variate. On liquefaction characteristics, the oil yield of dehydrated and deashed coals, asphaltene yield, hydrogen consumption, produced water and gas quantities, and oil+asphaltene yield were predicted. The theoretical gasification efficiency of each specimen was calculated to evaluate the liquefaction reaction obtained. As a result, the oil yield increased with H/C atomic ratio, while the theoretical gasification efficiency increased with O/C atomic ratio. 5 figs., 1 tab.

  11. The role of nitrogen and sulphur bearing compounds in the wettability of oil reservoir rocks: an approach with nuclear microanalysis and other related surface techniques

    International Nuclear Information System (INIS)

    Mercier, F.; Toulhoat, N.; Potocek, V.; Trocellier, P.

    1999-01-01

    Oil recovery is strongly influenced by the wettability of the reservoir rock. Some constituents of the crude oil (polar compounds and heavy fractions such as asphaltenes with heteroatoms) are believed to react with the reservoir rock and to condition the local wettability. Therefore, it is important to obtain as much knowledge as possible about the characteristics of the organic matter/mineral interactions. This study is devoted to the description at the microscopic scale of the distribution of some heavy fractions of crude oil (asphaltenes) and nitrogen molecules (pyridine and pyrrole) on model minerals of sandstone reservoir rocks such as silica and clays. Nuclear microanalysis, X-Ray Photoelectron Spectroscopy and other related microscopic imaging techniques allow to study the distribution and thickness of the organic films. The respective influences of the nature of the mineral substrate and the organic matter are studied. The important role played by the nitrogen compounds in the adsorption of organic matter is emphasized

  12. Easing the flow : update on diluent supply/demand, new technologies and diluent alternatives

    Energy Technology Data Exchange (ETDEWEB)

    Haukedal, C. [CCH Consulting, Calgary, AB (Canada); Rhodey, G. [Rhodey and Associates Inc., Calgary, AB (Canada)

    2003-07-01

    This PowerPoint presentation included a review of diluent supply and demand, and a series of graphs depicting natural gas reserves, and refined oil market opportunities. Alternative diluents were also discussed. These include: (1) gas cap and natural gas liquid (NGL) recycling schemes, refinery naphtha, light crude, synthetic crude, light fraction of light crude, international diluent recycle, upgrader naphtha plus hydrocracked naphtha, and re-routing of Alaska solution gas concentrate. The ramifications of using alternative diluents were examined. The acceptability and quantity of feedstock dictate the refinery process configurations and product specifications. To maximize profits while meeting refined product market forecasts, refiners optimize their operation. The various transportation alternatives to reduce diluent demand are: heated bitumen line, flow improvers, refined oil products, and diluent modification. The alternative technologies to reduce diluent demand are: upgrading to synthetic crude, removal of asphaltene components, combination of upgrading and asphaltene removal, partial upgrading, and refined oil. tabs., figs.

  13. Solid Organic Deposition During Gas Injection Studies

    DEFF Research Database (Denmark)

    Dandekar, Abhijit Y.; Andersen, Simon Ivar; Stenby, Erling Halfdan

    2000-01-01

    was also evident as oil fractions expelled from the top to bottom of the PVT cell were observed to vary in density, molecular weight, as well as darkness of color. The change in stability of the oil samples before and after the contact with gas was analyzed using flocculation threshold titration......Recently a series of first contact miscibility (swelling) experiments have been performed on undersaturated light and heavy oils using LPG rich and methane rich injection gases, in which solid organic deposition was observed. A compositional gradient in the oils during the gas injection process...... during the gas injection process in comparison with the standard asphaltenes in order to understand the mechanisms involved in asphaltene deposition....

  14. Connaissances actuelles sur les produits lourds du pétrole Present Knowledge on Heavy Constituents of Crude Oils

    Directory of Open Access Journals (Sweden)

    Tissot B.

    2006-11-01

    Full Text Available Les produits lourds du pétrole (résines et asphaltènes jouent un rôle important dans les problèmes de formation des gisements de pétrole, de récupération assistée - en particulier des pétroles lourds -, de traitement et même d'utilisation des produits pétroliers. Les résines et asphaltènes constituent le terme extrême des composés naphténo-aromatiques. Le squelette carboné des asphaltènes est probablement constitué par un empilement de quelques feuillets polyaromatiques, comportant des hétérocycles (N, S et supportant des groupements fonctionnels ainsi que des chaînes alkyle. Ces cristallites peuvent s'associer pour former des agrégats de poids moléculaire élevé. La viscosité des huiles lourdes est probablement due à la taille et à l'abondance d'agrégats de ce type. Dans les huiles normales, les résines joueraient un rôle important pour solubiliser les asphaltènes, grâce à des interactions par liaisons hydrogène. Lors d'un traitement thermique, les asphaltènes produisent des hydrocarbures par craquage des parties saturées, cependant que le résidu s'enrichit en carbone. A température élevée, l'apparition d'un ordre graphitique dépend largement des teneurs en hétéroatomes (O, N, S. L'origine de la plus grande partie des asphaltènes doit être recherchée dans l'évolution du kérogène lors de son enfouissement dans les bassins sédimentaires. A chaque type majeur de kérogène, pourrait correspondre un type d'asphaltènes. Ces derniers migrent moins facilement que les hydrocarbures hors de la roche mère et sont comparativement moins abondants dans les réservoirs de pétrole, lorsque ce dernier n'est pas dégradé. The heavy constituents of crude oil (resins and asphaltenes play an important role in the accumulation of petroleum, in enhanced oil recovery (particularly of heavy oils and in processing and utilizing petroleum. Resins and asphaltenes are the ultimate term of the naphtheno

  15. PLS models for determination of SARA analysis of Colombian vacuum residues and molecular distillation fractions using MIR-ATR

    Directory of Open Access Journals (Sweden)

    Jorge A. Orrego-Ruiz

    2014-06-01

    Full Text Available In this work, prediction models of Saturates, Aromatics, Resins and Asphaltenes fractions (SARA from thirty-seven vacuum residues of representative Colombian crudes and eighteen fractions of molecular distillation process were obtained. Mid-Infrared (MIR Attenuated Total Reflection (ATR spectroscopy in combination with partial least squares (PLS regression analysis was used to estimate accurately SARA analysis in these kind of samples. Calibration coefficients of prediction models were for saturates, aromatics, resins and asphaltenes fractions, 0.99, 0.96, 0.97 and 0.99, respectively. This methodology permits to control the molecular distillation process since small differences in chemical composition can be detected. Total time elapsed to give the SARA analysis per sample is 10 minutes.

  16. Understanding heavy-oil molecular functionality and relations to fluid properties

    Energy Technology Data Exchange (ETDEWEB)

    Andersen, S.I. [Schlumberger, DBR Technology Center, Edmonton AB (Canada)

    2011-07-01

    In the heavy oil industry, knowing oil properties is important to optimizing recovery, transport and refinery. Nitrogen, sulfur and oxygen compounds (NSOs) have an important impact on these properties but this is often overlooked. The purpose of this paper is to analyze the impact of functional groups in connection with heavy oil and asphaltenes. Experiments were carried out with asphaltenes altered by chemical surgery that removed specific functional interactions. Titration calorimetry and fluorescence spectroscopy were then done. Results highlighted the fact that functional groups are of key importance in the determination of heavy oil properties and that acidity can be considered the most important interaction. This paper demonstrated that the determination of specific interactions could be more important in assessing heavy oil properties than understanding their hydrocarbon structure; further work is needed to fully understand the role of sulfur and nitrogen species.

  17. Oil well flow assurance through static electric potential: An experimental investigation

    Science.gov (United States)

    Hashmi, Muhammad Ihtsham Asmat

    Flow assurance technology deals with the deposition of organic and inorganic solids in the oil flow path, which results in constriction of the production tubing and surface flow lines and drastically reduces the kinetic energy of the fluid. The major contributors to this flow restriction are inorganic scales, asphaltene, wax and gas hydrates, in addition to minor contribution from formation fines and corrosion products. Some of these materials (particularly asphaltene and inorganic scales) carry surface charges on their nuclei and seen to be attracted by electrode having opposite charge. The focus of the present research is to find the possibilities of inhibiting the deposition of asphaltene and inorganic scales in the production tubing by applying static electrical potential. With this objective, two flow set ups were made; one for asphaltene and the other for scale deposition studies, attached with precision pumps, pressure recording system and DC power supply. In each set up there were two flow loops, one was converted as Anode and the other as Cathode. A series of flow studies were conducted using the flow set ups, in which oil-dilution ratio, temperature and most importantly DC potential difference was varied and the deposition behavior of the asphaltene aggregates and calcium carbonate scale to the walls of the test loops were observed through rise of differential pressure across the loop due to possible deposition and constriction of the flow path. Two different sets of flow studies; one without oil dilution and other with the diluted oil (with n-heptane), were performed. Both experiments were investigated under the influence of static potential applied across the two test loops. Experimental results indicated that asphaltene deposition in the cathode can be retarded or stopped by applying a suitable negative potential; an increase in the static potential resulted in enhanced control over the asphaltene aggregation and hence the deposition. In the second

  18. Ash composition of oils of West Kazakhstan

    Energy Technology Data Exchange (ETDEWEB)

    Bakirova, S.F.; Aleshin, G.N.; Kalinin, S.K.; Kotova, A.V.; Nadirov, N.K.

    1982-01-01

    Results are presented of studying the distribution of trace elements in oils of new fields of West Kazakhstan. It is indicated that for the majority of oils studied, the concentration of trace elements does not depend on the ash content of oils. For resinous asphaltenes and highly sulfur oils of the Buzachi region, there is an increase in the content of iron, vanadium, nickel with a rise in ash content of oils. This is possibly associated with their secondary enrichment with trace elements.

  19. TECHNOLOGY AND EFFICIENT USE OF PEAT ASH IN MASTICS FOR WATERPROOFING OF BRIDGE AND TUNNEL STRUCTURES

    OpenAIRE

    G. D. Lyahevich; A. G. Lyahevich; Agababa Rangraz Alireza Najib; A. A. Dalidovskaya

    2015-01-01

    A prospective method for protection of  bridges and tunnels against aggressive water action is surface waterproofing on the basis of an organo-mineral binder. Its structural strength can be increased by introduction of particles which are similar to the size of  asphaltenes and an elasticity of disperse medium has been increased due to introduction of polymers. These theoretical suppositions point out the possibility for simultaneous provision of flexibility at low temperatures and high heat ...

  20. Rhenium concentration during petroleum deasphalting

    International Nuclear Information System (INIS)

    Troshkina, I.D.; Bel'kova, M.N.

    1994-01-01

    Rhenium distribution and concentration during fractional distillation of certain types of petroleum and natural bitumens from Tatarstan are studied. Rhenium concentration in the process of oil deasphalting is examined for petroleum produced by different techniques, as well as for heavy residues from petroleum distillation. Optimum conditions for the process are revealed fractions of resinous-asphaltene substances concentrating rhenium compounds are found. 5 refs., 3 tabs

  1. The tailings technology suite

    Energy Technology Data Exchange (ETDEWEB)

    Jaremko, Deborah

    2011-10-15

    Oilsands tailing ponds contain leftover bitumen and asphaltenes, which are dangerous to local wildlife. The Oil Sands Tailings Consortium (OSTCS) was founded by all major mining players and aims to prompt collaboration within the oilsands industry to reclaim the tailings area. Each company has hitherto worked on different tailings management technologies, often duplicating efforts. Some technologies proposed by these oilsands miners were introduced in this article.

  2. Deposition of heavy oil fractions: development of a computational tool to predict oil mixtures compatibility; Deposicao de fracoes pesadas do petroleo: desenvolvimento de uma ferramenta computacional para a previsao da compatibilidade de misturas de petroleo

    Energy Technology Data Exchange (ETDEWEB)

    Prucole, Elisia S.; Henriques, Fernanda P.; Silva, Leandro M.; Touma, Silvia L. [PETROBRAS S.A., Rio de de Janeiro, RJ (Brazil)

    2008-07-01

    The remarkable increase in production and processing of national heavy oils is a scenario in which the deposition problem of heavy oil fractions is important, leading to huge losses, not only in economical terms but also in regard to environmental aspects, and can occur in practically all areas of the oil industry. Thus, the knowledge about technology concerning this subject is essential. In terms of heavy fractions, the asphaltenes are the heaviest components of oil and have propensity to aggregate, flocculate, precipitate and be adsorbed on surfaces. The difficulties for modeling the behavior of asphaltenes phases occur because of the high uncertainties which take in the current knowledge about the asphaltenes, their structures, flocculation and precipitation mechanisms and the phenomenon reversibility. The main goal of this work is to propose a predictive methodology for oils compatibility. A fuzzy classifier was implemented in order to predict the compatibility of oil mixtures, assessing whether the mixture condition is stable or not. The results were satisfactory, indicating a good predictive power of the proposed computational tool. (author)

  3. A new generation of models for water-in-oil emulsion formation

    International Nuclear Information System (INIS)

    Fingas, M.

    2009-01-01

    Water-in-oil emulsions form after oil or petroleum products are spilled, and can make the cleanup of oil spills difficult. This paper discussed new modelling schemes designed for the formation of water-in-oil emulsions. Density, viscosity, asphaltene and resin contents were used to compute a class index for unstable, entrained water-in-oil states, meso-stable, or stable emulsions. Prediction schemes were used to estimate the water content and viscosity of the water-in-oil states and the time to formation with wave height inputs. A numerical values was used for each type of water-in-oil type. The properties of the starting oil were correlated with the numerical scheme. New regressions were then performed using a Gaussian-style regression expansion technique. Data obtained from the models suggested that water-in-oil types are stabilized by both asphaltenes and resins. The optimized model was then compared with earlier models. The study showed that the new model has the capacity to accurately predict oil-in-water types approximately 90 per cent of the time using only resin, saturate, asphaltene, viscosity, and density data. 17 refs., 8 tabs., 8 figs

  4. Characterization of oil and gas reservoir heterogeneity; Final report, November 1, 1989--June 30, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, G.D.

    1993-09-01

    The Alaskan North Slope comprises one of the Nation`s and the world`s most prolific oil province. Original oil in place (OOIP) is estimated at nearly 70 BBL (Kamath and Sharma, 1986). Generalized reservoir descriptions have been completed by the University of Alaska`s Petroleum Development Laboratory over North Slope`s major fields. These fields include West Sak (20 BBL OOIP), Ugnu (15 BBL OOIP), Prudhoe Bay (23 BBL OOIP), Kuparuk (5.5 BBL OOIP), Milne Point (3 BBL OOIP), and Endicott (1 BBL OOIP). Reservoir description has included the acquisition of open hole log data from the Alaska Oil and Gas Conservation Commission (AOGCC), computerized well log analysis using state-of-the-art computers, and integration of geologic and logging data. The studies pertaining to fluid characterization described in this report include: experimental study of asphaltene precipitation for enriched gases, CO{sup 2} and West Sak crude system, modeling of asphaltene equilibria including homogeneous as well as polydispersed thermodynamic models, effect of asphaltene deposition on rock-fluid properties, fluid properties of some Alaskan north slope reservoirs. Finally, the last chapter summarizes the reservoir heterogeneity classification system for TORIS and TORIS database.

  5. Could naphthenic acids be responsible for severe emulsion tightness for a low TAN value oil?

    Energy Technology Data Exchange (ETDEWEB)

    Pauchard, V.; Muller, H.; Al-Hajji, A. [Saudi Aramco, Dhahran (Saudi Arabia). Research and Development Center; Sjoblom, J. [Norwegian Univ. of Technology, Trondheim (Norway). Ugelstad Laboratory; Kokal, S. [Saudi Aramco, Dhahran (Saudi Arabia). EXPEC Advanced Research Center; Bouriat, P.; Dicharry, C. [Univ. de Pau, Pau Cedex (France). Laboratoire des Fluides Complexes, UMR CNRS; Rogers, R. [Florida State Univ., Tallahassee, FL (United States)

    2008-07-01

    This study re-analyzed the emulsion stabilizing properties of a low Total Acid Number (TAN) of a high asphaltene crude oil with respect to the role of naphthenic acids. The emulsion stability depended on the pressure/pH. The high interfacial activity of indigenous acids extracted from the crude oil was determined by means of Ion Exchange Resins and by the high organic acid content in the interfacial material extracted from a sludge emulsion. The physical origin of these phenomenological observations was identified using the Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR-MS) and pendant droplet experiments. The interfacial material was composed of a mixture of asphaltenes and organic acids having a wide range of structures (monoprotic, diprotic, fatty, naphthenic and perhaps aromatic) and molecular weights. The interfacial rheology was a 2D gel with an assumed glass transition temperature of approximately 40 degrees C. It was concluded that a synergistic effect of asphaltenes and organic acids promoted the build up of a very structured interface. This interface is more resistant to droplets coalescence than less structured interfaces. Therefore, the disruption of the interfacial layer requires the drainage of individual molecules as well as a collective yield of the gel.

  6. In-situ burning of heavy oils and Orimulsion : analysis of soot and residue

    International Nuclear Information System (INIS)

    Fingas, M.F.; Wang, Z.; Fieldhouse, B.; Brown, C.E.; Yang, C.; Landriault, M.

    2005-01-01

    Oil spilled on water can be cleaned up by in-situ burning which can rapidly reduce the volume of spilled oil and eliminate the need to collect, store, transport and dispose of recovered oil. In-situ burning also shortens the response time to an oil spill, preventing the oil from reaching shorelines and thereby protecting the environment and aquatic biota. However, the concern over atmospheric emissions is the greatest barrier to the widespread use of in-situ burning. In this study, a series of bench-scale in-situ burning tests were conducted on Bunker C, Orimulsion and bitumen in order to analyze the residue and soot to gain insight into the chemistry of burning. The maximum burn efficiency was 70 per cent and the residue was mostly asphaltenes and resins which solidified when cooled. Soot was collected from glass-fibre filters on a sampling pump and the extracts were analyzed for polyaromatic hydrocarbons (PAHs). The analysis revealed that PAHs are enriched in pyrogenic PAHs and derive from the petrogenic PAHs in the starting oils. The PAH content is less than in many other environmental impacts. The solid residues were also analyzed for saturates of aromatics resins and asphaltenes (SARA). Their viscosity was also measured. The SARA analysis of the residue demonstrates that most of the heavy components such as the resins and asphaltenes are not burned by the fire, but are accumulated in the residue. 7 refs., 8 tabs., 6 figs

  7. Rheological characteristics of coal hydro-liquefaction residue

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Ying-jie; Wei, An-ling; Zhang, De-xiang; Zhao, Jin-chao; Lin, Chun-dai; Gao, Jin-sheng [East China University of Science and Technology, Shanghai (China). Department of Chemical Engineering for Energy Resources

    2007-07-01

    Coal liquefaction residue (CLR), coming from a direct coal liquefaction pilot plant, was used to investigate its rheological characteristics and the effects of temperature and oil, asphaltene, as well as solid content on its rheological characteristics. CLR is a kind of non-Newtonian pseudoplastic fluid, whose viscosity index decreases with increasing temperature, and approaches Newtonian fluid behavior at high temperature. The apparent viscosity of CLR drops greatly without peak as it is sensitive to temperature. After adding a little recycled oil (REC) into CLR, its apparent viscosity decreases remarkably. However, after the addition of a little asphaltene into CLR, its apparent viscosity increases at a low temperature and decreases at a high temperature. In addition, solid content is the factor of making the apparent viscosity increase all the time. All the results indicate that the apparent viscosity of CLR has a close relation with oil, asphaltene, and solid contents. The relationship between the apparent viscosity and temperature can be expressed by Arrhenius Equation. But there is a flex point during heating, and the viscous flow activation energy at the low temperature is greater than that at the high temperature. 9 refs., 11 figs., 3 tabs.

  8. Influence of feedstock type on heavy coker gas oil quality; A influencia do tipo de carga na qualidade do gasoleo pesado de coque

    Energy Technology Data Exchange (ETDEWEB)

    Costa, Claudine T.A.S.; Barros, Francisco C.C. [PETROBRAS S.A., Rio de Janeiro, RJ (Brazil). Centro de Pesquisas (CENPES)

    2004-07-01

    Over the past few years, the great challenge to the Oil Industry has been the processing of increasingly heavier feedstock seeking to meet the growing demand for medium distillates and, at the same time, the reduction of the production of fuel oils. In this scenario, the Delayed Coking Unit (DCU) appears to be an attractive technology for the processing of heavy and ultra heavy crudes. The addition of Asphaltene Residue produced by the Solvent Deasphalting Unit (SDA) to the Vacuum Residue, traditional feedstock of these units, has been a new tendency in the composition of the feedstock, with the intention of converting the residual fractions into value added liquid oil products. Results obtained in pilot plants show that asphaltene residue alters the yield and the quality of the products of the DCU, especially those of Heavy Coker Gas Oil (HKGO) that is incorporated in the feedstock of the Fluid Catalytic Cracking Unit (FCCU). The alteration in the quality of the HKGO negatively impacts on the conservation of the FCCU. The insertion of DCU in refineries that possess SDA in their refining systems has shown itself to be fundamental for the reduction of the production of fuel oils. However, to define the quantity and quality of asphaltene residue to be incorporated in the feedstock of the UCR, the best operating conditions and the necessary project adaptations to this unit are fundamental and they should be analyzed with the objective of maximizing the profitability of the refineries. (author)

  9. Physical chemical characteristics of oil emulsions of North-West Konys and Zhanaozen oilfields

    Directory of Open Access Journals (Sweden)

    Akbota Adilbekova

    2016-06-01

    Full Text Available Physical chemical properties of oil emulsions of two different oilfields of Kazakhstan - NorthWest Konys and Zhanaozen by their densities related to light and heavy oils, respectively, were studied. Qualitative and quantitative compositions of main stabilizing components of oil emulsions (resins, asphaltenes and high molecular paraffins were determined. The dispersion degree of oil emulsions was determined using optical microscopy. It was found that samples relate to fine dispersed oil emulsions by dispersion, and to poorly stable (Konys and highly stable (Zhanaozen oil emulsions by ability to form emulsions. Light oil of Konys oilfield (ρ = 833 kg/m3 at 20°C contains 11.5% of paraffins, 0.69% resins, 0.19% asphaltenes. The same measurements were carried out for heavy oil of Zhanaozen (943 kg/m3 at 20°C where paraffin content exceeded 30%, amount of resins was 1.5% and asphaltenes – 0.6%. The sample of Zhanaozen oilfield contains 33% of water, 154.8 mg/L chlorides, 5.22 % mechanical impurities, and for oilfield samples of North-West Konys the water content was 7.5%, the content of chloride salts – 18 mg/L, and 0.002% of mechanical impurities.

  10. Studies of Catalytic Properties of Inorganic Rock Matrices in Redox Reactions

    Directory of Open Access Journals (Sweden)

    Nikolay M. Dobrynkin

    2017-09-01

    Full Text Available Intrinsic catalytic properties of mineral matrices of various kinds (basalts, clays, sandstones were studied, which are of interest for in-situ heavy oil upgrading (i.e., underground to create advanced technologies for enhanced oil recovery. The elemental, surface and phase composition and matrix particle morphology, surface and acidic properties were studied using elemental analysis, X-ray diffraction, adsorption and desorption of nitrogen and ammonia. The data on the catalytic activity of inorganic matrices in ammonium nitrate decomposition (reaction with a large gassing, oxidation of hydrocarbons and carbon monoxide, and hydrocracking of asphaltenes into maltenes (the conversion of heavy hydrocarbons into more valuable light hydrocarbons were discussed. In order to check their applicability for the asphaltenes hydrocracking catalytic systems development, basalt and clay matrices were used as supports for iron/basalt, nickel/basalt and iron/clay catalysts. The catalytic activity of the matrices in the reactions of the decomposition of ammonium nitrate, oxidation of hydrocarbons and carbon monoxide, and hydrocracking of asphaltens was observed for the first time.

  11. Study on Colloidal Model of Petroleum Residues through the Attraction Potential between Colloids

    Directory of Open Access Journals (Sweden)

    Long-li Zhang

    2016-01-01

    Full Text Available The samples of DaGang atmospheric residue (DG-AR, Middle East atmospheric residue (ME-AR, TaHe atmospheric residue (TH-AR, and their thermal reaction samples were chosen for study. All the samples were fractioned into six components separately, including saturates plus light aromatics, heavy aromatics, light resins, middle resins, heavy resins, and asphaltenes. The dielectric permittivity of the solutions of these components was measured, and the dielectric permittivity values of the components can be determined by extrapolation, which increased steadily from saturates plus light aromatics to asphaltenes. Moreover, the Hamaker constants of the components were calculated from their dielectric permittivity values. The Van der Waals attractive potential energy between colloids corresponding to various models could be calculated from the fractional composition and the Hamaker constants of every component. It was assumed that the cores of colloidal particles were formed by asphaltenes and heavy resins mainly; the other fractions acted as dispersion medium. For the three serials of thermal reaction samples, the Van der Waals attraction potential energy between colloids for this kind of model was calculated. For TH-AR thermal reaction samples, the Van der Waals attraction potential energy presented the maximum as thermal reaction is going on, which was near to the end of coke induction period.

  12. Abstracts of the 9. annual international conference on petroleum phase behavior and fouling

    Energy Technology Data Exchange (ETDEWEB)

    Muhammad, M. [Schlumberger Canada Ltd., Calgary, AB (Canada); Wiehe, I. [Soluble Solutions, Gladstone, NJ (United States)] (comps.)

    2008-07-01

    This conference provided a forum to discuss petroleum phase behaviour and present the latest understanding of the molecular structures and physical interactions of the larger molecules in petroleum. Participants came from universities, petroleum companies, service companies and government laboratories. Topics of discussion included the chemistry, thermodynamics and deposition related to heavy oil, bitumen, asphaltenes, wax, naphthenates and naphthenic acids, as well as petroleum-water emulsions and fouling mechanisms and mitigation. Solids, such as wax and asphaltenes have a tendency to precipitate with changes in temperature and pressure or upon mixing with other petroleum streams. These solid phases can impede or block flow during petroleum production, transport and refining operations. This presentations provided a better understanding of solids deposition to better predict when these problems may occur, so that mitigation methods might be devised. The 5 sessions of the conference were entitled: thermodynamics and rheology of petroleum fluids; asphaltenes; emulsions; flow assurance; and upgrading and refining. All 100 presentations at this conference have been catalogued separately for inclusion in this database. refs.

  13. Molecular modeling of interactions between heavy crude oil and the soil organic matter coated quartz surface.

    Science.gov (United States)

    Wu, Guozhong; Zhu, Xinzhe; Ji, Haoqing; Chen, Daoyi

    2015-01-01

    Molecular dynamic (MD) simulation was applied to evaluate the mobility, diffusivity and partitioning of SARA (saturates, aromatics, resins, asphaltenes) fractions of heavy crude oil on soil organic matter (SOM) coated quartz surface. Four types of SOM were investigated including Leonardite humic acid, Temple-Northeastern-Birmingham humic acid, Chelsea soil humic acid and Suwannee river fulvic acid. The SOM aggregation at oil-quartz interface decreased the adsorption of SARA on the quartz surface by 13-83%. Although the SOM tended to promote asphaltenes aggregation, the overall mobility of SARA was significantly greater on SOM-quartz complex than on pure quartz. Particularly, the diffusion coefficient of asphaltenes and resins increased by up to one-order of magnitude after SOM addition. The SOM increased the overall oil adsorption capacity but also mobilized SARA by driving them from the viscous oil phase and rigid quartz to the elastic SOM. This highlighted the potential of SOM addition for increasing the bioavailability of heavy crude oil without necessarily increasing the environmental risks. The MD simulation was demonstrated to be helpful for interpreting the role of SOM and the host oil phase for the adsorption and partitioning of SARA molecules, which is the key for developing more realistic remediation appraisal for heavy crude oil in soils. Copyright © 2014 Elsevier Ltd. All rights reserved.

  14. Flow of microemulsion through soil columns contaminated with asphaltic residue; Fluxo de microemulsoes atraves do solo contaminado com residuos asfalticos

    Energy Technology Data Exchange (ETDEWEB)

    Oliveira, Marcia C.K.; Oliveira, Jose F. [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Coordenacao dos Programas de Pos-graduacao de Engenharia (COPPE); Oliveira, Roberto C.G.; Gonzalez, Gazpar [PETROBRAS, Rio de Janeiro, RJ (Brazil). Centro de Pesquisas

    2004-07-01

    Nowadays, soil contamination with nonaqueous phase liquids (NAPLs) such as petroleum hydrocarbons is a major environmental problem. Significant efforts have been devoted to the development of processes to remediate sites contaminated with NAPLs. Unfortunately, most of the developed processes proved to be inefficient to remove the organic heavy fraction present in the NAPLs. Nevertheless, in our preliminary bench scale tests it was observed that, due to their high solubilization capacity and stability, microemulsions are able to remove organic heavy fractions like asphaltenes and resins, typically present in crude oils. The present work was dimensioned to evaluate, under up-flow condition, the performance of different microemulsions specially designed to remove asphaltenes fractions from soils using a column test set-up. The contaminant residual concentration was quantified by UV spectroscopy and the microemulsion efficiency determined using mass balance. The results showed that the microemulsions tested have a high capacity for removing asphaltenes fractions from contaminated soils. It was also observed that the predominant removal mechanism, solubilization or mobilization, depends essentially on the microemulsion's chemical formulation. Finally it was verified that microemulsion's formulations based on natural solvents compounds are also efficient for removing asphaltic residues. (author)

  15. Improving fuel quality by whole crude oil hydrotreating: A kinetic model for hydrodeasphaltenization in a trickle bed reactor

    International Nuclear Information System (INIS)

    Jarullah, A.T.; Mujtaba, I.M.; Wood, A.S.

    2012-01-01

    Highlights: ► Asphaltene contaminant must be removed to a large extent from the fuel to meet the regulatory demand. ► Kinetics for hydrodeasphaltenization are estimated via experimentation and modeling. ► Using the kinetic parameters, a full process model for the trickle bed reactor (TBR) is developed. ► The model is used for simulating the behavior of the TBR to get further insight of the process. ► The influences of operating conditions in the hydrodeasphaltenization process are reported. -- Abstract: Fossil fuel is still a predominant source of the global energy requirement. Hydrotreating of whole crude oil has the ability to increase the productivity of middle distillate fractions and improve the fuel quality by simultaneously reducing contaminants such as sulfur, nitrogen, vanadium, nickel and asphaltene to the levels required by the regulatory bodies. Hydrotreating is usually carried out in a trickle bed reactor (TBR) where hydrodesulfurization (HDS), hydrodenitrogenation (HDN), hydrodemetallization (HDM) and hydrodeasphaltenization (HDAs) reactions take place simultaneously. To develop a detailed and a validated TBR process model which can be used for design and optimization of the hydrotreating process, it is essential to develop kinetic models for each of these reactions. Most recently, the authors have developed kinetic models for all of these chemical reactions except that of HDAs. In this work, a kinetic model (in terms of kinetic parameters) for the HDAs reaction in the TBR is developed. A three phase TBR process model incorporating the HDAs reactions with unknown kinetic parameters is developed. Also, a series of experiments has been conducted in an isothermal TBR under different operating conditions affecting the removal of asphaltene. The unknown kinetic parameters are then obtained by applying a parameter estimation technique based on minimization of the sum of square errors (SSEs) between the experimental and predicted concentrations of

  16. Visualizing Oil Process Dynamics in Porous Media with Micromodels

    Science.gov (United States)

    Biswal, S. L.

    2016-12-01

    The use of foam in enhanced oil recovery (EOR) applications is being considered for gas mobility control to ensure pore-trapped oil can be effectively displaced. In fractured reservoirs, gas tends to channel only through the highly permeability regions, bypassing the less permeable porous matrix, where most of the residual oil remains. Because of the unique transport problems presented by the large permeability contrast between fractures and adjacent porous media, we aim to understand the mechanism by which foam transitions from the fracture to the matrix and how initially trapped oil can be displaced and ultimately recovered. My lab has generated micromodels, which are combined with high-speed imaging to visualize foam transport in models with permeability contrasts, fractures, and multiple phases. The wettability of these surfaces can be altered to mimic the heterogeneous wettability found in reservoir systems. We have shown how foam quality can be modulated by adjusting the ratio of gas flow ratio to aqueous flow rate in a flow focusing system and this foam quality influences sweep efficiency in heterogeneous porous media systems. I will discuss how this understanding has allowed us to design better foam EOR processes. I will also highlight our recent efforts in ashaltene deposition. Asphaltene deposition is a common cause of significant flow assurance problems in wellbores and production equipment as well as near-wellbore regions in oil reservoirs. I will present our results for visualizing real time asphaltene deposition from model and crude oils using microfluidic devices. In particular, we consider porous-media micromodel designs to represent various flow conditions typical of that found in oil flow processes. Also, four stages of deposition have been found and investigated in the pore scale and with qualitatively macroscopic total collector efficiency as well as Hamaker expressions for interacting asphaltenes with surfaces. By understanding the nature and

  17. Improvement of Heavy Oil Recovery in the VAPEX Process using Montmorillonite Nanoclays Amélioration de la récupération d’huile lourde par utilisation de nanoargiles de Montmorillonite dans le procédé VAPEX

    Directory of Open Access Journals (Sweden)

    Pourabdollah K.

    2011-10-01

    Full Text Available In this paper, the nanoclay particles were introduced as mobile adsorbents in oil reservoirs to adsorb the asphaltenes, reduce the viscosity and enhance the dispersion. The objective of this paper is experimental investigation of enhanced heavy oil recovery using in situ nanoparticles for the first time. Moreover, two thermal analysis methods (thermogravimetry and differential thermal analysis were used to analyze the asphaltene content of residue hydrocarbons in the swept chambers in nano-assisted and conventional VAPEX processes. Experiments were carried out using Iranian heavy oil and propane: the setup consisted of two sand-packed cells; one packed only with glass beads as the oil matrix and the other with glass beads and modified montmorillonite as the nanoclay, while they had similar porosity and permeability. The content of deposited asphaltene in swept matrixes, the propagation pattern of vapor chambers in heavy oil matrixes, and the rates of solvent consumption and oil production were determined. The results elucidated that montmorillonite changed the matrix heterogeneity and led to forming enhanced breakthroughs, to increasing the interfacial surface of vapor/bitumen and to accelerating the oil production. It was found that not only was the rate of vapor injection diminished, but the heavy oil recovery was also markedly enhanced by 30(±4%. Dans cet article, on decrit l’utilisation de particules de nanoargile en tant qu’adsorbant mobile dans des reservoirs d’huile afin d’adsorber les asphaltenes, reduire la viscosite de l’huile et renforcer la dispersion. L’objectif de cet article consiste en la description d’une etude experimentale de recuperation amelioree d’huile lourde par l’utilisation de nanoparticules in situ. Ce qui constitue une premiere. En outre, deux methodes d’analyse thermique (thermogravimetrie et analyse thermique differentielle ont ete utilisees pour analyser la teneur en asphaltene des residus d

  18. Hydrocarbons dating by Re-Os method: experimental study of the Re-Os couple geochemical behaviour in oils during the evolution of a petroleum system

    International Nuclear Information System (INIS)

    Mahdaoui, Fatima

    2013-01-01

    The Re-Os radiogenic system is well adapted to the dating of oils and bitumen. However the meaning of the obtained age is ambiguous. This is mainly due to gaps in our knowledge of the geochemical behavior and the speciation of Re and Os in oils. Specifically, use of the Re-Os geo-chronometer requires an understanding of how Re-Os behavior can lead to the fulfillment of the conditions necessary for the development of an isochron. These conditions are: i) the isotopic homogenization of oils at the scale of a petroleum field ii) the fractionation of Re from Os so as to obtain samples with various Re/Os ratios iii) the closure of the system during the period of radiogenic ingrowth of the daughter isotope, that is, from the time of the event of interest to the present day. Experimental investigation of the organic geochemical behavior of Re and Os in oils under various conditions, designed as analogs of the different stages of petroleum generation and evolution, were performed in order to evaluate the use of the Re-Os system as a geo-chronometer in the context of a direct use on petroleum. The possibility of Re-Os fractionation resulting from asphaltene loss during oil evolution was investigated by sequential asphaltene precipitation in the laboratory. This study determined that Re and Os are mainly located in the most polar asphaltene fractions, that is, in the first to precipitate. This study also demonstrated that Re/Os ratios are not disturbed by asphaltene loss during the evolution of oils, unless this loss is unrealistically large. Thus asphaltene precipitation during migration and emplacement is not responsible for the Re/Os fractionation required for the use of the geo-chronometer. The possibility of metal transfer from formation waters to petroleum was studied by performing contact experiments between oils and aqueous solutions of Re and Os of various concentrations over a wide range of temperatures and for varying periods of time. This study demonstrated a

  19. Naphthenic acids hydrates of gases: influence of the water/oil interface on the dispersing properties of an acidic crude oil; Acides naphteniques hydrates de gaz de l'interface eau/huile sur les proprietes dispersantes d'un brut acide

    Energy Technology Data Exchange (ETDEWEB)

    Arla, D.

    2006-01-15

    Nowadays, the development of offshore oil production under increasing water depths (high pressures and low temperatures) has led oil companies to focus on gas hydrates risks. Hydrates are crystals containing gas and water molecules which can plug offshore pipelines. It has been shown that some asphaltenic crude oils stabilize water-in-oil emulsions (W/O) during several months and exhibit very good anti-agglomerant properties avoiding hydrate plugs formation. In this work, we have studied the 'anti-hydrate' properties of a West African acidic crude oil called crude AH. This oil contains naphthenic acids, RCOOH hydrocarbons which are sensitive to both the pH and the salinity of the water phase.The emulsifying properties of the crude AH have firstly been explored. It has been shown that heavy resins and asphaltenes are the main compounds of the crude AH responsible for the long term stability of the W/O emulsions whereas the napthenates RCOO{sup -} lead to less stable W/O emulsions. Dealing with hydrates, the crude AH exhibits moderate anti-agglomerant properties due to the presence of heavy resins and asphaltenes. However, the naphthenates RCOO{sup -} drastically increase the formation of hydrate plugs. Moreover, it has been pointed out that hydrate particles agglomeration accelerates the kinetics of hydrate formation and enhances the water/oil separation. In order to explain these behaviours, a mechanism of agglomeration by 'sticking' between a hydrate particle and a water droplet has been proposed. Finally, we have developed a model which describes the physico-chemical equilibria of the naphthenic acids in the binary system water/crude AH, in order to transpose the results obtained in the laboratory to the real oil field conditions. (author)

  20. Origin of heavy crudes; Origine des huiles lourdes

    Energy Technology Data Exchange (ETDEWEB)

    Huc, A.Y. [Institut Francais du Petrole (IFP), 92 - Rueil-Malmaison (France)

    2005-12-15

    Viscous to highly viscous crude oils, named heavy or extra-heavy oils, are the result of a biological alteration of conventional crude oils by bacteria. The effects of this biodegradation is the sequential vanishing of light hydrocarbons, n-alkanes, ramified alkanes and cyclo-alkanes which leads to a progressive enrichment in aromatics and heavy fractions (resins and asphaltenes). The result is an increase of the viscosity and of the metals and sulfur content and also of the acidity of the oil. This short paper explains this process. (J.S.)

  1. Biotreatment of hydrocarbons from petroleum tank bottom sludges in soil slurries

    International Nuclear Information System (INIS)

    Ferrari, M.D.; Neirotti, E.; Albornoz, C.; Mostazo, M.R.; Cozzo, M.

    1996-01-01

    Biotreatment of oil wastes in aqueous slurries prepared with sandy loam soil and inoculated with selected soil cultures was evaluated. After 90 days, oil removal was 47%. Removal of each hydrocarbon class was 84% for saturates, 20% for aromatics, and 44% for asphaltenes. Resins increased by 68%. The use of a soil with a lower level of fine particles or minor organic matter content, or reinoculation with fresh culture did not improve oil elimination. Residual oil recovered from slurries was biotreated. Oil removal was 22%. Slurry-phase biotreatment showed less variability and faster oil removal than solid-phase biotreatment. (author)

  2. EPR and Fluorescence Spectroscopy in the Photodegradation Study of Arabian and Colombian Crude Oils

    Directory of Open Access Journals (Sweden)

    Carmen L. B. Guedes

    2006-01-01

    W/m2. The reduction in the linewidth of the free radical of 9.8% in Arabian oil and 18.5% in Colombian oil, as well as the decrease in radical numbers, indicated photochemical degradation, especially in Colombian oil. The linewidth narrowing corresponding to free radicals in the irradiated oils occurred due to the rearrangement among radicals and aromatic carbon consumption. The irradiated oils showed a reduction in the relative intensity of fluorescence of the aromatics with high molecular mass, polar aromatics, and asphaltene. The fluorescent fraction was reduced by 61% in Arabian oil and 72% in Colombian oil, corresponding to photochemical degradation of crude oil aromatic compounds.

  3. Characterization of bio-oils and bio-char obtained from the pyrolysis of a mixture of Lolium perenne, Festuca ovina, Festuca rubra and Poa pratensis grasses

    OpenAIRE

    Baysal, Mustafa; Yürüm, Yuda; Yurum, Yuda

    2016-01-01

    In this work, the yield and chemical characterization of products obtained from the pyrolysis of a mixture of Lolium perenne, Festuca ovina, Festuca rubra and Poa pratensis grasses under an inert atmosphere at 600 degrees C with a heating rate of 50 degrees C/min was studied. Distribution of the products of pyrolysis grass sample was: moisture: 8 +/- 2%, total volatiles: 78 +/- 7%, char: 14 +/- 5%. Bio-oils were acidic and dark brown liquids and they were separated into oils, asphaltenes and ...

  4. Evolution of wettability in terms of petroleum and petroleum fractions adsorption. An approach by the Wilhelmy method; Evolution de la mouillabilite en fonction de l`adsorption du petrole et de ses fractions. Approche par la methode des angles de contact dynamiques

    Energy Technology Data Exchange (ETDEWEB)

    Mattos Saliba, A.

    1996-12-06

    Reservoir wettability is very important to petroleum recovery by waterflooding and other processes. It is a key parameter controlling multiphase flow and fluids distribution in a porous medium. Nevertheless, the original water-wetness can be modified by the petroleum`s natural surfactants (asphaltenes and resins) adsorption onto the rock surface. This adsorption may reduce petroleum recovery. In this study, the adsorption of model molecules (pyridine and benzo-quinoline), of rude oil and of its heavier fractions (asphaltenes and resins) has been investigated in terms of wettability alteration for initially water-wet surfaces (glass or quartz). In this case, the dynamic Wilhelmy plate technique provides quantitative values of wetting preference to either oil or water. The results show that, at ambient conditions, adsorption depends on concentration, adsorbent/adsorbate interaction time, pH, solvent type, substrate surface, brine concentration and environment liquid phase (water or oil). However, the initial water film on the surface does not strongly influence this phenomena. (author) 222 refs.

  5. On the structure and formation of Bulgarian oil shale kerogen. Part 1. Some conclusions on the kerogen structure based on the results of thermal degradation

    International Nuclear Information System (INIS)

    Georgiev, I.B.

    1993-01-01

    Thermal degradation of kerogen under mild conditions, in an inert medium and under vacuum has been examined. The resulting products - gas, water, oil, semi-coke - have been analyzed applying a great number of physical and chemical methods of analysis. A complete material balance of the process has been done. Basing on the supposition that from one average fragment of the kerogen structure one mole of asphaltenes is removed. It was estimated that 4.5 moles of resins, 2.85 moles of bi aromatics with R av = C 10 , 2.34 moles of mono aromatics with R av = C 18 , 4.9 moles of alkanes C 23 in average, etc. are removed along with one mole of asphaltenes. The number of the atoms in the given fragment is calculated from these results. It is demonstrated that the number of aromatic carbon atoms is 50 % i.e. kerogen is of a high degree of aromatization and cyclization. It contradicts the results obtained during kerogen oxidation with KMnO 4 that gives a high yield of straight-chain di carbonic acids. This difference in the results is explained. The hetero elements are supposed to have a strong influence on the process of kerogen structure formation. (author). 11 tabs., 31 refs

  6. Vacuum Distillation Residue Upgrading by an Indigenous Bacillus Cereus

    Directory of Open Access Journals (Sweden)

    Mitra Sadat Tabatabaee

    2013-07-01

    Full Text Available Background:Biological processing of heavy fractions of crude oils offers less severe process conditions and higher selectivity for refining. Biochemical Processes are expected to be low demand energy processes and certainly ecofriendly.Results:A strain of biosurfactant producing bacterium was isolated from an oil contaminated soil at Tehran refinery distillation unit. Based on selected phenotypic and genotypic characteristic including morphology, biochemical proprety, and 16 SrRNA sequencing identified as a novel strain of Bacillus cereus (JQ178332. This bacterium endures a wide range of pH, salinity and temperature. This specific strain utilizes both paraffin and anthracene as samples of aliphatic and polycyclic aromatic hydrocarbons. The ability of this bacterium to acquire all its energy and chemical requirements from Vacuum Distillation Residue (VR, as a net sample of problematic hydrocarbons in refineries, was studied. SARA test ASTM D4124-01 revealed 65.5% decrease in asphaltenic, 22.1% in aliphatics and 30.3% in Aromatics content of the VR in MSM medium. Further results with 0.9% saline showed 55% decrease in asphaltene content and 2.1% Aromatics respectively.Conclusion:Remarkable abilities of this microorganism propose its application in an ecofriendly technology to upgrade heavy crude oils.

  7. Correlating the chemical and physical properties of a set of heavy oils from around the world

    Energy Technology Data Exchange (ETDEWEB)

    Amy Hinkle; Eun-Jae Shin; Matthew W. Liberatore; Andrew M. Herring; Mike Batzle [Colorado School of Mines, Golden, CO (United States). Department of Geophysics

    2008-10-15

    Variations in the viscosity and other physical properties of heavy oils are poorly understood. The viscosities measured for different heavy oils can vary by orders of magnitude even at the same API gravity, which is the standard metric for lighter oils. Heavy oils are viscoelastic materials, and the shear modulus and the viscosity are coupled. Understanding what controls heavy oil viscosity will provide insight into what controls heavy oil shear modulus. Therefore, using rheology, ultrasonic measurements and molecular beam mass spectroscopy (MBMS) the physical and chemical properties of seven heavy oils from around the globe are explored. The viscoelastic nature of the oils is quantified as a function of temperature. Overall, the heavy oil samples show little correlation between the viscosity or shear modulus and the API gravity, separate resin content or separate asphaltene content as measured from SARA analysis. However, the total resin plus asphaltene content collapses the viscosity and modulus values to provide empirical relations between these quantities. Also, a partial least squares regression analysis provides tight correlations for the chemical signatures from the MBMS. The rapid and quantitative nature of the MBMS make it an attractive substitute for the inconsistencies endemic to SARA analysis. 24 refs., 11 figs., 1 tab.

  8. A study of light hydrocarbons (C{sub 4}-C{sub 1}3) in source rocks and petroleum fluid

    Energy Technology Data Exchange (ETDEWEB)

    Odden, Wenche

    2000-07-01

    This thesis consists of an introduction and five included papers. Of these, four papers are published in international journals and the fifth was submitted for review in April 2000. Emphasis has been placed on both naturally and artificially generated light hydrocarbons in petroleum fluids and their proposed source rocks as well as direct application of light hydrocarbons to oil/source rock correlations. Collectively, these papers describe a strategy for interpreting the source of the light hydrocarbons in original oils and condensates as well as the source of the asphaltene fractions from the reservoir fluids. The influence of maturity on light hydrocarbon composition has also been evaluated. The papers include (1) compositional data on the light hydrocarbons from thermal extracts and kerogen pyrolysates of sediment samples, (2) light hydrocarbon data of oils and condensates as well as the pyrolysis products of the asphaltenes from these fluids, (3) assessment of compositional alteration effects, such as selective losses of light hydrocarbons due to evaporation, thermal maturity, phase fractionation and biodegradation, (4) comparison of naturally and artificially generated light hydrocarbons, and (5) compound-specific carbon isotope analysis of the whole range of hydrocarbons of all sample types. (author)

  9. Reactivity study on thermal cracking of vacuum residues

    Science.gov (United States)

    León, A. Y.; Díaz, S. D.; Rodríguez, R. C.; Laverde, D.

    2016-02-01

    This study focused on the process reactivity of thermal cracking of vacuum residues from crude oils mixtures. The thermal cracking experiments were carried out under a nitrogen atmosphere at 120psi between 430 to 500°C for 20 minutes. Temperature conditions were established considering the maximum fractional conversion reported in tests of thermogravimetry performed in the temperature range of 25 to 600°C, with a constant heating rate of 5°C/min and a nitrogen flow rate of 50ml/min. The obtained products were separated in to gases, distillates and coke. The results indicate that the behaviour of thermal reactivity over the chemical composition is most prominent for the vacuum residues with higher content of asphaltenes, aromatics, and resins. Finally some correlations were obtained in order to predict the weight percentage of products from its physical and chemical properties such as CCR, SARA (saturates, aromatics, resins, asphaltenes) and density. The results provide new knowledge of the effect of temperature and the properties of vacuum residues in thermal conversion processes.

  10. Wettability Studies Using Zeta Potential Measurements

    Directory of Open Access Journals (Sweden)

    Ghada Bassioni

    2015-01-01

    Full Text Available Wettability studies have been carried out on reservoir rocks using different techniques such as the Amott-Harvey method, the USBM method, and the contact angle method, all with limitations. In this study, the wettability is studied by discussing the surface charge using zeta potential measurements. The study relies on the finding that carbonated reservoir rocks, consisting of CaCO3 mainly, are positively charged and their surface has the potential to adsorb significant quantities of anions. Moreover, heavy fractions such as asphaltenes are reported to remain afloat depending on dispersive forces present in the oil and its various fractions. Experiments are carried out on aqueous limestone suspension with the addition of crude oil. The experiment is repeated with the use of polymeric inhibitors, A and B. The zeta potential is found to alter depending on the sequence of polymeric inhibitor in oil/water addition. The inhibitor is found to adsorb on the limestone surface, with a net negative charge, causing repulsion between crude oil and the inhibitor and, hence, preventing the deposition of heavy fractions and particularly asphaltenes. This study gives a comprehensive insight on the mechanism of polymeric inhibitor interaction with the surface and the effect of wettability on its performance.

  11. Organic metamorphism in the Lower Mississippian-Upper Devonian Bakken shales-II: Soxhlet extraction.

    Science.gov (United States)

    Price, L.C.; Ging, T.; Love, A.; Anders, D.

    1986-01-01

    We report on Soxhlet extraction (and subsequent related analyses) of 39 Lower Mississippian-Upper Devonian Bakken shales from the North Dakota portion of the Williston Basin, and analyses of 28 oils from the Basin. Because of the influence of primary petroleum migration, no increase in the relative or absolute concentrations of hydrocarbons or bitumen was observed at the threshold of intense hydrocarbon generation (TIHG), or during mainstage hydrocarbon generation in the Bakken shales. Thus, the maturation indices that have been so useful in delineating the TIHG and mainstage hydrocarbon generation in other studies were of no use in this study, where these events could clearly be identified only by Rock-Eval pyrolysis data. The data of this study demonstrate that primary petroleum migration is a very efficient process. Four distinctive classes of saturated hydrocarbon gas chromatograms from the Bakken shales arose from facies, maturation, and primary migration controls. As a consequence of maturation, the % of saturated hydrocarbons increased in the shale extract at the expense of decreases in the resins and asphaltenes. Measurements involving resins and asphaltenes appear to be excellent maturation indices in the Bakken shales. Two different and distinct organic facies were present in immature Bakken shales. -from Authors

  12. Characterization of oily sludge from a refinery and biodegradability assessment using various hydrocarbon degrading strains and reconstituted consortia.

    Science.gov (United States)

    Jasmine, Jublee; Mukherji, Suparna

    2015-02-01

    Oily sludge obtained from a refinery in India contained 10-11% oil associated with fine particulates. Along with Fe, Ca and Mg various toxic elements were associated with the sludge solids (Pb, Mn, Cu, Zn, As, Bi, Cd, Cr, Co, Ni and V). The oil contained 41-56% asphaltenes and the maltenes comprised of 49 ± 4%, 42 ± 2% and 4 ± 2%, aliphatic, aromatic and polar fractions, respectively. Biodegradation studies with the maltene fraction of oil provided as sole substrate revealed higher degradation by various 3-5 membered reconstituted consortia compared to pure bacterial strains and up to 42 ± 8% degradation could be achieved over 30 days. In contrast, over the same period up to 71.5 ± 2% oil degradation could be achieved using dried oily sludge (15% w/v) as sole substrate. Significant biodegradation observed in the un-inoculated controls indicated the presence of indigenous microorganisms in oily sludge. However, large variability in oil degradation was observed in the un-inoculated controls. Greater biodegradation of the maltene fraction led to significant enrichment of asphaltenes in residual oil associated with the sludge. Copyright © 2014 Elsevier Ltd. All rights reserved.

  13. Computer simulation of deasphalting vacuum residues in a pilot unit; Simulacao computacional de desasfaltacao de residuo de vacuo realizada em unidade piloto

    Energy Technology Data Exchange (ETDEWEB)

    Concha, Viktor Oswaldo Cardenas; Quirino, Filipe Augusto Barral; Koroisgi, Erika Tomie; Rivarola, Florencia Wisnivesky Rocca; Maciel, Maria Regina Wolf; Maciel Filho, Rubens [Universidade Estadual de Campinas (UNICAMP), SP (Brazil). Faculdade de Engenharia Quimica; Medina, Lilian Carmen; Barros, Ricardo Soares de [PETROBRAS S.A., Rio de Janeiro, RJ (Brazil). Centro de Pesquisas (CENPES)

    2008-07-01

    In the context of the national petroleum industry, it is interesting to keep the production of the paraffinic lubricant oil type I, which implies in the identification of new loads to ensure the feeding of the existing units. Therefore, it is important to carry out carefully the characterization of the oils, defining its potential for fuel, asphalt and lubricant. Aiming to introduce in the characterization and evaluation of petroleum for lubricant, carried out by PETROBRAS/CENPES, information of basic oils, more similar to industrial oils, was built up in the Laboratory of Process Separation Development - LDPS of UNICAMP/FEQ, a deasphalting pilot unit. In this work, the deasphalting process of a vacuum residue of Brazilian petroleum is simulated, using Aspen Plus{sup R} simulator, in order to remove asphaltenes, resins and other heavy components of vacuum residue. The simulations were carried out considering the configuration of the pilot plant, evaluating the extraction in near-critical operational condition applied to a petroleum, using propane as the solvent. The extraction efficiency and the solvent power were evaluated considering variations in temperature, pressure and in the solvent/feed ratio in order to obtain yields with more efficiency in the production of deasphalted oil (DAO), what means more asphaltene removal. (author)

  14. Prediction of ecotoxicity of hydrocarbon-contaminated soils using physicochemical parameters

    Energy Technology Data Exchange (ETDEWEB)

    Wong, D.C.L.; Chai, E.Y.; Chu, K.K.; Dorn, P.B.

    1999-11-01

    The physicochemical properties of eight hydrocarbon-contaminated soils were used to predict toxicity to earthworms (Eisenia fetida) and plants. The toxicity of these preremediated soils was assessed using earthworm avoidance, survival, and reproduction and seed germination and root growth in four plant species. No-observed-effect and 25% inhibitory concentrations were determined from the earthworm and plant assays. Physical property measurements and metals analyses of the soils were conducted. Hydrocarbon contamination was characterized by total petroleum hydrocarbons, oil and grease, and GC boiling-point distribution. Univariate and multivariate statistical methods were used to examine relationships between physical and chemical properties and biological endpoints. Soil groupings based on physicochemical properties and toxicity from cluster and principal component analyses were generally similar. Correlation analysis identified a number of significant relationships between soil parameters and toxicity that were used in univariate model development. Total petroleum hydrocarbons by gas chromatography and polars were identified as predictors of earthworm avoidance and survival and seed germination, explaining 65 to 75% of the variation in the data. Asphaltenes also explained 83% of the variation in seed germination. Gravimetric total petroleum hydrocarbons explained 40% of the variation in earthworm reproduction, whereas 43% of the variation in plant root growth was explained by asphaltenes. Multivariate one-component partial least squares models, which identified predictors similar to those identified by the univariate models, were also developed for worm avoidance and survival and seed germination and had predictive powers of 42 and 29%, respectively.

  15. Spatial and temporal changes of density and chemical composition of heavy oils of Eurasia

    Energy Technology Data Exchange (ETDEWEB)

    Polishchuk, Y.M.; Yashchenko, I.G. [Institute of Petroleum Chemistry, Siberian Branch of Russian Academy of Sciences, 3 Akademichesky Ave., 634021, Tomsk (Russian Federation)

    2011-07-01

    Paper is devoted to analytical review of regularities of spatial and temporal changes of chemical composition and density of heavy oils of Eurasia, which are envisaged as main reserve of world's oil production industry for future years. The contents of sulfur, paraffin, resin, asphaltene and light fraction in heavy oils and their density were analysed statistically with use the global database on petrochemistry created by Institute of petroleum chemistry. The database includes above 3,660 samples of heavy oils from 62 principal oil-bearing basins in Eurasia. The basic regularities of regional distribution of heavy oils are considered. It is shown that the heaviest oils of Eurasia are in oil-bearing basins of Southern Europe and Southern Asia. The regularities of heavy oil density changes depending on occurrence depth are given. It is shown oil density decreases with depth growth. Maximum values of density of heavy oils are observed in Cenozoic rocks and their minimum values are in Proterozoic rocks. In average, heavy oils are sulfur, high resin, high asphaltenes ones containing small paraffin and small light fractions.

  16. Production of jet fuel using heavy crude oil; Producao de combustiveis de aviacao a partir de petroleos pesados

    Energy Technology Data Exchange (ETDEWEB)

    Om, Neyda [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Escola de Quimica; Cavado, Alberto; Reyes, Yordanka [Centro de Pesquisas do Petroleo, Cidade de Havana (Cuba); Dominguez, Zulema [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Coordenacao dos Programas de Pos-graduacao de Engenharia (COPPE)

    2004-07-01

    The production of heavy crude oils increased in the last years in the world. Crude oils with high density, viscosity, acidity and sulfur, nitrogen, metals and asphaltenes contents, by the others hand, low stability and low product quality. The challenger of many refiners is find solutions to refine the heavy crude oils, and produce fuels with certify quality, such as Jet Fuel. The principal aviation technique on the world work with gas turbines engines feted for jet fuel (JET A1). The quality specifications of this fuel are establish by International Norms: ASTM-1655, DEF STAN 91-91-3 (DERD 2494) and joint Fuelling System Check List. The world technologies to obtain jet fuel from mixtures of heavy crude oil with middle crude oils are: Atmospheric distillation, with a posterior hydrogenation and finally the additivation. Studies carried out have demonstrates that the Cubans heavy crude oils is characterized for having API less than 10, raised viscosity, high sulfur content (>6%) and asphaltenes content (more than 15%). These properties provide to its derivatives of low quality. This paper define the characteristic of Cuban heavy crude oil, the technology and operational conditions to produce jet fuel (Jet A1) and the quality of fuel produced. (author)

  17. Effect of hydrate formation-dissociation on emulsion stability using DSC and visual techniques

    Energy Technology Data Exchange (ETDEWEB)

    Lachance, J.W.; Dendy Sloan, E.; Koh, C.A. [Colorado School of Mines, Golden, CO (United States). Center for Hydrates Research

    2008-07-01

    Many flow assurance operators are now focusing on preventing hydrates from agglomerating and forming plugs within pipelines. A key factor in reducing plug formation in oil-dominated systems is the stability of emulsified water in gas hydrate formation. In this study, differential scanning calorimetry (DSC) studies were used to show that gas hydrate formation has a destabilizing effect on water and oil emulsions, and can result in a free water phase through the coalescence and agglomeration of dissociated hydrate particles. The study focused on investigating the ability of the hydrates to stay segregated with hydrate formation. The stability of water-in-oil emulsions with hydrate formation was investigated with a range of different crude oils with varying emulsion stability levels. Thermal properties were measured at both atmospheric and pressurized conditions. Thermocouples in the calorimetric furnace were used to measure the temperature difference between reference and sample cells. Emulsion stability was measured over a 1-month time period. Results of the study showed that hydrate formation and dissociation destabilizes emulsions. However, the asphaltene fraction in crude oils resists hydrate-induced destabilization. The stability of the emulsion increased when asphaltene content increased. It was concluded that emulsion stability is a key factor in preventing agglomeration in flow lines. 14 refs., 3 tabs., 8 figs.

  18. Molecular characterization and comparison of shale oils generated by different pyrolysis methods

    Science.gov (United States)

    Birdwell, Justin E.; Jin, Jang Mi; Kim, Sunghwan

    2012-01-01

    Shale oils generated using different laboratory pyrolysis methods have been studied using standard oil characterization methods as well as Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) with electrospray ionization (ESI) and atmospheric photoionization (APPI) to assess differences in molecular composition. The pyrolysis oils were generated from samples of the Mahogany zone oil shale of the Eocene Green River Formation collected from outcrops in the Piceance Basin, Colorado, using three pyrolysis systems under conditions relevant to surface and in situ retorting approaches. Significant variations were observed in the shale oils, particularly the degree of conjugation of the constituent molecules and the distribution of nitrogen-containing compound classes. Comparison of FT-ICR MS results to other oil characteristics, such as specific gravity; saturate, aromatic, resin, asphaltene (SARA) distribution; and carbon number distribution determined by gas chromatography, indicated correspondence between higher average double bond equivalence (DBE) values and increasing asphaltene content. The results show that, based on the shale oil DBE distributions, highly conjugated species are enriched in samples produced under low pressure, high temperature conditions, and under high pressure, moderate temperature conditions in the presence of water. We also report, for the first time in any petroleum-like substance, the presence of N4 class compounds based on FT-ICR MS data. Using double bond equivalence and carbon number distributions, structures for the N4 class and other nitrogen-containing compounds are proposed.

  19. Oil-in-water nanocontainers as low environmental impact cleaning tools for works of art: two case studies.

    Science.gov (United States)

    Carretti, Emiliano; Giorgi, Rodorico; Berti, Debora; Baglioni, Piero

    2007-05-22

    A novel class of p-xylene-in-water microemulsions mainly based on nonionic surfactants and their application as low impact cleaning tool in cultural heritage conservation is presented. Alkyl polyglycosides (APG) and Triton X-100 surfactants allow obtaining very effective low impact oil-in-water (o/w) microemulsions as alternatives to pure organic solvents for the removal of polymers (particularly Paraloid B72 and Primal AC33) applied during previous conservation treatments. The ternary APG/p-xylene/water microemulsions have been characterized by quasi elastic light scattering to obtain the hydrodynamic radius and the polydispersity of the microemulsion droplets. Laplace inversion of the correlation function CONTIN analysis provided evidence of acrylic copolymers solubilization into the oil nanodroplets. Contact angle, Fourier transform infrared (FTIR), and scanning electron microscopy/energy-dispersive spectroscopy (SEM/EDS) data confirmed that microemulsions were effective in removing polymer coatings. The phase diagram of APG microemulsions showed that a reduction >90% (compared to the conventional cleaning methods) of the organic solvent can be achieved by using o/w microemulsions. The microemulsions were successfully tested in two real cases: (1) the APG based microemulsion was used in a Renaissance painting by Vecchietta in Santa Maria della Scala, Siena, Italy, degraded by the presence of a polyacrylate coating applied during a previous restoration and (2) a Triton X-100 oil-in-water microemulsion containing (NH4)2CO3 in the water continuous phase. The association of ammoniun carbonate to the microemusion led to the swelling of an organic deposit (mainly asphaltenes deposited on the fresco in the Oratorio di San Nicola al Ceppo in Florence, still contamined by the water of the Arno river during the 1966 flood) and a very efficient removal of highly insoluble inorganic deposits (mainly gypsum) strongly associated to asphaltenes. These innovative systems are

  20. Bituminization of simulated waste, spent resins, evaporator concentrates and animal ashes by extrusion process

    International Nuclear Information System (INIS)

    Grosche Filho, C.E.; Chandra, U.

    1987-01-01

    The results of the study of bituminization of simulated radwaste - spennt ion-exchange resins, borate evaporator/concentrates and animal ashes, are presented and discussed. Distilled and oxidizer bitumen were used. Characterization of the crude material and simulated wastes-bitumen mixtures of varying weigt composition (30, 40, 50, 60% by weight of dry waste material) was carried out. The asphaltene and parafin contents in the bitumens were also determined. Some additives and were used with an aim to improve the characteristcs of solidified wastes. For leaching studies, granular ion-exchange resins were with Cs - 134 and mixtures of resin-bitumen were prepared. The leaching studies were executed using the IAEA recommendation and the ISO method. A conventional screw-extruder, common in plastic industry, was used determine operational parameters and process difficulties. Mixtures of resin-bitumen and evaporator concentrate-bitumen obtained from differents operational conditions were characterized. (Author) [pt

  1. Using a Molecular Dynamics Simulation to Investigate Asphalt Nano-Cracking under External Loading Conditions

    Directory of Open Access Journals (Sweden)

    Yue Hou

    2017-07-01

    Full Text Available Recent research shows that macro-scale cracking in asphalt binder may originate from its intrinsic defects at the nano-scale. In this paper, a molecular dynamics (MD simulation was conducted to evaluate the nucleation of natural defects in asphalt. The asphalt microstructure was modeled using an ensemble of three different types of molecules to represent a constituent species: asphaltenes, naphthene aromatics and saturates, where the weight proportion of 20:60:20 was used to create an asphalt-like ensemble of molecules. Tension force was then applied on the molecular boundaries to study the crack initiation and propagation. It was discovered that the natural distribution of atoms at microscale would affect the intrinsic defects in asphalt and further influence crack initiation and propagation in asphalt.

  2. Four-component united-atom model of bitumen

    DEFF Research Database (Denmark)

    Hansen, Jesper Schmidt; Lemarchand, Claire; Nielsen, Erik

    2013-01-01

    We propose a four-component united-atom molecular model of bitumen. The model includes realistic chemical constituents and introduces a coarse graining level that suppresses the highest frequency modes. Molecular dynamics simulations of the model are carried out using graphic-processor-units based...... software in time spans in order of microseconds, which enables the study of slow relaxation processes characterizing bitumen. This paper also presents results of the model dynamics as expressed through the mean-square displacement, the stress autocorrelation function, and rotational relaxation...... the stress autocorrelation function, the shear viscosity and shear modulus are evaluated, showing a viscous response at frequencies below 100 MHz. The model predictions of viscosity and diffusivities are compared to experimental data, giving reasonable agreement. The model shows that the asphaltene, resin...

  3. Estimation of quality and yields of products from the process of future national oils indelayed coking units; Estimativa da qualidade e dos rendimentos de produtos de coqueamento a partir do processamento de petroleos nacionais

    Energy Technology Data Exchange (ETDEWEB)

    Filipakis, Sofia D.; Silva, Maria do Socorro A.J. da; Guimaraes, Regina C.L. [PETROBRAS, Rio de Janeiro, RJ (Brazil)

    2008-07-01

    As the importance of the delayed coking process increases in the Brazilian refinery scenario, it is necessary to perform a more detailed evaluation of vacuum residues potential on this kind of process. This work compares the performance of future produced and exported oils residues with those which are references nowadays as delayed coking feeding. This information is essential for the prediction of the future quality and yield of the products generated by this process, and for the determination of the oils value for exportation. For this purpose, a process simulator was used considering the operational conditions of a real delayed coking unit. The carbon residue and asphaltenes ratio from the residues were also evaluated. This simulation demonstrated that most of the future oils will produce a high quality coke from the point of view of crystallinity and metals content, and it will present high contents of both volatile matter and sulphur. The exported oils residues are likely to show good crystallinity. (author)

  4. [Multifunctional nanocomposite materials

    Energy Technology Data Exchange (ETDEWEB)

    1993-01-01

    These novel nanocomposites are microporous nanometal intercalated clays which have been prepared by a polyol process at 200C and a novel microwave-hydrothermal process using ethylene glycol. These novel nanocomposites have been found to be useful in the conversion of coal to asphaltenes. A crystalline tin (IV) arsenate hydroxide hydrate has been made and its lithium selective ion exchange properties have been measured. This exchanger has shown high lithium selectivity. Selective exchange of divalent transition metal ions in cryptomelane-type manganic acid with tunnel structure have also been studied. Several pillared clays have also been synthesized and their Mg[sup 2+], Li[sup +] and UO[sub 2][sup 2+] selectivity has been measured. The pillared clays appear to show some Li selectivity.

  5. [Multifunctional nanocomposite materials]. Progress report

    Energy Technology Data Exchange (ETDEWEB)

    1993-04-01

    These novel nanocomposites are microporous nanometal intercalated clays which have been prepared by a polyol process at 200C and a novel microwave-hydrothermal process using ethylene glycol. These novel nanocomposites have been found to be useful in the conversion of coal to asphaltenes. A crystalline tin (IV) arsenate hydroxide hydrate has been made and its lithium selective ion exchange properties have been measured. This exchanger has shown high lithium selectivity. Selective exchange of divalent transition metal ions in cryptomelane-type manganic acid with tunnel structure have also been studied. Several pillared clays have also been synthesized and their Mg{sup 2+}, Li{sup +} and UO{sub 2}{sup 2+} selectivity has been measured. The pillared clays appear to show some Li selectivity.

  6. A pre-Paleogene unconformity surface of the Sikeshu Sag, Junggar Basin: Lithological, geophysical and geochemical implications for the transportation of hydrocarbons

    Directory of Open Access Journals (Sweden)

    Xiaoyue Gao

    2013-11-01

    Full Text Available The unconformity surface at the bottom of the Paleogene is one of the most important migration pathways in the Sikeshu Sag of the Junggar Basin, which consists of three layers: upper coarse clastic rock, lower weathering crust and leached zone. The upper coarse clastic rock is characterized by higher density and lower SDT and gamma-ray logging parameters, while the lower weathering crust displays opposite features. The transport coefficient of the unconformity surface is controlled by its position in respect to the basal sandstone; it is higher in the ramp region but lower in the adjacent uplifted and sag areas. The content of saturated hydrocarbons increases with the decrease of the content of non-hydrocarbons and asphaltenes. The content of benzo[c] carbazole decreases as the content of benzo[a] carbazole and [alkyl carbazole]/[alkyl + benzo carbazole] increases. This suggests that the unconformity surface is an efficient medium for the transportation of hydrocarbons.

  7. Solvent extraction of oil-sand components for determination of trace elements by neutron activation analysis

    International Nuclear Information System (INIS)

    Jacobs, F.S.; Filby, R.H.

    1983-01-01

    Instrumental neutron activation analysis was used to measure the concentrations of 30 elements in Athabasca oil sands and oil-sand components. The oil sands were separated into solid residue, bitumen, and fines by Soxhlet extraction with toluene-bitumen extract. The mineral content of the extracted bitumen was dependent on the treatment of the oil sand prior to extraction. The geochemically important and organically associated trace element contents of the bitumen (and asphaltenes) were determined by subtracting the mineral contributions from the total measured concentrations. The method allows analysis of the bitumen without the necessity of ultracentrifugation or membrane filtration, which might remove geochemically important components of the bitumen. The method permits classification of trace elements into organic and inorganic combinations

  8. Investigations of the Montmorillonite and Aluminium Trihydrate Addition Effects on the Ignitability and Thermal Stability of Asphalt

    Directory of Open Access Journals (Sweden)

    Kai Zhu

    2014-01-01

    Full Text Available By means of limiting oxygen index (LOI, cone calorimeter, and TG-DSC tests, this paper investigated the effect of unmodified montmorillonite (MMT, organically modified montmorillonite (OMMT, and aluminium trihydrate (ATH additions on the flame retardancy for asphalt combustion. Experimental results showed that adding a small amount of montmorillonite did not significantly increase the oxygen index of the asphalt but reduced the heat release rate during asphalt combustion. TGA tests had indicated that the montmorillonite (MMT and OMMT could suppress the release of flammable volatiles and form more asphaltenes, which hence postponed the burnout time of asphalt. Furthermore, the combination of montmorillonite (MMT and OMMT and ATH had yielded a synergistic effect, which had further reduced the heat release rate and also increased the oxygen index of asphalt. In particular, after further addition of OMMT, the barrier layer showed less crack, leading to a significant decrease in the heat release rate as compared to the adding of ATH alone.

  9. Spectral characterization of crude oil using fluorescence (synchronous and time-resolved) and NIR (Near Infrared Spectroscopy); Caracterizacao espectral do petroleo utilizando fluorescencia (sincronizada e resolvida no tempo) e NIR (Near Infrared Spectroscopy)

    Energy Technology Data Exchange (ETDEWEB)

    Falla Sotelo, F.; Araujo Pantoja, P.; Lopez-Gejo, J.; Le Roux, G.A.C.; Nascimento, C.A.O. [Universidade de Sao Paulo (USP), SP (Brazil). Dept. de Engenharia Quimica. Lab. de Simulacao e Controle de Processos; Quina, F.H. [Universidade de Sao Paulo (USP), SP (Brazil). Inst. de Quimica. Centro de Capacitacao e Pesquisa em Meio Ambiente (CEPEMA)

    2008-07-01

    The objective of the present work is to evaluate the performance of two spectroscopic techniques employed in the crude oil characterization: NIR spectroscopy and fluorescence spectroscopy (Synchronous fluorescence - SF and Time Resolved Fluorescence - TRF) for the development of correlation models between spectral profiles of crude oil samples and both physical properties (viscosity and API density) and physico-chemical properties (SARA analysis: Saturated, Aromatic, Resins and Asphaltenes). The better results for viscosity and density were obtained using NIR whose prediction capacity was good (1.5 cP and 0.5 deg API, respectively). For SARA analysis, fluorescence spectroscopy revealed its potential in the model calibration showing good results (R2 coefficients greater than 0.85). TRF spectroscopy had better performance than SF spectroscopy. (author)

  10. STUDY OF THE THERMAL CRACKING DURING THE VACUUM DISTILLATION OF ATMOSPHERIC RESIDUE OF CRUDE OIL

    Directory of Open Access Journals (Sweden)

    JAOUAD ELAYANE

    2017-03-01

    Full Text Available This article concerns the study of the thermal cracking as undesirable phenomenon in the vacuum distillation of atmospheric residue of crude oil. In this point, we have sought to identify and characterize the effect of the increase in the temperature of vacuum distillation on the separation and the modification of the constituents of atmospheric residue of crude oil whose origin is Arabian Light. This study has been carried out by several techniques of analysis such as the density (ASTM D4052, distillation (ASTM D1160, determination of heavy metals nickel and vanadium (IFP9422, dosing of Conradson Carbon (ASTM D189, dosing of asphaltenes (ASTM D2549 and dosage of PCI (polycyclic aromatics (ASTM D 5186. The results showed a clear idea on the decomposition of the atmospheric residue and their influence on the performance of the vacuum distillation unit.

  11. Resolution of water in crude oil emulsion by some novel aromatic amine polyesters

    Directory of Open Access Journals (Sweden)

    A.M. Al-Sabagh

    2015-09-01

    Full Text Available In this work, three aromatic amines (p-toluidine, p-nitroaniline and p-chloroaniline were chosen as bases for the repatriation of some nonionic polyesters. These amines were ethoxylated with different total number of ethylene oxide units 6, 12, 18. The prepared ethoxylated amine diols were polyesterified with maleic anhydride and polypropylene oxide polyethylene oxide block copolymers in polyesterification reaction. The demulsification efficiency of these demulsifiers was investigated using the bottle test. The effects of the molecular weight, concentration, asphaltene content, water content, Hydrophile Lipophile Balance (HLB and temperature on the demulsification efficiency were investigated. The surface active properties were correlated with their demulsification efficiency. It was found that, NAE18D gave the best result in the demulsification process. The demulsification efficiency was discussed on the light of surface active properties, interfacial tension and the factors affecting the demulsification. The surface-active properties of the prepared demulsifiers were measured at 60 °C.

  12. Organosulphur Compounds in Coals as Determined by Reaction with Raney Nickel and Microscale Pyrolysis Techniques. Quarterly report, January-March, 1996

    International Nuclear Information System (INIS)

    Stalker, L.; Philip, P.

    1997-01-01

    Since the last report, we have concentrated on completing all the chemical degradation experimental work. This has involved the completion of a series of chemical degradation experiments using deuterium labeled sodium borohydride and deuterated methanol . The products of these desulphurization experiments have, as usual, been fractionated into aliphatic and aromatic hydrocarbons and NSO compounds. The aliphatic hydrocarbon fractions of each desulphurization experiment are currently being analysed by gas chromatography(GC) and gas chromatography-mass spectrometry(GCMS). The object of the deuterium labelling experiments is to determine the relative abundance of thioether, triolane, and thiophene organic sulphur units cleaved in the different coal fractions( i.e. pre- extracted coal matrix, asphaltene and free polars from the maltenes)

  13. Relation of sulfur with hydrocarbons in Brazilian heavy and extra-heavy crude oil; Relacao do enxofre com os hidrocarbonetos em petroleos pesados e extra pesados brasileiros

    Energy Technology Data Exchange (ETDEWEB)

    Iorio, Sonia Maria Badaro Mangueira; Guimaraes, Regina Celia Lourenco; Silva, Maria do Socorro A. Justo da [PETROBRAS S.A., Rio de Janeiro, RJ (Brazil); Costa, Alexander Vinicius Moraes da [Fundacao Gorceix, Ouro Preto, MG (Brazil)

    2008-07-01

    As the occurrence of heavy and extra-heavy oils increases sensitively, their participation in the refineries feeding also becomes greater. Heavy oils usually have lower price than a light one, because they produce lower quality derivatives and it's more difficult to meet the specifications. Crude oils are a complex mixture, mostly compounded by carbon and hydrogen and also by impurities like sulfur, nitrogen, oxygen and metals. Sulfur is the third most abundant component of crude oils, following carbon and hydrogen. In general there is a strong positive correlation between the concentrations of polar compounds (aromatics, resins and asphaltenes), and the sulfur content. This work presents graphically sulfur content and polar compounds concentrations for Brazilian and foreign heavy and extra-heavy oils (< 20 deg API). The results of the data analysis indicate that Brazilian crude oils behave differently from foreign heavy and extra-heavy oils. (author)

  14. Effect of Co Mo/HSO3-functionalized MCM-41 over heavy oil

    International Nuclear Information System (INIS)

    Schacht, P.; Ramirez G, M.; Ramirez, S.; Aguilar P, J.; Norena F, L.; Abu, I.

    2010-01-01

    The potential of Co-Mo metals supported on functionalized MCM-41 as catalyst to hydrodesulfurization of heavy oil has been explored in this work. The MCM-41 functionalized sample was synthesized according to method previously reported into the support by simultaneous impregnation. The catalyst was characterized by specific surface area and X-ray diffraction. The pore channel of MCM-41 was confirmed by transmission electronic microscopy and infra red spectroscopy. Catalytic activity tests were carried out using heavy oil from Gulf of Mexico. The API gravity was increased from 12.5 to 20.2, the kinematics viscosity was decreased from 18,700 to 110 c St at 298 K, the contents of asphaltene and sulfur were also reduced. (Author)

  15. Effect of Co Mo/HSO{sub 3}-functionalized MCM-41 over heavy oil

    Energy Technology Data Exchange (ETDEWEB)

    Schacht, P.; Ramirez G, M.; Ramirez, S. [Instituto Mexicano del Petroleo, Eje Central Lazaro Cardenas No. 152, 07730 Mexico D. F. (Mexico); Aguilar P, J.; Norena F, L. [Universidad Autonoma Metropolitana, Unidad Azcapotzalco, Av. San Pablo No. 180, 02200 Mexico D. F. (Mexico); Abu, I., E-mail: pschacha@imp.m [University of Calgary, Department of Chemical and Petroleum Engineering, 2500 University Drive NW, Calgary, Alberta T2N 1N4 (Canada)

    2010-07-01

    The potential of Co-Mo metals supported on functionalized MCM-41 as catalyst to hydrodesulfurization of heavy oil has been explored in this work. The MCM-41 functionalized sample was synthesized according to method previously reported into the support by simultaneous impregnation. The catalyst was characterized by specific surface area and X-ray diffraction. The pore channel of MCM-41 was confirmed by transmission electronic microscopy and infra red spectroscopy. Catalytic activity tests were carried out using heavy oil from Gulf of Mexico. The API gravity was increased from 12.5 to 20.2, the kinematics viscosity was decreased from 18,700 to 110 c St at 298 K, the contents of asphaltene and sulfur were also reduced. (Author)

  16. Hydrodynamic thickness of petroleum oil adsorbed layers in the pores of reservoir rocks.

    Science.gov (United States)

    Alkafeef, Saad F; Algharaib, Meshal K; Alajmi, Abdullah F

    2006-06-01

    The hydrodynamic thickness delta of adsorbed petroleum (crude) oil layers into the pores of sandstone rocks, through which the liquid flows, has been studied by Poiseuille's flow law and the evolution of (electrical) streaming current. The adsorption of petroleum oil is accompanied by a numerical reduction in the (negative) surface potential of the pore walls, eventually stabilizing at a small positive potential, attributed to the oil macromolecules themselves. After increasing to around 30% of the pore radius, the adsorbed layer thickness delta stopped growing either with time or with concentrations of asphaltene in the flowing liquid. The adsorption thickness is confirmed with the blockage value of the rock pores' area determined by the combination of streaming current and streaming potential measurements. This behavior is attributed to the effect on the disjoining pressure across the adsorbed layer, as described by Derjaguin and Churaev, of which the polymolecular adsorption films lose their stability long before their thickness has approached the radius of the rock pore.

  17. Organic palladium and palladium-magnesium chemical modifiers in direct determination of lead in fractions from distillation of crude oil by electrothermal atomic absorption analysis

    Science.gov (United States)

    Kowalewska, Zofia; Bulska, Ewa; Hulanicki, Adam

    1999-05-01

    Platinum reforming catalysts are easily poisoned by increased levels of lead, therefore a sensitive atomic absorption spectrometric procedure for lead determination in fractions from crude oil distillation was developed. Lead was present in organic form in the samples analysed therefore the behaviour of various lead compounds (Pb-alkylarylsulphonate, Pb-4-cyclohexanobutyrate, tetraethyllead, Pb in fuel oil) was studied. The best procedure for the determination of lead in different petroleum products, including those containing asphaltenes includes a pretreatment with iodine and methyltrioctylammonium chloride, followed by the use of an organic Pd-Mg modifier. Under these conditions an effective matrix removal is possible at a pyrolysis temperature up to approximately 1100°C and the behaviour of lead present in different forms is unified. The characteristic mass is 11-12 pg Pb, corresponding to a detection limit of 0.25 ng g -1 for 20 μl sample solution. This can be lowered by multiple injection.

  18. Numerical analysis of a one-dimensional multicomponent model of the in-situ combustion process

    DEFF Research Database (Denmark)

    Nesterov, Igor; Shapiro, Alexander; Stenby, Erling Halfdan

    2013-01-01

    parameter, the critical ignition saturation, is introduced, in order to describe the easiness of oil ignition. Its dependence on the different parameters of the oil mixture and injection gas is studied. The conclusions on the processes governing the ignition of oil in the presence of water are made......, the model is based on SARA representation of a petroleum mixture (saturates–aromatics–resins–asphaltenes), which may react differently with oxygen and produce other components (for example, light oils and coke). In total, the model contains 14 components, which may undergo 15 chemical reactions. The set...... of reactions in the original model of M.R. Kristensen has been modified in order to account for secondary combustion of the light oil fraction. The results of the model implementation are applied to the four heavy oil systems and qualitatively compared to the results of previous experimental studies. A new...

  19. Laboratory studies of the properties of in-situ burn residues: chemical composition of residues

    International Nuclear Information System (INIS)

    Trudel, B.K.; Buist, I.A.; Schatzke, D.; Aurand, D.

    1996-01-01

    The chemical composition of the residue from small-scale burns of thick oil slicks was studied. The objective was to describe the changes in chemical composition in oils burning on water and to determine how these changes were influenced by the condition of the burn. Small-scale test burns involved burning 40-cm diameter pools of oil on water. A range of eight oil types including seven crude oils and an automotive diesel were burned. For each oil, slicks of fresh oil of three different thicknesses were tested. Two of the oils were tested before and after weathering. Results showed that the composition of the residue differed greatly from the parent oil. Asphaltenes, high-boiling-point aromatics and resins remained concentrated in the burn residue. The burning of slicks appeared to remove most of the lower-molecular weight aromatic hydrocarbons which included the more toxic and more bioavailable components of the crude oils. 11 refs., 6 tabs

  20. The potential applications in heavy oil EOR with the nanoparticle and surfactant stabilized solvent-based emulsion

    Energy Technology Data Exchange (ETDEWEB)

    Qiu, F. [Texas A and M Univ., College Station, TX (United States)

    2010-07-01

    The main challenges in developing the heavy oil reservoirs in the Alaska North Slope (ANS) include technical challenges regarding thermal recovery; sand control and disposal; high asphaltene content; and low in-situ permeability. A chemical enhanced oil recovery method may be possible for these reservoirs. Solvent based emulsion flooding provides mobility control; oil viscosity reduction; and in-situ emulsification of heavy oil. This study evaluated the potential application of nano-particle-stabilized solvent based emulsion injection to enhance heavy oil recovery in the ANS. The optimized micro-emulsion composition was determined using laboratory tests such as phase behaviour scanning, rheology studies and interfacial tension measurements. The optimized nano-emulsions were used in core flooding experiments to verify the recovery efficiency. The study revealed that the potential use of this kind of emulsion flooding is a promising enhanced oil recovery process for some heavy oil reservoirs in Alaska, Canada and Venezuela. 4 refs., 2 tabs., 10 figs.

  1. Characterization of the viscoelastic behavior of the pure bitumen grades 10/20 and 35/50 with macroindentation and finite element computation

    KAUST Repository

    Hamzaoui, Rabah

    2013-06-23

    In this article, we present an identification procedure that allows the determination of the viscoelasticity behavior of different grades of pure bitumen (bitumen 35/50 and bitumen 10/20). The procedure required in the first stage a mechanical response based on macroindentation experiments with a cylindrical indenter. A finite element simulation was performed in the second stage to compute the mechanical response corresponding to a viscoelasticity model described by three mechanical parameters. The comparison between the experimental and numerical responses showed a perfect matching. In addition, the identification procedure helped to discriminate between different bitumens characterized by different asphaltene and maltene contents. Finally, the developed procedure could be used as an efficient tool to characterize the mechanical behavior of the viscoelastic materials, thanks to the quantified relationship between the viscoleastic parameters and the force-penetration response. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 130: 3440-3450, 2013 Copyright © 2013 Wiley Periodicals, Inc.

  2. Use of adsorption and gas chromatographic techniques in estimating biodegradation of indigenous crude oils

    International Nuclear Information System (INIS)

    Kokub, D.; Allahi, A.; Shafeeq, M.; Khalid, Z.M.; Malik, K.A.; Hussain, A.

    1993-01-01

    Indigenous crude oils could be degraded and emulsified upto varying degree by locally isolated bacteria. Degradation and emulsification was found to be dependent upon the chemical composition of the crude oils. Tando Alum and Khashkheli crude oils were emulsified in 27 and 33 days of incubation respectively. While Joyamair crude oil and not emulsify even mainly due to high viscosity of this oil. Using adsorption chromatographic technique, oil from control (uninoculated) and bio degraded flasks was fractioned into the deasphaltened oil containing saturate, aromatic, NSO (nitrogen, sulphur, oxygen) containing hydrocarbons) and soluble asphaltenes. Saturate fractions from control and degraded oil were further analysed by gas liquid chromatography. From these analyses, it was observed that saturate fraction was preferentially utilized and the crude oils having greater contents of saturate fraction were better emulsified than those low in this fraction. Utilization of various fractions of crude oils was in the order saturate> aromatic> NSO. (author)

  3. Compositional modification of crude oil during oil recovery

    Energy Technology Data Exchange (ETDEWEB)

    Zhu, Yangming; Weng, Huanxin [Department of Earth Sciences, Zhejiang University, Hangzhou 310027 (China); Chen, Zulin; Chen, Qi [Petroleum Geochemistry Research Center, Jianghan Petroleum University, Jingzhou, Hubei (China)

    2003-05-01

    Ten crude oils from two recovery stages spanning 5-10-year interval of five productive wells in the Tarim Basin, northwest China were analyzed for their compositional modification during production process. Significant compositional changes in polar and nonpolar fractions between the previous oil samples and the latter ones were noted at both bulk and molecular level. The latter oil samples appear to contain more aromatic fraction and less asphaltenes and resin, and their gas chromatography (GC) data for whole oil show reduced alkanes with low molecular weight and enhanced high homologue relative to the previous oil samples. Compared with the oils collected from the previous recovery stage, the concentration of basic type of nitrogen-containing compounds and organic acids in oils from the latter recovery stage have a reducing trend, suggesting the occurrence of interaction between crude oil and reservoir rock.

  4. Investigation of polymer material of the working camera-channel of the magnetic pumps for heavy oil

    Directory of Open Access Journals (Sweden)

    М. А. Васильева

    2016-11-01

    Full Text Available The article contains results the study of the basic properties of fluorinated polymers used as matrix in the manufacture of magnetically active elastomers (MAE. MAE belong to the group of so-called smart materials, they can be used in the creation of new techniques and technologies. Environments, which is in contact with an element of the MAE, specifically high viscosity asphaltenic oil impose substantial restrictions on the choice of the polymer matrix for its production, taking into consideration the influence of the material selected to modify the rheological properties of the resultant material. The use of magnetically active materials in the system instead of a roller system, pressing on the tube with the substance, and to push it forward will significantly expand the range of application of such equipment. Additionally, the magnetic treatment reduces the viscosity, the limit shear stress and the activation energy of the viscous flow of oil.

  5. Goodbye water use, tailings and Co2?

    Energy Technology Data Exchange (ETDEWEB)

    Stastny, R.P.

    2011-03-15

    Alberta Bitumen Link (ABL), a new integrated oilsands technology, is described. ABL combines the use of dimethyl ester (DME) as a solvent at lower temperatures in SAGD and the manufacture of DME by gasification of coal and asphaltenes so CO2 formation is reduced. The heat from the gasification process cogenerates electricity, while the produced DME is sent for use in the in-situ bitumen recovery. ABL finds the same mobility in bitumen stimulated with solvent at 80 C as a reservoir heated to 230 C by steam. The intellectual property now resides with Envirotech Consulting Inc. of Edmonton and Thermax Systems Co. of Japan and the technology is in small-scale testing. 1 fig.

  6. New ways of removing cyclic borehole noise from low- and high-resolution LWD images and its impact on image interpretation

    Energy Technology Data Exchange (ETDEWEB)

    Lalchan, C.; Wiggins, C.; Moriyama, C. [Trican Well Service (Canada)

    2011-07-01

    With the depletion of conventional oil reservoirs and increasing energy demand, the exploitation of unconventional resources is underway. Until now, the use of emulsified acids, which dissolve organic and inorganic deposits and strip off layered scales, has been restricted to conventional reservoirs, but it could also be used for thermal heavy oil reservoirs. The aim of this paper is to determine the appropriate acid blend for deposit and scale removal in thermal heavy oil reservoirs. Acid formulations were tested under 170 degrees Celsius and sensitivity testing was performed to find the optimal concentration. Results showed that a 5% or 10% acid acetic, emulsified in a 4:1 ratio with a modified wax and asphaltenes solvent blend, is the optimal acid formulation for removal of scales and organic deposits. This paper demonstrated that emulsified acids can be used to stimulate water injection and production in thermal heavy oil reservoirs and provided the optimum acid formulation.

  7. Combustion characteristics of Athabasca froth treatment tailings in a simulated fluidilized bed

    Energy Technology Data Exchange (ETDEWEB)

    Esmaeili, P.; Ghosh, M.; Speirs, B. C. [Imperial Oil Resources (Canada); Leon, M. A.; Rao, S.; Dutta, A.; Basu, P. [Greenfield Research Inc. (Canada)

    2011-07-01

    In surface-mined oil sands, a stream of water, asphaltenes, solids and residual bitumen/solvent, known as PFT tailings, is created during the bitumen production process. The aim of this study was to investigate the use of this PFT tailings stream as a fuel source for combustion in a fluidized bed for energy recovery. To do so, physical and fluidization characteristics of the fuel as well as combustion kinetics were assessed through laboratory analysis. In addition, the fuel's combustion characteristics were investigated through experiments in a quartz wool matrix tubular reactor and theoretical calculations at various moisture contents. Results showed that this fuel can be burned in a fluidized bed with a reactivity comparable to that of coal samples. This research found that PFT tailings could be used to generate energy during disposal but further work will have to be undertaken in a hot CFB combustor to confirm this.

  8. Analysis of chemical composition of high viscous oils

    Directory of Open Access Journals (Sweden)

    Irina Germanovna Yashchenko

    2014-07-01

    Full Text Available The spatial distribution of viscous oils which are considered as an important reserve for oil-production in future were studied on base of information from global database on oil physical and chemical properties. Changes in chemical composition of viscous oils in different basins and continents were analyzed as well. It is shown, on average, viscous oils are sulfur-bearing, low paraffin, highly resinous oils with an average content of asphaltenes and low content of the fraction boiling at 200 C. Study results of viscous oils peculiarities of Canada, Russia and Venezuela are given. The analysis results can be used to determine the optimal layouts and conditions of oil transportation, to improve the search methods of geochemical exploration, and to solve other problems in the oil chemistry.

  9. Twin screw subsurface and surface multiphase pumps

    Energy Technology Data Exchange (ETDEWEB)

    Dass, P. [CAN-K GROUP OF COMPANIES, Edmonton, Alberta (Canada)

    2011-07-01

    A new subsurface twin screw multiphase pump has been developed to replace ESP and other artificial lift technologies. This technology has been under development for a few years, has been field tested and is now going for commercial applications. The subsurface twin screw technology consists of a pair of screws that do not touch and can be run with a top drive or submersible motor; and it carries a lot of benefits. This technology is easy to install and its low slippage makes it highly efficient with heavy oil. In addition twin screw multiphase pumps are capable of handling high viscosity fluids and thus their utilization can save water when used in thermal applications. It also induces savings of chemicals because asphaltenes do not break down easily as well as a reduction in SOR. The subsurface twin screw multiphase pump presented herein is an advanced technology which could be used in thermal applications.

  10. Comparison of catalytic hydroliquefaction of Xiaolongtan lignite over FeS, FeS+S and SO{sub 4}{sup 2-}/ZrO{sub 2}

    Energy Technology Data Exchange (ETDEWEB)

    Kang, S.G.; Zong, Z.M.; Shui, H.F.; Wang, Z.C.; Wei, X.Y. [China University of Mining & Technology, Xuzhou (China)

    2011-01-15

    The catalytic hydroliquefaction of Xiaolongtan lignite (XL, a Chinese lignite) was investigated in a batch autoclave. The effects of reaction temperature, time and initial H{sub 2} pressure on the yields of gaseous and extractable portions (GEPs) were discussed. The catalytic activity of FeS+S was compared with that of FeS and SO{sub 4}{sup 2-}/ZrO{sub 2}, respectively. The results show that FeS+S is more active for XL hydroliquefaction than the other two catalysts and affords the highest gas and oil (G & O) yields in the three catalysts. The highest total yield of GEPs from XL hydroliquefaction gets to 90.0%, while total yield of G & O is 61.1% at 420 {sup o}C for 30 min over FeS+S. The assistant catalysis of the added sulfur was discussed. The structural features of asphaltenes and preasphaltenes were examined by elemental and FTIR analyses.

  11. Nanodiamond finding in the hyblean shallow mantle xenoliths.

    Science.gov (United States)

    Simakov, S K; Kouchi, A; Mel'nik, N N; Scribano, V; Kimura, Y; Hama, T; Suzuki, N; Saito, H; Yoshizawa, T

    2015-06-01

    Most of Earth's diamonds are connected with deep-seated mantle rocks; however, in recent years, μm-sized diamonds have been found in shallower metamorphic rocks, and the process of shallow-seated diamond formation has become a hotly debated topic. Nanodiamonds occur mainly in chondrite meteorites associated with organic matter and water. They can be synthesized in the stability field of graphite from organic compounds under hydrothermal conditions. Similar physicochemical conditions occur in serpentinite-hosted hydrothermal systems. Herein, we report the first finding of nanodiamonds, primarily of 6 and 10 nm, in Hyblean asphaltene-bearing serpentinite xenoliths (Sicily, Italy). The discovery was made by electron microscopy observations coupled with Raman spectroscopy analyses. The finding reveals new aspects of carbon speciation and diamond formation in shallow crustal settings. Nanodiamonds can grow during the hydrothermal alteration of ultramafic rocks, as well as during the lithogenesis of sediments bearing organic matter.

  12. Development of a chromatographic method for the study of the stability and compatibility of Mexican fuel oils; Desarrollo de un metodo cromatografico para el estudio de estabilidad y compatibilidad de combustoleos mexicanos

    Energy Technology Data Exchange (ETDEWEB)

    Blass Amador, Georgina; Panama Tirado, Luz Angelica [Instituto de Investigaciones Electricas, Cuernavaca (Mexico)

    1992-11-01

    In Mexico, the largest part of the generated electric energy comes from the use of residual heavy oils known as fuel oils which have suffered quality degradation due to a combination of factors, among which stands out the changes in the refining process. It is necessary to develop methods capable of indicating the instability (formation of sediment or viscosity increase during storage or heating) or incompatibility (formation of sediment in mixing two or more fuel oils) of the fuel oils employed in fossil fuel power plants. This work objective was to develop an alternative test for the study of the compatibility and/or stability of Mexican fuel oils using high resolution liquid chromatography (CLAR) and so to determine structural aspects of the fuel oil that determine its stability. Since the formation of sediments occurs when the dissolving ability of the fuel is inadequate to keep the asphaltenes in solution, it is important to know the solvent power degree or aromaticity of the diluent; so, in the first part of this work the attention was centered in the determination of the profile of aromatic compounds of the fuel oil diluents, the other part was dedicated to the determination of the distribution profile the molecular weights of the asphaltenes present in the fuel oils. The profiles of the aromatic fraction, as well as of the molecular weight distribution were determined using liquid chromatography, in which a variety of columns and solvents were used. A combination of routine tests was accomplished, such as asphaltenes content, toluene equivalence, viscosity, etc., in order to obtain correlation with the chromatographic method developed. In this article it is only discussed the section corresponding to the obtainment of the profile of aromatics content in the fuel oils. It has been found a correlation among the asphaltenes content, toluene equivalence, aromaticity profiles and stability. As a direct consequence, it is expected to be able to predict the

  13. Association models for petroleum applications

    DEFF Research Database (Denmark)

    Kontogeorgis, Georgios

    2013-01-01

    Thermodynamics plays an important role in many applications in the petroleum industry, both upstream and downstream, ranging from flow assurance, (enhanced) oil recovery and control of chemicals to meet production and environmental regulations. There are many different applications in the oil & gas...... industry, thus thermodynamic data (phase behaviour, densities, speed of sound, etc) are needed to study a very diverse range of compounds in addition to the petroleum ones (CO2, H2S, water, alcohols, glycols, mercaptans, mercury, asphaltenes, waxes, polymers, electrolytes, biofuels, etc) within a very...... extensive range of conditions, up to very high pressures. Actually, the petroleum industry was one of the first industrial sectors which used extensively thermodynamic models and even contributed to the development of several of the most popular and still widely used approaches. While traditional...

  14. Dust evolution, a global view I. Nanoparticles, nascence, nitrogen and natural selection … joining the dots

    Science.gov (United States)

    Jones, A. P.

    2016-12-01

    The role and importance of nanoparticles for interstellar chemistry and beyond is explored within the framework of The Heterogeneous dust Evolution Model for Interstellar Solids (THEMIS), focusing on their active surface chemistry, the effects of nitrogen doping and the natural selection of interesting nanoparticle sub-structures. Nanoparticle-driven chemistry, and in particular the role of intrinsic epoxide-type structures, could provide a viable route to the observed gas phase OH in tenuous interstellar clouds en route to becoming molecular clouds. The aromatic-rich moieties present in asphaltenes probably provide a viable model for the structures present within aromatic-rich interstellar carbonaceous grains. The observed doping of such nanoparticle structures with nitrogen, if also prevalent in interstellar dust, could perhaps have important and observable consequences for surface chemistry and the formation of precursor pre-biotic species.

  15. Molecular characterization and comparison of shale oils generated by different pyrolysis methods using FT-ICR mass spectrometry

    Science.gov (United States)

    Jin, J.M.; Kim, S.; Birdwell, J.E.

    2011-01-01

    Fourier transform ion cyclotron resonance mass spectrometry (FT ICR-MS) was applied in the analysis of shale oils generated using two different pyrolysis systems under laboratory conditions meant to simulate surface and in situ oil shale retorting. Significant variations were observed in the shale oils, particularly the degree of conjugation of the constituent molecules. Comparison of FT ICR-MS results to standard oil characterization methods (API gravity, SARA fractionation, gas chromatography-flame ionization detection) indicated correspondence between the average Double Bond Equivalence (DBE) and asphaltene content. The results show that, based on the average DBE values and DBE distributions of the shale oils examined, highly conjugated species are enriched in samples produced under low pressure, high temperature conditions and in the presence of water.

  16. Chemical composition of Pechora Sea crude oil

    Directory of Open Access Journals (Sweden)

    Derkach S. R.

    2017-03-01

    Full Text Available The physicochemical properties of the Pechora Sea shelf oil and its chemical composition have been studied using the methods of refractometry, titrimetry, viscometry, rheometry and standard methods for the analysis of oil and petroleum products. The fractionation of oil is held at atmospheric pressure, some fractions boiling at the temperature below and above 211 °C have been received. Chemical structural-group composition of oil and its components has been investigated using a Fourier infrared (IR spectroscopy method. The density of oil has been obtained, it is equal to 24.2 API. The chemical composition analysis shows that water content in the investigated oil sample is about 0.03 % (by weight. The oil sample contains hydrocarbons (including alkanes, naphthenes, arenes and asphaltenes with resins; their content is equal to 89 and 10 % (by weight respectively. Alkane content is about 66 %, including alkanes of normal structure – about 37 %. The solidification temperature of oil sample is equal to –43 °C. This low temperature testifies obliquely low content of solid alkanes (paraffin. Bearing in mind the content of asphaltenes with resins we can refer the investigated oil sample to resinous oils. On the other hand spectral coefficient values (aromaticity quotient and aliphaticity quotient show that oil sample belongs to naphthenic oils. According to the data of Fourier IR spectroscopy contents of naphthenes and arenes are 5.9 and 17.8 % respectively. Thus, the obtained data of chemical structural-group composition of crude oil and its fractions indicate that this oil belongs to the heavy resinous naphthenic oils. The rheological parameters obtained at the shear deformation conditions characterize the crude oil as a visco-plastic medium.

  17. Micro-scale displacement of NAPL by surfactant and microemulsion in heterogeneous porous media

    Science.gov (United States)

    Javanbakht, Gina; Arshadi, Maziar; Qin, Tianzhu; Goual, Lamia

    2017-07-01

    Industrial processes such as remediation of oil-contaminated aquifers and enhanced oil recovery (EOR) often utilize chemical additives to increase the removal of non-aqueous phase liquids (NAPLs) from subsurface formations. Although the majority of crude oils are classified as LNAPLs, they often contain heavy molecules (DNAPLs) such as asphaltenes that tend to adsorb on minerals and alter their wettability. Effective additives are therefore those that can reduce the threshold capillary pressure, thus mobilizing LNAPL inside pore spaces and solubilizing DNAPL from rock surfaces. Nonionic surfactants in brine have often been injected to oil or contaminated aquifer formations in order to enhance NAPL displacement through IFT reduction. Recent studies revealed that surfactant-based microemulsions have a higher tendency to alter the wettability of surfaces, compared to surfactants alone, leading to more effective NAPL removal. However, the impact of these additives on pore-scale displacement mechanisms and multi-phase fluid occupancy in porous media is, to date, still unclear. In this study, x-ray microtomography experiments were performed to investigate the impact of surfactants and microemulsions on the mobilization and solubilization of NAPL in heterogeneous rocks. Saturation profiles indicated that an incremental NAPL removal was attained by addition of microemulsion to brine, compared with surfactant. Residual cluster size distributions revealed that microemulsions could break up large clusters into smaller disconnected ones, improving their mobilization in the rock. In-situ contact angle measurements showed that microemulsions could reverse the wettability of rough contaminated surfaces to a higher extent than surfactants. Unlike surfactant alone, the surfactant-solvent blend in the carrier fluid of microemulsions was able to penetrate rough grain surfaces, particularly those of dolomite cement, and desorb asphaltenes in the form of small-emulsified NAPL droplets

  18. Sequential Isolation of Saturated, Aromatic, Resinic and Asphaltic Fractions Degrading Bacteria from Oil Contaminated Soil in South Sumatera

    Directory of Open Access Journals (Sweden)

    Pingkan Aditiawati

    2012-04-01

    Full Text Available Sequential isolation has been conducted to obtain isolates of saturated, aromatic, resin, and asphaltene fractions degrading bacteria from oil contaminated sites. Five soil samples were collected from South Sumatera. These were analyzed using soil extract medium enriched with oil recovery or Remaining-Oil recovery Degradated (ROD as sole carbon and energy sources according to the isolation stage. ROD at the end of every isolation stage analyzed oil fractions by use of the SARA analysis method. Six isolates of bacteria have been selected, one isolate was fraction saturates degrading bacteria that are Mycobacterium sp. T1H2D4-7 at degradation rate 0.0199 mgs/h with density 8.4x106 cfu/g from stage I. The isolate T2H1D2-4, identified as Pseudomonas sp. was fraction aromatics degrading bacteria at accelerate 0.0141 mgs/h with density 5.1x106 cfu/g are obtained at stage II. Two isolates namely Micrococcus sp. T3H2D4-2 and Pseudomonas sp. T1H1D5-5 were fraction resins degrading bacteria by accelerate 0.0088 mgs/h at density 5.6x106 cfu/g and 0.0089 mgs/h at density 5.7x106 cfu/g are obtained at stage III. Isolation of stage IV has been obtained two isolates Pseudomonas sp. T4H1D3-1and Pseudomonas sp. T4H3D5-4 were fraction asphaltenes degrading bacteria by accelerate 0.0057 mgs/h at density 5.6x106 cfu/g and accelerate 0.0058 mgs/h at density 5.7x106 cfu/g.

  19. SOVENT BASED ENHANCED OIL RECOVERY FOR IN-SITU UPGRADING OF HEAVY OIL SANDS

    Energy Technology Data Exchange (ETDEWEB)

    Munroe, Norman

    2009-01-30

    With the depletion of conventional crude oil reserves in the world, heavy oil and bitumen resources have great potential to meet the future demand for petroleum products. However, oil recovery from heavy oil and bitumen reservoirs is much more difficult than that from conventional oil reservoirs. This is mainly because heavy oil or bitumen is partially or completely immobile under reservoir conditions due to its extremely high viscosity, which creates special production challenges. In order to overcome these challenges significant efforts were devoted by Applied Research Center (ARC) at Florida International University and The Center for Energy Economics (CEE) at the University of Texas. A simplified model was developed to assess the density of the upgraded crude depending on the ratio of solvent mass to crude oil mass, temperature, pressure and the properties of the crude oil. The simplified model incorporated the interaction dynamics into a homogeneous, porous heavy oil reservoir to simulate the dispersion and concentration of injected CO2. The model also incorporated the characteristic of a highly varying CO2 density near the critical point. Since the major challenge in heavy oil recovery is its high viscosity, most researchers have focused their investigations on this parameter in the laboratory as well as in the field resulting in disparaging results. This was attributed to oil being a complex poly-disperse blend of light and heavy paraffins, aromatics, resins and asphaltenes, which have diverse behaviors at reservoir temperature and pressures. The situation is exacerbated by a dearth of experimental data on gas diffusion coefficients in heavy oils due to the tedious nature of diffusivity measurements. Ultimately, the viscosity and thus oil recovery is regulated by pressure and its effect on the diffusion coefficient and oil swelling factors. The generation of a new phase within the crude and the differences in mobility between the new crude matrix and the

  20. Prediction of compatibility of crude oils with condensate (C5+); Previsao de compatibilidade de petroleos e condensado (C5+)

    Energy Technology Data Exchange (ETDEWEB)

    Zilio, Evaldo Lopez; Santos, Maria de Fatima Pereira dos [PETROBRAS S.A., Rio de Janeiro, RJ (Brazil); Ramos, Antonio Carlos da Silva; Rolemberg, Marlus Pinheiro [Universidade Federal do Maranhao (UFMA), Sao Luis, MA (Brazil)

    2008-07-01

    Due to the recent raise of the national natural gas demand and to the need of flowing the condensates (C5+) produced from the NGPP (Natural Gas Processing Plant) by adding them to the streams of the crude oil, there was the need to carry out the compatibility prediction of one condensate with two onshore crude oils from Espirito Santo. The model to predict the compatibility among crude oils and among crude oils and oil products is based on the use of the solubility parameter of the oils. To apply it, the solubility parameter of each crude oil or oil product is measured and the parameter of their blend is calculated. If this value is beneath the asphaltenes flocculation parameter, the blend is incompatible; if it is above, the blend is compatible. In this article, the compatibility predictions were done according to the Solubility Parameter Model to two blends: the condensate C with the crude oil X and with the crude oil Y. The model predictions are that both blends are incompatible at given proportions. To check the predictions, the same two blends were experimentally carried out. It must be emphasized that the compatibility tests were done at atmospheric pressure and at the temperature of 15 deg C. These tests consist in adding the condensate to the crude oil with a titrater and visualizing the asphaltenes precipitation at an optical microscope. The experimental results were equivalent to the values predicted by the model. It is worth mentioning that there were several practical difficulties, as the high volatility of the condensate and the fact that the temperatures to determine the parameters and to carry out the tests were very lower than the operation temperature. Therefore, a security factor was applied on the predictions (less 20%). (author)

  1. High temperature ceramic membrane reactors for coal liquid upgrading

    Energy Technology Data Exchange (ETDEWEB)

    Tsotsis, T.T. (University of Southern California, Los Angeles, CA (United States). Dept. of Chemical Engineering); Liu, P.K.T. (Aluminum Co. of America, Pittsburgh, PA (United States)); Webster, I.A. (Unocal Corp., Los Angeles, CA (United States))

    1992-01-01

    Membrane reactors are today finding extensive applications for gas and vapor phase catalytic reactions (see discussion in the introduction and recent reviews by Armor [92], Hsieh [93] and Tsotsis et al. [941]). There have not been any published reports, however, of their use in high pressure and temperature liquid-phase applications. The idea to apply membrane reactor technology to coal liquid upgrading has resulted from a series of experimental investigations by our group of petroleum and coal asphaltene transport through model membranes. Coal liquids contain polycyclic aromatic compounds, which not only present potential difficulties in upgrading, storage and coprocessing, but are also bioactive. Direct coal liquefaction is perceived today as a two-stage process, which involves a first stage of thermal (or catalytic) dissolution of coal, followed by a second stage, in which the resulting products of the first stage are catalytically upgraded. Even in the presence of hydrogen, the oil products of the second stage are thought to equilibrate with the heavier (asphaltenic and preasphaltenic) components found in the feedstream. The possibility exists for this smaller molecular fraction to recondense with the unreacted heavy components and form even heavier undesirable components like char and coke. One way to diminish these regressive reactions is to selectively remove these smaller molecular weight fractions once they are formed and prior to recondensation. This can, at least in principle, be accomplished through the use of high temperature membrane reactors, using ceramic membranes which are permselective for the desired products of the coal liquid upgrading process. An additional incentive to do so is in order to eliminate the further hydrogenation and hydrocracking of liquid products to undesirable light gases.

  2. High temperature ceramic membrane reactors for coal liquid upgrading. Final report, September 21, 1989--November 20, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Tsotsis, T.T. [University of Southern California, Los Angeles, CA (United States). Dept. of Chemical Engineering; Liu, P.K.T. [Aluminum Co. of America, Pittsburgh, PA (United States); Webster, I.A. [Unocal Corp., Los Angeles, CA (United States)

    1992-12-31

    Membrane reactors are today finding extensive applications for gas and vapor phase catalytic reactions (see discussion in the introduction and recent reviews by Armor [92], Hsieh [93] and Tsotsis et al. [941]). There have not been any published reports, however, of their use in high pressure and temperature liquid-phase applications. The idea to apply membrane reactor technology to coal liquid upgrading has resulted from a series of experimental investigations by our group of petroleum and coal asphaltene transport through model membranes. Coal liquids contain polycyclic aromatic compounds, which not only present potential difficulties in upgrading, storage and coprocessing, but are also bioactive. Direct coal liquefaction is perceived today as a two-stage process, which involves a first stage of thermal (or catalytic) dissolution of coal, followed by a second stage, in which the resulting products of the first stage are catalytically upgraded. Even in the presence of hydrogen, the oil products of the second stage are thought to equilibrate with the heavier (asphaltenic and preasphaltenic) components found in the feedstream. The possibility exists for this smaller molecular fraction to recondense with the unreacted heavy components and form even heavier undesirable components like char and coke. One way to diminish these regressive reactions is to selectively remove these smaller molecular weight fractions once they are formed and prior to recondensation. This can, at least in principle, be accomplished through the use of high temperature membrane reactors, using ceramic membranes which are permselective for the desired products of the coal liquid upgrading process. An additional incentive to do so is in order to eliminate the further hydrogenation and hydrocracking of liquid products to undesirable light gases.

  3. Rheology of unstable mineral emulsions

    Directory of Open Access Journals (Sweden)

    Sokolović Dunja S.

    2013-01-01

    Full Text Available In this paper, the rheology of mineral oils and their unstable water emulsion were investigated. The oil samples were domestic crude oil UA, its fractions UA1, UA4 and blend semi-product UP1, while the concentration of oil in water emulsions was in the range from 1 up to 30%. The results were analyzed based on shear stress. The oil samples UA, UA1 and UP1 are Newtonian fluids, while UA4 is pseudoplastic fluid. The samples UA and UA4 show higher value of shear stress (83.75 Pa, 297 Pa, then other two samples UA1 and UP1 (18.41 Pa, 17.52 Pa. Rheology of investigated oils due to its complex chemical composition should be analyzed as a simultaneous effect of all their components. Therefore, structural composition of the oils was determined, namely content of paraffins, naphthenes, aromatics and asphaltenes. All samples contain paraffins, naphthenes and aromatics but only oils UA and UA4 contain asphaltenes as well. All investigated emulsions except 30% EUA4 are Newtonian fluids. The EUA4 30% emulsion shows pseudoplastic behaviour, and it is the only 30% emulsion among investigated ones that achieves lower shear stress then its oil. The characteristics of oil samples that could have an influence on their properties and their emulsion rheology, were determined. These characteristics are: neutralization number, interfacial tension, dielectric constant, and emulsivity. Oil samples UA and UA4 have significantly higher values of neutralization number, dielectric constants, and emulsivity. The sample UA has the lowest value of interface tension and the greatest emulsivity, indicating that this oil, among all investigated, has the highest preference for building emulsion. This could be the reason why 20% and 30% emulsions of the oil UA achieve the highest shear stress among all investigated emulsions.

  4. Effect of Extracted Compositions of Liquefaction Residue on the Structure and Properties of the Formed-coke

    Directory of Open Access Journals (Sweden)

    Song Yong-hui

    2016-01-01

    Full Text Available The purpose of this paper is to study the effect of extracted compositions of the de-ash liquefaction residue (D-DCLR on pyrolysis products yields, compressive strength and composition of the formed-coke, which was prepared by co-pyrolysis of the low metamorphic pulverized coal and D-DCLR. The scanning electron microscope (SEM and the Fourier Transform Infrared (FT-IR were used to characterize the morphology and functional group of the formed-coke, respectively. The results showed that the extracted compositions of D-DCLR were heavy oil (HS, asphaltene (A, pre-asphaltene (PA and tetrahydrofuran isolusion (THFIS, whose contents were 5.10%, 40.90%, 14.4%, 39.60%, respectively. During the pyrolysis process, HS was the main source of tar, and HS, A as well as PA were conducive to improve gas yields. The THFIS helped to improve the yield of the formed-coke up to 89.5%, corresponding to the compressive strength was only 147.7N/ball for the coke. A and PA were the key factors affecting the compressive strength and surface structure of the formed-coke. The compressive strength of coke could be up to 728.0N/ball with adding D-DCLR, which reduced by 50% after the removal of A and PA. The FT-IR analysis showed that the types of surface functional groups of the formed-coke were remained the same after co-pyrolysis, but the absorption peak intensity of each functional group was changed.

  5. Decrease of noxious emissions in the residual fuel oil combustion; Disminucion de emisiones nocivas en la combustion de aceite combustible residual

    Energy Technology Data Exchange (ETDEWEB)

    Mandoki W, Jorge [Econergia S. de R. L. de C. V. Mexico, D. F. (Mexico)

    1994-12-31

    The residual fuel oil combustion emits noxious substances such as carbonaceous particulate, nitrogen oxides, and sulfur trioxide at unacceptable levels. Water emulsified in the fuel substantially reduces such emissions, achieving besides, in most of the cases, a net saving in the fuel consumption. The beneficial effects are shown in burning the residual fuel oil as a water emulsion, as well as the method to produce an adequate emulsion. The emulsified fuel technology offers a low cost option to reduce air pollution. The fuel oil quality has been declining during the last decades due to: 1. Increase in the production of crude heavy oils, generally with higher content of asphaltens and sulfur. 2. Less availability of vacuum distillation residues due to its conversion into greater value products. 3. More intensive conversion processes such as catalytic cracking, visbreaking, etc. that increase the asphaltenes concentration in the bottoms, causing instability problems. 4. The increase in the vanadium and other metals content as the concentration of asphaltenes increases. The use of emulsified fuel oil provides an efficient and economical method to substantially reduce the noxious emissions to the atmosphere. The emulsion contains water particles in a diameter between 2 and 20 microns, uniformly distributed in the fuel oil, generally in a proportion generally of 5 to 10%; besides, it contains a tensioactive agent to assure a stable emulsion capable of withstanding the shearing forces of the pumping and distribution systems. When the atomized oil drops get into the combustion chamber, the emulsified water flashes into high pressure steam, originating a violent secondary atomization. The effect of this secondary atomization is the rupture of the oil drops of various hundred microns, producing drops of 5 to 15 microns in diameter. Since the necessary time for combustion is an exponential function of the drop diameter, a very substantial improvement in the combustion is

  6. WETTABILITY AND IMBIBITION: MICROSCOPIC DISTRIBUTION OF WETTING AND ITS CONSEQUENCES AT THE CORE AND FIELD SCALES

    Energy Technology Data Exchange (ETDEWEB)

    Jill S. Buckley; Norman R. Morrow; Chris Palmer; Purnendu K. Dasgupta

    2003-02-01

    The questions of reservoir wettability have been approached in this project from three directions. First, we have studied the properties of crude oils that contribute to wetting alteration in a reservoir. A database of more than 150 different crude oil samples has been established to facilitate examination of the relationships between crude oil chemical and physical properties and their influence on reservoir wetting. In the course of this work an improved SARA analysis technique was developed and major advances were made in understanding asphaltene stability including development of a thermodynamic Asphaltene Solubility Model (ASM) and empirical methods for predicting the onset of instability. The CO-Wet database is a resource that will be used to guide wettability research in the future. The second approach is to study crude oil/brine/rock interactions on smooth surfaces. Contact angle measurements were made under controlled conditions on mica surfaces that had been exposed to many of the oils in the CO-Wet database. With this wealth of data, statistical tests can now be used to examine the relationships between crude oil properties and the tendencies of those oils to alter wetting. Traditionally, contact angles have been used as the primary wetting assessment tool on smooth surfaces. A new technique has been developed using an atomic forces microscope that adds a new dimension to the ability to characterize oil-treated surfaces. Ultimately we aim to understand wetting in porous media, the focus of the third approach taken in this project. Using oils from the CO-Wet database, experimental advances have been made in scaling the rate of imbibition, a sensitive measure of core wetting. Application of the scaling group to mixed-wet systems has been demonstrated for a range of core conditions. Investigations of imbibition in gas/liquid systems provided the motivation for theoretical advances as well. As a result of this project we have many new tools for studying

  7. New insights into the effects of styrene-butadiene-styrene polymer modifier on the structure, properties, and performance of asphalt binder: The case of AP-5 asphalt and solvent deasphalting pitch

    Energy Technology Data Exchange (ETDEWEB)

    Nciri, Nader, E-mail: nader.nciri@koreatech.ac.kr [Department of Energy, Materials, and Chemical Engineering, Korea University of Technology and Education, 1600 Chungjeol-ro, Byeongcheon-myeon, Dongnam-gu, Cheonan-City, Chungnam-Province 330-708 (Korea, Republic of); Kim, Namho [Department of Architectural Engineering, Korea University of Technology and Education, 1600 Chungjeol-ro, Byeongcheon-myeon, Dongnam-gu, Cheonan-City, Chungnam-Province 330-708 (Korea, Republic of); Cho, Namjun, E-mail: njuncho@koreatech.ac.kr [Department of Energy, Materials, and Chemical Engineering, Korea University of Technology and Education, 1600 Chungjeol-ro, Byeongcheon-myeon, Dongnam-gu, Cheonan-City, Chungnam-Province 330-708 (Korea, Republic of)

    2017-06-01

    This paper deals with the poorly understood effects of styrene-butadiene-styrene (SBS) copolymer on the bitumen performance. It focuses on determining the impact of various concentrations (e.g., 0, 4, 8, and 12 wt. %) of SBS on the attributes of two types of asphalt namely AP-5 asphalt and solvent deasphalting (SDA) pitch. The unmodified and modified binders were investigated in terms of their chemical compositions, microstructures, thermo-analytical behaviors, and physical properties. The intricate chemical compositions were evaluated by elemental analysis and thin layer chromatography-ionization detection (TLC-FID). Fourier transform infrared (FT-IR) and nuclear magnetic resonance (NMR) spectroscopies, scanning electron microscopy (SEM), and X-ray diffraction (XRD) were utilized to examine the microstructures. Whereas, thermal characteristics were evaluated by thermogravimetric analysis (TGA/DTGA) and differential scanning calorimetry (DSC). The physical behaviors were monitored through the softening point, penetration, viscosity, and ductility tests. The findings showed that the blending of asphalt with different amounts of SBS resulted into different rheological behaviors. This was reflected from the difference in the SARA (i.e., saturates, aromatics, resins, and asphaltenes) compositions and colloidal instability indexes of the modified asphalts. SEM exhibited a continuous asphalt phase with distributed SBS particles, a continuous polymer phase with distributed asphalt globules, or two interconnected continuous phases. FT-IR, {sup 1}H {sup 13}C NMR, and XRD data revealed that the AP-5 asphalt and SDA pitch experienced a number of distinct structural changes. TGA/DSC studies determined the occurrence of diverse events during thermal treatment. It is concluded that the degree of SBS modification depends strongly on SARA composition and polymer content. If the polymers are molded at higher concentrations along with aromatics-rich SDA pitches, then the mixtures

  8. Surface microstructure of bitumen characterized by atomic force microscopy.

    Science.gov (United States)

    Yu, Xiaokong; Burnham, Nancy A; Tao, Mingjiang

    2015-04-01

    Bitumen, also called asphalt binder, plays important roles in many industrial applications. It is used as the primary binding agent in asphalt concrete, as a key component in damping systems such as rubber, and as an indispensable additive in paint and ink. Consisting of a large number of hydrocarbons of different sizes and polarities, together with heteroatoms and traces of metals, bitumen displays rich surface microstructures that affect its rheological properties. This paper reviews the current understanding of bitumen's surface microstructures characterized by Atomic Force Microscopy (AFM). Microstructures of bitumen develop to different forms depending on crude oil source, thermal history, and sample preparation method. While some bitumens display surface microstructures with fine domains, flake-like domains, and dendrite structuring, 'bee-structures' with wavy patterns several micrometers in diameter and tens of nanometers in height are commonly seen in other binders. Controversy exists regarding the chemical origin of the 'bee-structures', which has been related to the asphaltene fraction, the metal content, or the crystallizing waxes in bitumen. The rich chemistry of bitumen can result in complicated intermolecular associations such as coprecipitation of wax and metalloporphyrins in asphaltenes. Therefore, it is the molecular interactions among the different chemical components in bitumen, rather than a single chemical fraction, that are responsible for the evolution of bitumen's diverse microstructures, including the 'bee-structures'. Mechanisms such as curvature elasticity and surface wrinkling that explain the rippled structures observed in polymer crystals might be responsible for the formation of 'bee-structures' in bitumen. Despite the progress made on morphological characterization of bitumen using AFM, the fundamental question whether the microstructures observed on bitumen surfaces represent its bulk structure remains to be addressed. In addition

  9. The experimental study on H2S generation during thermal recovery process for heavy oil from the Eastern Venezuela Basin

    Directory of Open Access Journals (Sweden)

    Jingkui Mi

    2017-06-01

    Full Text Available Hydrogen sulfide (H2S is toxic, corrosive and environmentally damaging. It is not only found in oil and gas development, but is also often found in heavy oil exploitation. In this study, three heavy oils were selected from the Orinoco Heavy Oil Belt in the southern part of the Eastern Venezuela Basin. Thermal cracking experiments in gold sealed tubes were then conducted using the heavy oils. The objective of the experiment is to unravel the H2S generation mechanism and utility in establishing a development program for heavy oil thermal recovery. The results of the oil isothermal cracking experiments show that the H2S yield increases with the increasing cracking temperature and holding time at 150 °C and 250 °C. Carbon dioxide (CO2 is the main component in gaseous products and its concentration is more than 80% in our experiments. The yields of CO2, H2S and total hydrocarbon gas present similar varying trend that increases with increasing isothermal time. The sulfur contents in group compositions of the original oil from the CJS-48 well and that of the residual oils with different cracking time at 250 °C were then measured. The analytical results show that most sulfur (>75% exists in aromatics both in original oil and in the residual oils cracked at 250 °C, not to mention, no sulfur was measured in saturates. Although the decrease of sulfur in aromatics with the increased cracking time is low, it has great significance to the H2S generation during thermal recovery of heavy oil for more than 75% sulfur existed in aromatics. The decrease of sulfur content in resin and asphaltene of cracking residues with increased cracking time indicates that the sulfur existed in resin and asphaltene has some contribution to H2S generation during the thermal recovery process of heavy oil. Keywords: Venezuela, Heavy oil, Thermal recovery, H2S, Gold tube experiments

  10. Deceased Slabs Drive Oil

    Science.gov (United States)

    Stein, H. J.; Hannah, J. L.

    2017-12-01

    The application of Re-Os isotope geochemistry to dating single oils is a nascent field [1,2]. Challenges include dissection of oils into asphaltene-maltene (ASPH-MALT) components in a way that preserves meaningful chronologic and source information. Significantly, oil-water mixing rapidly transfers Os to the oil, while Re exchange is sluggish [3]. The Os initial ratio of the oil is shifted in the direction of Os carried in the aqueous fluid, whereas the Re-Os isotopic age is preserved. We show that this phenomenon is operative in natural systems. Further, we show that deserpentinization of old oceanic slabs [4], may be linked to expulsion of Os-enriched waters into overlying sedimentary sections - a process that may be of fundamental importance for oil generation. This conclusion does not diminish the role of traditional organic-rich shales as source rocks for the hydrocarbon, but shows that external fluids are essential to petroleum generation. Moreover, the external fluids may be an important driver for expulsion and migration of oils. We have taken apart several petroleum systems from source rock, to residual oil, to tar mat development, to in situ live oil, through to produced oil. In many cases, a fluid with low 187Os/188Os - unlike that of normal basinal brines - provides a critical component to the oil-water mixture. Funding - CHRONOS project supported by Norwegian petroleum industry (Eni-Norge, Lundin, Aker BP) Acknowledgement - Christine Fichler [4], who first queried us on old slabs and oil, and stimulated ideas. [1] Georgiev, S.V., Stein, H.J., Hannah, J.L., Galimberti, R., Nali, M., Yang, G., and Zimmerman, A. (2016) Re-Os dating of maltenes and asphaltenes within single samples of crude oil: Geochim. Cosmochim. Acta 179: 53-75. [doi.org/10.1016/j.gca.2016.01.016] [2] DiMarzio, J., Georgiev, S.V., Stein, H.J., and Hannah, J.L. (in press) Residency of rhenium and osmium in a heavy crude oil: Geochim. Cosmochim. Acta. [3] Hurtig, N.C., Georgiev, S

  11. Solids precipitation in crude oils, gas-to-liquids and their blends

    Science.gov (United States)

    Ramanathan, Karthik

    Gas-to-liquids (GTL) liquids are obtained from syngas by the Fischer-Tropsch synthesis. The blending of GTL liquids produced from natural gas/coal reserves and crude oils is a possibility in the near future for multiple reasons. Solids precipitation is a major problem in pipelines and refineries leading to significant additional operating costs. The effect of the addition of a paraffinic GTL liquid to crude oils on solids precipitation was investigated in this study. A Fourier transform infrared (FT-IR) spectroscopic technique was used to obtain solid-liquid equilibria (SLE) data for the various samples. The SLE of multiple systems of model oils composed of n-alkanes was investigated preliminarily. Blends of a model oil simulating a GTL liquid composition and a crude oil showed that the wax precipitation temperature (WPT) decreased upon blending. Three crude oils from different geographic regions (Alaskan North Slope, Colorado and Venezuela) and a laboratory-produced GTL liquid were used in the preparation of blends with five different concentrations of the GTL liquid. The wax precipitation temperatures of the blends were found to decrease with the increasing addition of the GTL liquid for all the oils. This effect was attributed to the solvent effect of the low molecular weight-paraffinic GTL liquid on the crude oils. The weight percent solid precipitated that was estimated as a function of temperature did not show a uniform trend for the set of crude oils. The asphaltene onset studies done on the blends with near-infrared spectroscopy indicated that the addition of GTL liquid could have a stabilizing effect on the asphaltenes in some oils. Analytical techniques such as distillation, solvent separation, HPLC, GC, and GPC were used to obtain detailed composition data on the samples. Two sets of compositional data with 49 and 86 pseudo-components were used to describe the three crude oils used in the blending work. The wax precipitation was calculated using a

  12. Analyse quantitative des effluents de pyrolyse en milieu ouvert et fermé Quantitative Analysis of Pyrolysis Effluents in an Open and Closed System

    Directory of Open Access Journals (Sweden)

    Behar F.

    2006-11-01

    Full Text Available Dans la première partie de l'article, nous décrivons une technique de pyrolyse en milieu ouvert qui permet de caractériser les matières organiques complexes comme le kérogène, le charbon, les asphaltènes de roche et d'huiles, les substances humiques et fulviques etc. Les effluents de pyrolyse sont récupérés et fractionnés quantitativement puis analysés par des techniques spécifiques comme la chromatographie en phase gazeuse et le couplage chromatographie/spectrométrie de masse. Dans la deuxième partie, est présentée une technique de pyrolyse en milieu fermé pour simuler au laboratoire l'évolution thermique des kérogènes, asphaltènes ou huiles. Nous nous sommes surtout attachés à dresser des bilans massiques et des bilans de l'hydrogène sur l'ensemble des produits de pyrolyse. Pour cela, nous avons distingué cinq classes de poids moléculaire croissant : C1, C2-C5, C6-C13, C14+ et coke. La récupération quantitative et la séparation de chacune des cinq fractions permet une analyse moléculaire détaillée de chacune d'elles. The first part of this article describes an open pyrolysis system in order to characterize complex organic matter such as kerogen, coal, rock and oil asphaltenes and humic substances, etc. Pyrolysis effluents are recovered, fractionated quantitatively by liquid chromatography, and then they are analyzed by specific techniques such as gas chromatography and chromatography/mass-spectrometry coupling. The second part describes a pyrolysis technique in a closed system, used for the laboratory simulation of the thermal evolution of kerogens, asphaltenes or oils. A special effort has been made to give the mass and hydrogen balances for all pyrolysis products. For this, five classes have been distinguised with increasing molecular weight: C1, C2-C5, C6-C13, C14+ and coke. The quantitative recovery and the separation of each of the five fractions is used to make a detailed molecular analysis of each of

  13. Computer Modeling of the Displacement Behavior of Carbon Dioxide in Undersaturated Oil Reservoirs

    Directory of Open Access Journals (Sweden)

    Ju Binshan

    2015-11-01

    Full Text Available The injection of CO2 into oil reservoirs is performed not only to improve oil recovery but also to store CO2 captured from fuel combustion. The objective of this work is to develop a numerical simulator to predict quantitatively supercritical CO2 flooding behaviors for Enhanced Oil Recovery (EOR. A non-isothermal compositional flow mathematical model is developed. The phase transition diagram is designed according to the Minimum Miscibility Pressure (MMP and CO2 maximum solubility in oil phase. The convection and diffusion of CO2 mixtures in multiphase fluids in reservoirs, mass transfer between CO2 and crude and phase partitioning are considered. The governing equations are discretized by applying a fully implicit finite difference technique. Newton-Raphson iterative technique was used to solve the nonlinear equation systems and a simulator was developed. The performances of CO2 immiscible and miscible flooding in oil reservoirs are predicted by the new simulator. The distribution of pressure and temperature, phase saturations, mole fraction of each component in each phase, formation damage caused by asphaltene precipitation and the improved oil recovery are predicted by the simulator. Experimental data validate the developed simulator by comparison with simulation results. The applications of the simulator in prediction of CO2 flooding in oil reservoirs indicate that the simulator is robust for predicting CO2 flooding performance.

  14. Pressurized thermal and hydrothermal decomposition of algae, wood chip residue, and grape marc: A comparative study

    International Nuclear Information System (INIS)

    Subagyono, Dirgarini J.N.; Marshall, Marc; Jackson, W. Roy; Chaffee, Alan L.

    2015-01-01

    Pressurized thermal decomposition of two marine algae, Pinus radiata chip residue and grape marc using high temperature, high pressure reactions has been studied. The yields and composition of the products obtained from liquefactions under CO of a mixture of biomass and H 2 O (with or without catalyst) were compared with products from liquefaction of dry biomass under N 2 , at different temperatures, gas pressures and for CO runs, water to biomass ratios. Thermochemical reactions of algae produced significantly higher dichloromethane solubles and generally higher product yields to oil and asphaltene than Pinus radiata and grape marc under the reaction conditions used. Furthermore, the biofuels derived from algae contained significant concentrations of aliphatic hydrocarbons as opposed to those from radiata pine and grape marc which were richer in aromatic compounds. The possibility of air transport fuel production from algae thus appears to have considerable advantages over that from radiata pine and grape marc. - Highlights: • Liquefaction of algae gave more oil than that of Pinus radiata and grape marc. • Reactions under CO/H 2 O produced higher yields of oil than N 2 . • Water to biomass ratio had little effect on the yields. • Bio-oil from algae contained substantial amounts of aliphatic hydrocarbons. • Pinus radiata oil was low in N but high in O

  15. Isolation and Characterization of Oil-Degrading Bacteria from One of South Sumatera’s Oilfield

    Science.gov (United States)

    Purwasena, I. A.; Astuti, D. I.; Fatmawati, R.; Afinanisa, Q.

    2018-01-01

    Microbial Enhanced Oil Recovery (MEOR) is a tertiary oil recovery method that utilizes microbes to enhance oil production. This research was focused on the isolation and characterization of indigenous bacteria from a South Sumatra’s oilfield which were able to degrade heavy crude oil and decrease oil viscosity. The total of 33 colonies were successfully isolated based on sequential isolation method and screened based on oil degradation activity and SARA analysis. Isolate G3, G7, and N6 were choosen as the best candidate as they were able to reduce oil viscosity up to 22,67%; 23,14%; and 24,36% respectively. Based on 16S rRNA analysis, isolate G3 which was able to degrade aromatic fraction (38,27%) and resin (29,26%) was identified as Pseudoxhantomonas taiwanensis. Isolate G7 which degraded aromatic fraction (61,14%) was identified as Brevibacillus agri while N6 which degraded asphaltene fraction (51.76%) was identified as Bacillus subtilis. In addition, the change in nalkana fraction (C11 – C28) abundance relative to phytan showed that all of the bacterial isolates were able to change those fractions of crude oil. This study showed that three bacterial species isolated from South Sumatran Oilfield were able to degrade heavier fraction of crude oil and reduce its viscosity. This result suggests that those bacteria are highly potential to be applied for MEOR technology.

  16. An integrated approach to combating flow assurance problems

    Energy Technology Data Exchange (ETDEWEB)

    Abney, Laurence; Browne, Alan [Halliburton, Houston, TX (United States)

    2005-07-01

    Any upset to the internal pipe surface of a pipeline can significantly impact both pipeline through-put and energy requirements for maintaining design flow rates. Inefficient flow through pipelines can have a significant negative impact on operating expense (Opex) and the energy requirements necessary to maintain pipeline through-put. Effective flow maintenance helps ensure that Opex remains within budget, processing equipment life is extended and that excessive use of energy is minimized. A number of events can result in debris generation and deposition in a pipeline. Corrosion, hydrate formation, paraffin deposition, asphaltene deposition, development of 'black powder' and scale formation are the most common sources of pipeline debris. Generally, a combination of pigging and chemical treatments is used to remove debris; these two techniques are commonly used in isolation. Incorporation of specialized fluids with enhanced solid-transport capabilities, specialized dispersants, or specialized surfactants can improve the success of routine pigging operations. An array of alternative and often complementary remediation technologies can be used to effect the removal of deposits or even full restrictions from pipelines. These include the application of acids, specialized chemical products, and intrusive interventions techniques. This paper presents a review of methods of integrating existing technologies. (author)

  17. Economic evaluation of organic deposition inhibition treatment: case study; Avaliacao economica de tratamentos de inibicao de deposicao organica: estudo de casos

    Energy Technology Data Exchange (ETDEWEB)

    Lechuga, Fernanda Curty; Seidl, Peter Rudolf; Guimaraes, Maria Jose de Oliveira [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Escola de Quimica; Lucas, Elizabete Fernandes [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Inst. de Macromoleculas

    2008-07-01

    During the production process the temperature and pressure decrease along the well, that generate an increase in viscosity, changes in the composition of the oil and chemical changes in the balance of oil. These changes in the balance may lead to precipitation and deposition of organic components of heavy oil. These occurrences cause serious economic consequences. To solve problems related to organic deposition, it is proposed some actions to prevent the formation of these deposits. Chemical additives interfere in precipitation of paraffins and aggregation of asphaltenes, increasing stability. This paper aims to examine, in economic terms, treatments prevention in different wells by the mechanism of inhibition of organic deposition by the action of chemical additives. The methodology applied for the economic analysis was the return on investment (ROI - Return-on-investments) that could estimate when there was an economic gain in problems of organic deposition treated with chemical additives. The results showed that if these wells use prevention methods it could get a return of more than $ 100.00 per dollar invested in treatment, which would be beneficial, since these treatments increase the production of oil and reduce the idle time in wells. (author)

  18. Fuel quality control: Five years of activity in laboratories

    International Nuclear Information System (INIS)

    Bettinelli, M.; Cimini, G.; Durello, G.; Lucchesi, P.L.

    1991-01-01

    A description of how ENEL (Italian National Electricity Board) carries out the activity of fuel quality control is given, and the results of the Round Robin circuit which has been operating for five years in laboratories regulary performing the control analyses of these products are reported. The laboratories taking part in the Round Robin circuit are 41 (out of which 35 are ENEL laboratories and 6 are owned by external companies) and they are situated throughout Italy; the controlled parameters are the following: heat of combustion (PCS), sulphur (S), vanadium (V) and asphaltenes (ASF); the adopted methods are the official ASTM or IP ones. The statistical analysis of the results has permitted, for every parameter, the calculation of the repeatability and the reproducibility which, in most cases, have turned out to be in keeping with the values provided for in the regulations. Among the collateral initiatives promoted in the framework of this Round Robin, the following are reported: preparation of standards of fuel oil with a known content of a sulphur and vanadium; expediting visits to all the ENEL laboratories participating in the RRT; publication of a handbook of the adopted analysis methods (in Italian); definition of guide-lines on the right selection of new automatic equipment

  19. Benthic Bioprocessing of Hydrocarbons in the Natural Deep-Sea Environment

    Science.gov (United States)

    Sultan, N.; MacDonald, I. R.; Bohrmann, G.; Schubotz, F.; Johansen, C.

    2017-12-01

    Science is accustomed to quantifying ecosystem processes that consume carbon from primary production as it drifts downward through the photic zone. Comparably efficient processes operate in reverse, as living and non-living components sequester and re-mineralize a large fraction of hydrocarbons that migrate out of traps and reservoirs to the seafloor interface. Together, they comprise a sink that prevents these hydrocarbons from escaping upward into the water column. Although quantification of the local or regional magnitude of this sink poses steep challenges, we can make progress by classifying and mapping the biological communities and geological intrusions that are generated from hydrocarbons in the deep sea. Gulf of Mexico examples discussed in this presentation extend across a broad range of depths (550, 1200, and 3200 m) and include major differences in hydrocarbon composition (from gas to liquid oil to asphaltene-dominated solids). Formation of gas hydrate is a dynamic process in each depth zone. At upper depths, gas hydrate is unstable at a timescale of months to years and serves as a substrate for microbial consortia and mussel symbiosis. At extreme depths, gas hydrate supports large and dense tubeworm colonies that conserve the material from decomposition. Timescales for biogeochemical weathering of oil and asphalts are decadal or longer, as shown by sequential alterations and changing biological colonization. Understanding these processes is crucial as we prepare for wider and deeper energy exploitation in the Gulf of Mexico and beyond.

  20. Bioremediation of soils contaminated by hydrocarbons at the coastal zone of “Punta Majagua”.

    Directory of Open Access Journals (Sweden)

    Jelvys Bermúdez Acosta

    2012-03-01

    Full Text Available The purpose of this research was to describe and assess the main results in the process of bioremediation of 479 m3 of petroleum residuals spilled on the soil and restrained into four deposits of fuel on the coastal zone of “Punta Majagua”, Cienfuegos. The volume of hydrocarbons spilled and contained into the tanks was determined by means of their previous mixture with fertile ground in a ratio of 3/1. The hydrocarbons were disposed in a bioremediation area of 115 m X 75m built in situ. In turn 54, 5 m3 of BIOIL - FC were applied, which were fermented in an industrial bioreactor of 12000 L. An initial sampling was carried out registering values of total hydrocarbons (HTP higher than 41880 mg/kg, with high concentrations of Saturated hydrocarbons, aromatics, resins, asphaltens (SARA. Three subsequent samples were taken with a sampling interval of 0, 45, 90 and 120 days of the application. An average concentration of 1884.57 mg/kg of total hydrocarbons was obtained at 120 days with an average removal rate of 94.8%, moreover values of 94.6%, 90.78%, 86.99% y 79.9% of SARA were respectively reported.

  1. Caractérisation de quelques stabilisants naturels de l'émulsion d'eau dans le pétrole brut, grace à l'extension de la technique de "moussage" au système liquide-liquide eau-huile Characterising Several Natural Stabilizants of Water Emulsion in Crude Oil by Extending the "Foaming" Technique to Oil/Water Liquid-Liquid Systems

    Directory of Open Access Journals (Sweden)

    Coste J. -F.

    2006-11-01

    Full Text Available L'extension de la technique, de " moussage "au système liquide-liquide eau-pétrole brut a permis d'augmenter la concentration d'une fraction du pétrole en acides naphténiques, amines, asphaltènes et porphyrines, grâce à l'accroissement de l'aire de l'interface entre les deux phases non miscibles. Ces espèces chimiques présentes à l'interface favorisent la formation des films entre les gouttelettes de phase aqueuse dispersée. Elles sont à l'origine de la stabilité de I'émulsion d'eau dans le pétrole. The " foaming " technique was extended to a water/crude-oil liquid-liquid system so as to increase the concentration of naphthenic acids, amines, asphaltenes and porphyrins in an oil fraction by enlarging the interface orea between the two immiscible phases. The presence of these chemical species at the interface promotes the formation of films between the dispersed aqueuss-phase droplets. They are at the origin of the stability of a water in oil emulsion.

  2. Catalytic activity of pyrite for coal liquefaction reaction; Tennen pyrite no shokubai seino ni kansuru kento

    Energy Technology Data Exchange (ETDEWEB)

    Hirano, K.; Kozu, M.; Okada, T.; Kobayashi, M. [Nippon Coal Oil Co. Ltd., Tokyo (Japan)

    1996-10-28

    Since natural pyrite is easy to obtain and cheap as coal liquefaction catalyst, it is to be used for the 150 t/d scale NEDOL process bituminous coal liquefaction pilot plant. NEDO and NCOL have investigated the improvement of catalytic activity of pulverized natural pyrite for enhancing performance and economy of the NEDOL process. In this study, coal liquefaction tests were conducted using natural pyrite catalyst pulverized by dry-type bowl mill under nitrogen atmosphere. Mechanism of catalytic reaction of the natural pyrite was discussed from relations between properties of the catalyst and liquefaction product. The natural pyrite provided an activity to transfer gaseous hydrogen into the liquefaction product. It was considered that pulverized pyrite promotes the hydrogenation reaction of asphaltene because pulverization increases its contact rate with reactant and the amount of active points on its surface. It was inferred that catalytic activity of pyrite is affected greatly by the chemical state of Fe and S on its surface. 3 refs., 4 figs., 1 tab.

  3. Characteristics estimation of coal liquefaction residue; Sekitan ekika zansa seijo no suisan ni kansuru kento

    Energy Technology Data Exchange (ETDEWEB)

    Itonaga, M.; Imada, K. [Nippon Steel Corp., Tokyo (Japan); Okada, Y.; Inokuchi, K. [Mitsui SRC Development Co. Ltd., Tokyo (Japan)

    1996-10-28

    The paper studied a possibility of estimating characteristics of coal liquefaction residue from liquefaction conditions in the case of fixing coal kind in the NEDOL process coal liquefaction PSU. Wyoming coal was used for the study, and the already proposed simplified liquefaction reaction models were used. Among material balances explained by the models, those of asphaltene, preasphaltene, THF insoluble matters are concerned with residue composition. Ash content is separately calculated from ash balance. Reaction velocity constants of simplified liquefaction reaction models which influence the residue composition were obtained by the multiple regression method from experimental results in the past. The estimation expression of residue viscosity was introduced from residue ash/composition. When the residue composition is estimated by the model from liquefaction conditions, and the residue viscosity is obtained using it, the higher the liquefaction temperature is, the higher the residue viscosity is. The result obtained well agreed the measuring result. The simplified liquefaction model of a certain coal kind has been established, and characteristics of residue can be estimated even at liquefaction conditions which have never been experienced before if there is a certain amount of the accumulated data on residue composition/characteristics. 4 refs., 4 figs., 4 tabs.

  4. Pyrolysis thermocatalytic of the residues generated in the process of oil refining; Pirolise termocatalitica de residuos gerados no processo de refino de petroleo

    Energy Technology Data Exchange (ETDEWEB)

    Lima, Regineide Oliveira; Castro, Kesia Kelly Vieira de; Lima, Cicero de Souza; Araujo, Aruzza Mabel de Morais; Silva, Edjane Fabiula Buriti da; Araujo, Antonio Souza de [Universidade Federal do Rio Grande do Norte (UFRN), RN (Brazil)

    2012-07-01

    The pyrolysis process is a catalytic thermal defined as the degradation of waste which occurs by the action of temperature and presence of catalysts. Thus promoting disruption of the original molecular structure of a given compound by the catalytic action in an environment with little or no oxygen. Investigations have been developed in the pyrolysis due to be a promising technique, due to the application of catalytic materials. In this work, the catalyst used Al/MCM-41 was synthesized in a ratio Si / Al = 50 by the hydrothermal method. Being in this promising oil industry because of their structural characteristics. This material was characterized by XRD analysis, which was observed three major peaks typical of mesoporous materials. The analysis of the adsorption / desorption of nitrogen this material was performed to determine the textural parameters, which are peculiar to the mesoporous materials. The residue samples were characterized with a view to meet some properties such as through elemental analysis of the compounds and saturates, aromatics, resins and asphaltenes. The pyrolysis reaction system catalytic thermal residue is mounted to test the pyrolysis of residue pure and the Al-MCM-41. For both pyrolysis liquid fractions were obtained, gaseous and solid. And only the liquid fractions were characterized by chromatography coupled to mass spectrometry. Thus, there was an increase in the range hydrocarbons (C6-C12 and C13-C17) for products obtained from the pyrolysis catalyst. (author)

  5. Production of petroleum bitumen by oxidation of heavy oil residue with sulfur

    Science.gov (United States)

    Tileuberdi, Ye.; Akkazyn, Ye. A.; Ongarbayev, Ye. K.; Imanbayev, Ye. I.; Mansurov, Z. A.

    2018-03-01

    In this paper production of bitumen adding elemental sulfur at oxidation of oil residue are investigated. The objects of research were distilled residue of Karazhanbas crude oil and elemental sulfur. These oil residue characterized by a low output of easy fractions and the high content of tar-asphaltene substances, therefore is the most comprehensible feedstock for producing bitumen. The sulfur is one of the oil product collected in oil extraction regions. Oxidation process of hydrocarbons carried out at temperatures from 180 up to 210 °С without addition of sulfur and with the addition of sulfur (5-10 wt. %) for 4 hours. At 200 °С oxidation of hydrocarbons with 5, 7 and 10 wt.% sulfur within 3-4 h allows receiving paving bitumen on the mark BND 200/300, BND 130/200, BN 90/130 and BN 70/30. Physical and mechanical characteristics of oxidation products with the addition of 5-7 wt. % sulfur corresponds to grade of paving bitumen BND 40/60. At the given temperature oxidized for 2.5-3 h, addition of 10 wt. % sulfur gave the products of oxidation describing on parameters of construction grades of bitumen (BN 90/10).

  6. Change of isoprenoids, steranes and terpanes during ex situ bioremediation of mazut on industrial level

    Directory of Open Access Journals (Sweden)

    Beškoski Vladimir P.

    2010-01-01

    Full Text Available The paper presents results of the ex situ bioremediation of soil contaminated by mazut (heavy residual fuel oil in the field scale (600 m3. A treatment-bed (thickness 0.4 m consisted of mechanically mixed mazut-contaminated soil, softwood sawdust as the additional carbon source and crude river sand, as bulking and porosity increasing material. The inoculation/reinoculation was conducted periodically using a biomass of a consortium of zymogenous microorganisms isolated from the bioremediation substrate. The biostimulation was performed through addition of nutritious substances (N, P and K. The aeration was improved by systematic mixing of the bioremediation system. After 50 days, the number of hydrocarbon degraders increased 100 times. Based on the changes in the group composition, the average biodegradation rate during bioremediation was 24 mg/kg/day for the aliphatic fraction, 6 mg/kg/day for the aromatic fraction, and 3 mg/kg/day for the nitrogen-sulphuroxygen compounds (NSO-asphaltene fraction. In the saturated hydrocarbon fraction, gas chromatography-mass spectrometry (GC-MS in the single ion-monitoring mode (SIM was applied to analyse isoprenoids pristane and phytane and polycyclic molecules of sterane and triterpane type. Biodegradation occurred during the bioremediation process, as well as reduction of relative quantities of isoprenoids, steranes, tri- and tetracyclic terpanes and pentacyclic terpanes of hopane type.

  7. Removal Capacities of Polycyclic Aromatic Hydrocarbons (PAHs by a Newly Isolated Strain from Oilfield Produced Water

    Directory of Open Access Journals (Sweden)

    Yi-Bin Qi

    2017-02-01

    Full Text Available The polycyclic aromatic hydrocarbon (PAH-degrading strain Q8 was isolated from oilfield produced water. According to the analysis of a biochemical test, 16S rRNA gene, house-keeping genes and DNA–DNA hybridization, strain Q8 was assigned to a novel species of the genus Gordonia. The strain could not only grow in mineral salt medium (MM and utilize naphthalene and pyrene as its sole carbon source, but also degraded mixed naphthalene, phenanthrene, anthracene and pyrene. The degradation ratio of these four PAHs reached 100%, 95.4%, 73.8% and 53.4% respectively after being degraded by Q8 for seven days. A comparative experiment found that the PAHs degradation efficiency of Q8 is higher than that of Gordonia alkaliphila and Gordonia paraffinivorans, which have the capacities to remove PAHs. Fourier transform infrared spectra, saturate, aromatic, resin and asphaltene (SARA and gas chromatography–mass spectrometry (GC–MS analysis of crude oil degraded by Q8 were also studied. The results showed that Q8 could utilize n-alkanes and PAHs in crude oil. The relative proportions of the naphthalene series, phenanthrene series, thiophene series, fluorene series, chrysene series, C21-triaromatic steroid, pyrene, and benz(apyrene were reduced after being degraded by Q8. Gordonia sp. nov. Q8 had the capacity to remediate water and soil environments contaminated by PAHs or crude oil, and provided a feasible way for the bioremediation of PAHs and oil pollution.

  8. In-situ burning of heavy oils and Orimulsion : mid-scale burns

    International Nuclear Information System (INIS)

    Fingas, M.F.; Fieldhouse, B.; Brown, C.E.; Gamble, L.

    2004-01-01

    In-situ burning is considered to be a viable means to clean oil spills on water. In-situ burning, when performed under the right conditions, can reduce the volume of spilled oil and eliminate the need to collect, store, transport and dispose of the recovered oil. This paper presented the results of bench-scale in-situ burning tests in which Bunker C, Orimulsion and weathered bitumen were burned outdoors during the winter in burn pans of approximately 1 square metre. Each test was conducted on salt water which caused the separation of the bitumen from the water in the Orimulsion. Small amounts of diesel fuel was used to ignite the heavy oils. Quantitative removal of the fuels was achieved in all cases, but re-ignition was required for the Orimulsion. Maximum efficiency was in the order of 70 per cent. The residue was mostly asphaltenes and resins which cooled to a solid, glass like material that could be readily removed. The study showed that the type of oil burned influences the behaviour of the burns. Bunker C burned quite well and Orimulsion burned efficiently, but re-ignition was necessary. It was concluded that there is potential for burning heavy oils of several types in-situ. 6 refs., 7 tabs., 18 figs

  9. Synthesis and evaluation of some new demulsifiers based on bisphenols for treating water-in-crude oil emulsions

    Directory of Open Access Journals (Sweden)

    Ahmed M. Al-Sabagh

    2011-06-01

    Full Text Available The present paper endeavors to synthesize nine types of demulsifiers based on bisphenols (bisphenol A (BA, bisphenol AC (BAC and bisphenol CH (BCH having different ethylene oxide units (n = 27, 34, 45 namely; E (x + y (where E represents BA, BCH or BAC and (x + y which represents the ethylene oxide units (27, 34, 45. The chemical structures of the prepared demulsifier were elucidated using FT-IR and 1H NMR spectra. Effect of the chemical structure (hydrophobic and ethoxylated degree of hydrophilic parts and the mechanism of demulsification process was investigated. The data were discussed on the light of the chemical structure of the demulsifiers and the factors, effecting the demulsification process. The efficiency of these demulsifiers was tested on water-in-oil emulsions (w/o at different concentrations (100, 200 and 300 ppm, 7.4% asphaltene content and 30%, 50% and 70% water content. From the obtained data the best demulsifier was E(34BA which shows 100% demulsification after 58 min at 30% water content and 300 ppm of the demulsifier.

  10. Effect of demineralization on yield and composition of the volatile products evolved from temperature-programmed pyrolysis of Beypazari (Turkey) Oil Shale

    Energy Technology Data Exchange (ETDEWEB)

    Ballice, Levent [University of Ege, Faculty of Engineering, Department of Chemical Engineering, 35100 Bornova, Izmir (Turkey)

    2005-03-25

    In this study, the effect of the mineral matter of Beypazari Oil Shale on the conversion of organic carbon of oil shale into volatile hydrocarbon, polycyclic aromatic hydrocarbons (asphaltenes, preasphaltenes) and carbon in solid residue was investigated. Kerogen was isolated by successive HCl, HNO{sub 3} and HF treatments. A series of temperature-programmed pyrolysis operation was performed with raw Beypazari Oil Shale, and each product of every demineralization process. A carbon balance of the pyrolysis process was established by determination of the recovery of total organic carbon as organic products, and carbon remaining in the reactor because of the coking reactions. The removal of the material soluble in HCl washing affected the conversion of organic materials in the pyrolysis reactions. Alkali and alkaline earth metal cations affect the reactivity of oil shales and the leaching of these mineral matters with HCl caused a slightly decrease in the conversion to volatile hydrocarbons. The removal of pyrites with HNO{sub 3} did not affect the reactivity of the organic material in pyrolysis. But, removal of the material soluble in HF increased the conversion in pyrolysis reactions. It can be explained by the inhibitive effect of the silicate minerals. Complete removal of mineral matrix and isolation of kerogen increased the driving force for heat transfer since more heat was transferred from outside towards the inside of the oil shale particles, thus pyrolysis reaction might have occurred with ease and diffusion limitation might have decreased due to absence of mineral matrix.

  11. Effect of catalyst deactivation on vacuum residue hydrocracking

    Directory of Open Access Journals (Sweden)

    Hoda S. Ahmed

    2013-12-01

    Full Text Available Accelerated deactivation tests of the pre-sulfided Mo–W/SiO2–Al2O3 commercial catalyst were performed using heavy vacuum petroleum feedstock. High reaction temperature employed in the accelerated catalyst aging resulted in large amounts of carbonaceous deposition with high aromaticity, which was found to be the principal deactivation cause. The effect of catalyst deactivation on hydrocracking of vacuum residue was studied. Experiments were carried out in a batch reactor at 60 bar, feed to catalyst ratio 10:1 and temperature 425 °C. The duration time for a cycle-run was 4 h. On increasing the interval duration times from 4 to 20 h (i.e. five cycles, the quality of the hydrocracked products was decreased. In each cycle-run, a fresh feedstock was used with the same sulfide catalyst. The quality of distillate products, such as hydrodesulfurization (HDS was decreased from 61.50% to 39.52%, while asphaltene contents of the total liquid product were increased from 2.7% to 5.2% and their boiling ranges were increased during these duration times due to the successive catalyst deactivation during the 5 cycle-runs, caused by successive adsorption of coke formation.

  12. Trace metals in heavy crude oils and tar sand bitumens

    Energy Technology Data Exchange (ETDEWEB)

    Reynolds, J.G.

    1990-11-28

    Fe, Ni, and V are considered trace impurities in heavy crude oils and tar sand bitumens. In order to understand the importance of these metals, we have examined several properties: (1) bulk metals levels, (2) distribution in separated fractions, (3) size behavior in feeds and during processing, (4) speciation as a function of size, and (5) correlations with rheological properties. Some of the results of these studies show: (1) V and Ni have roughly bimodal size distributions, (2) groupings were seen based on location, size distribution, and Ni/V ratio of the sample, (3) Fe profiles are distinctively different, having a unimodal distribution with a maximum at relatively large molecular size, (4) Fe concentrations in the tar sand bitumens suggest possible fines solubilization in some cases, (5) SARA separated fractions show possible correlations of metals with asphaltene properties suggesting secondary and tertiary structure interactions, and (6) ICP-MS examination for soluble ultra-trace metal impurities show the possibility of unexpected elements such as U, Th, Mo, and others at concentrations in the ppB to ppM range. 39 refs., 13 figs., 5 tabs.

  13. Nonlinear machine learning in soft materials engineering and design

    Science.gov (United States)

    Ferguson, Andrew

    The inherently many-body nature of molecular folding and colloidal self-assembly makes it challenging to identify the underlying collective mechanisms and pathways governing system behavior, and has hindered rational design of soft materials with desired structure and function. Fundamentally, there exists a predictive gulf between the architecture and chemistry of individual molecules or colloids and the collective many-body thermodynamics and kinetics. Integrating machine learning techniques with statistical thermodynamics provides a means to bridge this divide and identify emergent folding pathways and self-assembly mechanisms from computer simulations or experimental particle tracking data. We will survey a few of our applications of this framework that illustrate the value of nonlinear machine learning in understanding and engineering soft materials: the non-equilibrium self-assembly of Janus colloids into pinwheels, clusters, and archipelagos; engineering reconfigurable ''digital colloids'' as a novel high-density information storage substrate; probing hierarchically self-assembling onjugated asphaltenes in crude oil; and determining macromolecular folding funnels from measurements of single experimental observables. We close with an outlook on the future of machine learning in soft materials engineering, and share some personal perspectives on working at this disciplinary intersection. We acknowledge support for this work from a National Science Foundation CAREER Award (Grant No. DMR-1350008) and the Donors of the American Chemical Society Petroleum Research Fund (ACS PRF #54240-DNI6).

  14. Analytical filtration model for nonlinear viscoplastic oil in the theory of oil production stimulation and heating of oil reservoir in a dual-well system

    Science.gov (United States)

    Ivanovich Astafev, Vladimir; Igorevich Gubanov, Sergey; Alexandrovna Olkhovskaya, Valeria; Mikhailovna Sylantyeva, Anastasia; Mikhailovich Zinovyev, Alexey

    2018-02-01

    Production of high-viscosity oil and design of field development systems for such oil is one of the most promising directions in the development of world oil industry. The ability of high-viscosity oil to show in filtration process properties typical for non-Newtonian systems is proven by experimental studies. Nonlinear relationship between the pressure gradient and the rate of oil flow is due to interaction of high-molecular substances, in particular, asphaltenes and tars that form a plastic structure in it. The authors of this article have used the analytical model of stationary influx of nonlinear viscoplastic oil to the well bottom in order to provide rationale for the intensifying impact on a reservoir. They also have analyzed the method of periodic heating of productive reservoir by means of dual-wells. The high-temperature source is placed at the bottom of the vertical well, very close to the reservoir; at the same time the side well, located outside the zone of expected rock damage, is used for production. Suggested method of systemic treatment of reservoirs with dual wells can be useful for small fields of high-viscosity oil. The effect is based on the opportunity to control the structural and mechanical properties of high-viscosity oil and to increase depletion of reserves.

  15. Effectiveness of bioremediation for the Prestige fuel spill : a summary of case studies

    International Nuclear Information System (INIS)

    Gallego, J.R.; Gonzalez-Rojas, E.; Pelaez, A.I.; Sanchez, J; Garcia-Martinez, M.J.; Llamas, J.F.

    2006-01-01

    This paper described novel bioremediation strategies used to remediate coastal areas in Spain impacted by the Prestige fuel oil spill in 2002. The bioremediation techniques were applied after hot pressurized water washing was used to remove hydrocarbons adhering to shorelines and rocks. Bioremediation strategies included monitored natural attenuation as well as accelerating biodegradation by stimulating indigenous populations through the addition of exogenous microbial populations. The sites selected for bioremediation were rocky shorelines of heterogenous granitic sediments with grain sizes ranging from sands to huge boulders; limestone-sandstone pebbles and cobbles; and fuel-coated limestone cliffs. Total surface area covered by the fuel was determined through the use of image analysis calculations. A statistical measurement of the fuel layer thickness was calculated by averaging the weights of multiple-fuel sampling increments. Bioremediation products included the use of oleophilic fertilizers; a biodegradable surfactant; and a microbial seeding agent. Determinations of saturate, aromatic, resins, and asphaltene (SARA) were performed using maltenes extraction and liquid chromatography. Microbial plating and selective enrichment with fuel as the sole carbon source were used to monitor the evolution of microbial populations in a variety of experiments. It was concluded that the biostimulation technique enhanced the efficiency of the in situ oleophilic fertilizers. 17 refs., 2 tabs., 6 figs

  16. Post Retort, Pre Hydro-treat Upgrading of Shale Oil

    Energy Technology Data Exchange (ETDEWEB)

    Gordon, John

    2012-09-30

    Various oil feedstocks, including oil from oil shale, bitumen from tar sands, heavy oil, and refin- ery streams were reacted with the alkali metals lithium or sodium in the presence of hydrogen or methane at elevated temperature and pressure in a reactor. The products were liquids with sub- stantially reduced metals, sulfur and nitrogen content. The API gravity typically increased. Sodi- um was found to be more effective than lithium in effectiveness. The solids formed when sodium was utilized contained sodium sulfide which could be regenerated electrochemically back to so- dium and a sulfur product using a "Nasicon", sodium ion conducting membrane. In addition, the process was found to be effective reducing total acid number (TAN) to zero, dramatically reduc- ing the asphaltene content and vacuum residual fraction in the product liquid. The process has promise as a means of eliminating sulfur oxide and carbon monoxide emissions. The process al- so opens the possibility of eliminating the coking process from upgrading schemes and upgrad- ing without using hydrogen.

  17. Effects of the components of coal hydro-liquefaction residue on its rheological characteristics

    Energy Technology Data Exchange (ETDEWEB)

    Ren, Y.; Jin, S.; Xu, Y.; Wei, A.; Zhang, D.; Gao, J. [East China University of Science & Technology, Shanghai (China)

    2009-07-01

    Four kinds of typical coal liquefaction residue samples, coming from Shenhua coal liquefaction pilot plant, were used to investigate the effects of components of residue, separation time, and temperature on its rheological characteristics. Coal liquefaction residue is a non-Newtonian pseudoplastic fluid whose apparent viscosity decreases with increasing shear rate. Moreover, the residue has high viscosity at the initial softening temperature, and its viscosity drops greatly with increasing temperature. The oil content in residue has a great effect on the decline of the apparent viscosity of residue. The asphaltene can increase the apparent viscosity at lower temperatures but decrease it at higher temperatures. However, the solid only increases the apparent viscosity as it can be neither softened nor dissolved to become fluid. After simulating the separation condition, it is found that prolonging the separation time and enhancing the separation temperature will increase the apparent viscosity of residue, which is bad for preventing pipes from being blocked. So choosing the right separation time and separation temperature is necessary to actual industrial production.

  18. Study of the processes of radionuclides transfer, heavy metals and aero-particles among the solid, dissolved phase and the air; Estudio de los procesos de transferencia de radionuclidos, metales pesados y aeroparticulas entre la fase solida, disuelta y el aire

    Energy Technology Data Exchange (ETDEWEB)

    Romero G, E. T.; Ordonez R, E. [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico); Reyes G, L. R. [Instituto Potosino de Investigacion Cientifica y Tecnologica, Division de Geociencias Aplicadas, Camino a la Presa San Jose 2055, Col. Lomas 4 seccion, 78216 San Luis Potosi (Mexico); Jose Y, M., E-mail: elizabeth.romero@inin.gob.m [University of Texas at San Antonio, Department of Physics and Astronomy, One UTSA Circle, San Antonio TX 78249 (United States)

    2010-07-01

    In this chapter the investigations developed in the Instituto Nacional de Investigaciones Nucleares (ININ) are presented, in collaboration with specialists in diverse fields of the science. In the first place, is presented the objective and an introduction of each one of the following projects: Study of the uranium migration through the not saturated area, and Synthesis and characterization of phosphate materials by conventional techniques, projects developed under the direction and collaboration of the Ph D. Eduardo Ordonez Regil. Identification of the chemical-morphologic composition of painting mural pigments: the blue Mayan, indigo blue, the secret of the color, and investigation of the physiochemical components of the asphaltenes and malthenes of heavy crudes and vacuum residual, with the supervision of the Ph D. Miguel Jose Yacaman. Evaluation of the water quality and type of sediments of the lake-crater The Pool: one of the seven stars of Santiago Valley, Guanajuato; Study of the sorption kinetics of Cr(Vi) in floor of a container of chromium residuals in Buenavista, Guanajuato, Mexico; Investigation of the underground water hydrochemistry of the basin of the Avenues River in Pachuca de Soto, Hidalgo, and Characterization of the particle material and modeled of the dispersion and pollutants transport in the air of the Metropolitan Area of the Toluca Valley, projects carried out under the direction and collaboration of the Ph D. Lazaro Raymundo Reyes Gutierrez. Finally, is presented the most representative of the obtained results, as well as a discussion of the same ones. (Author)

  19. Action of microwave radiation in emulsion of oil demulsification by copolymers of poly (ethylene oxide-b-propylene oxide); Acao da radiacao micro-ondas na desemulsificacao de emulsoes de petroleo por copolimeros de poli(oxido de etileno-b-oxido de propileno)

    Energy Technology Data Exchange (ETDEWEB)

    Ferreira, Bianca M.S.; Ramalho, Joao B.V.; Guimaraes, Regina C.L.; Guarnieri, Ricardo A. [Petrobras Petroleo Brasileiro - CENPES/TPEP/TPP, Rio de Janeiro, RJ (Brazil)], e-mail: bmachado@petrobras.com.br; Lucas, Elizabete F. [Universidade Federal do Rio de Janeiro, Instituto de Macromoleculas, Laboratorio de Macromoleculas e Coloides na Industria do Petroleo,Rio de Janeiro, RJ (Brazil)], e-mail: elucas@ima.ufrj.br

    2011-07-01

    Emulsions of water-in-petroleum are generally formed during crude oil production. The emulsion needs to be destabilized, along the process in the production units, so as to allow the water-oil separation. This process is accomplished by heating and addition of demulsifier, like poly (ethylene oxide-b-propylene oxide) which promotes the removal of the natural emulsifier from the water droplets interfaces. Normally, the conventional heating is used, but the microwave radiation has been suggested to heat de emulsions. The results obtained in this work show that microwave radiation can really enhance the demulsification rate of petroleum emulsions by gravitational mechanism. It is also shown that demulsification enhancement is greatly related to the selective and higher heating of the water phase induced by the microwave radiation, which causes the lowering of the interfacial film rigidity and the increase of the film drainage, after the demulsifier is added to the dispersed system. It was also observed that the higher the density, viscosity, acidity and asphaltenes content of the crude oil, the lower the demulsification rate. (author)

  20. Kinetics of hydrocarbon extraction from oil shale using biosurfactant producing bacteria

    Energy Technology Data Exchange (ETDEWEB)

    Haddadin, Malik S.Y.; Abou Arqoub, Ansam A.; Abu Reesh, Ibrahim [Faculty of Graduate Studies, Jordan University, Queen Rania Street, Amman, 11942 (Jordan); Haddadin, Jamal [Faculty of Agriculture, Mutah University, P.O. Box 59, Mutah 61710 (Jordan)

    2009-04-15

    This study was done to extract hydrocarbon compounds from El-Lajjun oil shale using biosurfactant produced from two strains Rhodococcus erythropolis and Rhodococcus ruber. The results have shown that, optimal biosurfactant production was found using naphthalene and diesel as a carbon source for R. erthropolis and R. ruber, respectively. Optimum nitrogen concentration was 9 g/l and 7 g/l for R. erthropolis and R. ruber, respectively. Optimum K{sub 2}HPO{sub 4} to KH{sub 2}PO{sub 4} ratio, temperature, pH, and agitation speeds were 2:1, 37 C, 7 and 200 rpm. Under optimal conditions R. erthropolis and R. ruber produced 5.67 and 6.9 g/l biosurfactant, respectively. Maximum recovery of oil achieved with hydrogen peroxide pre-treatment was 25% and 26% at biosurfactant concentration of 8 g/l and 4 g/l for R. erthropolis and R. ruber, respectively. The extent desorption of hydrocarbons from the pre-treated oil shale by biosurfactant were inversely related to the concentration of high molecular weight hydrocarbons, asphaltenes compounds. Pre-treatment of oil shale with hydrogen peroxide produced better improvement in aromatic compounds extraction in comparison with improvement which resulted from demineralization of the oil shale. (author)

  1. Reaction of carbon-14-labeled reagents with coal

    Energy Technology Data Exchange (ETDEWEB)

    Collins, C. J.; Raaen, V. F.; Hilborn, C.; Roark, W. H.; Maupin, P. H.

    1980-01-01

    Both asphaltenes and preasphaltenes from Illinois No. 6 vitrain exhibit enhanced uptake of /sup 14/CH/sub 2/N/sub 2/ after air exposure. Preasphaltenes however exhibit decreased /sup 14/CC1/sub 2/ uptake after oxygen treatment. These results are in agreement with a scheme in which aryl alkyl ethers and benzylic-type linkages are oxidized to ketones and then carboxylic acids. Heat treatment of Wyodak coal appears to destroy most of the aryl alkyl ethers present, since HBr-treated Wyodak, after reacting with diazomethane-/sup 14/C contains twice the acid-hydrolyzable methyl-/sup 14/C groups exhibited by heat-treated Wyodak. Thermolysis of ..cap alpha..-naphthol-/sup 14/C and of ..beta..-naphthol-/sup 14/C in the presence of Illinois No. 6 coal results in loss of hydroxyl to produce water as well as in alkylation of the naphthalene nucleus, processes which we presume also occur in the phenolic moieties in the coal itself. Thiophenol-/sup 14/C yields hydrogen sulfide, toluene, ethylbenzene, thianthrene, and dibenzothiophene. The results for the thermolyses of ..cap alpha..- and ..beta..-naphthol-/sup 14/C and of thiophenol-/sup 14/C are explained through free radical mechanisms quite similar to those previously postulated for the thermolyses of model compounds in the presence of tetralin.

  2. Kinetics of hydrocarbon extraction from oil shale using biosurfactant producing bacteria

    International Nuclear Information System (INIS)

    Haddadin, Malik S.Y.; Abou Arqoub, Ansam A.; Abu Reesh, Ibrahim; Haddadin, Jamal

    2009-01-01

    This study was done to extract hydrocarbon compounds from El-Lajjun oil shale using biosurfactant produced from two strains Rhodococcus erythropolis and Rhodococcus ruber. The results have shown that, optimal biosurfactant production was found using naphthalene and diesel as a carbon source for R. erthropolis and R. ruber, respectively. Optimum nitrogen concentration was 9 g/l and 7 g/l for R. erthropolis and R. ruber, respectively. Optimum K 2 HPO 4 to KH 2 PO 4 ratio, temperature, pH, and agitation speeds were 2:1, 37 deg. C, 7 and 200 rpm. Under optimal conditions R. erthropolis and R. ruber produced 5.67 and 6.9 g/l biosurfactant, respectively. Maximum recovery of oil achieved with hydrogen peroxide pre-treatment was 25% and 26% at biosurfactant concentration of 8 g/l and 4 g/l for R. erthropolis and R. ruber, respectively. The extent desorption of hydrocarbons from the pre-treated oil shale by biosurfactant were inversely related to the concentration of high molecular weight hydrocarbons, asphaltenes compounds. Pre- treatment of oil shale with hydrogen peroxide produced better improvement in aromatic compounds extraction in comparison with improvement which resulted from demineralization of the oil shale

  3. Bioremediation of oil-contaminated sites

    Energy Technology Data Exchange (ETDEWEB)

    Balba, T. [Conestoga-Rovers and Associates, Calgary, AB (Canada)

    2003-07-01

    One of the most prevalent contaminants in subsurface soil and groundwater are petroleum hydrocarbons. This paper presented bioremediation of petroleum hydrocarbons as one of the most promising treatment technologies. Petroleum hydrocarbons are categorized into four simple fractions: saturates, aromatics, resins, and asphaltenes. Bioremediation refers to the treatment process whereby contaminants are metabolized into less toxic or nontoxic compounds by naturally occurring organisms. The various strategies include: use of constitutive enzymes, enzyme induction, co-metabolism, transfer of plasmids coding for certain metabolic pathways, and production of biosurfactants to enhance bioavailability of hydrophobic compounds. Three case studies were presented: (1) bioremediation of heavy oils in soil at a locomotive maintenance yard in California, involving a multi-step laboratory treatability study followed by a field demonstration achieving up to 94 per cent removal of TPH in less than 16 weeks, (2) bioremediation of light oils in soil at an oil refinery in Germany where a dual process was applied (excavation and in-situ treatment), achieving an 84 per cent reduction within 24 weeks, and (3) bioremediation of oil-contaminated desert soil in Kuwait which involved landfarming, composting piles, and bioventing soil piles, achieving an 80 per cent reduction within 12 months. 7 refs., 1 tab., 3 figs.

  4. Effect of biosurfactants on crude oil desorption and mobilization in a soil system

    Energy Technology Data Exchange (ETDEWEB)

    Kuyukina, M.S.; Ivshina, I.B. [Ural Branch of the Russian Academy of Sciences, Perm (Russian Federation). Institute of Ecology and Genetics of Microorganisms; Makarov, S.O.; Litvinenko, L.V. [Perm State University, Perm (Russian Federation); Cunningham, C.J. [University of Edinburgh (United Kingdom). Contaminated Land Assessment and Remediation Research Centre; Philp, J.C. [Napier University, Edinburgh (United Kingdom). School of Life Sciences

    2005-02-01

    Microbially produced biosurfactants were studied to enhance crude oil desorption and mobilization in model soil column systems. The ability of biosurfactants from Rhodococcus ruber to remove the oil from the soil core was 1.4-2.3 times greater than that of a synthetic surfactant of suitable properties, Tween 60. Biosurfactant-enhanced oil mobilization was temperature-related, and it was slower at 15{sup o}C than at 22-28{sup o}C. Mathematical modelling using a one-dimensional filtration model was applied to simulate the process of oil penetration through a soil column in the presence of (bio)surfactants. A strong positive correlation (R{sup 2} = 0.99) was found between surfactant penetration through oil-contaminated soil and oil removal activity. Biosurfactant was less adsorbed to soil components than synthetic surfactant, thus rapidly penetrating through the soil column and effectively removing 65-82% of crude oil. Chemical analysis showed that crude oil removed by biosurfactant contained a lower proportion of high-molecular-weight paraffins and asphaltenes, the most nonbiodegradable compounds, compared to initial oil composition. This result suggests that oil mobilized by biosurfactants could be easily biodegraded by soil bacteria. Rhodococcus biosurfactants can be used for in situ remediation of oil-contaminated soils. (author)

  5. Bioremediation in oil-contaminated sites: Bacteria and surfactant accelerated remediation

    International Nuclear Information System (INIS)

    Strong-Gunderson, J.M.

    1996-01-01

    In Mexico, there are several environmental issues which are being addressed under the current governmental legislation. One of the important issues is restoring sites belonging to Petroleos Mexicanos (PEMEX). PEMEX is a large government owned oil company that regulates and manages the oil reserves. These sites are primarily contaminated with weathered hydrocarbons which are a consequence of extracting millions of barrels of oil. Within the southern regions of Mexico there are sites which were contaminated by activities and spills that have occurred during the past 30 years. PEMEX has taken the leadership in correcting environmental problems and is very concerned about cleaning up the contaminated sites as quickly as possible. The most significant contaminated sites are located to the north of Veracruz and south of Tabasco. These site areas are close to refineries or locations of oil exploration. The primary category of contaminants are hydrocarbons, among them asphaltenes, aromatic and other contaminants. The concentration of the contaminants varies depending on the location of the sites, but it can reach as high as 500,000 ppm. PEMEX has been searching for appropriate, and cost-effective technologies to clean up these sites. Biologically based remediation activities are of primary interest to PEMEX. However, other treatment technologies such as chemical-physical methods, encapsulation and incineration are also being considered. The present report summarizes preliminary experiments that measured the feasibility of bioremediation for a contaminated site in southern Mexico

  6. Bioremediation in oil-contaminated sites: bacteria and surfactant accelerated remediation

    Science.gov (United States)

    Strong-Gunderson, Janet M.; Guzman, Francisco

    1996-11-01

    In Mexico, there are several environmental issues which are being addressed under the current governmental legislation. One important issue is restoring sites belonging to Petroleos Mexicanos (PEMEX). PEMEX is a large government owned oil company that regulates and manages the oil reserves. These sites are primarily contaminated with weathered hydrocarbons which are a consequence of extracting millions of barrels of oil. Within the southern regions of Mexico there are sites which were contaminated by activities and spills that have occurred during the past 30 years. PEMEX has taken the leadership in correcting environmental problems and is very concerned about cleaning up the contaminated sites as quickly as possible. The most significant contaminated sites are located to the north of Veracruz and south of Tabasco. These sites areas are close to refineries or locations of oil exploration. The primary category of contaminants are hydrocarbons, among them asphaltens, aromatic and other contaminants. The concentration of the contaminants varies depending on the location of the sites, but it can reach as high as 500,000 ppm. PEMEX has been searching for appropriate, and cost- effective technologies to clean up these sites. Biologically based remediation activities are of primary interest to PEMEX. However, other treatment technologies such as chemical-physical methods, encapsulation and incineration are also being considered. The present report summarizes preliminary experiments that measured the feasibility of bioremediation for a contaminated site in southern Mexico.

  7. SIMULATION AND OPTIMIZATION OF THE HYDRAULIC FRACTURING OPERATION IN A HEAVY OIL RESERVOIR IN SOUTHERN IRAN

    Directory of Open Access Journals (Sweden)

    REZA MASOOMI

    2017-01-01

    Full Text Available Extraction of oil from some Iranian reservoirs due to high viscosity of their oil or reducing the formation permeability due to asphaltene precipitation or other problems is not satisfactory. Hydraulic fracturing method increases production in the viscous oil reservoirs that the production rate is low. So this is very important for some Iranian reservoirs that contain these characteristics. In this study, hydraulic fracturing method has been compositionally simulated in a heavy oil reservoir in southern Iran. In this study, the parameters of the fracture half length, the propagation direction of the cracks and the depth of fracturing have been considered in this oil reservoir. The aim of this study is to find the best scenario which has the highest recovery factor in this oil reservoir. For this purpose the parameters of the length, propagation direction and depth of fracturing have been optimized in this reservoir. Through this study the cumulative oil production has been evaluated with the compositional simulation for the next 10 years in this reservoir. Also at the end of this paper, increasing the final production of this oil reservoir caused by optimized hydraulic fracturing has been evaluated.

  8. Upgrading Unconventional Oil Resources with the EST Process

    Energy Technology Data Exchange (ETDEWEB)

    Delbianco, Alberto; Meli, Salvatori; Panariti, Nicolleta; Rispoli, Giacomo

    2007-07-01

    We strongly believe that unconventional oils will play a much larger role in the growth of supply than is currently recognized. As a matter of fact, whereas the earth's conventional proven world oil reserves are 1.3 trillion barrels, extra-heavy plus bitumen resources amount to about 4 trillion barrels. The unconventional oils are characterized by low API gravity (<10), high viscosity and high concentration of poisons such as sulphur, nitrogen, metals, and asphaltenes. For this reason, a key role for the full exploitation of these hydrocarbon resources is played by the downstream processes that are required to upgrade and convert them into valuable products. In this scenario, Eni has developed a novel hydrocracking process (EST: Eni Slurry Technology) which is particularly well-suited for the conversion and upgrading of heavy feedstocks (conventional vacuum residues, extra-heavy oils and bitumen). EST employs nano-sized hydrogenation catalysts and an original process scheme that allow complete feedstock conversion to an upgraded synthetic crude oil (SCO) with an API gravity gain greater than 20 and avoid the production of residual by-products, such as pet-coke or heavy fuel oil. A Commercial Demonstration Unit (CDP) of 1200 bbl/d capacity is successfully operating in the Eni's Taranto refinery since November 2005. (auth)

  9. Improved cracking characteristics of bitumen through advanced froth treatment process

    Energy Technology Data Exchange (ETDEWEB)

    Ng, S.H. [National Centre for Upgrading Technology, Devon, AB (Canada); Dabros, T. [Natural Resources Canada, Devon, AB (Canada). CANMET Advanced Separation Technologies Laboratory; Humphries, A. [Albemarle Catalysts Co., Houston, TX (United States)

    2006-07-01

    Fluid catalytic cracking (FCC) is the dominant refinery conversion process for producing transportation fuels. Feed to the FCC unit is heavy gas oil (HGO). Its quality depends on the crude used and the processes involved. Bitumen-derived crude (BDC), including synthetic crude oil (SCO) is less superior to produce FCC feed than stocks from conventional sources. As a result, North American refiners have limited the use of BDC in their conventional FCC-based operations. This paper examined the improved cracking characteristics of bitumen through an advanced froth treatment process. This involved processing of the bitumen with paraffinic solvent in froth treatment with removal of some asphaltenes, CCR precursors, and metals. The paper discussed the experimental and subsequent results and discussion, including cracking characteristics; product quality; synergetic effect; and economic benefits. It was concluded that the poisoning effect by some deleterious components such as nitrogen compounds in feeds on the catalyst could be reduced or compensated for by higher C/O ratios (more catalyst per unit weight of feed). In addition, as conversion increased, sulfur in gasoline decreased slightly and linearly with more or less the same magnitude for the two bitumens. 5 refs., 1 tab., 3 figs.

  10. Comparative evaluation of online oil and gas monitor; Avaliacao de monitores de teor de oleo e graxa em linha

    Energy Technology Data Exchange (ETDEWEB)

    Louvisse, Ana Maria Travalloni; Pereira Junior, Oswaldo de Aquino; Jesus, Rafael Ferreira de; Santos, Lino Antonio Duarte dos; Lopes, Humberto Eustaquio [PETROBRAS, Rio de Janeiro, RJ (Brazil)

    2004-07-01

    Petroleum is predominantly recovered in form of water in oil emulsions, which are stabilised by petroleum resins and asphaltenes, the colloidal disperse components of crude oil. The water phase, separated during the production process, consists of a dilute oil in water emulsion, commonly called produced water.There are a wide variety of methods for determination of oil in produced water that are commercially based on a number of technique. On line continuously monitoring shall be particularly useful in providing information to assist in optimising the separation process and also to attend the environmental legislation for discharge the produced water. There are a wide variety of on line oil in water monitors that are commercially available based on a number of technique. In this paper, a comparative evaluation was made between some methods of on line oil in water detecting. These are light scattering and ultraviolet fluorescence technique. A brief description of the optical methods will be discussed and some of associated problems and limitation are pointed. The work was done in a specific experimental set up that allows the simultaneous pumping of crude oil and water through a calibrated restriction in a pipe has been used. A permanent pressure drop induced by the restriction leads to the dispersion of the oil droplets in the water phase. The monitors based on light scattering technique tested show good agreement between monitor reading and the oil dispersion used. Otherwise for ultraviolet fluorescence based monitors show a significant effect of the variation of oil type. (author)

  11. Biofuel production by liquefaction of kenaf (Hibiscus cannabinus L.) biomass.

    Science.gov (United States)

    Meryemoğlu, Bahar; Hasanoğlu, Arif; Irmak, Sibel; Erbatur, Oktay

    2014-01-01

    In this study, kenaf biomass, its dried hydrolysate residue (solid residue left after removing water from hydrolysate) and non-hydrolyzed kenaf residue (solid residue left after hydrolysis process) were liquefied at various temperatures. Hydrolysis of biomass was performed in subcritical water condition. The oil+gas yield of biomass materials increased as the temperature increased from 250 to 300°C. Increasing temperature to 350°C resulted in decreases in oil+gas contents for all biomass feeds studied. On the other hand, preasphaltene+asphaltene (PA+A) and char yields significantly decreased with increasing the process temperature. The use of carbon or activated carbon supported Ru catalyst in the process significantly decreased char and PA+A formations. Oils produced from liquefaction of kenaf, dried kenaf hydrolysate and non-hydrolyzed kenaf residue consist of fuel related components such as aromatic hydrocarbons, benzene and benzene derivative compounds, indane and trans/cis-decalin. Copyright © 2013 Elsevier Ltd. All rights reserved.

  12. Thermal Adsorption Processing Of Hydrocarbon Residues

    Directory of Open Access Journals (Sweden)

    Sudad H. Al.

    2017-04-01

    Full Text Available The raw materials of secondary catalytic processes must be pre-refined. Among these refining processes are the deasphalting and demetallization including their thermo adsorption or thermo-contact adsorption variety. In oil processing four main processes of thermo-adsorption refining of hydrocarbon residues are used ART Asphalt Residual Treating - residues deasphaltizing 3D Discriminatory Destructive Distillation developed in the US ACT Adsorption-Contact Treatment and ETCC Express Thermo-Contact Cracking developed in Russia. ART and ACT are processes with absorbers of lift type reactor while 3D and ETCC processes are with an adsorbing reactor having ultra-short contact time of the raw material with the adsorbent. In all these processes refining of hydrocarbon residues is achieved by partial Thermo-destructive transformations of hydrocarbons and hetero-atomic compounds with simultaneous adsorption of the formed on the surface of the adsorbents resins asphaltene and carboids as well as metal- sulphur - and nitro-organic compounds. Demetallized and deasphalted light and heavy gas oils or their mixtures are a quality raw material for secondary deepening refining processes catalytic and hydrogenation cracking etc. since they are characterized by low coking ability and low content of organometallic compounds that lead to irreversible deactivation of the catalysts of these deepening processes.

  13. Mobis HRH process residue hydroconversion using a recoverable nano-catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Romocki, S.; Rhodey, G. [Mobis Energy Inc., Calgary, AB (Canada)

    2009-07-01

    This presentation described a newly developed pseudo-homogeneous catalyst (PHC) for hydroconversion of heavy hydrocarbon feeds with high levels of sulphur, nitrogen, resins, asphaltenes and metals. An active catalyst is formed in the reaction system, consisting of particles that are 2-9 nm in size and whose properties resemble those of a colloid solution at both room and reaction temperature. Residue processing with this pseudo-homogeneous catalyst system results in better cracking and hydrogenation at lower process severity. The PHC system in heavy residue hydroconversion (HRH) process achieves up to 95 per cent residue conversion at pressures below 7.3 MPa, reaction temperatures between 400 to 460 degrees C, and with feed space velocity between 1 to 2 per hour, thus rendering the PHC catalyst system suitable for deep conversion of hydrocarbon residues. As much as 95 per cent of the catalyst can be recovered and regenerated within the process. Pilot plants are in operation for the hydroconversion of Athabasca vacuum bottoms using this technology. The use of the HRH process in oilsands and refinery operations were discussed along with comparative yields and economics. tabs., figs.

  14. Toxicity of Flare and Crude Hydrocarbon Mixtures

    Directory of Open Access Journals (Sweden)

    Sonja V. Cook

    2002-01-01

    Full Text Available The toxicity of whole, saturate, and aromatic hydrocarbon mixtures from flare pit and crude oil sources were evaluated using Lumbricus terrestris. Body burden analysis was used to analyze the intrinsic toxicity of the six hydrocarbon mixtures. The major fractions of the whole mixtures, the saturate, and aromatic fractions had different intrinsic toxicities; the aromatics were more toxic than the saturates. The toxicity of the saturate and aromatic fractions also differed between the mixtures. The flare saturate mixture was more toxic than the crude saturate mixture, while the crude aromatic mixture was more toxic than the flare aromatic mixture. The most dramatic difference in toxicity of the two sources was between the flare whole and crude whole mixtures. The crude whole mixture was very toxic; the toxicity of this mixture reflected the toxicity of the crude aromatic fraction. However, the flare whole mixture was not toxic, due to a lack of partitioning from the whole mixture into the lipid membrane of the exposed worms. This lack of partitioning appears to be related to the relatively high concentrations of asphaltenes and polar compounds in the flare pit whole mixture.

  15. Aerobic remediation of petroleum sludge through soil supplementation: Microbial community analysis

    Energy Technology Data Exchange (ETDEWEB)

    Reddy, M. Venkateswar; Devi, M. Prathima; Chandrasekhar, K.; Goud, R. Kannaiah [Bioengineering and Environmental Centre (BEEC), Indian Institute of Chemical Technology CSIR-IICT, Hyderabad 500 607 (India); Mohan, S. Venkata, E-mail: vmohan_s@yahoo.com [Bioengineering and Environmental Centre (BEEC), Indian Institute of Chemical Technology CSIR-IICT, Hyderabad 500 607 (India)

    2011-12-15

    Highlights: Black-Right-Pointing-Pointer Enhanced aerobic-degradation of PAHs was noticed with increasing soil concentration. Black-Right-Pointing-Pointer Lower ring PAHs showed superior degradation over higher ring PAHs. Black-Right-Pointing-Pointer Role of dehydrogenase activity, redox pattern and dissolved oxygen was investigated. Black-Right-Pointing-Pointer Community analysis detected survival of efficient aromatic degrading microorganisms. - Abstract: The effect of soil concentration on the aerobic degradation of real-field petroleum sludge was studied in slurry phase reactor. Total petroleum hydrocarbons (TPH) and polycyclic aromatic hydrocarbons (PAHs) showed effective removal but found to depend on the soil concentration. Aromatic fraction (48.12%) documented effective degradation compared to aliphatics (47.31%), NSO (28.69%) and asphaltenes (26.66%). PAHs profile showed efficient degradation of twelve individual aromatic compounds where lower ring compounds showed relatively higher degradation efficiency compared to the higher ring compounds. The redox behaviour and dehydrogenase activity showed a linear increment with the degradation pattern. Microbial community composition and changes during bioremediation were studied using denaturing gradient gel electrophoresis (DGGE). Among the 12 organisms identified, Proteobacteria was found to be dominant representing 50% of the total population (25% of {gamma}-proteobacteria; 16.6% of {beta}-proteobacteria; 8.3% of {alpha}-proteobacteria), while 33.3% were of uncultured bacteria and 16.6% were of firmicutes.

  16. Investigation of the Physical and Molecular Properties of Asphalt Binders Processed with Used Motor Oils

    Directory of Open Access Journals (Sweden)

    Mohyeldin Ragab

    2015-01-01

    Full Text Available In this work we investigated the performance aspects of addition of used motor oils (UMO to neat and crumb rubber modified asphalts (CRMA and related that to the change of molecular size distribution of modified asphalt’s fractions; asphaltenes, saturates, naphthene aromatics, and polar aromatics. Based on the results of temperature sweep viscoelastic tests, addition of crumb rubber modifier (CRM alone or with UMO results in the formation of internal network within the modified asphalt. Based on the results of short and long term aged asphalts, the utilization of combination of UMO and CRM enhanced the aging behavior of asphalt. Bending beam rheometer was utilized to investigate the low temperature behavior of UMO modified asphalts. Based on those tests, the utilization of the UMO and CRM enhanced the low temperature properties of asphalts. Based on the results of the asphalt separation tests and the Gel Permeation Chromatography (GPC analysis, it was found that saturates and naphthene aromatics are the two asphalt fractions that have similar molecular size fractions as those of UMO. However, UMO only shifts the molecular sizes of saturates after interaction with asphalt. Results also show that polar aromatics pose higher molecular size structures than UMO.

  17. Viscosity, relaxation time, and dynamics within a model asphalt of larger molecules

    Energy Technology Data Exchange (ETDEWEB)

    Li, Derek D.; Greenfield, Michael L., E-mail: greenfield@egr.uri.edu [Department of Chemical Engineering, University of Rhode Island, Kingston, Rhode Island 02881 (United States)

    2014-01-21

    The dynamics properties of a new “next generation” model asphalt system that represents SHRP AAA-1 asphalt using larger molecules than past models is studied using molecular simulation. The system contains 72 molecules distributed over 12 molecule types that range from nonpolar branched alkanes to polar resins and asphaltenes. Molecular weights range from 290 to 890 g/mol. All-atom molecular dynamics simulations conducted at six temperatures from 298.15 to 533.15 K provide a wealth of correlation data. The modified Kohlrausch-Williams-Watts equation was regressed to reorientation time correlation functions and extrapolated to calculate average rotational relaxation times for individual molecules. The rotational relaxation rate of molecules decreased significantly with increasing size and decreasing temperature. Translational self-diffusion coefficients followed an Arrhenius dependence. Similar activation energies of ∼42 kJ/mol were found for all 12 molecules in the model system, while diffusion prefactors spanned an order of magnitude. Viscosities calculated directly at 533.15 K and estimated at lower temperatures using the Debye-Stokes-Einstein relationship were consistent with experimental data for asphalts. The product of diffusion coefficient and rotational relaxation time showed only small changes with temperature above 358.15 K, indicating rotation and translation that couple self-consistently with viscosity. At lower temperatures, rotation slowed more than diffusion.

  18. Mechanics and upscaling of heavy oil bitumen recovery by steam-over-solvent injection in fractured reservoirs method

    Energy Technology Data Exchange (ETDEWEB)

    Singh, R.; Babadagli, T. [Alberta Univ., Edmonton, AB (Canada)

    2011-01-15

    This paper discussed a numerical modelling scheme applied to the steam-over-solvent injection in fractured reservoirs (SOS-FR) method for a single-matrix block. After modelling the process at the core scale, sensitivity tests were performed to determine the optimal injection conditions for efficient oil recovery and solvent retrieval. The basic mechanisms and physics of the process were described along with the amount of injectant and the time required for recovering target oil for field-scale application. In the physics of the recovery mechanism, gravity was found to have a substantial effect on oil recovery when the matrix was exposed to solvent. Special attention was paid to the solvent retrieval rate and amount in the third cycle and the permeability reduction caused by asphaltene precipitation in the solvent injection phase; the latter factor was observed to be substantially critical for the process. An upscaling analysis yielded an encouraging straight-line relationship between the time value to reach ultimate recovery and the matrix size with a non-integer exponent less than 2. 21 refs., 1 tab., 15 figs.

  19. Guidance on air emissions and monitoring requirements during combustion of non-gaseous fuels

    Energy Technology Data Exchange (ETDEWEB)

    NONE

    2011-07-15

    These guidelines, based on technical studies conducted for Alberta Environment on the use of non-gaseous fuels for steam production in the oil sands, help project proponents and regulators with air emissions and monitoring expectations when non-gaseous fuels (i.e. bitumen, petroleum coke, and asphaltenes) are used with boilers or steam generators, and cogeneration equipment. For example, the emission guideline for sulphur dioxide (SO2) ranges from 70 to 116 (grams/gigajoules of energy input) while the oxides of nitrogen (Total NOx) range is between 40 and 50 (grams/gigajoules of energy input), depending on the efficiency of the steam generator. Three steam generator capacity sections are distinguished: less than 105 gigajoules/hour, more than 264 gigajoules/hour, and in-between. Other existing regulations, standards, and policies setting approval limits and monitoring requirements for equipment and fuels must also be respected in the environmental evaluation. For specific applications, professional judgment on necessary requirements will also apply.

  20. Biomarkers of metabolism disturbance in bivalve molluscs induced by environmental pollution with processed by-products of oil

    Directory of Open Access Journals (Sweden)

    E. V. Sukharenko

    2017-05-01

    Full Text Available Processed by-products of oil are the most common pollutants in all river and sea water. The increase in oxidative stress in bivalve molluscs was studied in both tissues of the hepatopancreas and the gill. The model for artificial treatment with processed by-products of oil was performed in a laboratory experiment with the river mollusc Dreissena polymorpha Pallas, 1771. The exposure of the molluscs over 28 days to mazut 50 mg/l induced significant increase of both final product of lipid peroxidation (LPO and antioxidant enzime activity. A significant increase in LPO was observed in the hepatopancreas and gill of D. polymorpha treated with mazut compared to the control group. Antioxidant enzyme activity of cartalase, supeoxide dismutase, glutathione reductase and glutathione-S-transferase showed a greater increase (by almost 1.5 times in the hepatopancreas than in the gill of D. polymorpha. A similar LPO growth and modulation of antioxidant enzyme activity were determined in the hepatopancreas and gill of the mussel Mytilus galloprovincialis Lamarck, 1879 collected in an area polluted with resins, hydrocarbons and asphaltenes, Donuzlav lake in the Kerch gulf. Varied cellular reactivation of the antioxidant enzyme system in the hepatopancreas rather than the gill was observed in both kinds of mollusc Dreissena and Mytilus. The obtained results are evidence of the higher sensitivity of the hepatopancreas cells of bivalve molluscs to organic pollutants compared to the gill cells.

  1. Double twist : Can-K's electric submersible twin screw pump is designed to handle the nastiest crudes

    Energy Technology Data Exchange (ETDEWEB)

    Byfield, M.

    2010-12-15

    This article described the Can-K Group of Companies' electric submersible twin screw pump (ESTSP) designed for pumping heavy crudes with high levels of asphaltenes, hydrogen sulphide, wax, and methane. The technology was awarded the 2010 winner of best production technology for a company with fewer than 100 employees. The ESTSP can pump at a greater depth than other lift technologies. The design challenges included making the pump small enough to fit inside the well casing while also able to generate the high pressures necessary for pumping heavy oil. The ESTSP can compete directly against other lift technologies, including electric submersible pumps (ESPs). In the design, two shafts are separated by a timing gear. Each shaft has short sections of interlocking screws that do not touch, which lessens tension and the need for torque, lowering electricity consumption. The ESTSP is more efficient than ESP systems, particularly in more viscous mediums with high gas-to-oil ratios. The positive displacement pump interprets only volume and does not distinguish between gas and oil, functioning with gas content up to 97 percent. ESTSP can also handle more sand than ESP because it does not rely on centrifugal force. A patented screw design also helps prevent pump seizure resulting from sand and other solids. The pump uses downhole electric motors from other manufacturers. The inherent efficiencies of twin screw pumps give the technology the potential to replace conventional ESPs. 2 figs.

  2. Influence of Polyphosphoric Acid on the Consistency and Composition of Formulated Bitumen: Standard Characterization and NMR Insights

    Directory of Open Access Journals (Sweden)

    Catarina Varanda

    2016-01-01

    Full Text Available Over the recent years, bitumen modification with polymers, acids, or mineral fillers has gained relevance to adjust its performance properties. This work reports the use of polyphosphoric acid (PPA for the modification of formulated bitumen. With this objective, an in-depth literature review on PPA modification was firstly performed. Subsequently, five individual refinery components were selected for the preparation of bitumen blends, namely, asphaltic residue, vacuum residue, and three lube oils extracts. Seven binary/ternary bitumen blends were prepared and then treated with PPA. Afterwards, the five components and the unmodified and PPA-modified bitumen were characterized by standard methods (penetration, softening point, and penetration index, SARA analysis, elemental analysis, and 31P and 1H nuclear magnetic resonance (NMR spectroscopy. The results evidenced higher asphaltenes and lower saturates/resins contents in PPA-modified bitumen. The NMR data suggest that the paraffinic chains became longer, the content of condensed aromatics increased, more substituted aromatic structures appeared, and α-hydrogen in aromatic structures diminished. These findings disclosed the improved consistency and oxidation stability of PPA-modified bitumen blends.

  3. Caractérisation des huiles lourdes et des résidus pétroliers. Symposium international, Lyon, 25-27 juin 1984 Characterization of Heavy Crude Oils and Petroleum Residues. International Symposium, 25-27 June 1984

    Directory of Open Access Journals (Sweden)

    Dorbon M.

    2006-11-01

    Full Text Available Ce symposium a permis aux chercheurs et ingénieurs qui étudient les bruts lourds et les résidus pétroliers de confronter les résultats de leurs travaux. II fut en particulier beaucoup question des asphaltènes et on a pu constater que de réels progrès avaient été réalisés en ce qui concerne la caractérisation de ces fractions. Furent également présentées les techniques d'analyse les plus aptes à fournir des informations sur ces produits ainsi que les manières spécifiques de les mettre en oeuvre. Enfin, on a vu comment l'analyse des produits lourds contribuait à la mise au point ou à l'optimisation des procédés de traitement de ces huiles. This symposium enabled research scientists and engineers working with heavy oils and petroleum residues to compare their findings. Much attention was paid to asphaltenes, and it could be seen that real progress had been made with regard to the characterization of such fractions. The analysis techniques best able to provide information were described along with the specific ways of implementing them. Then the topic of how the analysis of heavy products was contributing to the development or optimization of methods for processing such oils was discussed.

  4. Mathematical model for the prediction of the dead heavy crude oil viscosity produced in Monagas State, Venezuela

    Directory of Open Access Journals (Sweden)

    Tomás Darío Marín Velásquez

    2017-06-01

    Full Text Available Viscosity is the property of fluids to oppose movement when a cutting effort is applied on them to convey them from one point to another. Heavy oil has a high viscosity greater than 1000 cP, which makes it difficult to transport. The present work shows a mathematical model for the prediction of the viscosity of dead heavy oils produced in the fields of Monagas State, Venezuela. For the development of the work, 25 samples of oil were collected and the viscosity was measured at 5 temperatures, in addition to the API gravity and the percentage of Asphaltenes. The data were introduced in the Statgraphics Centurion XVI statistical package and through multiple regression analysis two mathematical models were obtained, 1 linear multiple and 2 multiple nonlinear; The best model being divided according to its coefficient of determination R2 and the average relative error (ARE. The selected model was compared with the Glaso, Bennison and Naseri models. The nonlinear multiple model with R2 of 0.9792 and ARE of 5.05% was obtained as the best model, surpassing the models of Glaso (35.5% ARR, Bennison (107.5% ARE and Naseri (61.7% ARE.

  5. Enhanced Heavy Oil Recovery in Mild Conditions by SO42-/TiO2-ZrO2 Solid Superacid Prepared by Different Methods

    Directory of Open Access Journals (Sweden)

    Chen Li

    2016-01-01

    Full Text Available The important key of heavy oil efficient exploring is to decrease the viscosity and increase the flowability. Solid acid catalyst is one of the commonly used catalysts to reducing the viscosity of heavy oil, but good dispersion in oil phase and better catalytic activity are difficult to achieve. Herein, ZrO2-TiO2 was selected as the fundamental catalyst because of its superior solid superacid properties, and CTAB was selected as the surfactant package coat to help enhance catalytic activity. The as-prepared catalysts were characterized systematically by TEM, XRD, FTIR, and N2 adsorption-desorption isotherms measurement. The reduction efficiency of the heavy oil viscosity achieved as high as 66.3% at 180°C. At the same time, the portion of asphaltenes and resins slipped down by 4.93% and 3.78%, respectively, while saturated and aromatic hydrocarbon component increased by 5.37% and 3.26%, respectively, indicating that our catalyst showed a good activity for reducing the viscosity and improving the quality of heavy crude oil.

  6. Polar non-hydrocarbon contaminants in reservoir core extracts

    Directory of Open Access Journals (Sweden)

    Bennett B

    2000-08-01

    Full Text Available A geochemical investigation of oils in sandstone core plugs and drill stem test oils was carried out on samples from a North Sea reservoir. A sample of diesel used as a constituent of the drilling fluids was also analysed. The aliphatic and aromatic hydrocarbons and polar non-hydrocarbons were isolated using solid phase extraction methods. GC analysis of the hydrocarbon fraction of the core extract indicated that contamination may be diesel derived. From analysis of diesel some compound classes are less likely to be affected by contamination from diesel itself including: steranes, hopanes, aromatic steroid hydrocarbons, benzocarbazoles and C0–C3-alkylphenols. Large quantities of sterols (ca. 30 mg g-1 total soluble extract were identified in the polar non-hydrocarbon fractions of the core extract petroleum, presumably resulting from contamination. The origin of sterols is likely to be due to an additive introduced into the drilling fluid. Sterols are surface active compounds and in significant quantities may affect engineering core property measurements including wettability determinations. In addition, bulk petroleum composition screening methods, such as Iatroscan, used for determining saturated and aromatic hydrocarbons, resins and asphaltenes (SARA content of core extract petroleum may also be affected.

  7. Removal Capacities of Polycyclic Aromatic Hydrocarbons (PAHs) by a Newly Isolated Strain from Oilfield Produced Water

    Science.gov (United States)

    Qi, Yi-Bin; Wang, Chen-Yu; Lv, Cheng-Yuan; Lun, Zeng-Min; Zheng, Cheng-Gang

    2017-01-01

    The polycyclic aromatic hydrocarbon (PAH)-degrading strain Q8 was isolated from oilfield produced water. According to the analysis of a biochemical test, 16S rRNA gene, house-keeping genes and DNA–DNA hybridization, strain Q8 was assigned to a novel species of the genus Gordonia. The strain could not only grow in mineral salt medium (MM) and utilize naphthalene and pyrene as its sole carbon source, but also degraded mixed naphthalene, phenanthrene, anthracene and pyrene. The degradation ratio of these four PAHs reached 100%, 95.4%, 73.8% and 53.4% respectively after being degraded by Q8 for seven days. A comparative experiment found that the PAHs degradation efficiency of Q8 is higher than that of Gordonia alkaliphila and Gordonia paraffinivorans, which have the capacities to remove PAHs. Fourier transform infrared spectra, saturate, aromatic, resin and asphaltene (SARA) and gas chromatography–mass spectrometry (GC–MS) analysis of crude oil degraded by Q8 were also studied. The results showed that Q8 could utilize n-alkanes and PAHs in crude oil. The relative proportions of the naphthalene series, phenanthrene series, thiophene series, fluorene series, chrysene series, C21-triaromatic steroid, pyrene, and benz(a)pyrene were reduced after being degraded by Q8. Gordonia sp. nov. Q8 had the capacity to remediate water and soil environments contaminated by PAHs or crude oil, and provided a feasible way for the bioremediation of PAHs and oil pollution. PMID:28241412

  8. Filtration of oil and transformation of its composition in porous media

    Energy Technology Data Exchange (ETDEWEB)

    Chakhmakhchev, V.A.; Punanova, S.A.; Zharkov, N.I.

    1981-01-01

    Experiments on filtration of oil through sandy, sandy-clayey, and sandy-carbonate mixtures which are air-dry and also saturated by bidistillate and mineral water were conducted under laborabory conditions. The original oil and the obtained filtrates underwent a broad spectrum of geochemical studies: we studied the phycical properties, the hydrocarbon, isotope, and microelement compositions. The degree of information content of the change of all these parameters of oil during filtration through the sandy-clay models is not identical. Remaining unchanged is the distribution of normal alkanes and isoprenoids. Slightly changing during filtration is the physical density, the index of refraction, the content or resin-asphaltene components, aromatic and saturated hydrocarbons. Changing most regularly and with most contrast are the following indices: optic density, content of vanadium, nickel, cobalt, copper, and the ratios V/Cu, Ni/Cu, and Co/Cu. These criteria are most applicable in estimating the vertical migration of oil through slightly permeable clay covers and interfaces.

  9. Application of Nanoparticles in Enhanced Oil Recovery: A Critical Review of Recent Progress

    Directory of Open Access Journals (Sweden)

    Xiaofei Sun

    2017-03-01

    Full Text Available The injected fluids in secondary processes supplement the natural energy present in the reservoir to displace oil. The recovery efficiency mainly depends on the mechanism of pressure maintenance. However, the injected fluids in tertiary or enhanced oil recovery (EOR processes interact with the reservoir rock/oil system. Thus, EOR techniques are receiving substantial attention worldwide as the available oil resources are declining. However, some challenges, such as low sweep efficiency, high costs and potential formation damage, still hinder the further application of these EOR technologies. Current studies on nanoparticles are seen as potential solutions to most of the challenges associated with these traditional EOR techniques. This paper provides an overview of the latest studies about the use of nanoparticles to enhance oil recovery and paves the way for researchers who are interested in the integration of these progresses. The first part of this paper addresses studies about the major EOR mechanisms of nanoparticles used in the forms of nanofluids, nanoemulsions and nanocatalysts, including disjoining pressure, viscosity increase of injection fluids, preventing asphaltene precipitation, wettability alteration and interfacial tension reduction. This part is followed by a review of the most important research regarding various novel nano-assisted EOR methods where nanoparticles are used to target various existing thermal, chemical and gas methods. Finally, this review identifies the challenges and opportunities for future study regarding application of nanoparticles in EOR processes.

  10. Analysis of petroleum oily sludge producing in petroleum field of Rio Grande do Norte, Brazil

    Energy Technology Data Exchange (ETDEWEB)

    Lima, Cicero de Souza; Lima, Regineide Oliveira; Silva, Edjane Fabiula Buriti da; Castro, Kesia Kelly Vieira de; Chiavone Filho, Osvaldo; Araujo, Antonio Souza de [Universidade Federal do Rio Grande do Norte (UFRN), RN (Brazil)

    2012-07-01

    In exploration and production of petroleum is generated solid waste different and components other. The petroleum oily sludge is a complex mix of components different (water, oil and solid). The petroleum oily sludge generally has other residues and is formed during production and operations, transport, storage and petroleum refining (atmospheric residue, vacuum residue and catalytic cracking residue). However, according to its origin, the compositions can be found quite varied for sludge. Observing the process steps production and refining is possible to locate its main sources and percentage contributions in terms of waste generation. The elemental analysis was performed with oily sludge from region and it showed different composition. For carbon element and hydrogen, small differences was observed, but for was observed greater differences for Oxygen element. The sludge has different inorganic and organic composition. The sludge from oil water separator (OWS) 2 showed a greater amount of oil (94.88%), this may indicate a residue of aggregate high for petroleum industry. In analysis of Saturates, Aromatics, Resins and Asphaltenes (SARA), the sludge from unloading showed amount high of saturates. The inorganic material separated from sludge was characterized and sludge from OWS 2 had high amount sulfur (41.57%). The sludge analyzed showed organic components high values, so it can be treated and reprocessed in process units petroleum industry. The analysis thermal degradation had a better setting for treated oily sludge. (author)

  11. Flow assurance

    Energy Technology Data Exchange (ETDEWEB)

    Mullins, O.C.; Dong, C. [Schlumberger-Doll Research Center, Cambridge, MA (United States); Elshahawi, H. [Shell Exploration and Production Company, The Hague (Netherlands)

    2008-07-01

    This study emphasized the need for considering flow assurance for producing oil and gas, particularly in high cost areas such as deepwater. Phase behaviour studies, sticking propensities, and interfacial interactions have been investigated in many laboratory studies using asphaltenes, wax, hydrates, organic and inorganic scale, and even diamondoids. However, the spatial variation of reservoir fluids has received little attention, despite the fact that it is one of the most important factors affecting flow assurance. This issue was difficult to address in a systematic way in the past because of cost constraints. Today, reservoir fluid variation and flow assurance can be considered at the outset of a project given the technological advances in downhole fluid analysis. This study described the origins of reservoir fluid compositional variations and the controversies surrounding them. It also described the indispensable chemical analytical technology. The impact of these reservoir fluid compositional variations on flow assurance considerations was also discussed. A methodology that accounts for these variations at the outset in flow assurance evaluation was also presented.

  12. Modifications structurales des résidus lors du procédé de viscoréduction Structural Changes in Residues During the Visbreaking Process

    Directory of Open Access Journals (Sweden)

    Favre A.

    2006-11-01

    Full Text Available Les asphaltènes et les maltènes d'un résidu sous vide Safaniya et ceux issus de la recette de viscoréduction correspondante sont étudiés. Vu la complexité des produits, plusieurs fractionnements sont pratiqués (chromatographie en phase liquide, chromatographie échangeuse d'ions. Les produits et leurs fractions sont ensuite caractérisés par RMN, IR, analyse élémentaire, tonométrie, diffraction et diffusion centrale des rayons X. Les résultats mettent en évidence des différences notables et permettent de comprendre le comportement des produits lourds du pétrole au cours du craquage thermique et ainsi tenter d'améliorer te taux de conversion. The asphaltenes and maltenes from a Safaniya vacuum residue and those coming from the corresponding visbreaking product are analyzed. Given the complexity of the products, several fractionations are performed (liquid chromatography, ion-exchange chromatography. The products and their fractions are then characterized by NMR, IR, elemental analysis, tonometry, X-ray diffraction and small ange X-ray scattering. The results reveal appreciable differences and enable the behavior of heavy petroleum products to be understood during thermal cracking. So an effort can be made to improve the rate of conversion.

  13. Study of the processes of radionuclides transfer, heavy metals and aero-particles among the solid, dissolved phase and the air

    International Nuclear Information System (INIS)

    Romero G, E. T.; Ordonez R, E.; Reyes G, L. R.; Jose Y, M.

    2010-01-01

    In this chapter the investigations developed in the Instituto Nacional de Investigaciones Nucleares (ININ) are presented, in collaboration with specialists in diverse fields of the science. In the first place, is presented the objective and an introduction of each one of the following projects: Study of the uranium migration through the not saturated area, and Synthesis and characterization of phosphate materials by conventional techniques, projects developed under the direction and collaboration of the Ph D. Eduardo Ordonez Regil. Identification of the chemical-morphologic composition of painting mural pigments: the blue Mayan, indigo blue, the secret of the color, and investigation of the physiochemical components of the asphaltenes and malthenes of heavy crudes and vacuum residual, with the supervision of the Ph D. Miguel Jose Yacaman. Evaluation of the water quality and type of sediments of the lake-crater The Pool: one of the seven stars of Santiago Valley, Guanajuato; Study of the sorption kinetics of Cr(Vi) in floor of a container of chromium residuals in Buenavista, Guanajuato, Mexico; Investigation of the underground water hydrochemistry of the basin of the Avenues River in Pachuca de Soto, Hidalgo, and Characterization of the particle material and modeled of the dispersion and pollutants transport in the air of the Metropolitan Area of the Toluca Valley, projects carried out under the direction and collaboration of the Ph D. Lazaro Raymundo Reyes Gutierrez. Finally, is presented the most representative of the obtained results, as well as a discussion of the same ones. (Author)

  14. Molecular Simulation Study on Modification Mechanism of Red Mud Modified Asphalt

    Science.gov (United States)

    Tao, FU; Hui-ming, BAO; xing-xing, Duan

    2017-12-01

    This article used red mud, the aluminum industrial wastes, as modified asphalt material, through the study of the routine test of modified asphalt properties, and the micro test of electron microscope scanning, infrared spectrum and differential scanning calorimetry analysis etc. to discuss its performance and modification mechanism . The test results show that after mixing red mud, asphalt’s penetration index and 15 °C ductility reduced, softening point enhanced, thus the temperature sensitivity and high temperature stability of asphalt improved; Red mud after mixing the matrix asphalt, can form a uniform, stable and matrix asphalt blending system, and improve the asphalt’s thermal stability. Using molecular simulation technology to analyze the asphalt with the temperature change of energy and find in the process of asphalt melting, the largest is the key to influence on bituminous, and van der waals energy is small. It concludes that red mud -modified asphalt material is mainly controlled by bond energy, in order to obtain its favorable property of modification mechanism, red mud of senior activation and molecular bond energy of asphalt is needed to be enhanced.The results of molecular simulation show that the main component of hematite in red mud is the most adsorbed in the asphalt, the asphaltene is the second, the colloid is the worst, but the adsorption capacity of the colloid is the highest.

  15. Photolysis of petroleum

    International Nuclear Information System (INIS)

    Bobra, M.

    1992-05-01

    A study was conducted to examine the chemical and physical changes that occur in oils as a result of photooxidation. A literature review of recent studies in petroleum photochemistry revealed reported effects of photo-induced reactions in petroleum, including changes in color, polymerization, solidification, increases in solubility and toxicity, and changes in interfacial properties. A list of products reported as a result of photolysis of petroleum is presented, including such compounds as aldehydes, ketones, esters, and lactones. The photoreactivity of various petroleum components is discussed and mechanisms of photooxidation of petroleum are suggested. In the experimental portion of the study, a variety of crude oils and petroleum products were used to determine how different oils are affected by photolysis, and to examine the importance of photolysis as a weathering process. Photooxidation products from several oils were isolated and identified, including aliphatic and aromatic acids, alcohols, and phenols. Some physical manifestations attributed to photolysis included yellowing, formation of precipitates or crusts, increases in density and viscosity with time, increases of asphaltene content in some oils, changes in pH of the surrounding water, and emulsification. 51 refs., 38 figs., 18 tabs

  16. CFD modeling of fouling in crude oil pre-heaters

    International Nuclear Information System (INIS)

    Bayat, Mahmoud; Aminian, Javad; Bazmi, Mansour; Shahhosseini, Shahrokh; Sharifi, Khashayar

    2012-01-01

    Highlights: ► A conceptual CFD-based model to predict fouling in industrial crude oil pre-heaters. ► Tracing fouling formation in the induction and developing continuation periods. ► Effect of chemical components, shell-side HTC and turbulent flow on the fouling rate. - Abstract: In this study, a conceptual procedure based on the computational fluid dynamic (CFD) technique has been developed to predict fouling rate in an industrial crude oil pre-heater. According to the developed CFD concept crude oil was assumed to be composed of three pseudo-components comprising of petroleum, asphaltene and salt. The binary diffusion coefficients were appropriately categorized into five different groups. The species transport model was applied to simulate the mixing and transport of chemical species. The possibility of adherence of reaction products to the wall was taken into account by applying a high viscosity for the products in competition with the shear stress on the wall. Results showed a reasonable agreement between the model predictions and the plant data. The CFD model could be applied to new operating conditions to investigate the details of the crude oil fouling in the industrial pre-heaters.

  17. Metal Oxide Nanoparticles Supported on Macro-Mesoporous Aluminosilicates for Catalytic Steam Gasification of Heavy Oil Fractions for On-Site Upgrading

    Directory of Open Access Journals (Sweden)

    Daniel López

    2017-10-01

    Full Text Available Catalytic steam gasification of extra-heavy oil (EHO fractions was studied using functionalized aluminosilicates, with NiO, MoO3, and/or CoO nanoparticles with the aim of evaluating the synergistic effect between active phase and the support in heavy oil on-site upgrading. Catalysts were characterized by chemical composition through X-ray Fluorescence, surface area, and pore size distribution through N2 adsorption/desorption, catalyst acidity by temperature programmed desorption (TPD, and metal dispersion by pulse H2 chemisorption. Batch adsorption experiments and catalytic steam gasification of adsorbed heavy fractions was carried out by thermogravimetric analysis and were performed with heavy oil model solutions of asphaltenes and resins (R–A in toluene. Effective activation energy estimation was used to determine the catalytic effect of the catalyst in steam gasification of Colombian EHO. Additionally, R–A decomposition under inert atmosphere was conducted for the evaluation of oil components reactions with active phases and steam atmosphere. The presence of a bimetallic active phase Inc.reases the decomposition of the heavy compounds at low temperature by an increase in the aliphatic chains decomposition and the dissociation of heteroatoms bonds. Also, coke formation after steam gasification process is reduced by the application of the bimetallic catalyst yielding a conversion greater than 93%.

  18. Bioremediation of petroleum hydrocarbons in soil environments

    International Nuclear Information System (INIS)

    Rowell, M.J.; Ashworth, J.; Qureshi, A.A.

    1992-12-01

    The bioremediation of petroleum hydrocarbons in soil environments was reviewed via a literature survey and discussions with workers in relevant disciplines. The impacts of hydrocarbons on soil are discussed along with a range of methods available to assist in their decomposition by soil microorganisms. The range of petroleum-based materials considered includes conventional and synthetic crude oils, refined oils, sludges, asphalts and bitumens, drilling mud residues, creosote tars, and some pesticides. The degradability of hydrocarbons largely depends upon their aqueous solubility and their adsorption on soil surfaces and, therefore, is related to their molecular structures. The ease of decomposition decreases with increasing complexity of structure, in the order aliphatics > aromatics > heterocyclics and asphaltenes (most recalcitrant). Most soils contain an adequate population of microorganisms and hence bioaugmentation may only be needed in special circumstances. Decomposition is fastest in soils where the hydrocarbon loading rate, aeration, nutrition, moisture, and pH are all optimized. At spill sites there is little control over the application rate, although containment measures can assist in either limiting contamination or distributing it more evenly. The enhancement of bioremediation is discussed in light of all these factors. Other techniques such as enhanced aeration, hydrocarbon decomposition by anaerobic processes, surfactants, and burning are also discussed. 211 refs., 11 figs., 10 tabs

  19. Identifying the effect of polar constituents in coal-derived NAPLs on interfacial tension

    Energy Technology Data Exchange (ETDEWEB)

    Jianzhong Zheng; Susan E. Powers [Clarkson University, Potsdam, NY (United States). Dept. of Civil and Environmental Engineering

    2003-07-15

    Interfacial tension, which is a critical variable affecting multiphase flow of nonaqueous phase liquids (NAPLs) in the subsurface, varies greatly with the composition of complex NAPLs recovered from field sites. Much of this variability stems from the presence of acid and base molecules in the NAPL mixture. The interfacial tension and acid and base concentration in six coal-derived NAPLs were measured. Creosotes generally have lower interfacial tensions due to their higher concentrations of organic acid and base macromolecules as compared with coal tar samples. Interfacial tension is a function of pH, with lower values measured at pH greater than approximately 9. At a neutral pH, the interfacial tensions are inversely proportional to the total acid concentration. Asphaltenes in these coal-derived NAPLs account for most of the acid and base constituents. It is found in this study that acid and base numbers are valuable indicators of interfacial tension and, therefore, the capillary phenomena associated with multiphase flow behavior of NAPLs in the subsurface. 29 refs., 5 figs., 2 tabs.

  20. Co-contaminated sites: Biodegradation of fossil fuels in the presence of PCBs

    International Nuclear Information System (INIS)

    Morris, P.J.; Shelton, M.E.; Chapman, P.J.

    1995-01-01

    Polychlorinated biphenyl (PCB)-contaminated sites are often co-contaminated with fossil fuels making biodegradation of the fossil fuel components of two PCB-contaminated sites: (1) a former racing Drag Strip soil contaminated with Aroclor 1242 and (2) a sediment from Silver Lake contaminated with Aroclor 1260. The sandy surface soil at the Drag Strip site contains 1.9% organic carbon and 1.5% fossil fuel component. Analysis of the solvent-extractable organic fraction, by alumina column chromatography, shows the distribution of organics to be 91.2% hydrocarbons, 7.8% polars, and 1.1% asphaltenes. This oil is extremely weathered and contains few readily biodegradable components. Enrichments have yielded undefined mixed cultures of bacteria capable of extensive degradation of components of both the Drag Strip and Silver Lake site materials. One culture, enriched from a creosote-contaminated soil adjacent to a utility pole, transformed approximately 28% and 37% (by weight) of the Drag Strip and Silver Lake oils, respectively. While the presence of fossil fuels has been shown to inhibit aerobic PCB degradation, the studies show that the presence of PCBs negatively impacts fossil fuel biodegradation. Continuing studies will examine the nature of PCB inhibition of fossil fuel biodegradation

  1. HYDRO-IMP technology for upgrading of heavy petroleum

    Directory of Open Access Journals (Sweden)

    Хорхе Анчита

    2017-04-01

    Full Text Available Hydroprocessing is one of the most important processes in petroleum refining industry, not only for upgrading of heavy oils but also for producing low-impurity content fuels and preparing feeds for various conversion processes. Experimental results obtained in pilot plant and semi-commercial scales for hydroprocessing of heavy oils are reported in this work. Mexican heavy crude oils (10, 13 and 16°API with high amount of impurities were used for all tests. Hydroprocessing was conducted at moderate reaction severity in two fixed-bed reactors in series. Removals of sulfur, metals and asphaltenes, as well as changes of API gravity and viscosity were monitored at different reaction conditions with time-on-stream. Upgraded oils with reduced amounts of impurities and increased API were obtained, keeping sediment formation below maximum allowable content. Removal of impurities was higher in semi-commercial scale compared with pilot plant test. Have been proved that the heavier the feed the greater the gain in product quality. For instance, 10°API crude can increase its gravity up to ~22°API (Δ°API = 12, while 16°API crude increases its gravity up to ~25°API (Δ°API = 9. Sediment formation was also kept below 0.05 wt % and no other problems (excessive reactor delta-P, plugging, etc. were observed during the test.

  2. Choosing mineral carrier of nanoscale additives for asphalt concrete

    Directory of Open Access Journals (Sweden)

    Inozemtsev Sergey Sergeevich

    2014-03-01

    Full Text Available At present time the operation life of the majority of roads is essentially shorter than required. The reason for it is the increase in traffic intensity and axle loads of automobile transport. The obvious reasons for early wear of roads are the low quality of the components used and low industrial standards while producing asphalt pavement. In this paper the mineral material was selected as a carrier of nanoscale additives for asphalt. The optimal modes for grinding mineral materials were identified, which provide correspondence of their structure parameters with the developed model. The influence of different mineral nanomodifier carriers on the structure formation processes was estimated. It is shown that among a number of mineral materials diatomite has high activity in relation to the bitumen, because it has a highly porous structure. It is also shown that as a result of lighter fractions of bitumen adsorption on the border of phase interface, diatomite and bitumen changes from the free state to the film, and solvate shell of bitumen is saturated with asphaltenes. With the help of IR spectroscopy the authors defined the nature of the diatomite and bitumen interaction and proved that in the process of their interaction there occurs physical adsorption with additional absorption of bitumen components into the pore space of diatomite grains.

  3. An investigation of problematic solids in oil sands processing : separation and characterization of organic matter strongly bound to oil sands solids

    Energy Technology Data Exchange (ETDEWEB)

    McCracken, T.; Woods, J.R.; Kung, J.; Fu, D.; Kingston, D.; Kotlyar, L.S. [National Research Council of Canada, Ottawa, ON (Canada). Inst. for Chemical Process and Environmental Technology; Sparks, B.D. [V. Bede Technical Associates, Ottawa, ON (Canada)

    2009-07-01

    Some of the solid fractions in Athabasca oilsands are associated with strongly bound organic matter that is insoluble in toluene, a solvent commonly used to extract bitumen. The presence of toluene insoluble organic matter (TIOM) increases oil wettability of solids which may adversely affect the release of bitumen from the oilsands. Some of the solid material from the coking operation may be carried over to downstream operations where it can cause fouling. This study used supercritical fluid extraction with methanol to remove TIOM from oilsands after extraction of bitumen by toluene. The methanol extract (ME) is soluble in toluene and was analyzed. Results were compared with corresponding bitumen fractions prepared using a modified HPLC SARA separation technique. Number average molecular weights for the ME were similar to those for resins separated from bitumen. The study also showed that the number of alkyl substituents on aromatic ring systems and the lengths of paraffinic straight chains for resins and ME samples were similar, with only minor differences in terms of H/C atomic ratios and aromaticities. The ME was more polar than the resin and asphaltene fractions, which may explain the selective adsorption of this fraction. tabs., figs.

  4. Heavy oil processing impacts refinery and effluent treatment operations

    Energy Technology Data Exchange (ETDEWEB)

    Thornthwaite, P. [Nalco Champion, Northwich, Cheshire (United Kingdom)

    2013-11-01

    Heavy oils are becoming more common in Europe. The processing of heavier (opportunity or challenge) crudes, although financially attractive, introduce additional challenges to the refiner. These challenges are similar whether they come from imported crudes or in the future possibly from shale oils (tight oils). Without a strategy for understanding and mitigating the processing issues associated with these crudes, the profit potential may be eroded by decreased equipment reliability and run length. This paper focuses on the impacts at the desalter and how to manage them effectively while reducing the risks to downstream processes. Desalters have to deal with an increased viscosity, density (lower API gravity), higher solids loading, potential conductivity issues, and asphaltene stability concerns. All these factors can lead to operational problems impacting downstream of the desalter, both on the process and the water side. The other area of focus is the effluent from the desalter which can significantly impact waste water operations. This can take the form of increased oil under-carry, solids and other contaminants originating from the crudes. Nalco Champion has experience in working with these challenging crudes, not only, Azeri, Urals and African crudes, but also the Canadian oil sands, US Shale oil, heavy South American crudes and crudes containing metal naphthenates. Best practices will be shared and an outlook on the effects of Shale oil will be given. (orig.)

  5. DEVELOPMENT OF SHALLOW VISCOUS OIL RESERVES IN NORTH SLOPE

    Energy Technology Data Exchange (ETDEWEB)

    Kishore K. Mohanty

    2004-12-01

    North Slope of Alaska has huge oil deposits in heavy oil reservoirs such as Ugnu, West Sak and Shrader Bluff etc. The viscosity of the last two reservoir oils vary from {approx}30 cp to {approx}3000 cp and the amount in the range of 10-20 billion barrels. High oil viscosity and low formation strength impose problems to high recovery and well productivity. Water-alternate-gas injection processes can be effective for the lower viscosity end of these deposits in West Sak and Shrader Bluff. Several gas streams are available in the North Slope containing NGL and CO{sub 2} (a greenhouse gas). The goal of this research is to develop tools to find optimum solvent, injection schedule and well-architecture for a WAG process in North Slope shallow sand viscous oil reservoirs. Coreflood, quarter 5-spot study, compositional simulation, wettability, relative permeability study and streamline-based simulation were conducted in this project. 1D compositional simulation results agree reasonably well with those of the slim tube experiments. Injection of CO{sub 2}-NGL is preferable over that of PBG-NGL. MME is sensitive to pressure (in the range of 1300-1800 psi) for the injection of PBG-NGL, but not for CO{sub 2}-NGL. Three hydrocarbon phases form in this pressure range. As the mean thickness of the adsorbed organic layer on minerals increases, the oil-water contact angle increases. The adsorbed organic films left behind after extraction of oil by common aromatic solvents used in core studies, such as toluene and decalin, are thinner than those left behind by non-aromatic solvents, such as cyclohexane. The force of adhesion for minerals aged with just the asphaltene fraction is similar to that of the whole oil implying that asphaltenes are responsible for the mixed-wettability in this reservoir. A new relative permeability model for a four-phase, mixed-wet system has been proposed. A streamline module is developed which can be incorporated in an existing finite-difference based

  6. Multiscale nuclear magnetic relaxation dispersion of complex liquids in bulk and confinement.

    Science.gov (United States)

    Korb, Jean-Pierre

    2018-02-01

    The nuclear magnetic relaxation dispersion (NMRD) technique consists of measurement of the magnetic-field dependence of the longitudinal nuclear-spin-lattice relaxation rate 1/T 1 . Usually, the acquisition of the NMRD profiles is made using a fast field cycling (FFC) NMR technique that varies the magnetic field and explores a very large range of Larmor frequencies (10 kHz relaxation is sensitive. The FFC technique thus offers opportunities on multiple scales of both time and distance for characterizing the molecular dynamics and transport properties of complex liquids in bulk or embedded in confined environments. This review presents the principles, theories and applications of NMRD for characterizing fundamental properties such as surface correlation times, diffusion coefficients and dynamical surface affinity (NMR wettability) for various confined liquids. The basic longitudinal and transverse relaxation equations are outlined for bulk liquids. The nuclear relaxation of a liquid confined in pores is considered in detail in order to find the biphasic fast exchange relations for a liquid at proximity of a solid surface. The physical-chemistry of liquids at solid surfaces induces striking differences between NMRD profiles of aprotic and protic (water) liquids embedded in calibrated porous disordered materials. A particular emphasis of this review concerns the extension of FFC NMR relaxation to industrial applications. For instance, it is shown that the FFC technique is sufficiently rapid for following the progressive setting of cement-based materials (plasters, cement pastes, concretes). The technique also allows studies of the dynamics of hydrocarbons in proximity of asphaltene nano-aggregates and macro-aggregates in heavy crude oils as a function of the concentration of asphaltenes. It also gives new information on the wettability of petroleum fluids (brine and oil) embedded in shale oil rocks. It is useful for understanding the relations and correlations

  7. Expediting the chemistry of hematite nanocatalyst for catalytic aquathermolysis of heavy crude oil

    Science.gov (United States)

    Khalil, Munawar

    In upstream exploration and production of heavy and extra heavy oil, catalytic aquathermolysis is a process where steam (along with catalyst) is injected into the reservoir to improve oil production. The improvement of oil production has been associated with the reduction of heavy oil's viscosity due to the degradation of large hydrocarbon molecules (resin and asphaltene fractions) which mostly the result of desulphurization of organosulphur compounds. In this work, the potential of hematite (alpha-Fe2O3) nanoparticles, a nontoxic, inexpensive and the most stable phase of iron oxide, was investigated for aquathermolysis application. This dissertation encompasses the synthesis, surface modification, catalytic activity, and catalysis mechanism of hematite nanoparticles in aquathermolysis. In the first part of this study, a simple hydrothermal method was successfully developed to synthesize hematite nanoparticles with high purity and good crystallinity. Using this method, the size, crystal's growth rate, shape, and dispersity of the nanoparticles can be controlled by the amount of iron precursor, precipitation agent, temperature and reaction time. Furthermore, the surface chemistry of hematite nanoparticle was modified in order to improve particle dispersibility in hydrocarbon phase. Based on the result, oleic acid (OA) was successfully grafted on the surface of hematite nanoparticles by forming a monodentate interaction and changed the surface property of the nanoparticles from hydrophilic to hydrophobic. As the result, nanoparticles were able to be transferred from aqueous phase to non-polar phase, vice versa, depending on the amount of oleic acid used for modification. In the third part of this work, the catalytic activity and catalytic mechanism of hematite nanoparticles to catalyze desulphurization reaction were studied. It is found that hematite nanoparticles have a good catalytic activity to decompose a highly stable aromatic organosulphur compound, i

  8. The use of modified tyre derived fuel for compression ignition engines.

    Science.gov (United States)

    Pilusa, T J

    2017-02-01

    This study investigated physical and chemical modification of tyre-derived fuel oil (TDFO) obtained from pyrolysis of waste tyres and rubber products for application as an alternative fuel for compression ignition engines (CIE's). TDFO collected from a local waste tyre treatment facility was refined via a novel "oxidative gas-phase fractional distillation over 13× molecular sieves" to recover the light to medium fractions of the TDFO while oxidising and capturing some sulphur compounds in a gas phase. This was followed by desulphurization and chemical modification to improve cetane number, kinematic viscosity and fuel stability. The resulting fuel was tested in an ADE407T truck engine to compare its performance with petroleum diesel fuel. It was discovered that gas phase oxidative fractional distillation reduces the low boiling point sulphur compounds in TDFO such as mercaptans. Using petroleum diesel fuel as a reference, it was observed that the produced fuel has a lower cetane number, flash point and viscosity. On storage the fuel tends to form fibrous microstructures as a result of auto-oxidation of asphaltenes present in the fuel. Mixtures of alkyl nitrate, vinyl acetate, methacrylic anhydride, methyl-tert butyl ether, n-hexane and n-heptane were used to chemically modify the fuel in accordance with the minimum fuel specifications as per SANS 342. The engine performance tests results did not show any sign of engine ceasing or knocking effect. The power-torque trend was very consistent and compared well with petroleum diesel fuelled engine. The levels of total sulphur are still considerably high compared to other cleaner fuel alternatives derived from zero sulphur sources. Copyright © 2016. Published by Elsevier Ltd.

  9. Characterization of coal-derived liquids and other fossil-fuel-related materials employing mass spectrometry. Final report, September 30, 1976-September 29, 1980

    Energy Technology Data Exchange (ETDEWEB)

    Scheppele, S E

    1982-05-01

    A document was prepared which assessed the state-of-the art in the mass spectrometric characterization of fossil fuel materials and the relevance of these data to the fossil fuel industry. A Kratos DS50 SM data system was successfully interfaced to a CEC 21-110B mass spectrometer. Communications between the NOVA 3/12 computer in the data system and the OSU central computer were established. A Grant Comparator/Microdensitometer was acquired and made operational. Plans were developed and hardware acquired for interfacing the densitometer to the NOVA 3/12 computer. A quartz direct introduction probe was acquired for the CEC 21-110B. A temperature controller for the probe was acquired and interfaced to the slow speed ADC on the auxillary board in the data system/mass spectrometer interface. The combined FI/EI source was modified to operate in the FD mode and an apparatus was fabricated for conditioning FD emitters. A CSI supergrater 3 was interfaced to the PE 3920 gas chromatograph. The upgraded facility was used to develop mass spectrometric methods for the characterization of fossil fuel materials and to apply methods to the characterization of these materials. Activities included: (1) initial development of field-ionization mass spectrometry for the characterization of saturated hydrocarbons, (2) computerization of the technique of probe microdistillation/mass spectrometry, (3) initation of the development of a new method for the computer assisted assignment of formulas to ion masses, (4) characterization of neutral fractions from a hydrotreated tar-sands oil, and (5) characterization of coal-derived oils and asphaltenes.

  10. Correlating Bacharach opacity in fuel oil exhaust. Prediction of the operating parameters that reduce it; Correlation de l'opacite Bacharach des gaz d'echappement. Prediction des parametres operateurs qui la reduisent

    Energy Technology Data Exchange (ETDEWEB)

    Blanco, M.; Coello, J.; Maspoch, S.; Puigdomenech, A. [Universitat Autonoma de Barcelona, Dept. de Quimica (Spain); Peralta, X.; Gonzalez, J.M.; Torres, J. [Asfaltos Espanoles SA, Refineria de Tarragona (Spain)

    2000-07-01

    A study was conducted with a view to determining the steps to be taken in order to control the Bacharach opacity of smoke released by different types of engines powered by fuel oil through the same chimney. A statistical model was constructed to relate Bacharach opacity to the operational parameters of the burning equipment on the basis of information recorded during its routine functioning over a period of about one year, with no laboratory experiments nor intentional alteration of such parameters. Different chemo-metric tools were applied to the data recorded over a period long enough to ensure a good model. Owing to the high complexity of the data handled (equipment parameters, fuel oil properties, operating conditions, etc.), the model was constructed by using different tools that were tested in order of increasing complexity. Thus, a Principal Component Analysis (PCA) was initially conducted on the variables defining the different types of fuel oil used in order to suppress their high correlation. The scores obtained from this analysis were used as the fuel data in the subsequent steps. Owing to the high complexity of the parameters involved, linear regression methods were not functional, so the non-linear regression method Alternating Conditional Expectations (ACE) had to be used instead to determine the influence of these parameters on Bacharach opacity. After the model was constructed, the parameters that govern opacity were determined and the model was experimentally validated by exploring the variables that can be modified at plant level (viz. the combination of conradson coke and asphaltenes in the fuel, the oil viscosity at burner and the proportion of oxygen in the furnace). Changes in these variables were found to alter the properties of the stack; also, the predictions of the ACE model were confirmed. Consequently, the proposed methodology allows the effective control of smoke released by the equipment. (authors)

  11. XANES spectroscopy of sulfur in earth materials

    Energy Technology Data Exchange (ETDEWEB)

    Fleet, M.E. [University of Western Ontario, London, ON (Canada). Dept. of Earth Science

    2005-12-15

    X-ray absorption near-edge structure (XANES) spectroscopy is the ideal non-destructive technique for characterizing and quantifying S species in compositionally complex natural materials such as silicate glasses and minerals, coals, asphalts and asphaltenes, kerogens and humic substances. Sulfur absorption edges represent the transition of S 1s and 2p core electrons to unoccupied antibonding orbitals at the bottom of the conduction band. Shifts in the position of the absorption-edge feature of S K- and L-edge XANES spectra constitute a chemical ruler for oxidation state of both inorganic and organic species of S. However, chemical state of S in earth materials is most readily assigned by comparing the overall XANES profile with spectra for reference compounds. Sulfur XANES spectra are reviewed for pyrite, troilite, pyrrhotite and NiAs-type Co{sub 0.923}S and Ni{sub 0.923}S, niningerite (NI-S), oldhamite (CaS), alabandite (MnS) and cubic FeS, and sphalerite and related phases, its well as for selected solid-solutions of the monosulfides. Sulfur XANES spectra for FeS, CoS, NiS, MgS, CaS, MnS and ZnS have been simulated by multiple scattering calculations. Various applications of S K- and L-edge XANES fingerprinting are discussed, including speciation of inorganic S in basaltic glasses, and identification of organic functional groups of S in coals, kerogens and humic substances extracted from subtropical soils and marine sediments.

  12. In Situ Catalytic Upgrading of Heavy Crude with CAPRI: Influence of Hydrogen on Catalyst Pore Plugging and Deactivation due to Coke

    Directory of Open Access Journals (Sweden)

    Abarasi Hart

    2018-03-01

    Full Text Available Heavy crude oil is known to have low hydrogen-to-carbon ratios compared to light oil. This is due to the significant content of carbon-rich species such as resins and asphaltenes; hence their upgrading is commonly through carbon-rejection. However, carbon-rejection promotes rapid fouling of catalyst and pore plugging, yielding low upgraded oil and consequently low fuel distillate fractions when distilled. The roles of hydrogen-addition on in situ catalytic upgrading were investigated at pre-established conditions (425 °C, LHSV 11.8 h−1, and 20–40 bars using a simulated fixed-bed reactor that mimics the annular sheath of catalyst (CAPRI surrounding the horizontal producer well of the Toe-to-Heel Air Injection (THAI process. It was found that with H-addition, the upgraded oil American Petroleum Institute (API gravity increased to about 5° compared to 3° obtained with N2 above 13° (THAI feed oil. The fuel distillate fractions increased to 62% (N2, 20 bar, 65% (H2, 20 bar, and 71.8% (H2, 30 bar relative to 40.6% (THAI feed oil; while the coke contents of the catalyst after experiments were 35.3 wt % (N2, and 27.2 wt % (H2. It was also found that catalyst pore plugging and deactivation due to coke was significantly lower under hydrogen than with nitrogen; hence the catalyst is less susceptible to coke fouling when the upgrading reaction is carried out under hydrogen. The coke fouling further decreases with increasing hydrogen pressure while the API gravity of the upgraded oil marginally increases by 0.3° for every 10 bar increase in pressure from 20 to 40 bar.

  13. Property Analysis of Exfoliated Graphite Nanoplatelets Modified Asphalt Model Using Molecular Dynamics (MD Method

    Directory of Open Access Journals (Sweden)

    Hui Yao

    2017-01-01

    Full Text Available This Molecular Dynamics (MD simulation paper presents a physical property comparison study between exfoliated graphite nanoplatelets (xGNP modified and control asphalt models, including density, glass transition temperature, viscosity and thermal conductivity. The three-component control asphalt model consists of asphaltenes, aromatics, and saturates based on previous references. The xGNP asphalt model was built by incorporating an xGNP and control asphalt model and controlling mass ratios to represent the laboratory prepared samples. The Amber Cornell Extension Force Field (ACEFF was used with assigned molecular electro-static potential (ESP charge from NWChem analysis. After optimization and ensemble relaxation, the properties of the control and xGNP modified asphalt models were computed and analyzed using the MD method. The MD simulated results have a similar trend as the test results. The property analysis showed that: (1 the density of the xGNP modified model is higher than that of the control model; (2 the glass transition temperature of the xGNP modified model is closer to the laboratory data of the Strategic Highway Research Program (SHRP asphalt binders than that of the control model; (3 the viscosities of the xGNP modified model at different temperatures are higher than those of the control model, and it coincides with the trend in the laboratory data; (4 the thermal conductivities of the xGNP modified asphalt model are higher than those of the control asphalt model at different temperatures, and it is consistent with the trend in the laboratory data.

  14. The life cycle greenhouse gas emissions implications of power and hydrogen production for oil sands operations

    International Nuclear Information System (INIS)

    McKellar, J.M.; Bergerson, J.A.; MacLean, H.L.

    2009-01-01

    'Full text:' The Alberta Oil Sands represent a major economic opportunity for Canada, but the industry is also a significant source of greenhouse gas (GHG) emissions. One of the sources of these emissions is the use of natural gas for the production of electricity, steam and hydrogen. Due to concerns around resource availability and price volatility, there has been considerable discussion regarding the potential replacement of natural gas with an alternative fuel. While some of the options are non-fossil and could potentially reduce GHG emissions (e.g., nuclear, geothermal, biomass), others have the potential to increase emissions. A comparative life cycle assessment was completed to investigate the relative GHG emissions, energy consumption and financial implications of replacing natural gas with coal, coke, asphaltenes or bitumen for the supply of electricity, steam and hydrogen to oil sands operations. The potential use of carbon capture and storage (CCS) was also investigated as a means of reducing GHG emissions. Preliminary results indicate that, without CCS, the natural gas systems currently in use have lower life cycle GHG emissions than gasification systems using any of the alternative fuels analysed. However, when CCS is implemented in both the coke gasification and natural gas systems, the coke systems have lower GHG emissions and financial costs than the natural gas systems (assuming a 30-year project life and a natural gas price of 6.5 USD/gigajoule). The use of CCS does impose a financial penalty though, indicating that it is unlikely to be implemented without some financial incentive. While this study has limitations and uncertainties, the preliminary results indicate that although the GHG emissions of oil sands development pose a challenge to Canada, there are opportunities available for their abatement. (author)

  15. A Theoretical Investigation of the Structure and Reactivity of the Molecular Constituents of Oil Sand and Oil Shale

    Energy Technology Data Exchange (ETDEWEB)

    Parish, Carol A. [Univ. of Richmond, VA (United States)

    2016-11-28

    We used a variety of small organic models of asphaltenes to investigate the molecular mechanism for the high temperature decomposition that would take place as part of the oil refinery process. We determined that the decomposition is initiated via four different types of hydrogen migration reactions. According to the energetics of the reactions, the dominant 1,2-H shift mechanism involves two competitive product channels, namely, C2H2 + CH2CS and CS + CH3CCH. The minor channels include the formation of CS + CH2CCH2, H2S + C4H2, HCS + CH2CCH, CS + CH2CHCH, H + C4H3S, and HS + C4H3. We also investigated the alkyl substitution effect by exploring the decomposition pathways of models with alkyl arms. The energetics of such systems were very similar to that for unsubstituted model compounds, which suggests that asphaltene alkylation may not play a significant role in the decomposition of asphaltene compounds. This work was published in the Journal of Physical Chemistry A 2011, 115, 2882-2891. A MECHANISTIC STUDY OF THE 2-THIENYLMETHYL + HO2 RADICAL RECOMBINATION REACTION Radicals are molecules which contain single electrons. They are very reactive. Radical recombination reactions are important in the combustion of fuel oils. Shale oil contains radicals. We used quantum mechanics to explore the reactivity of shale oil model radical compounds. Seventeen product channels corresponding to either addition/elimination or direct hydrogen abstraction were characterized. Direct hydrogen abstraction proceeds via a weakly bonded complex, which leads to 2-methylthiophene, 2-methylene-2,3-dihydrothiophene or 2-methylene-2,5-dihydrothiophene depending upon the 2-thienylmethyl radical reaction site. The addition pathway for the two radical reactants is barrierless with the formation of three adducts, as distinguished by HO

  16. First commercial HDHPLUS{sup R}/SHP plant in Puerto La Cruz refinery, Venezuela

    Energy Technology Data Exchange (ETDEWEB)

    Negretti, V. [PDVSA Petroleos de Venezuela SA, Caracas (Venezuela, Bolivarian Republic of); Rivas, G. [INTEVEP, Caracas, (Venezuela, Bolivarian Republic of); Funatsu, S. [JGC Corp., Yokohama (Japan)

    2009-07-01

    Plans are underway to upgrade Petroleos de Venezuela SA's Puerto La Cruz (PLC) refinery by installing the first commercial HDHPLUS/SHP unit licensed by INTEVEP. This paper presented the main features of the HDHPLUS/SHP technology; a description of the overall project, including the process flow scheme and plot plan; and achievements during the Front-end Engineering and Design (FEED) stage. HDHPLUS is a hydroconversion process that converts vacuum residue (VR) of Orinoco extra heavy crude oil into lighter materials. A two-train HDHPLUS/SHP complex has been incorporated into the PLC refinery to process a total of 50,000 BPSD of VR with more than a 85 per cent VR conversion rate. The PLC refinery will be able to process much heavier crude and improve the product slate without depending on products imported from other PDVSA refineries. HDHPLUS uses slurry bed technology to achieve deep hydrocracking of the heavy residue. Most of the hydroconverted materials are sent to the SHP unit for further hydrotreating and hydrocracking while unconverted residue in the HDHPLUS unit is sent to the flaker unit for solidification via a vacuum flash tower. This process enables converting almost any type of feedstock without any limitation on metals, conradson carbon and asphaltene levels. Most of the facilities and equipment, such as piping, pumps, valves, furnaces, heat exchangers and vessels in the HDHPLUS unit, reactors and high-pressure-high-temperature separator, must be designed for slurry service, because the HDHPLUS process uses slurry bed reaction technology and coke particles are present in the feed. Up to 114 volume per cent liquid yield can be obtained. 2 tabs., 4 figs.

  17. Formation of organic solid phases in hydrocarbon reservoir fluids. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Andersen, S.I.; Lindeloff, N.; Stenby, E.H.

    1998-12-31

    The occurrence of solid phases during oil recovery is a potential problem. The present work has mainly been concerned with wax formation due to cooling of oils with a large paraffin content. 8 oils have been included in this project, although only a few of these have till now been subject to all the experimental techniques applied. The oils and wax fractions from these have been characterized using techniques such as GC-MS and Ftir. The goal has in part been to get a detailed description of the oil composition for use in model evaluation and development and in part to get a fundamental understanding of waxy oil properties and behaviour. A high pressure (200 bar) equipment has been developed for automatic detection of wax appearance using a filtration technique and laser light turbidimetry. The latter was found to be far superior to the filtration. The filtration was used to sample the incipient solid phase for characterization. However entrapment of liquid in the filters currently used have hampered this part. A number of model systems and one gas condensate have been investigated. The GC-MS procedure was found only to been able to detect molecules up to n-C45 and the group type analysis was not accurate enough for modelling purposes. Using Ftir it was obvious that incipient phases may contain very complex molecules (asphaltenes) which are not captured by GC-MS especially when fractionation is done using the acetone precipitation at elevated temperature. The latter fractionation procedure has been investigated thoroughly as a tool for understanding wax distribution etc. Within thermodynamic modelling a delta lattice parameter model has been developed which incorporates the non-ideality of the solid phases into the calculation of SLE. The non-ideality is estimated from pure component properties. A new algorithm for phase equilibria involving gas-liquid-solid has been developed. Currently both the model work and the experimental works are continued. (au)

  18. Investigation of γ-(2,3-Epoxypropoxy)propyltrimethoxy Silane Surface Modified Layered Double Hydroxides Improving UV Ageing Resistance of Asphalt

    Science.gov (United States)

    Zhang, Canlin; Yu, Jianying; Xue, Lihui; Sun, Yubin

    2017-01-01

    γ-(2,3-Epoxypropoxy)propyltrimethoxy silane surface modified layered double hydroxides (KH560-LDHs) were prepared and used to improve the ultraviolet ageing resistance of asphalt. The results of X-ray photoelectron spectrometry (XPS) indicated that KH560 has been successfully grafted onto the surface of LDHs. The agglomeration of LDHs particles notably reduced after KH560 surface modification according to scanning electron microscopy (SEM), which implied that the KH560 surface modification was helpful to promote the dispersibility of LDHs in asphalt. Then, the influence of KH560-LDHs and LDHs on the physical and rheological properties of asphalt before and after UV ageing was thoroughly investigated. The storage stability test showed that the difference in softening point (ΔS) of LDHs modified asphalt decreased from 0.6 °C to 0.2 °C at an LDHs content of 1% after KH560 surface modification, and the tendency became more pronounced with the increase of LDH content, indicating that KH560 surface modification could improve the stability of LDHs in asphalt. After UV ageing, the viscous modulus (G’’) of asphalt significantly reduced, and correspondingly, the elastic modulus (G’) and rutting factor (G*/sin δ) rapidly increased. Moreover, the asphaltene increased and the amount of “bee-like” structures of the asphalt decreased. Compared with LDHs, KH560-LDHs obviously restrained performance deterioration of the asphalt, and helped to relieve the variation of the chemical compositions and morphology of asphalt, which suggested that the improvement of KH560-LDHs on UV ageing resistance of asphalt was superior to LDHs. PMID:28772438

  19. Investigation of γ-(2,3-Epoxypropoxypropyltrimethoxy Silane Surface Modified Layered Double Hydroxides Improving UV Ageing Resistance of Asphalt

    Directory of Open Access Journals (Sweden)

    Canlin Zhang

    2017-01-01

    Full Text Available γ-(2,3-Epoxypropoxypropyltrimethoxy silane surface modified layered double hydroxides (KH560-LDHs were prepared and used to improve the ultraviolet ageing resistance of asphalt. The results of X-ray photoelectron spectrometry (XPS indicated that KH560 has been successfully grafted onto the surface of LDHs. The agglomeration of LDHs particles notably reduced after KH560 surface modification according to scanning electron microscopy (SEM, which implied that the KH560 surface modification was helpful to promote the dispersibility of LDHs in asphalt. Then, the influence of KH560-LDHs and LDHs on the physical and rheological properties of asphalt before and after UV ageing was thoroughly investigated. The storage stability test showed that the difference in softening point (ΔS of LDHs modified asphalt decreased from 0.6 °C to 0.2 °C at an LDHs content of 1% after KH560 surface modification, and the tendency became more pronounced with the increase of LDH content, indicating that KH560 surface modification could improve the stability of LDHs in asphalt. After UV ageing, the viscous modulus (G’’ of asphalt significantly reduced, and correspondingly, the elastic modulus (G’ and rutting factor (G*/sin δ rapidly increased. Moreover, the asphaltene increased and the amount of “bee-like” structures of the asphalt decreased. Compared with LDHs, KH560-LDHs obviously restrained performance deterioration of the asphalt, and helped to relieve the variation of the chemical compositions and morphology of asphalt, which suggested that the improvement of KH560-LDHs on UV ageing resistance of asphalt was superior to LDHs.

  20. Wettability and Oil Recovery by Imbibition and Viscous Displacement from Fractured and Heterogeneous Carbonates

    Energy Technology Data Exchange (ETDEWEB)

    Norman R. Morrow; Jill Buckley

    2006-04-01

    About one-half of U.S. oil reserves are held in carbonate formations. The remaining oil in carbonate reservoirs is regarded as the major domestic target for improved oil recovery. Carbonate reservoirs are often fractured and have great complexity even at the core scale. Formation evaluation and prediction is often subject to great uncertainty. This study addresses quantification of crude oil/brine/rock interactions and the impact of reservoir heterogeneity on oil recovery by spontaneous imbibition and viscous displacement from pore to field scale. Wettability-alteration characteristics of crude oils were measured at calcite and dolomite surfaces and related to the properties of the crude oils through asphaltene content, acid and base numbers, and refractive index. Oil recovery was investigated for a selection of limestones and dolomites that cover over three orders of magnitude in permeability and a factor of four variation in porosity. Wettability control was achieved by adsorption from crude oils obtained from producing carbonate reservoirs. The induced wettability states were compared with those measured for reservoir cores. The prepared cores were used to investigate oil recovery by spontaneous imbibition and viscous displacement. The results of imbibition tests were used in wettability characterization and to develop mass transfer functions for application in reservoir simulation of fractured carbonates. Studies of viscous displacement in carbonates focused on the unexpected but repeatedly observed sensitivity of oil recovery to injection rate. The main variables were pore structure, mobility ratio, and wettability. The potential for improved oil recovery from rate-sensitive carbonate reservoirs by increased injection pressure, increased injectivity, decreased well spacing or reduction of interfacial tension was evaluated.

  1. Oil-source correlation for the paleo-reservoir in the Majiang area and remnant reservoir in the Kaili area, South China

    Science.gov (United States)

    Fang, Yunxin; Liao, Yuhong; Wu, Liangliang; Geng, Ansong

    2011-05-01

    There are different viewpoints on the oil-source correlation of the Majiang paleo-reservoir and the neighbouring Kaili remnant reservoir in the Southern Guizhou Depression of China. Three potential source rocks in this depression could be inferred: the Lower-Cambrian marine mudstone, Lower-Silurian shale and Lower-Permian mudstone. Most of the potential source rocks are of high maturity. The solid bitumens and oil seepages in the Southern Guizhou Depression suffered severe secondary alterations, such as thermal degradation and biodegradation. The solid bitumens of the Majiang paleo-reservoir are also of high maturity. The oil seepages and soft bitumen of the Kaili remnant reservoir were severely biodegraded. All these secondary alterations may obscure oil-source correlations by routine biomarkers. Thus, it is very important to select appropriate biomarker parameters for the oil-source correlation. In this work, biomarkers resistant to thermal degradation and biodegradation and the data of organic carbon isotopic compositions were used for the correlation. The δ 13C values of n-alkanes in asphaltene pyrolysates were also used to make oil-oil and oil-source correlations between severely biodegraded oils. The results indicate that the Lower-Cambrian marine mudstones are the main source for the Ordovician-Silurian (O-S) solid bitumens of the Majiang area and the Ordovician-Silurian oil seepages and soft bitumens of the Kaili area. Remnant reservoir in the eastern Kaili area might have been charged at least twice by the oil generated from the Lower-Cambrian marine source rocks.

  2. The Structure of Sandstones in Productive Horizons of the Permian Bituminous Deposits of Tatarstan (Russia

    Directory of Open Access Journals (Sweden)

    R.R. Khasanov

    2017-03-01

    Full Text Available The features of sandstones in productive horizons of the Permian bituminous deposits of Tatarstan (Russia have been considered. The composition and internal structure of sandstones have been studied by optical microscopy, electron paramagnetic resonance (EPR, and electron microscopy, as well as using a number of physical and chemical methods to solve special problems. The investigated sandstones belong to the greywacke group. The clastic material of sandstones contains grains of feldspar, quartz, mica, and particles of volcanic rocks. The nature and composition of cement are important parameters that determine the filtration-capacity properties of sedimentary rocks. Bituminous deposits are characterized by vertical zoning, which is expressed in the alternation of sites with varying degrees of cementation of rocks. Atten-tion has been also paid to post-sedimentation processes, such as pyritization and calcification. Pyrite forms rare xenomorphic isometric grains. The formation of pyrite occurs in diagenesis and is associated with the processes of biogenic sulfate reduction. The source of calcium for the crystallization of dispersed cal-cite in the porous space of sandstones is the underground waters of red-colored Ufimian deposits characterized by the alkaline properties favorable for calcium migration. According to the data of X-ray computed tomography, the internal space of the studied rocks is not homogeneous and represented by a system of communicated and isolated pores. In the studied samples, two types of organic matter differing in organic radicals have been detected. The first type is an organic substance of coal origin. The second type of organic matter belongs to the oil origin and refers to bitumens in its properties. The presence of a significant percentage of asphaltenes in the bitumen composition indicates the destruction of the oil substance in the near-surface conditions.

  3. Assessing Biodegradation Susceptibilities of Selected Petroleum Hydrocarbons at Contaminated Soils

    Directory of Open Access Journals (Sweden)

    Markus Heryanto Langsa

    2010-01-01

    Full Text Available The susceptibility to biodegradation of selected saturated hydrocarbons (SHCs, polycyclic aromatichydrocarbons (PAHs and asphaltenes in a Barrow crude oil and extracts isolated from soils contaminated with theBarrow crude oil at day 0 and 39 was determined. Soil samples were contaminated with a Barrow crude oil across thesurface (5% w/w as part of a mesocosm experiment in order to mimic similar conditions in the environment. Theextent of biodegradation of the Barrow oil extracted from the contaminated soils at day 0 and day 39 was assessed byGC-MS analyses of SHCs and PAHs fractions. Changes in the relative abundances of n-alkanes (loss of low-molecularweighthydrocarbons and pristane relative to phytane (Pr/Ph and their diastereoisomers were determined. Changesin the diastereoisomer ratios of Pr and Ph relate to the decrease in abundance of the phytol-derived 6(R,10(Sisoprenoids with increasing biodegradation. The percentage change in abundances of each of selectedalkylnaphathalenes with time (day 0 to 39 was determined, enabling an order of susceptibility of their isomers tobiodegradation. It was established that the 2-methylnaphthalene isomers (2-MN is more susceptible to microbialattack than 1-MN isomer indicated by decreasing in percent abundance from day 0 to 39 for the 2-MN isomer. TheGC-MS analyses of the original Barrow oil indicated the oil had not undergone biodegradation. When this oil wasused in the soil mesocosm experiments the oil was shown to biodegrade to about a level 2 -3 based on the biodegradationsusceptibility of the various SHCs and PAHs described above

  4. An experimental study of the effect of water content on combustion of coal tar/water emulsion droplets

    International Nuclear Information System (INIS)

    Deng, Shengxiang; Zhou, Jiemin

    2011-01-01

    Isolated high asphaltene droplets of coal tar/water emulsion were studied to investigate the non-steady behavior of the burning droplets. Data on size and temperature histories were obtained. Coke residues were analyzed by scanning electron microscope. Lower and upper limits for ignition time delay were established. The error, defined as the time lag between these two limits, was less than 8 ms. Ignition time delays of emulsions were longer than for ordinary coal tar (CT) droplets of the same size but the peak temperature of emulsions occurred much earlier. A steeper temperature rise observed in the emulsions during portions of their combustion history is evidence not only of soot reduction but also the extent of burnout of the cenospheres. The latter is an important aspect in the reduction of pollutant emissions. The emulsion droplets indicated swelling of considerable magnitude compared with that of CT. Coke particles formed from emulsions were more porous, with thinner and fragile shells. The CT residues were harder and more resistant to burning. Excess burnout time or the ratio of burnout time of the emulsions depended on the water concentration, indicating that longer oxidation time was required for coke particles from coal tar than from emulsions. -- Highlights: → The droplet was subject to disruptive behavior in the pre-ignition and visible flame period. → The coke particle from the emulsion presented more fragile and thinner shells than that of the CT. → The steeper temperature rise was observed in the emulsions. → Swelling of the emulsions occurred earlier than for CT-A droplet. → The morphology of the CT carbonaceous residue was denser than that of the emulsion carbonaceous residue.

  5. Pyrolysis and liquefaction of acetone and mixed acetone/ tetralin swelled Mukah Balingian Malaysian sub-bituminous coal-The effect on coal conversion and oil yield

    International Nuclear Information System (INIS)

    Mohd Pauzi Abdullah; Mohd Azlan Mohd Ishak; Khudzir Ismail

    2008-01-01

    The effect of swelling on Mukah Balingian (MB) Malaysian sub-bituminous coal macrostructure was observed by pyrolysing the swelled coal via thermogravimetry under nitrogen at ambient pressure. The DTG curves of the pyrolyzed swelled coal samples show the presence of evolution peaks at temperature ranging from 235 - 295 degree Celsius that are due to releasing of light molecular weight hydrocarbons. These peaks, however, were not present in the untreated coal, indicating some changes in the coal macrostructure has occurred in the swelled coal samples. The global pyrolysis kinetics for coal that follows the first-order decomposition reaction was used to evaluate the activation energy of the pyrolyzed untreated and swelled coal samples. The results thus far have shown that the activation energy for the acetone and mixed acetone/ tetralin-swelled coal samples exhibit lower values than untreated coal, indicating less energy is required during the pyrolysis process due to the weakening of the coal-coal macromolecular interaction network. Moreover, liquefaction on the swelled coal samples that was carried out at temperatures ranging from 360 to 450 degree Celsius at 4 MPa of nitrogen pressure showed the enhancement of the coal conversion and oil yield at temperature of 420 degree Celsius, with retrogressive reaction started to dominate at higher temperature as indicated by decreased and increased in oil yield and high molecular weight pre-asphaltene, respectively. These observations suggest that the solvent swelling pre-treatment using acetone and mixed acetone/ tetralin can improve the coal conversion and oil yields at less severe liquefaction condition. (author)

  6. Thermoresponsive Microcarriers for Smart Release of Hydrate Inhibitors under Shear Flow.

    Science.gov (United States)

    Lee, Sang Seok; Park, Juwoon; Seo, Yutaek; Kim, Shin-Hyun

    2017-05-24

    The hydrate formation in subsea pipelines can cause oil and gas well blowout. To avoid disasters, various chemical inhibitors have been developed to prevent or delay the hydrate formation and growth. Nevertheless, direct injection of the inhibitors results in environmental contamination and cross-suppression of inhibition performance in the presence of other inhibitors against corrosion and/or formation of scale, paraffin, and asphaltene. Here, we suggest a new class of microcarriers that encapsulate hydrate inhibitors at high concentration and release them on demand without active external triggering. The key to the success in microcarrier design lies in the temperature dependence of polymer brittleness. The microcarriers are microfluidically created to have an inhibitor-laden water core and polymer shell by employing water-in-oil-in-water (W/O/W) double-emulsion drops as a template. As the polymeric shell becomes more brittle at a lower temperature, there is an optimum range of shell thickness that renders the shell unstable at temperature responsible for hydrate formation under a constant shear flow. We precisely control the shell thickness relative to the radius by microfluidics and figure out the optimum range. The microcarriers with the optimum shell thickness are selectively ruptured by shear flow only at hydrate formation temperature and release the hydrate inhibitors. We prove that the released inhibitors effectively retard the hydrate formation without reduction of their performance. The microcarriers that do not experience the hydration formation temperature retain the inhibitors, which can be easily separated from ruptured ones for recycling by exploiting the density difference. Therefore, the use of microcarriers potentially minimizes the environmental damages.

  7. Capillary meniscus dynamometry—method for determining the surface tension of drops and bubbles with isotropic and anisotropic surface stress distributions.

    Science.gov (United States)

    Danov, Krassimir D; Stanimirova, Rumyana D; Kralchevsky, Peter A; Marinova, Krastanka G; Alexandrov, Nikola A; Stoyanov, Simeon D; Blijdenstein, Theodorus B J; Pelan, Eddie G

    2015-02-15

    The stresses acting in interfacial adsorption layers with surface shear elasticity are, in general, anisotropic and non-uniform. If a pendant drop or buoyant bubble is covered with such elastic layer, the components of surface tension acting along the "meridians" and "parallels", σ(s) and σ(φ), can be different and, then, the conventional drop shape analysis (DSA) is inapplicable. Here, a method for determining σ(s) and σ(φ) is developed for axisymmetric menisci. This method, called 'capillary meniscus dynamometry' (CMD), is based on processing data for the digitized drop/bubble profile and capillary pressure. The principle of the CMD procedure for data processing is essentially different from that of DSA. Applying the tangential and normal surface stress balance equations, σ(s) and σ(φ) are determined in each interfacial point without using any rheological model. The computational procedure is fast and could be used in real time, during a given process. The method is applied to determine σ(s) and σ(φ) for bubbles and drops formed on the tip of a capillary immersed in solutions of the protein HFBII hydrophobin. Upon a surface compression, meridional wrinkles appear on the bubble surface below the bubble "equator", where the azimuthal tension σ(φ) takes negative values. The CMD method allows one to determine the local tensions acting in anisotropic interfacial layers (films, membranes), like those formed from proteins, polymers, asphaltenes and phospholipids. The CMD is applicable also to fluid interfaces (e.g. surfactant solutions), for which it gives the same surface tension as the conventional methods. Copyright © 2014 Elsevier Inc. All rights reserved.

  8. The comparison of naturally weathered oil and artificially photo-degraded oil at the molecular level by a combination of SARA fractionation and FT-ICR MS

    International Nuclear Information System (INIS)

    Islam, Ananna; Cho, Yunju; Yim, Un Hyuk; Shim, Won Joon; Kim, Young Hwan; Kim, Sunghwan

    2013-01-01

    Highlights: • Weathered oils from the Hebei Spirit oil spill and photo degraded oils are compared. • We investigate changes of polar species at the molecular level by 15T FT-ICR MS. • Significant reduction of sulfur class compounds in saturates fraction is observed. • The relative abundance of protonated compounds (presumably basic nitrogen compounds) increase after degradation. • Changes of polar compounds occurred by natural and photo degradation are similar. -- Abstract: Two sets of oil samples, one obtained from different weathering stages of the M/V Hebei Spirit oil spill site and the other prepared by an in vitro photo-degradation experiment, were analyzed and compared at the molecular level by atmospheric pressure photo-ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). For a more detailed comparison at the molecular level, the oil samples were separated into saturate, aromatic, resin, and asphaltene (SARA) fractions before MS analysis. Gravimetric analysis of the SARA fractions revealed a decreased weight percentage of the aromatic fraction and an increased resin fraction in both sets of samples. Molecular-level investigations of the SARA fractions showed a significant reduction in the S 1 class in the saturate fraction and increase of S 1 O 1 class compounds with high DBE values in resin fraction. Levels of N 1 and N 1 O 1 class compounds resulting in protonated ions (presumably basic nitrogen compounds) increased after degradation compared to compounds generating molecular ions (presumably non-basic nitrogen compounds). This study revealed changes occurring in heteroatom polar species of crude oils such as sulfur and nitrogen containing compounds that have not been easily detected with conventional GC based techniques

  9. Additives in fuel oils - phase 2

    International Nuclear Information System (INIS)

    Dyrke, J.; Rudling, L.

    1997-06-01

    The project 'additives in fuel oils -phase 2' is a continuation of the prior study, which yielded in the Vaermeforsk report no 569 'Effects of using fuel oil additives in oil-fired burners'. As opposed to the first phase, which was a research study, the follow-up had more the dignity of testing a number of fuel oils with different additives in order to obtain results from combustion experiments under laboratory circumstances. The experiments were conducted in a 50 kW tube burner and the results from these trials can then be used as indications on how fuel oil additives can affect the emissions at large energy production plants. The conclusion of the project is that the additives could reduce the particle emissions for the low sulphureous oils by contribution to improved combustion of cenospherical particles and reducing the content of unburnt particles in the flue gases. The additives had no significant effect on the high sulphureous oils, which probably have different causes: The high content of asphaltenes yield particles, which are difficult to combust. Furthermore is the relatively high metal content in the oils an obstacle for the effect of the metal additives, since the adding of the catalyzing metals from the additives only marginally changes the total metal content of the composition. Any major differences between the different commercial additives could not be documented with the applied examination method. Despite that it could be verified that the catalytic additives had a better particle reducing effect than additives based on non-catalytic substance. General conclusions of the above mentioned results should only be drawn with large precaution. At the same time it should be said that the results gained with the experimental setup in this project can be looked upon and used as indications for expected results in commercial energy plants

  10. Support vector machine regression (SVR/LS-SVM)--an alternative to neural networks (ANN) for analytical chemistry? Comparison of nonlinear methods on near infrared (NIR) spectroscopy data.

    Science.gov (United States)

    Balabin, Roman M; Lomakina, Ekaterina I

    2011-04-21

    In this study, we make a general comparison of the accuracy and robustness of five multivariate calibration models: partial least squares (PLS) regression or projection to latent structures, polynomial partial least squares (Poly-PLS) regression, artificial neural networks (ANNs), and two novel techniques based on support vector machines (SVMs) for multivariate data analysis: support vector regression (SVR) and least-squares support vector machines (LS-SVMs). The comparison is based on fourteen (14) different datasets: seven sets of gasoline data (density, benzene content, and fractional composition/boiling points), two sets of ethanol gasoline fuel data (density and ethanol content), one set of diesel fuel data (total sulfur content), three sets of petroleum (crude oil) macromolecules data (weight percentages of asphaltenes, resins, and paraffins), and one set of petroleum resins data (resins content). Vibrational (near-infrared, NIR) spectroscopic data are used to predict the properties and quality coefficients of gasoline, biofuel/biodiesel, diesel fuel, and other samples of interest. The four systems presented here range greatly in composition, properties, strength of intermolecular interactions (e.g., van der Waals forces, H-bonds), colloid structure, and phase behavior. Due to the high diversity of chemical systems studied, general conclusions about SVM regression methods can be made. We try to answer the following question: to what extent can SVM-based techniques replace ANN-based approaches in real-world (industrial/scientific) applications? The results show that both SVR and LS-SVM methods are comparable to ANNs in accuracy. Due to the much higher robustness of the former, the SVM-based approaches are recommended for practical (industrial) application. This has been shown to be especially true for complicated, highly nonlinear objects.

  11. Mechanism and environmental effects on MEOR induced by the alpha process. Final report

    Energy Technology Data Exchange (ETDEWEB)

    Hiebert, F.K.; Zumberge, J.; Rouse, B.; Cowes, A.; Lake, L.W.

    1993-04-01

    This project was an interdisciplinary investigation of the enhanced oil recovery effects of a commercial microbial enhanced oil recovery (MEOR) system. The purpose was to investigate in parallel laboratory and field studies the response of a portion of the Shannon Sandstone reservoir to two single-well treatments with a commercial MEOR system, to investigate basic bacteria/rock interactions, and to investigate mechanisms of oil release. The MEOR system consisted of a mixed culture of hydrocarbon-utilizing bacteria, inorganic nutrients, and other growth factors. Parallel field and laboratory investigations into the effect and mechanisms of the treatment were carried out by independent principal investigators. The Shannon Sandstone at the Naval Petroleum Reserve {number_sign}3 (NPR {number_sign}3), Teapot Dome Field, Wyoming, was the location of the pilot field treatment. The treated and adjacent observation wells showed production and microbiological perturbations that are attributed to the effects of treatment during the first four post-treatment months. Effects of treatment declined to background levels within four months of inoculation. No production response was recorded in control wells unaffected by microbial stimulation. Laboratory research resulted in descriptions of colonization patterns of hydrocarbon-utilizing bacteria in the reservoir rock environment. Core-flooding research utilizing various components of the MEOR system did not result in the isolation of an oilrelease mechanism or measure incremental oil recovery from cores at residual oil saturation to waterflood. Chemical analysis of pre- and post-treatment produced oil identified large organic acid molecules concentrated in the asphaltenic fraction of posttreatment oil, but not in the oil from untreated control wells. No significant changes were measured in the overall quality of the oil produced from MEOR treated wells.

  12. Mechanism and environmental effects on MEOR induced by the alpha process

    Energy Technology Data Exchange (ETDEWEB)

    Hiebert, F.K.; Zumberge, J.; Rouse, B.; Cowes, A.; Lake, L.W.

    1993-04-01

    This project was an interdisciplinary investigation of the enhanced oil recovery effects of a commercial microbial enhanced oil recovery (MEOR) system. The purpose was to investigate in parallel laboratory and field studies the response of a portion of the Shannon Sandstone reservoir to two single-well treatments with a commercial MEOR system, to investigate basic bacteria/rock interactions, and to investigate mechanisms of oil release. The MEOR system consisted of a mixed culture of hydrocarbon-utilizing bacteria, inorganic nutrients, and other growth factors. Parallel field and laboratory investigations into the effect and mechanisms of the treatment were carried out by independent principal investigators. The Shannon Sandstone at the Naval Petroleum Reserve [number sign]3 (NPR [number sign]3), Teapot Dome Field, Wyoming, was the location of the pilot field treatment. The treated and adjacent observation wells showed production and microbiological perturbations that are attributed to the effects of treatment during the first four post-treatment months. Effects of treatment declined to background levels within four months of inoculation. No production response was recorded in control wells unaffected by microbial stimulation. Laboratory research resulted in descriptions of colonization patterns of hydrocarbon-utilizing bacteria in the reservoir rock environment. Core-flooding research utilizing various components of the MEOR system did not result in the isolation of an oilrelease mechanism or measure incremental oil recovery from cores at residual oil saturation to waterflood. Chemical analysis of pre- and post-treatment produced oil identified large organic acid molecules concentrated in the asphaltenic fraction of posttreatment oil, but not in the oil from untreated control wells. No significant changes were measured in the overall quality of the oil produced from MEOR treated wells.

  13. Non-Newtonian Flow Characteristics of Heavy Oil in the Bohai Bay Oilfield: Experimental and Simulation Studies

    Directory of Open Access Journals (Sweden)

    Xiankang Xin

    2017-10-01

    Full Text Available In this paper, physical experiments and numerical simulations were applied to systematically investigate the non-Newtonian flow characteristics of heavy oil in porous media. Rheological experiments were carried out to determine the rheology of heavy oil. Threshold pressure gradient (TPG measurement experiments performed by a new micro-flow method and flow experiments were conducted to study the effect of viscosity, permeability and mobility on the flow characteristics of heavy oil. An in-house developed novel simulator considering the non-Newtonian flow was designed based on the experimental investigations. The results from the physical experiments indicated that heavy oil was a Bingham fluid with non-Newtonian flow characteristics, and its viscosity-temperature relationship conformed to the Arrhenius equation. Its viscosity decreased with an increase in temperature and a decrease in asphaltene content. The TPG measurement experiments was impacted by the flow rate, and its critical flow rate was 0.003 mL/min. The TPG decreased as the viscosity decreased or the permeability increased and had a power-law relationship with mobility. In addition, the critical viscosity had a range of 42–54 mPa∙s, above which the TPG existed for a given permeability. The validation of the designed simulator was positive and acceptable when compared to the simulation results run in ECLIPSE V2013.1 and Computer Modelling Group (CMG V2012 software as well as when compared to the results obtained during physical experiments. The difference between 0.0005 and 0.0750 MPa/m in the TPG showed a decrease of 11.55% in the oil recovery based on the simulation results, which demonstrated the largely adverse impact the TPG had on heavy oil production.

  14. Clean and Secure Energy from Domestic Oil Shale and Oil Sands Resources

    Energy Technology Data Exchange (ETDEWEB)

    Spinti, Jennifer [Inst. for Clean and Secure Energy, Salt Lake City, UT (United States); Birgenheier, Lauren [Inst. for Clean and Secure Energy, Salt Lake City, UT (United States); Deo, Milind [Inst. for Clean and Secure Energy, Salt Lake City, UT (United States); Facelli, Julio [Inst. for Clean and Secure Energy, Salt Lake City, UT (United States); Hradisky, Michal [Inst. for Clean and Secure Energy, Salt Lake City, UT (United States); Kelly, Kerry [Inst. for Clean and Secure Energy, Salt Lake City, UT (United States); Miller, Jan [Inst. for Clean and Secure Energy, Salt Lake City, UT (United States); McLennan, John [Inst. for Clean and Secure Energy, Salt Lake City, UT (United States); Ring, Terry [Inst. for Clean and Secure Energy, Salt Lake City, UT (United States); Ruple, John [Inst. for Clean and Secure Energy, Salt Lake City, UT (United States); Uchitel, Kirsten [Inst. for Clean and Secure Energy, Salt Lake City, UT (United States)

    2015-09-30

    (March, 2012); Conjunctive Surface and Groundwater Management in Utah: Implications for Oil Shale and Oil Sands Development (May, 2012); Development of CFD-Based Simulation Tools for In Situ Thermal Processing of Oil Shale/Sands (February, 2012); Core-Based Integrated Sedimentologic, Stratigraphic, and Geochemical Analysis of the Oil Shale Bearing Green River Formation, Uinta Basin, Utah (April, 2011); Atomistic Modeling of Oil Shale Kerogens and Asphaltenes Along with their Interactions with the Inorganic Mineral Matrix (April, 2011); Pore Scale Analysis of Oil Shale/Sands Pyrolysis (March, 2011); Land and Resource Management Issues Relevant to Deploying In-Situ Thermal Technologies (January, 2011); Policy Analysis of Produced Water Issues Associated with In-Situ Thermal Technologies (January, 2011); and Policy Analysis of Water Availability and Use Issues for Domestic Oil Shale and Oil Sands Development (March, 2010)

  15. Studies of water-in-oil emulsions : testing of emulsion formation in OHMSETT

    International Nuclear Information System (INIS)

    Fingas, M.; Fieldhouse, B.

    2001-01-01

    A study was conducted to determine the stability of water-in-oil emulsions in the OHMSETT tank facility. The results were then compared with previous laboratory studies which suggested that the stability of emulsions can be grouped into four categories, stable, unstable, meso-stable and entrained. It has been determined that entrained emulsions can retain oil by viscous forces long enough for interfacial agents, resins and asphaltenes to stabilize the droplets. This paper also described the difference in viscosity between the 4 categories of emulsion stability. The OHMSETT tests were conducted in two series of one week each. The first series of tests were conducted in July and involved 12 experiments on 2 different types of oils which were placed at varying thicknesses on the water. The second set of tests were conducted in November and involved 12 experiments on 6 oils. The rheological properties of the oils were measured and compared to the same oils undergoing emulsification in the laboratory. The oils and water-in-oil states produced were found to have analogous properties between the laboratory and the first set of tests at the OHMSETT facility. All the oils tested produced entrained water-in-oil states in both the laboratory and the test tank. The energy in the two test conditions was found to be similar, with the OHMSETT emulsions similar to one produced in the laboratory at high energies. The second series of tests at OHMSETT did not result in the expected water in-oil- states. This unexpected result was most likely due to the residual surfactant from an earlier dispersant experiment. The study showed that the conditions for emulsion formation are analogous in the OHMSETT tank and in the laboratory tests. The level of energy is considered to be the major variant. It was concluded that the energy levels between the laboratory mixing experiments and the OHMSETT is similar. It was shown that surfactants left over from dispersant testing inhibited the formation

  16. Effect of steam and oil sludge ash additive on the products of oil sludge pyrolysis

    International Nuclear Information System (INIS)

    Cheng, Shuo; Wang, Yuhua; Fumitake, Takahashi; Kouji, Tokimatsu; Li, Aimin; Kunio, Yoshikawa

    2017-01-01

    Highlights: • Pyrolysis of oil sludge with steam or/and oil sludge ash was carried out. • Oil product yield was increased by steam and oil sludge ash presence. • Steam injection and oil sludge ash addition improved the oil product quality. • Synergetic effect of steam and oil sludge ash on the oil product was reported. • A possible catalytic mechanism was proposed. - Abstract: In this study, a strategy of combining steam injection with oil sludge ash addition to improve the yield and quality of the oil products of oil sludge pyrolysis process is proposed. Oil sludge pyrolysis with the addition of different amounts of steam and oil sludge ash was conducted under inert conditions at 450 °C by employing a stirred tank reactor. This procedure was performed to investigate the effect of steam injection and oil sludge ash addition on the distribution and quality of the oil products. The possible catalytic mechanism occurring during the pyrolysis process was proposed. The quality of the oil product was determined based on the results of the boiling point distribution, the carbon residue, the ultimate analysis, the Saturates, Asphaltenes, Resins and Aromatics (SARA) composition and the Nuclear Magnetic Resonance (NMR) analysis. The results indicate that both steam injection and oil sludge ash addition caused the oil yield to increase. Steam injection increased the proportions of the heavy and middle fractions in the oil product and reduced the carbon residue by improving the stability of the oil system. Oil sludge ash addition reduced the carbon residue and lessened the decrease in the light oil/heavy oil ratio by converting the heavy fraction or coke precursors to lighter fractions. The synergetic effect of steam injection and oil sludge ash addition can further reduce the carbon residue of the oil product. The presence of oil sludge ash significantly reduced the S, N, and O mobilities from the oil sludge feedstock to the oil product. These performances can be

  17. Refines Efficiency Improvement

    Energy Technology Data Exchange (ETDEWEB)

    WRI

    2002-05-15

    Refinery processes that convert heavy oils to lighter distillate fuels require heating for distillation, hydrogen addition or carbon rejection (coking). Efficiency is limited by the formation of insoluble carbon-rich coke deposits. Heat exchangers and other refinery units must be shut down for mechanical coke removal, resulting in a significant loss of output and revenue. When a residuum is heated above the temperature at which pyrolysis occurs (340 C, 650 F), there is typically an induction period before coke formation begins (Magaril and Aksenova 1968, Wiehe 1993). To avoid fouling, refiners often stop heating a residuum before coke formation begins, using arbitrary criteria. In many cases, this heating is stopped sooner than need be, resulting in less than maximum product yield. Western Research Institute (WRI) has developed innovative Coking Index concepts (patent pending) which can be used for process control by refiners to heat residua to the threshold, but not beyond the point at which coke formation begins when petroleum residua materials are heated at pyrolysis temperatures (Schabron et al. 2001). The development of this universal predictor solves a long standing problem in petroleum refining. These Coking Indexes have great potential value in improving the efficiency of distillation processes. The Coking Indexes were found to apply to residua in a universal manner, and the theoretical basis for the indexes has been established (Schabron et al. 2001a, 2001b, 2001c). For the first time, a few simple measurements indicates how close undesired coke formation is on the coke formation induction time line. The Coking Indexes can lead to new process controls that can improve refinery distillation efficiency by several percentage points. Petroleum residua consist of an ordered continuum of solvated polar materials usually referred to as asphaltenes dispersed in a lower polarity solvent phase held together by intermediate polarity materials usually referred to as

  18. La conversion des résidus et huiles lourdes : au carrefour du thermique et du catalytique Conversion of Residues and Heavy Oils At the Crossroads of Thermal Cracking and Catalytic Reactions

    Directory of Open Access Journals (Sweden)

    Le Page J. F.

    2006-11-01

    Full Text Available Cet article passe en revue les diverses familles de procédés de conversion des résidus et huiles lourdes. Tous les résultats semblent converger pour accréditer l'idée que dans tous ces procédés, y compris les procédés dits catalytiques, l'essentiel de la conversion des espèces de poids moléculaire élevé, résines et asphaltènes, procède par mécanisme radicalaire : la clef de la conversion profonde, c'est paradoxalement la maîtrise de la condensation radicalaire de ces espèces. Hydrogène seul, hydrogène en présence de solvant donneur, d'additifs ou encore mieux de catalyseurs, sont les armes dont dispose tout raffineur pour affirmer cette maîtrise, dans la mesure où il ne tient pas à fabriquer du coke. Tous ces procédés de conversion des résidus donnent par ailleurs naissance à des produits craqués dont la nature et la distribution rappellent celles des produits de première distillation du pétrole brut dont est issu le résidu soumis au craquage. This article reviews the different families of conversion processes for residues and heavy oils. All the results seem to converge to support the idea that in all these processes, including so-called catalytic processes, most of the conversion of high-molecular-weight species (resins and asphaltenes operates by a radical mechanism. The key to in-depth conversion is, paradoxically, the mastery of the radical condensation of these species. Hydrogen alone, hydrogen in the presence of a donor solvent, of additives or, better yet, of catalysts, are the arms at the disposal of all refiners to assert this mastery, to the extent that they do not want to manufacture coke. All such conversion processes for residues also give rise to cracked products whose nature and distribution recall those of first-distillation products of crude oil, from which the residue comes that is subjected to cracking.

  19. Evaluation of methods to test chemicals suitability for umbilical applications

    Energy Technology Data Exchange (ETDEWEB)

    Allenson, S. J.; Lindeman, O. E.; Cenegy, L. M.

    2006-03-15

    Offshore deep-water projects are increasingly deploying chemicals to sub-sea wellheads through umbilical lines. There is no margin for error in umbilical chemical treatment programs since any flow blockage in a sub-sea line would result in a multi-million dollar problem. Chemicals for umbilical delivery must also meet strict requirements in their performance and especially their handling properties. Umbilical delivery must be effective at low concentrations in preventing corrosion, scale, hydrates, asphaltenes, paraffin and a host of other problems. Chemical transiting an umbilical can experience pressures as high as 15,000 psi and temperatures ranging from near 0 deg C to greater than 120 deg C. Since some umbilicals are as long as 80 km, a week or more can elapse from the time the chemical is injected at the platform until it reaches the sub-sea well. Therefore, the chemical must not only be stable under all temperature and pressure conditions that it may experience in the umbilical line, it must also be stable under these conditions for a long period of time. Since many umbilical lines actually terminate into sub-sea valves and connectors that are only a few hundred microns in diameter, it is critical that the injected chemical have a low viscosity at sub-sea temperatures and pressures and that it be completely free of particles. These issues present substantial challenges in formulating and manufacturing chemicals for umbilical applications that must be addressed prior to approval of a product for use. Each of these challenges was taken into consideration and a series of tests were developed to assure reliable chemical pump ability through an umbilical line. The tests developed included enhanced formulation stability tests under umbilical temperature and pressure conditions, NAS Class rating, extensive material compatibility testing to include all metals and elastomers that may be used in umbilical injection systems and comprehensive physical property testing

  20. Genesis and distribution of hydrogen sulfide in deep heavy oil of the Halahatang area in the Tarim Basin, China

    Directory of Open Access Journals (Sweden)

    Guangyou Zhu

    2017-02-01

    Full Text Available As the largest oil-and-gas-bearing basin in China, the Tarim Basin contains rich oil and gas resources buried deep underground. In recent years, large oil fields have been discovered in the Halahatang area of the northern Tarim Basin. The reservoir is buried 6000–7300 m underground. This reservoir is dominated by the Ordovician carbonate rocks, and the crude oil is mainly heavy oil. As a crude oil-associated gas, the natural gas generally contains hydrogen sulfide (H2S. The heavy oil in this region is the deepest buried heavy oil found in the world. H2S is also associated with the deepest buried natural gas. The burial, preservation and degree of biodegradation of a paleo-reservoir can be used to predict the distribution of H2S. According to research findings, there is a clear planar distribution pattern of H2S content: high in the east and north, and low in the west and south. We compared the physical properties of crude oil and the analysis of the composition of natural gas and isotopes, biomarker compounds of crude oil and groundwater. We find that the content of H2S in natural gas bears some relation to the physical properties and degree of biodegradation of crude oil. Crude oil density, sulfur content, colloid, and asphaltene have positive correlations with H2S content in natural gas. The formation of H2S is controlled by the degradation and densification of crude oil. Crude oil densification can lead to an increase of the sulfur content. The rise in the temperature of the reservoir resulting from the depth of burial causes the thermal decomposition of sulfur compounds to produce H2S. The generation of H2S by the thermal decomposition of sulfur compounds is confirmed by data on sulfur isotopes. The distribution of H2S can then be predicted based on the burial conditions of the paleo-reservoir and the degree of biodegradation. In the south Rewapu of the Halahatang area, the thick cap rock of the Ordovician oil reservoir was preserved well

  1. Characterization of asphalt materials containing bio oil from michigan wood

    Science.gov (United States)

    Mills-Beale, Julian

    oxidation in petroleum-based asphalt increases with increasing bioasphalt modifiers; 4) bioasphalt causes the asphaltene fractions in petroleum-based asphalt to precipitate out of the solvent maltene fractions; 5) there is no definite improvement or decline in the dynamic mix behavior of bio-modified mixes at low temperatures; 6) bio-modified asphalt mixes exhibit better rutting performance than traditional asphalt mixes; 7) bio-modified asphalt mixes have lower susceptibility to moisture damage; 8) more field compaction energy is needed to compact bio-modified mixes.

  2. TECHNOLOGY AND EFFICIENT USE OF PEAT ASH IN MASTICS FOR WATERPROOFING OF BRIDGE AND TUNNEL STRUCTURES

    Directory of Open Access Journals (Sweden)

    G. D. Lyahevich

    2015-01-01

    Full Text Available A prospective method for protection of  bridges and tunnels against aggressive water action is surface waterproofing on the basis of an organo-mineral binder. Its structural strength can be increased by introduction of particles which are similar to the size of  asphaltenes and an elasticity of disperse medium has been increased due to introduction of polymers. These theoretical suppositions point out the possibility for simultaneous provision of flexibility at low temperatures and high heat resistance for mastics on the basis  of organo-mineral binders. In this regard a goal has been set to obtain a mastic high flexibility and high heat resistance  while using finely divided activated peat ash.Rubber crushed in accordance with ТУ (Technical Specifications 38.108035–87,  divinyl-styrene thermoelastoplast DСT-30Р-20ПС,  bitumen of grade 20/30 in accordance with СТБ ЕН 12591–2010, ash from burning peat at the Lida Peat Briquette Plant, multi-purpose industrial oil of solvent refining with high viscosity index, super-plasticizer – sodium salt which is a condensation product of aromatic carbon sulfo-oxidation with formaldehyde and neutralization with the help of sodium hydroxide (type 1 have been used in order to obtain the stated objective. While using these materials compositions and technology for preparation of organo-mineral mastics have been developed in the paper. Their tests have shown that a modification of finely divided  mastics carried out with the help of peat ash which is activated by super-plasticizer НСПКСАУсФ-1, various polymer additives, contributes to an increase in their heat resistance, elasticity, water resistance, and also allows to control their technological and operational characteristics. The paper has experimentally confirmed that peat ash can be successfully used for preparation of high-quality waterproofing mastics which are so necessary for  protection of bridge and tunnel

  3. Structures des fractions lourdes. Méthodes d'analyse et préparation des charges Structures of Heavy Fractions. Feedstock Analysis and Preparation Methods

    Directory of Open Access Journals (Sweden)

    Vercier P.

    2006-11-01

    Full Text Available Après avoir défini les termes fractions lourdes et pétroles bruts lourds, et avoir souligné l'intérêt économique qu'il y a à utiliser ces matériaux, on passera en revue les techniques analytiques disponibles pour aborder les difficiles problèmes technologiques que soulève l'emploi des équipements et des méthodes conventionnels. On montrera que les analystes auront besoin de techniques améliorées ou même entièrement nouvelles pour séparer ces produits en des fractions plus simples, susceptibles d'être alors analysées par les méthodes plus traditionnelles : distillation à haute température (jusqu'à 650 °C ; séparation en asphaltènes, résines et huile ; séparation en acides, bases, neutres, saturés, mono-, di-, poly-aromatiques ; analyses structurales (analyses élémentaires, détermination des masses moléculaires, spectrométrie de masse, RMN, pyrolyse et détection à l'aide de détecteurs spécifiques pour le soufre et l'azote. Comme le facteur temps est important dans les études pilote, il sera montré que la mise au point des méthodes rapides et modernes de chromatographie liquide sera l'objectif prioritaire de la recherche analytique dans le futur proche. After defining the terms heavy fractionsand heavy crudesand then stressing the economic interest there is in using such materials, a survey is made of the analytical techniques available for tackling the difficult technological problems arising from the use of conventional equipment and methods. It is shown that analysts will need improved or even completely new techniques for separating such products into simpler fractions so that they can be analyzed by more traditional methods, i. e. high-temperature distillation (up to 650°C; separation into asphaltenes, resins and oils; structural analyses (elemental analyses, determining molecular weights, mass spectrometry, NMR, pyrolysis and detection with specific sulfur and nitrogen detectors. Since the time

  4. Role of NSO compounds during primary cracking of a Type II kerogen and a Type III lignite

    Science.gov (United States)

    Behar, F.; Lorant, F.; Lewan, M.

    2008-01-01

    The aim of this work is to follow the generation of NSO compounds during the artificial maturation of an immature Type II kerogen and a Type III lignite in order to determine the different sources of the petroleum potential during primary cracking. Experiments were carried out in closed system pyrolysis in the temperature range from 225 to 350 ??C. Two types of NSOs were recovered: one is soluble in n-pentane and the second in dichloromethane. A kinetic scheme was optimised including both kerogen and NSO cracking. It was validated by complementary experiments carried out on isolated asphaltenes generated from the Type II kerogen and on the total n-pentane and DCM extracts generated from the Type III lignite. Results show that kerogen and lignite first decompose into DCM NSOs with minor generation of hydrocarbons. Then, the main source of petroleum potential originates from secondary cracking of both DCM and n-pentane NSOs through successive decomposition reactions. These results confirm the model proposed by Tissot [Tissot, B., 1969. Premie??res donne??es sur les me??canismes et la cine??tique de la formation du pe??trole dans les bassins se??dimentaires. Simulation d'un sche??ma re??actionnel sur ordinateur. Oil and Gas Science and Technology 24, 470-501] in which the main source of hydrocarbons is not the insoluble organic matter, but the NSO fraction. As secondary cracking of the NSOs largely overlaps that of the kerogen, it was demonstrated that bulk kinetics in open system is a result of both kerogen and NSO cracking. Thus, another kinetic scheme for primary cracking in open system was built as a combination of kerogen and NSO cracking. This new kinetic scheme accounts for both the rate and amounts of hydrocarbons generated in a closed pyrolysis system. Thus, the concept of successive steps for hydrocarbon generation is valid for the two types of pyrolysis system and, for the first time, a common kinetic scheme is available for extrapolating results to natural

  5. The use of solvent extractions and solubility theory to discern hydrocarbon associations in coal, with application to the coal-supercritical CO2 system

    Science.gov (United States)

    Kolak, Jonathan J.; Burruss, Robert A.

    2014-01-01

    Samples of three high volatile bituminous coals were subjected to parallel sets of extractions involving solvents dichloromethane (DCM), carbon disulfide (CS2), and supercritical carbon dioxide (CO2) (40 °C, 100 bar) to study processes affecting coal–solvent interactions. Recoveries of perdeuterated surrogate compounds, n-hexadecane-d34 and four polycyclic aromatic hydrocarbons (PAHs), added as a spike prior to extraction, provided further insight into these processes. Soxhlet-DCM and Soxhlet-CS2 extractions yielded similar amounts of extractable organic matter (EOM) and distributions of individual hydrocarbons. Supercritical CO2 extractions (40 °C, 100 bar) yielded approximately an order of magnitude less EOM. Hydrocarbon distributions in supercritical CO2 extracts generally mimicked distributions from the other solvent extracts, albeit at lower concentrations. This disparity increased with increasing molecular weight of target hydrocarbons. Five- and six-ring ring PAHs generally were not detected and no asphaltenes were recovered in supercritical CO2 extractions conducted at 40 °C and 100 bar. Supercritical CO2 extraction at elevated temperature (115 °C) enhanced recovery of four-ring and five-ring PAHs, dibenzothiophene (DBT), and perdeuterated PAH surrogate compounds. These results are only partially explained through comparison with previous measurements of hydrocarbon solubility in supercritical CO2. Similarly, an evaluation of extraction results in conjunction with solubility theory (Hildebrand and Hansen solubility parameters) does not fully account for the hydrocarbon distributions observed among the solvent extracts. Coal composition (maceral content) did not appear to affect surrogate recovery during CS2 and DCM extractions but might affect supercritical CO2 extractions, which revealed substantive uptake (partitioning) of PAH surrogates into the coal samples. This uptake was greatest in the sample (IN-1) with the highest vitrinite content. These

  6. Bulk and Surface Aqueous Speciation of Calcite: Implications for Low-Salinity Waterflooding of Carbonate Reservoirs

    KAUST Repository

    Yutkin, Maxim P.

    2017-08-25

    Low-salinity waterflooding (LSW) is ineffective when reservoir rock is strongly water-wet or when crude oil is not asphaltenic. Success of LSW relies heavily on the ability of injected brine to alter surface chemistry of reservoir crude-oil brine/rock (COBR) interfaces. Implementation of LSW in carbonate reservoirs is especially challenging because of high reservoir-brine salinity and, more importantly, because of high reactivity of the rock minerals. Both features complicate understanding of the COBR surface chemistries pertinent to successful LSW. Here, we tackle the complex physicochemical processes in chemically active carbonates flooded with diluted brine that is saturated with atmospheric carbon dioxide (CO2) and possibly supplemented with additional ionic species, such as sulfates or phosphates. When waterflooding carbonate reservoirs, rock equilibrates with the injected brine over short distances. Injected-brine ion speciation is shifted substantially in the presence of reactive carbonate rock. Our new calculations demonstrate that rock-equilibrated aqueous pH is slightly alkaline quite independent of injected-brine pH. We establish, for the first time, that CO2 content of a carbonate reservoir, originating from CO2-rich crude oil and gas, plays a dominant role in setting aqueous pH and rock-surface speciation. A simple ion-complexing model predicts the calcite-surface charge as a function of composition of reservoir brine. The surface charge of calcite may be positive or negative, depending on speciation of reservoir brine in contact with the calcite. There is no single point of zero charge; all dissolved aqueous species are charge determining. Rock-equilibrated aqueous composition controls the calcite-surface ion-exchange behavior, not the injected-brine composition. At high ionic strength, the electrical double layer collapses and is no longer diffuse. All surface charges are located directly in the inner and outer Helmholtz planes. Our evaluation of

  7. From the local structure of the catalytic materials to the colloidal macrostructure of systems of the petroleum industry; De la structure locale des materiaux catalytiques a la macrostructure colloidale des systemes d'interet petrolier

    Energy Technology Data Exchange (ETDEWEB)

    Espinat, D.

    2006-01-15

    insight in the macrostructure of these colloidal systems, as for instance, asphaltenes solutions and petroleum heavy fractions, clay suspensions and anti-wear additives. Other techniques can be used in order to reduce particle size poly-dispersity of these systems. (author)

  8. Soil-Water Repellency and Critical Humidity as Cleanup Criteria for Remediation of a Hydrocarbon Contaminated Mud

    Science.gov (United States)

    Guzmán, Francisco Javier; Adams, Randy H.

    2010-05-01

    The majority of soil remediation programs focus mainly on reducing the hydrocarbon concentration, based on the assumption that the primary impact is toxicity and/or leachates and that these are directly proportional to concentration. None-the-less, interference with natural soil-water interactions are frequently more damaging, especially for sites contaminated with very viscous, weathered hydrocarbons. Therefore, the kind of hydrocarbons present in the soil and their interactions with soil surfaces may be more important than the overall hydrocarbon concentration in terms of soil restoration. One recently patented technology, the Chemical-Biological Stabilization process, focuses specifically on restoring soil fertility as the main objective for remediation of sites with agricultural use. This method was recently validated at an industrial scale by the treatment of 150 cubic meters of bentonitic drilling muds (70,5% fines) from an old sulphur mine, which were contaminated with very weathered oil (4° API), consisting of 31% asphaltenes. This material was treated by adding 4% (w/w, dry) of calcium hydroxide, followed by 4% (w/w, dry) of sugar cane cachasse (a fine fibered agricultural waste), thoroughly mixing between additions using an excavator. After the soil had dried sufficiently and the pH was seed. Over a two year period this material was monitored for several factors including field moisture (%H), field capacity (FC), and soil water repellency. MED was measured on air dried soil and WDPT values were calculated from the extrapolation of penetration time vs. ethanol molarity functions (Rx=0,99). Additionally, water penetration times were measured at different humidities to determine critical moisture levels for absorption in vigorous vegetative growth was established. During two years of treatment the MED values were reduced 30% from 5,13 to 3,58M, and WDPT values were reduced over 25 times (from 10 exp5,6 s to 10 exp4,2 s). Critical humidity values varied from

  9. Development of hydrate risk quantification in oil and gas production

    Science.gov (United States)

    Chaudhari, Piyush N.

    Subsea flowlines that transport hydrocarbons from wellhead to the processing facility face issues from solid deposits such as hydrates, waxes, asphaltenes, etc. The solid deposits not only affect the production but also pose a safety concern; thus, flow assurance is significantly important in designing and operating subsea oil and gas production. In most subsea oil and gas operations, gas hydrates form at high pressure and low temperature conditions, causing the risk of plugging flowlines, with a undesirable impact on production. Over the years, the oil and gas industry has shifted their perspective from hydrate avoidance to hydrate management given several parameters such as production facility, production chemistry, economic and environmental concerns. Thus, understanding the level of hydrate risk associated with subsea flowlines is an important in developing efficient hydrate management techniques. In the past, hydrate formation models were developed for various flow-systems (e.g., oil dominated, water dominated, and gas dominated) present in the oil and gas production. The objective of this research is to extend the application of the present hydrate prediction models for assessing the hydrate risk associated with subsea flowlines that are prone to hydrate formation. It involves a novel approach for developing quantitative hydrate risk models based on the conceptual models built from the qualitative knowledge obtained from experimental studies. A comprehensive hydrate risk model, that ranks the hydrate risk associated with the subsea production system as a function of time, hydrates, and several other parameters, which account for inertial, viscous, interfacial forces acting on the flow-system, is developed for oil dominated and condensate systems. The hydrate plugging risk for water dominated systems is successfully modeled using The Colorado School of Mines Hydrate Flow Assurance Tool (CSMHyFAST). It is found that CSMHyFAST can be used as a screening tool in

  10. Simultaneous cleanup of soil polluted with crude oil and heavy metals

    International Nuclear Information System (INIS)

    Groudeva, V.; Doycheva, A.; Groudev, S.

    2005-01-01

    Some soils in a site located in the Northwestern part of Bulgaria were heavily polluted with crude oil and some heavy metals (copper, zinc, cadmium, lead). The oil was light, with a specific gravity of about 0.8 g/cm 3 , rich in paraffins and with a very low content of asphaltene-resinous substances. The heavy metals were present mainly as the relevant sulphide minerals but products from the oxidation of sulphides were also present. The oil and the above-mentioned heavy metals were present mainly in the upper soil layers (mainly in the horizon A). Preliminary laboratory experiments in reactors and lysimeters revealed that it was possible to remove most of the contaminants in the soil by using the activity of the indigenous soil microflora. This activity was enhanced by suitable changes in the levels of some essential environmental factors such as pH and water, oxygen and nutrient contents of the soil. It was also found that the inoculation of the soil with active oil-degrading and metal-solubilizing microorganisms caused a considerable positive effect on the soil clean up. A pilot-scale operation for a simultaneous biological removal of the oil and heavy metals from the soil was carried out using the heap technique. Some data about this pilot-scale operation are presented in this paper. At the end of the treatment, the contents of pollutants in the soil were decreased below the permissible levels for soil of such type. At the same time, the chemical composition, structure and main physical and water properties of the soil were altered to a small extent, regardless of the fact that its pH was decreased to about 3.5. The addition of lime to the treated soil increased this pH to about 5.5 and in this way prevented the further acidification of the soil and the generation of acid drainage after rainfall. It must be noted that the removal of contaminants from the control heap was negligible, even after a period of about three years

  11. Reactivity of Athabasca residue and of its SARA fractions during residue hydroconversion

    Energy Technology Data Exchange (ETDEWEB)

    Verstraete, J.; Danial-Fortain, P.; Gauthier, T.; Merdrignac, I. [IFP-Lyon, Vermaison (France); Budzinski, H. [Bordeaux Univ. (France). ISM-LPTC, UMR CNRS

    2009-07-01

    Residue conversion processes are becoming increasingly important because of the declining market for residual fuel oil and a greater demand for middle distillates. Ebullated-bed hydroconversion is a commercially proven technology for converting heavy feedstocks with high amounts of impurities. The process enables the conversion of atmospheric or vacuum residues at temperatures up to 440 degrees C, and at liquid hourly space velocity (LHSV) conditions in the range of 0.15 to 0.5 per hour. A 540 degrees C conversion of up to 80 weight per cent can be achieved under these conditions. This paper reported on a research study conducted at IFP Lyon in which the residue hydroconversion in a large-scale ebullated bed bench unit was investigated to determine the impact of operating conditions and feed properties on yield and product qualities. Hydrogen was added to the feed in the bench units to keep a high hydrogen partial pressure and favour the catalytic hydroconversion reactions. In a typical test, the reactor was fed with 50 g of feedstock and 0.45 g of crushed equilibrium industrial NiMo catalyst, pressurized hydrogen and quickly heated at the reaction temperature. This paper also discussed the conversion of Athabasca bitumen residue in the large-scale pilot plant and also in the small scale batch reactor. The effect of operating temperature and space velocity was examined. The reactivity of the saturates, aromatics, resins and asphaltenes (SARA) fractions of the bitumen was studied separately in order to better understand the conversion mechanisms and reactivities. The Athabasca bitumen feed and SARA fractions were also analyzed in terms of standard petroleum analysis, SARA fractionation, elemental analysis, size exclusion chromatography (SEC) and 13C NMR. Hydroconversion experiments were conducted in the batch unit at different reaction temperatures and reaction times. A comparison of small-scale batch results with those obtained with the continuous large-scale bench

  12. Diagenetic and compositional controls of wettability in siliceous sedimentary rocks, Monterey Formation, California

    Science.gov (United States)

    Hill, Kristina M.

    Modified imbibition tests were performed on 69 subsurface samples from Monterey Formation reservoirs in the San Joaquin Valley to measure wettability variation as a result of composition and silica phase change. Contact angle tests were also performed on 6 chert samples from outcrop and 3 nearly pure mineral samples. Understanding wettability is important because it is a key factor in reservoir fluid distribution and movement, and its significance rises as porosity and permeability decrease and fluid interactions with reservoir grain surface area increase. Although the low permeability siliceous reservoirs of the Monterey Formation are economically important and prolific, a greater understanding of factors that alter their wettability will help better develop them. Imbibition results revealed a strong trend of decreased wettability to oil with increased detrital content in opal-CT phase samples. Opal-A phase samples exhibited less wettability to oil than both opal-CT and quartz phase samples of similar detrital content. Subsurface reservoir samples from 3 oil fields were crushed to eliminate the effect of capillary pressure and cleansed of hydrocarbons to eliminate wettability alterations by asphaltene, then pressed into discs of controlled density. Powder discs were tested for wettability by dispensing a controlled volume of water and motor oil onto the surface and measuring the time required for each fluid to imbibe into the sample. The syringe and software of a CAM101 tensiometer were used to control the amount of fluid dispensed onto each sample, and imbibition completion times were determined by high-speed photography for water drops; oil drop imbibition was significantly slower and imbibition was timed and determined visually. Contact angle of water and oil drops on polished chert and mineral sample surfaces was determined by image analysis and the Young-Laplace equation. Oil imbibition was significantly slower with increased detrital composition and faster

  13. Formation et stabilisation des émulsions inverses eau de mer-pétrole. Rôle de la tension et de la viscosité d'interface Formation and Stabilization of Reverse Seawater-Oil Emulsions. Role of Tension and Interfacial Viscosity

    Directory of Open Access Journals (Sweden)

    Desmaison M.

    2006-11-01

    Full Text Available On a étudié l'évolution au cours du temps de la tension et de la viscosité à l'interface d'un pétrole brut arabe léger et d'eau de mer reconstituée. D'une valeur initiale moyenne de 18 mNm-1, la tension interfaciale s'abaisse au niveau de 1 mNm-1 après 40 jours de contact. L'influence de l'oxygène et de la lumière, l'action des antioxydants et le rôle des constituants isolés du pétrole montrent que cette évolution est due à une oxydation photochimique de composés de la fraction aromatique. Inversement, la viscosité interfaciale augmente avec le temps selon une allure exponentielle. Cette évolution est liée à la présence d'asphaltènes dont les structures s'organisent au cours du temps. La superposition de ces deux phénomènes entraîne la formation et la stabilisation des émulsions inverses, dites mousses au chocolat que l'on observe lors des déversements accidentels de pétrole en mer. This article examines the evolution in time of the tension and interfacial viscosity of the Arabian Light crude oil reconstituted seawater interface. From an initial level of 18 mNm-1, the interfacial tension decreases to 1 mNm-1 after 40 days of contact. The influence of oxygen and light, the effect of antioxidants and the rote of constituents isolated from the oil show that this evolution is due to photochemical oxidation of compounds in the aromatic fraction. On the contrary, interfacial viscosity increases at an exponential rate with time. This evolution is linked to the presence of asphaltenes having structures which become organized with time. The combined effect of these two phenomena causes the formation and stabilization of reverse emulsions, called chocolate mousse, which are seen during accidental offshore oil spills.

  14. Evaluation des méthodes chimiques, spectroscopiques et chromatographiques utilisables pour l'identification des polluants pétroliers en mer Evaluation of Chemical, Spectroscopic and Chromatographic Methods Used to Identify Offshore Oil Pollutants

    Directory of Open Access Journals (Sweden)

    Albaigés J.

    2006-11-01

    Full Text Available Dans cet article on passe en revue les différentes méthodes utilisables pour l'identification des principaux polluants pétroliers de la mer par l'analyse quantitativé de leurs « marqueurs passifs x (soufre, azote, nickel, vanadium, paraffine et asphaltènes et la détermination d'autres caractéristiques intrinsèques. II s'agit de méthodes chimiques, spectroscop iques (infrarouge, ultraviolette et chromatographiques (chromatographie en phase gazeuse à haute résolution avec détection par ionisation de flamme, photométrie de flamme et capture d'électrons. Les mesures ont concerné une grande variété de produits susceptibles de polluer la côte méditerranéenne espagnole - pétrole brut des gisements offshore d'Amposta et de Castellôn; - pétroles bruts importés traités dans les raffineries côtières (Boscan, Es Sider, Kuwait, Arabian light, etc.; - fractions lourdes provenant de ces raffineries (fuel-cils, asphaltes, lubrifiants; - polluants réels; - échantillons altérés artificiellement en laboratoire afin de mettre en évidence l'action progressive des éléments naturels. On a trouvé que les méthodes les plus intéressantes étaient : - le dosage chimique du soufre, du nickel et du vanadium; - la spectroscopie infrarouge; - la chromatographie en phase gazeuse à haute résolution avec détection par ionisation et photométrie de flamme. This article reviews the different methods that con be used to identify the leading petroleum pollutants of the sea by quantitative analysis of their a passive markers » (sulfur, nitrogen, nickel, vanadium, paraffin, asphaltenes and by determining other intrinsic properties. These methods are chemical, spectroscopic (infrared, ultraviolet and chromatographic (high-resolution gas chromatography with flame ionization detection, flame photometry and electron capture. Measurements were made of a great variety of products capable of polluting the Spanish Mediterranean coast, including

  15. Transformation of Resources to Reserves: Next Generation Heavy-Oil Recovery Techniques

    Energy Technology Data Exchange (ETDEWEB)

    Stanford University; Department of Energy Resources Engineering Green Earth Sciences

    2007-09-30

    This final report and technical progress report describes work performed from October 1, 2004 through September 30, 2007 for the project 'Transformation of Resources to Reserves: Next Generation Heavy Oil Recovery Techniques', DE-FC26-04NT15526. Critical year 3 activities of this project were not undertaken because of reduced funding to the DOE Oil Program despite timely submission of a continuation package and progress on year 1 and 2 subtasks. A small amount of carried-over funds were used during June-August 2007 to complete some work in the area of foamed-gas mobility control. Completion of Year 3 activities and tasks would have led to a more thorough completion of the project and attainment of project goals. This progress report serves as a summary of activities and accomplishments for years 1 and 2. Experiments, theory development, and numerical modeling were employed to elucidate heavy-oil production mechanisms that provide the technical foundations for producing efficiently the abundant, discovered heavy-oil resources of the U.S. that are not accessible with current technology and recovery techniques. Work fell into two task areas: cold production of heavy oils and thermal recovery. Despite the emerging critical importance of the waterflooding of viscous oil in cold environments, work in this area was never sanctioned under this project. It is envisioned that heavy oil production is impacted by development of an understanding of the reservoir and reservoir fluid conditions leading to so-called foamy oil behavior, i.e, heavy-oil solution gas drive. This understanding should allow primary, cold production of heavy and viscous oils to be optimized. Accordingly, we evaluated the oil-phase chemistry of crude oil samples from Venezuela that give effective production by the heavy-oil solution gas drive mechanism. Laboratory-scale experiments show that recovery correlates with asphaltene contents as well as the so-called acid number (AN) and base number

  16. Investigation of hydrate formation and transportability in multiphase flow systems

    Science.gov (United States)

    Grasso, Giovanny A.

    The oil and gas industry is moving towards offshore developments in more challenging environments, where evaluating hydrate plugging risks to avoid operational/safety hazards becomes more difficult (Sloan, 2005). Even though mechanistic models for hydrate plug formation have been developed, compo