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Sample records for asphaltenes

  1. 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.

  2. Asphaltene based photovoltaic devices

    Science.gov (United States)

    Chianelli, Russell R.; Castillo, Karina; Gupta, Vipin; Qudah, Ali M.; Torres, Brenda; Abujnah, Rajib E.

    2016-03-22

    Photovoltaic devices and methods of making the same, are disclosed herein. The cell comprises a photovoltaic device that comprises a first electrically conductive layer comprising a photo-sensitized electrode; at least one photoelectrochemical layer comprising metal-oxide particles, an electrolyte solution comprising at least one asphaltene fraction, wherein the metal-oxide particles are optionally dispersed in a surfactant; and a second electrically conductive layer comprising a counter-electrode, wherein the second electrically conductive layer comprises one or more conductive elements comprising carbon, graphite, soot, carbon allotropes or any combinations thereof.

  3. 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.

  4. 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.

  5. 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

  6. 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.

  7. 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.

  8. On the Mass Balance of Asphaltene Precipitation

    DEFF Research Database (Denmark)

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

    2001-01-01

    In the evaluation of experimental data as well as in calculation of phase equilibria the necessity of the application of mass balances is obvious. In the case of asphaltenes the colloidal nature of these compounds may highly affect the mass balance. In the present paper several experiments...... 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...... indicates that in temperature experiments as well as in solvent series experiments the precipitation of heavy asphaltenes affects the following precipitation of lighter asphaltenes. In both cases the mass balance using standard separation techniques cannot be closed, as less material is precipitated...

  9. 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.

  10. 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.

  11. 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)

  12. 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...

  13. 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.

  14. Examining Asphaltene Solubility on Deposition in Model Porous Media

    OpenAIRE

    Lin, Yu-Jiun; He, Peng; Tavakkoli, Mohammad; Mathew, Nevin Thunduvila; Yap, Yit-Fatt; Chai, John; Goharzadeh, Ashfin; Vargas, F. M.; Biswal, S.L.

    2016-01-01

    Asphaltenes are known to cause severe flow\\ud 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 k...

  15. 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 ...

  16. 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...

  17. Colloidal interactions between asphaltene surfaces in aqueous solutions.

    Science.gov (United States)

    Liu, Jianjun; Zhang, Liyan; Xu, Zhenghe; Masliyah, Jacob

    2006-02-14

    Asphaltene at oil/water interfaces plays a dominant role in the recovery of crude oil. In this study, asphaltene monolayer films were deposited on hydrophobic silicon wafers and silica spheres from oil-water interfaces using a Langmuir interfacial trough. The morphology of the deposited asphaltene films was characterized with an atomic force microscope (AFM). The colloidal forces between the prepared asphaltene films in aqueous solutions were measured with AFM to shed light on the stabilization of water or oil droplets coated with asphaltene films. Factors such as solution pH, KCl concentration, calcium addition, and temperature all showed a strong impact on colloidal forces between the prepared asphaltene films. The findings provided a better understanding of asphaltene interfacial films at an oil/water interface in stabilizing bitumen-in-water and water-in-bitumen emulsions.

  18. Direct Observation of Asphaltene Nanoparticles on Model Mineral Substrates.

    Science.gov (United States)

    Raj, Gijo; Lesimple, Alain; Whelan, Jamie; Naumov, Panče

    2017-06-27

    The propensity for adherence to solid surfaces of asphaltenes, a complex solubility class of heteropolycyclic aromatic compounds from the heavy fraction of crude oil, has long been the root cause of scale deposition and remains an intractable problem in the petroleum industry. Although the adhesion is essential to understanding the process of asphaltene deposition, the relationship between the conformation of asphaltene molecules on mineral substrates and its impact on adhesion and mechanical properties of the deposits is not completely understood. To rationalize the primary processes in the process of organic scale deposition, here we use atomic force microscopy (AFM) to visualize the morphology of petroleum asphaltenes deposited on model mineral substrates. High imaging contrast was achieved by the differential adhesion of the tip between asphaltenes and the mineral substrate. While asphaltenes form smooth continuous films on all substrates at higher concentrations, they deposit as individual nanoparticles at lower concentrations. The size, shape, and spatial distribution of the nanoaggregates are strongly affected by the nature of the substrate; while uniformly distributed spherical particles are formed on highly polar and hydrophilic substrates (mica), irregular islands and thicker patches are observed with substrates of lower polarity (silica and calcite). Asphaltene nanoparticles flatten when adsorbed on highly oriented pyrolytic graphite due to π-π interactions with the polycyclic core. Force-distance profiles provide direct evidence of the conformational changes of asphaltene molecules on hydrophilic/hydrophobic substrates that result in dramatic changes in adhesion and mechanical properties of asphaltene deposits. Such an understanding of the nature of adhesion and mechanical properties tuned by surface properties, on the level of asphaltene nanoaggregates, would contribute to the design of efficient asphaltene inhibitors for preventing asphaltene

  19. 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...

  20. 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.

  1. 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.

  2. 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...... 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...... 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...

  3. 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.)

  4. 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...... stress measurement and compared with the original crude oil. A complex asphaltene−wax interaction as a function of asphaltene concentration and degree of asphaltene dispersion under dynamic and static condition was observed. The crystallization and the wax network strength was strongly dependent...... influence the wax crystallization at static condition more significantly than the more flocculated....

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

    DEFF Research Database (Denmark)

    Andersen, Simon Ivar; Christensen, S. D.

    2000-01-01

    of asphaltenes obtained by solvent extraction with toluene/heptane mixtures. These subfractions get more complex in structure as the toluene content of the extraction solvent increases and at the same time the CMC of the asphaltenes in pure toluene decreases. There is an indication that the presence of "lower...

  6. 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

  7. 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

  8. Role of asphaltenes in stabilizing thin liquid emulsion films.

    Science.gov (United States)

    Tchoukov, Plamen; Yang, Fan; Xu, Zhenghe; Dabros, Tadeusz; Czarnecki, Jan; Sjöblom, Johan

    2014-03-25

    Drainage kinetics, thickness, and stability of water-in-oil thin liquid emulsion films obtained from asphaltenes, heavy oil (bitumen), and deasphalted heavy oil (maltenes) diluted in toluene are studied. The results show that asphaltenes stabilize thin organic liquid films at much lower concentrations than maltenes and bitumen. The drainage of thin organic liquid films containing asphaltenes is significantly slower than the drainage of the films containing maltenes and bitumen. The films stabilized by asphaltenes are much thicker (40-90 nm) than those stabilized by maltenes (∼10 nm). Such significant variation in the film properties points to different stabilization mechanisms of thin organic liquid films. Apparent aging effects, including gradual increase of film thickness, rigidity of oil/water interface, and formation of submicrometer size aggregates, were observed for thin organic liquid films containing asphaltenes. No aging effects were observed for films containing maltenes and bitumen in toluene. The increasing stability and lower drainage dynamics of asphaltene-containing thin liquid films are attributed to specific ability of asphaltenes to self-assemble and form 3D network in the film. The characteristic length of stable films is well beyond the size of single asphaltene molecules, nanoaggregates, or even clusters of nanoaggregates reported in the literature. Buildup of such 3D structure modifies the rheological properties of the liquid film to be non-Newtonian with yield stress (gel like). Formation of such network structure appears to be responsible for the slower drainage of thin asphaltenes in toluene liquid films. The yield stress of liquid film as small as ∼10(-2) Pa is sufficient to stop the drainage before the film reaches the critical thickness at which film rupture occurs.

  9. 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

  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

    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......-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...

  11. The distribution of polycyclic aromatic hydrocarbons in asphaltenes

    Energy Technology Data Exchange (ETDEWEB)

    Ruiz-Morales, Y. [Inst. Mexicano del Petroleo, Lazaro (Mexico). Programa de Ingenieria Molecular; Ballard Andrews, A.; Mullins, O.C. [Schlumberger-Doll Research Center, Cambridge, MA (United States)

    2008-07-01

    The distribution of polycyclic aromatic hydrocarbons (PAHs) in asphaltenes is a strong determinant for asphaltene physical properties. PAHs also provide the UV and visible absorption and emission profiles of asphaltenes. All PAHs absorb light in the UV-visible spectrum and many also emit light in this spectral range. This study combined a molecular orbital theory with an experimental approach to quantitatively link the UV-visible absorption and emission profiles to the asphaltene PAH distribution. Key features of the absorption and emission spectral data were found to be reproduced with PAH distributions centered at 7 fused rings. The study also identified other highly different distributions of PAHs in terms of plausibility to account for the measured optical data. The paper also described the affect that heteroatoms had on the analysis.

  12. Asphaltene laboratory assessment of a heavy onshore reservoir during pressure, temperature and composition variations to predict asphaltene onset pressure

    Energy Technology Data Exchange (ETDEWEB)

    Bahrami, Peyman; Ahmadi, Yaser [Islamic Azad University, Tehran (Iran, Islamic Republic of); Kharrat, Riyaz [Petroleum University of Technology, Tehran (Iran, Islamic Republic of); Mahdavi, Sedigheh; James, Lesley [Memorial University of Newfoundland, Saint John' s (Canada)

    2015-02-15

    An Iranian heavy oil reservoir recently encountered challenges in oil production rate, and further investigation has proven that asphaltene precipitation was the root cause of this problem. In addition, CO{sub 2} gas injection could be an appropriate remedy to enhance the production of heavy crudes. In this study, high pressure-high temperature asphaltene precipitation experiments were performed at different temperatures and pressures to investigate the asphaltene phase behavior during the natural depletion process and CO{sub 2} gas injection. Compositional modeling of experimental data predicted onset points at different temperatures which determine the zone of maximum probability of asphaltene precipitation for the studied heavy oil reservoir. Also, the effect of CO{sub 2} gas injection was investigated as a function of CO{sub 2} concentration and pressure. It was found that a CO{sub 2}-oil ratio of 40% is the optimum for limiting precipitation to have the least formation damage and surface instrument contamination.

  13. Effects of the asphaltene structure and the tetralin/heptane solvent ratio on the size and shape of asphaltene aggregates.

    Science.gov (United States)

    Lee, Hwankyu; Lee, Yong-Kul

    2017-05-31

    Asphaltene molecules, which consist of differently hydrogenated polyaromatic cores grafted with side alkyl chains of different sizes and grafting densities, were simulated with a solvent mixture of heptane and tetralin using coarse-grained force fields. Starting with the initial configuration of randomly distributed asphaltene molecules and solvents, the asphaltene molecules aggregate because of the attractive force between their polyaromatic cores, but their sizes and shapes differ. The average aggregate size decreases with an increase in the hydrogenated polycyclic core, side-chain length, and tetralin concentration, which agree with experimental observations in the hydrocracking process. The number of side chains also influences the aggregate size but only in the presence of tetralin. In particular, the effect of tetralin addition occurs more significantly for asphaltene molecules with more side chains because side chains sterically block the intermolecular interactions between polyaromatic cores, which makes it easier for the aromatic ring of tetralin to bind to the polyaromatic core of asphaltene. These steric effects of side chains yield different shapes of aggregates, showing parallel stacking (face-to-face) for aromatic cores with many side chains, and T-shape (edge-to-face) or offset-parallel stacking for those with fewer side chains. These findings agree with the experimental observation regarding the effect of tetralin on the solubility of asphaltene, and indicate that the extent of the tetralin effect depends on the number of side alkyl chains, implying that tetralin solvents need to be added with consideration for the structural change of asphaltene under hydrogenation or dealkylation conditions.

  14. 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.

  15. 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.

  16. 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.

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

    Indian Academy of Sciences (India)

    Asphaltenes separated from two different crude oils from upper Assam, India, having different geological origins, viz. DK(eocene) and JN (oligocene–miocene) were pyrolysed at 600 °C and the products were analysed by gas chromatography–mass spectrometry (GC/MS) especially for the generated alkylnaphthalenes and ...

  18. 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...

  19. Permeability reduction by asphaltenes and resins deposition in porous media

    Energy Technology Data Exchange (ETDEWEB)

    R. Hamadou; M. Khodja; M. Kartout; A. Jada [Sonatrach/Division Centre de Recherche et Developpement, Boumerdes (Algeria)

    2008-08-15

    The deposition of crude oil polar fractions such as asphaltenes and resins in oil reservoir rocks reduce considerably the rock permeability and the oil production. In the present work, a crude oil and various core samples were extracted from Rhourd-Nouss (RN) reservoir rock. Afterwards, core flow experiments were carried out in the laboratory to investigate permeability reduction that causes formation damage. The core permeability damage was evaluated by flooding Soltrol, through the sample and measuring the solvent permeabilities, K{sub I} and K{sub f}, respectively, before and after injection of a given pore volume number of the crude oil. The data indicate that upon flooding the crude oil through the porous medium, considerable permeability reduction, expressed as the ratio (K{sub I} - K{sub f})/K{sub I}, and ranging from 72.4% to 98.3% were observed. The permeability reduction is found to result from irreversible retention of asphaltenes and resins in the porous core sample. However, no correlations could be established between the depth of the well, the core porosity, the core mineral compositions determined by X-ray analysis, and the permeability damage factors. In addition, effluents flowing away from RN wells were collected and analysed at various periods, after carrying out aromatic solvents squeezes. The amount of saturates, aromatics, resins, and asphaltenes (SARA analysis), of the crude oil, the deposited crude oil fraction, and the effluent's residues were measured and compared. The asphaltenes weight percent was found to increase from 1.56% for the crude oil to 11.42% for the deposited oil fraction, and was in the range 1.37-2.36% for the effluent's residues. Such results indicate that the deposited oil fraction and the effluent's residues consist mainly of asphaltenes and resins. 26 refs., 1 fig., 11 tabs.

  20. Hindered diffusion of asphaltenes at elevated temperature and pressure. [Semi-annual report], September 20, 1995--March 20, 1996

    Energy Technology Data Exchange (ETDEWEB)

    Guin, J.A.

    1996-04-12

    In this study equilibrium adsorption isotherms were determined for two petroleum asphaltenes, AAD-1 and AAK-1, and one coal asphaltene, called No. 97500. Isotherms were determined for three different temperatures, namely 20, 35 and 50{degrees}C. The experimental data for the petroleum asphaltenes were fitted with a Freundlich isotherm. For the coal asphaltene a Freundlich isotherm was used to fit the experimental data for lower concentrations; however, for higher concentrations a linear isotherm fitted the experimental data better. The coal asphaltene showed a tendency to form multilayers on the catalyst surface. Upon comparison of the adsorption isotherms for the three different temperatures, an interesting effect was observed. Although a decrease of the asphaltenes adsorption for higher temperatures was expected, the adsorption as a function of the temperature in fact showed a maximum for the petroleum asphaltenes and a minimum for the coal asphaltenes. This interesting and unexpected behavior was speculated to be due to the formation of micelles in the coal asphaltene solution and the different dependence of micelle formation and adsorption on temperature. Comparing the adsorption isotherms for the three different asphaltenes revealed that the adsorption of the coal asphaltenes was initially lower than the adsorption of the petroleum asphaltenes, but increased more rapidly, finally becoming near and even greater than the adsorption of the petroleum asphaltenes. This was suggested to be due to the tendency of coal asphaltenes for multilayer adsorption on the solid surface.

  1. 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

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

    Science.gov (United States)

    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.

  3. Transportation and adhesion of asphaltenes in a heat exchanger tube through CFD simulations

    Science.gov (United States)

    Emani, Sampath; Ramasamy, M.; Shaari, Ku Zilati Ku

    2017-07-01

    Asphaltenes are identified as the main cause of crude oil fouling in preheat trains. The understanding of individual trajectory of asphaltenes particles, transportation behavior of the fouling precursors in the domain and the effect of various attractive and/or repulsive forces acting on the asphaltenes particles, which lead to an increase/decrease in the deposition, have been impeded by a shortage of information. In the present work, an attempt has been made to understand the transportation and adhesion behavior of asphaltenes in a heat exchanger tube through Computational Fluid Dynamics approach. A Lagrangian based discrete-phase model has been implemented to understand the hydrodynamics of asphaltenes particles and the effect of various forces on the asphaltenes particles deposition on the heat transfer surfaces. The effect of wall shear stress, surface roughness, and temperature difference on asphaltenes deposition is also reported. From the CFD analysis, the net mass deposition of the asphaltenes particles is minimized with an increase in wall shear stress and surface roughness. The asphaltenes particles in the region where the temperature difference between the bulk and wall is lower at a constant wall temperature are carried forward with the flow and particles with higher temperature difference between the bulk and wall at constant wall temperature are attracted towards the heat transfer surface and deposited on the wall of the heat exchanger tube.

  4. 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.

  5. 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.

  6. 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

  7. 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

  8. Mixture Effect on the Dilatation Rheology of Asphaltenes-Laden Interfaces.

    Science.gov (United States)

    Liu, Fang; Darjani, Shaghayegh; Akhmetkhanova, Nelya; Maldarelli, Charles; Banerjee, Sanjoy; Pauchard, Vincent

    2017-02-28

    Asphaltenes are a solubility class of crude oils comprising polyaromatic and heterocyclic molecules with different interfacial activities. The previously neglected effects of compositional mixture on dilatational rheology are discussed in the light of diffusional relaxation models. It is demonstrated that the reported deviations from the Lucassen-van den Tempel model for a single-component solution could largely originate from a distribution in adsorption coefficients within the asphaltenes class. This particularly applies to the peculiar gel point rheology previously ascribed to asphaltenes cross-linking at the interface. Furthermore, an extensive bibliographical review shows that asphaltenes dilatational rheology data always verify the main features of diffusional relaxation, including a decrease in modulus at high bulk concentrations and phase shift values always lower than 45°. Using diffusional relaxation concepts, the reanalysis of the most extensive dataset so far confirmed recently published studies, showing that asphaltenes exhibit a unique equation of state (EOS) irrespective of adsorption conditions. This EOS proves to be very similar for bitumen and petroleum asphaltenes. Finally, a numerical application of a binary diffusional model proved efficient to capture both dynamic interfacial tension and dilatational rheology, with the same parameters. It appears that a minority of asphaltenes (less than 10%) have a much stronger interfacial activity than the bulk of them, as previously demonstrated by fractionation. These results open up the need for a reinterpretation of the physical mechanisms of asphaltenes adsorption in terms of classical amphiphilic behavior, with a potential impact on emulsion breaking and enhanced oil recovery strategies.

  9. An electron spin resonance probe method for the understanding of petroleum asphaltene macrostructure

    Energy Technology Data Exchange (ETDEWEB)

    Wong, G.K.; Yen, T.F. [Department of Civil and Environmental Engineering, University of Southern California, 3620 South Vermont Avenue 224A, 90089-2531 Los Angeles, CA (United States)

    2000-10-01

    Molecularly, petroleum asphaltenes are induced dipoles, which agglomerate into nanometer-sized colloids of different aggregation states. The electron spin resonance (ESR) vanadyl probe method is used to investigate the asphaltene macrostructures under different temperatures and microwave powers. Oxovanadium complexes native to an asphaltene isolated from Boscan crude oil, Venezuela, function as tracers to examine the behavior of micelle agglomerates when subjected to a microwave field. Both mobile and bounded oxovanadium compounds in colloidal asphaltene solution are in a state of equilibrium. It is noted that a greater amount of mobile vanadyl complexes can be stabilized in a dispersing medium (single-aromatic ring solvent series) with a higher-valued Hansen hydrogen bonding solubility parameter. We found that conversion of ESR vanadyl hyperfine lines occurs from anisotropic to isotropic as the temperature of a 4% Boscan asphaltene solution in o-xylene increased from 25C to 100C. Free tumbling of total vanadyl complexes in organic solvent signifies dissociation of micelles at packing imperfections prior to their release from aromatic hosts. Coupling of petroleum asphaltenes with microwave power can overcome charge transfer and charge balance interactions within micelle agglomerates. The relative content of mobile to bounded vanadyl complexes in 4% Boscan asphaltene solution of o-xylene was found to increase with microwave power at 45C. Microwave energy will enable effective dispersion of colloidal asphaltene in heavy oil refining and upgrading.

  10. A study of the processes related to coagulation of asphaltenes by electronic spin resonance

    Energy Technology Data Exchange (ETDEWEB)

    Tagirzyanov, M.I.; Yakubov, M.R.; Romanov, G.V. [A.E. Arbuzov Inst. of Organic and Physical Chemistry, Russian Academy of Sciences (Russian Federation)

    2004-07-01

    This study examined the coagulation of asphaltenes in crude oil from the Volga-Ural region in Russia. In particular, it examined the contents of vanadyl complexes and free radicals in crude oils and asphaltenes by electron spin resonance. Asphaltenes fall into two major structural categories based on vanadium content. The interactions between vanadyl complexes and free radicals of the asphaltenes liquid phase were modelled in order to determine if they can form diamagnetic associations. Asphaltenes with low vanadium content (less than 0.1 per cent by weight), have large polyaromatic fragments in the molecules. Therefore, more than half of the free radicals recombine when the asphaltene are separated from the crude oil. Vanadium rich asphaltenes (greater than 0.3 per cent by weight) have polyaromatic fragments in the inner part of the structure. It was concluded that interaction between vanadyl complexes and asphaltene fragments containing free radicals do not result in the formation of diamagnetic associations. 23 refs., 3 tabs., 3 figs.

  11. 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

    Asphaltene precipitation/deposition and its imposing difficulties are drastic issues in petroleum industry. Monitoring the asphaltene stability conditions in crude oil systems is still a challenge and has been subject of many studies. In this work, the Refractive Index (RI) of several oil samples...

  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...

  13. 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

  14. 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

    of DeltaH(a) obtained suggest that a fraction of asphaltenes is not active in the calorimetric experiments. Asphaltenes from Venezuela (LM1) and Mexico (KU) have been fractionated by precipitation with a mixture of acetone and toluene. It is considered that the most polar compounds are collected...

  15. 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.

  16. Asphaltene adsorption on quartz sand in the presence of pre-adsorbed water.

    Science.gov (United States)

    Gonzalez, Valeska; Taylor, Spencer E

    2016-10-15

    In the oil industry, asphaltenes are known for their tendency to aggregate in solution and to deposit on surfaces, with both properties being connected with operational problems associated with recovery, production and refining. Interactions involving asphaltenes and other crude oil components have been a major aspect of investigation in attempting to understand the full nature of these problems. Water is implicated in asphaltene behavior in solution, for example, where it has been found to delay the deposition of asphaltene aggregates. At interfaces, there is evidence that water-in-crude oil emulsion stability is enhanced through asphaltene-water interactions, and there have been a few reports that asphaltene adsorption on mineral surfaces is reduced in the presence of water. We consider the latter aspect, because the instances of reduced adsorption to date have not attempted to quantify the effect. Previous studies showed that vapor-phase adsorption of organic molecules is reduced in the presence of pre-adsorbed water and we were interested to determine whether the same is true for liquid-phase adsorption of asphaltenes. The surface of quartz sand was controlled by pre-adsorption of water from different relative humidity (RH) environments as the water adsorption isotherm is known from previous studies. These pre-conditioned sand samples were used as substrates for the adsorption from toluene solutions of n-heptane-precipitated asphaltenes (C7A) from an Athabasca oil sands bitumen. To supplement the adsorption behavior, atomic force microscopy (AFM) images were taken of the resultant sand grains at 0 and 80% RH, and low-field NMR was used to estimate the sand wettability. Asphaltene adsorption on sand is sensitive to surface-adsorbed water, with ∼4-fold reduction in adsorption when increasing the RH from 0 to 100%. This is in general agreement with previous vapor-phase adsorption of small organic molecules, and is therefore believed to be the first demonstration

  17. 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

    usually found in the literature as the CMC region of asphaltenes indicates that this concept is not appropriate for asphaltene self-association. Tests were performed down to concentrations of 34ppm without any sign of a critical micellization or aggregation concentration. Based on the various techniques a......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...... that asphaltenes may also have a concentration at which self-association occurs (CMC). This article presents evidence found by calorimetry and spectroscopic techniques, that suggest that this concept may not be adequate for asphaltene self-association in toluene solutions. Isothermal titration calorimetry has been...

  18. Discussion of the role of asphaltene in heavy crudes and tar sands

    Energy Technology Data Exchange (ETDEWEB)

    Yen, T.F.

    1981-01-01

    A discussion of the role of asphaltene in heavy crudes and tar sands covers a definition of heavy oil as a dark-colored, high-density, and high-viscosity oil, rich in heteroatom components, such as asphaltics (asphaltenes plus resin), and metallo complexes, such as vanadyl porphyrin; the classification of heavy oil into thermally transformed, biodegraded, and severely cracked oil; the structural parameters of various asphaltenes derived from petroleum, shale, and coal; and the relationship of asphaltene content in heavy oil to the metals and sulfur contents, to upgrading via thermal and hydrocracking processes, to reactivity, to mesophase growth, to enhanced oil recovery, and to weathering, which was shown in one study of an oilspill to increase the asphaltenes and carbene content.

  19. 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)

  20. Charge dependent asphaltene adsorption onto metal substrate : electrochemistry and AFM, STM, SAM, SEM analysis

    Energy Technology Data Exchange (ETDEWEB)

    Batina, N.; Morales-Martinez, J. [Univ. Autonoma Metropolitana-Iztapalapa (Mexico). Lab. de Nanotecnologia e Ingenieria Molecular; Ivar-Andersen, S. [Technical Univ. of Denmark (Denmark). Dept. Hem. Eng; Lira-Galeana, C. [Inst. Mexicano del Petroleo, Lazaro (Mexico). Molecular Simulation Research Program; De la Cruz-Hernandez, W.; Cota-Araiza, L.; Avalos-Borja, M. [Univ. Nacional Autonoma de Mexico (Mexico)

    2008-07-01

    Asphaltenes have been identified as the main component of pipeline molecular deposits that cause plugging of oil wells. In this study, Atomic Force Microscopy (AFM), Scanning Tunneling Microscopy (STM), Scanning Auger Microprobe Spectroscopy (SAM) and Scanning Electron Microscopy (SEM) were used to characterized molecular deposits of Mexican crude oil and asphaltenes formed at a charged metal surface. The qualitative and quantitative characterization involved determining the size and shape of adsorbed molecules and aggregates, and the elemental analysis of all components in molecular films. Samples were prepared by electrolytic deposition under galvanostatic or potentiostatic conditions directly from the crude oil or asphaltene in toluene solutions. The study showed that the formation of asphaltene deposit depends on the metal substrate charge. Asphaltenes as well as crude oil readily adsorbed at the negatively charged metal surface. Two elements were present, notably carbon and sulfur. Their content ratio varied depending on the metal substrate charge.

  1. 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......, eventually leading to road deterioration. This paper focuses on understanding the mechanisms behind nanoaggregate size and stability. We used molecular dynamics simulations to quantify the probability of having a nanoaggregate of a given size in the stationary regime. To model this complicated behavior, we...

  2. Simultaneous removal of asphaltenes and water from water-in-bitumen emulsion. I. Fundamental development

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Yingxian; Wei, Feng [Ningbo Institute of Technology, Zhejiang University, 1 Xuefu Road, Ningbo Higher Education Zone, Zhejiang, 315100 (China)

    2008-10-15

    Simultaneous removal of asphaltenes and water from a water-in-bitumen emulsion by adding light paraffinic solvents was investigated with a bench-scale unit. Asphaltene precipitation in bitumen, emulsion breaking, and phase separation were found to be largely dependent on solvency and temperature. Increasing temperature facilitated the precipitation of asphaltenes in bitumen, and accelerated the separation of the light deasphalting oil (DAO)/solvent phase and the heavy asphaltenes/water phase. The removal of 98 +% asphaltenes and 99.9 +% water from the emulsion was achieved with the n-pentane/bitumen volumetric ratio of 3.0 in temperature range of 423-453 K. The interaction between asphaltene particles and water droplets is actually beneficial to the removal process. For process design and optimization, the operation pathway including two-step solvent injections at different temperature, the supercritical recovery of solvent from DAO stream and the solidification of asphaltenes by depressurization, as well as other important issues have been addressed. (author)

  3. 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.

  4. Droplet Coalescence and Spontaneous Emulsification in the Presence of Asphaltene Adsorption.

    Science.gov (United States)

    Bochner de Araujo, Simone; Merola, Maria; Vlassopoulos, Dimitris; Fuller, Gerald G

    2017-10-10

    In a refinery, undesired high levels of salt concentration in crude oils are reduced by the contact of water with crude oils, where an emulsion is formed. Later, the separation of the water from the desalted oil is essential for the quality of both wastewater discharge and refined oil. However, complex components of crude oils such as asphaltenes may stabilize these emulsions, causing difficulties in efficient separation. Here, we show the coalescence inhibition caused by asphaltene adsorption for both water-in-oil and oil-in-water emulsions, where the oil phase consists of a simple model of asphaltenes dissolved in toluene. We find that oil-in-water emulsions are less stable than water-in-oil emulsions by using a newly developed instrument where controlled experiments can be performed to measure the coalescence time of a single droplet against an oil/water interface as a function of asphaltene aging (associated with the adsorption process of asphaltene molecules onto the interfaces) and asphaltene concentration. Furthermore, we find that the coalescence time for water droplets exhibits a maximum because of a spontaneous emulsification at the oil/water interface that produces droplets consisting of asphaltene-laden water droplets.

  5. 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.

  6. Effect of hydrophobic ionic liquids on petroleum asphaltene dispersion and determination using UV-visible spectroscopy

    Science.gov (United States)

    Rashid, Zeeshan; Wilfredand, Cecilia Devi; Murugesan, Thanabalan

    2017-10-01

    Asphaltene aggregation and flocculation is one of the main problems faced by upstream industry. The aim of this research activity is to explore the effect of synthesized imidazolium and pyridinium based ionic liquids on the prevention of asphaltene aggregation problem in crude oil. In this research, number of hydrophobic and hydrophilic ionic liquids were tested. The investigations were performed for evaluating; the dispersion yield, effect of temperature, effect of stirring time and effect of solvent to flocculant ratio. Analysis were done using UV-visible Spectroscopy. The results depicted that the investigated hydrophobic ionic liquids have the tendency to abate asphaltene aggregation and can be considered as deflocculants.

  7. 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

    of asphaltenes have not been fully elucidated. It is especially important to characterize the polar functionalities of these fractions, because they participate in the intermolecular aggregation by means of hydrogen bonds. The chemical derivatization of asphaltenes has been used, in combination with suitable...... 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...

  8. The zeta potential and surface properties of asphaltenes obtained with different crude oil/n-heptane proportions

    Energy Technology Data Exchange (ETDEWEB)

    Hilda Parra-Barraza; Daniel Hernandez-Montiel; Jaime Lizardi; Javier Hernandez; Ronaldo Herrera Urbina; Miguel A. Valdez [Universidad de Sonora, Sonora (Mexico). Departamento de Ciencias Quimico Biologicas

    2003-05-01

    We have investigated some surface properties of asphaltenes precipitated from crude oil with different volumes of n-heptane. According to the crude oil/n-heptane proportions used, asphaltenes are identified as 1:5, 1:15 and 1:40. Zeta potential results indicate that the amount of n-heptane determines the electrokinetic behaviour of asphaltenes in aqueous suspensions. Asphaltene 1:5 exhibits an isoelectric point (IEP) at pH 4.5 whereas asphaltenes 1:15 and 1:40 show an IEP at about pH 3. Surface charge on asphaltenes arises from the dissociation of acid functionalities and the protonation of basic functional groups. The presence of resins remaining on the asphaltene molecules may be responsible for the different IEP of asphaltene 1:5. Both sodium dodecyl sulfate (an anionic surfactant) and cetylpyridinium chloride (a cationic surfactant) were found to adsorb specifically onto asphaltenes. They reverse the sign of the zeta potential under certain conditions. These surfactants may be potential candidates to aid in controlling the stability of crude oil dispersions. Critical micelle concentration, interfacial tension measurements, and Langmuir isotherms at the air water interface confirm the different nature of asphaltene 1:5, which also showed more solubility and a larger molecular size. 26 refs., 3 figs., 1 tab.

  9. 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.

  10. Extraction methods influence in asphaltenes structure; Influencia de metodos de extracao na estrutura de asfaltenos

    Energy Technology Data Exchange (ETDEWEB)

    Carvalho, C.C.V.; Moreira, L.C.; Pereira, A. [Universidade Federal, Rio de Janeiro, RJ (Brazil); Chrisman, E.C.A.N. [Universidade Federal Rural do Rio de Janeiro, RJ (Brazil)]. E-mail: erikanunes@openlink.com.br; Seidl, P.R. [Universidade Federal Fluminense, Niteroi, RJ (Brazil)]. E-mail: pseidl@eq.ufrj.br

    2003-07-01

    The oil is a balanced mixture of different fractions (saturated hydro-carbons and insaturated, aromatical, sulphurated composites, oxygen and nitrogen, asphaltenes and resins). The majority of the components is found in the residue proceeding from the unit of distillation the vacuum. This fraction, called heavy or deep barrel possesses a low commercial value. Adding it this, its constituent are most difficult to characterize, between which if it finds the asphaltene that forms a complex subgroup still more. The asphaltenes are recognized as being a complex mixture of species of molecular weights, diversified polarity and functional classrooms. They are a soluble classroom that it precipitates for the addition of an excess of paraffinic hydro-carbons that contains condensed aromatical ring systems polynuclear, loaded of alquil chains. In the industry of the oil they are a problem of increasing importance therefore since the stage of attainment of the oil still in the reservoirs, the presence of asphaltenes in its structure already becomes a bother in the perforation process. Moreover, it causes to serious problems of clogging and corrosivity in the tubings of the refining process. Recent studies have been directed with sufficient attention to the case of the asphaltenes. Currently, the performance of a refinery can be evaluated from the capacity that the same one possesses to transform residual fractions into products of bigger commercial value. The attainment, or better, the isolation of the asphaltenes from vacuum residues would be the first step to extend possibilities in this line of research. This would collaborate in the resolution of the diverse problems that the asphaltene generates in the field of chemistry. This work had as purpose the comparison of two methods of extraction of asphaltenes (IP-143 and Method HEPT) how much the quantification of this fraction and determination of molecular characteristics of three different residues of vacuum: A, B and C

  11. 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.

  12. 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.

  13. Evaluating the hydrophilic-lipophilic nature of asphaltenic oils and naphthenic amphiphiles using microemulsion models.

    Science.gov (United States)

    Kiran, Sumit K; Acosta, Edgar J; Moran, Kevin

    2009-08-01

    Asphaltenes and naphthenic acid derivatives, which are polar and surface-active species, are known to interfere with the recovery of heavy crude oil by promoting the formation of stable emulsions. In this study, previously established microemulsion phase behavior models were applied to quantify the hydrophilic-lipophilic nature of asphaltenic oils (bitumen, deasphalted bitumen, asphalt, naphthalene) and surface-active species found in heavy oils (naphthenic compounds and asphaltenes). For the test oils, the equivalent alkane carbon number (EACN) was determined by evaluating the "salinity shifts" of microemulsions formulated with a reference surfactant (sodium dihexyl sulfosuccinate--SDHS) and a reference oil (toluene) as a function of test oil volume fraction. Similarly, the characteristic curvature (C(C)) of surface-active species was determined by evaluating the salinity shifts as a function of the molar fraction of the surface-active species in mixture with SDHS. As a part of the oil phase, asphaltenes and asphaltene-like species are highly hydrophilic, which lead to low EACN values despite their large molecular weight. As a surface-active material, asphaltenes are hydrophobic species that lead to the formation of water-in-oil emulsions. Naphthenates, particularly sodium naphthenates, are highly hydrophilic compounds that lead to the formation of oil-in-water emulsions. These hydrophilic-lipophilic characterization parameters, and the methods used to determine them, can be used in the future to understand the phase behavior of complex oil-water systems.

  14. Chemistry and structure of coal derived asphaltenes and preasphaltenes. Quarterly progress report, April-June 1980

    Energy Technology Data Exchange (ETDEWEB)

    Yen, T. F.

    1980-01-01

    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. These asphaltene fractions may be further separated by both gradient elution through column chromatography, and molecular size distribution through gel permeation chromatography. Those coal-derived asphaltene and preasphaltene fractions will 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 in the United States. 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.

  15. 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.

  16. CFD modelling of shell-side asphaltenes deposition in a shell and tube heat exchanger

    Science.gov (United States)

    Emani, Sampath; Ramasamy, M.; Shaari, Ku Zilati Ku

    2017-07-01

    Asphaltenes are identified as the main cause of crude oil fouling in the shell and tube exchangers. There are occasions where the crude oil flows through the shell side of the heat exchangers and some fouling is reported in the shell side of those heat exchangers. Understanding the fouling phenomena in the shell sides requires the knowledge on the irregular fluid flow paths and most susceptible locations of particles deposition. In the present work, an attempt has been made to investigate the effect of shear stress and surface roughness on shell-side asphaltenes deposition in a shell and tube heat exchanger through Computational Fluid Dynamics approach. The hydrodynamics of asphaltenes particles and the effect of various forces on the asphaltenes deposition on the heat transfer surfaces has been investigated through a Lagrangian based discrete-phase model. From the CFD analysis, the net mass deposition of the asphaltenes particles reduces with an increase in surface roughness from 0 to 0.04 mm and wall shear stress from 0 to 0.04 Pa for flow velocity 1 m/s, respectively. The asphaltenes mass deposition becomes constant with further increase in wall shear stress and surface roughness.

  17. 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.

  18. The colloidal structure of crude oils and suspensions of asphaltenes and resins

    Energy Technology Data Exchange (ETDEWEB)

    Bardon, C.; Barre, L.; Espinat, D.; Guille, V.; Li, M.H.; Lambard, J.; Ravey, J.C.; Rosenberg, E.; Zemb, T. [Institut Francais du Petrole, Rueil Malmaison (France)

    1996-05-01

    This paper presents new results that contribute to the understanding of the colloidal macrostructure of the heavy petroluem products and their complex fractions. Scattering methods (using X-rays and neutrons) are applied to study both the fractionated products (asphaltene and resin solutions in more or less good solvents) and the real systems (Safaniya vacuum residue). The lamellar structural model for asphaltenes and resins is confirmed and the molecular weight of these species determined using a polydisperse size distribution. Discussion is presented concerning he specificity of X-ray and neutron scattering: X-ray experiments are more sensitive to the aromatic-rich regions, whereas the neutron scattering data provide information about all the particle volume. Viscosimetry measurements provide information on the molecular shape of asphaltenes and confirm the disk-like model. Critical micellar concentration has been obtained using Vapour Pressure Osmometry for asphaltene suspensions in toluene and in pyridine. The resin molecules are smaller than asphaltenes, and appear to be a good solvent for asphaltenes. One of the major conclusions of this work is the wide-spread presence of density heterogeneities in diluted solutions of asphaltenes and resins as well as in the pure product (Safaniya vacuum residue). The heating effects were studied: a temperature increase leads to the decrease of molecular weight, but heterogeneities remain present. The structure of vacuum residue exhibits large density fluctuations which are thermally stable. These dense regions remain connected into a network up to 393 K and determine the yield value of the rheological behaviour. 66 refs., 19 figs., 5 tabs.

  19. Molecular Dynamics Simulation to Investigate the Interaction of Asphaltene and Oxide in Aggregate

    Directory of Open Access Journals (Sweden)

    Rui Li

    2016-01-01

    Full Text Available The asphalt-aggregate interface interaction (AAI plays a significant role in the overall performances of asphalt mixture, which is caused due to the complicated physicochemical processes and is influenced by various factors, including the acid-base property of aggregates. In order to analyze the effects of the chemical constitution of aggregate on the AAI, the average structure C65H74N2S2 is selected to represent the asphaltene in asphalt and magnesium oxide (MgO, calcium oxide (CaO, aluminium sesquioxide (Al2O3, and silicon dioxide (SiO2 are selected to represent the major oxides in aggregate. The molecular models are established for asphaltene and the four oxides, respectively, and the molecular dynamics (MD simulation was conducted for the four kinds of asphaltene-oxide system at different temperatures. The interfacial energy in MD simulation is calculated to evaluate the AAI, and higher value means better interaction. The results show that interfacial energy between asphaltene and oxide reaches the maximum value at 25°C and 80°C and the minimum value at 40°C. In addition, the interfacial energy between asphaltene and MgO was found to be the greatest, followed by CaO, Al2O3, and SiO2, which demonstrates that the AAI between asphalt and alkaline aggregates is better than acidic aggregates.

  20. 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.

  1. Estimation of vanadyl porphyrin concentration in sedimentary kerogens and asphaltenes

    Energy Technology Data Exchange (ETDEWEB)

    Premovic, P.I.; Allard, T.; Nikolic, N.D.; Tonsa, I.R.; Pavlovic, M.S. [University of Nis, Nis (Yugoslavia). Dept. of Chemistry

    2000-05-01

    The authors describe a new, rapid method for determining the concentration of vanadyl prophyrins (VO{sup 2+}-P) associated with the kerogen of bituminous sedimentary rocks using electron spin resonance (ESR). The method is simple, straightforward and inexpensive. Several concentrations of a vanadyl (VO{sup 2+}) standard dissolved in glycerol-lignite-mixture were prepared. The VO{sup 2+} concentrations ranged from 100 to 1000 ppm. The anisotropic ESR spectra of both the standards and kerogen samples were recorded at room temperature and the integrated areas of the pre-selected ESR line (attributed to nuclear spin m{sub 1} = -5/2) were computed. The concentrations of VO{sup 2+} found in the kerogen samples were calculated using the relative ratio of the integrated areas for the standards and the kerogen samples. The VO{sup 2+}-P concentrations of the kerogen materials were then calculated using 450 as the mean molecular weight of these species. Quantitative determination of VO{sup 2+}-P in the kerogen fractions in the range of 800-8000 ppm and higher is feasible by the method reported. The method of analysis was also extended to the asphaltene samples (enriched with VO{sup 2+}-P) and a coal sample containing non-porphyrin VO{sup 2+} associated with its organic fraction. 20 refs., 5 figs., 1 tab.

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

    Science.gov (United States)

    Premović, P I; Tonsa, I R; López, L; Pavlović, M S; Nesković, O M; LoMonaco, S; Dordević, D M; Veljković, M V

    2000-05-30

    High-resolution mass spectrometry indicates that the isotopic abundance of 50V of the Late Cretaceous La Luna petroleum asphaltenes of marine origin (highly enriched with V > 2000 ppm) is higher by about 3.5% than that of the inorganic source (VOSO4 x 5H2O, Merck). We propose that the difference in the 50V/51V values between the La Luna petroleum asphaltenes and the inorganic source can be best ascribed to the biological processing of seawater vanadium. The fact that the V isotopic compositions of petroleum asphaltenes vary over a very narrow range (2.46-2.52) suggests essentially the same (or similar) and fixed biological source of vanadium.

  3. 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...... 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...... the PC-SAFT EoS based approach does not. A comparison between the approaches shows that the CPA EoS based approaches, developed in this work, give more reliable results. The predictions from the PC-SAFT EoS based approach result in behavior that is unphysical: the mole fraction of n-paraffin (at...

  4. Structural modifications of petroleum asphaltenes by reductive alkylation investigated by TLC-FID

    Energy Technology Data Exchange (ETDEWEB)

    Cagniant, D.; Nosyrev, I.; Cebolla, V.; Vela, J.; Membrado, L.; Gruber, R. [Universite de Metz, Metz (France). Laboratoire de Thermodynamique et d' Analyses Chimiques

    2001-01-01

    The reductive alkylation of a French petroleum asphaltene (Lagrave) was studied with potassium in THF, in absence of an electron transfer reagent. From the number of butyl and benzyl groups added to the starting asphaltene, the difference of reactivity of the alkyl reagents, butyl iodide and benzyl bromide, was pointed out. Special attention was focused on the cleavage of C-S and C-O linkages in relation to the structural modifications. From the number of hydrogen atoms added during the reduction step, it was concluded that the sulphide linkages are mainly of aryl-S-aryl, aryl-S-alkyl or alkyl-S-alkyl types. The TLC-FID (Iatroscan) analysis was found to be very suitable to follow the 'depolymerization' process of the asphaltene, qualitatively as well as quantitatively, by the application hydrocarbon group type analysis. 23 refs., 2 figs., 5 tabs.

  5. 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)

  6. Asphaltene-laden interfaces form soft glassy layers in contraction experiments: a mechanism for coalescence blocking.

    Science.gov (United States)

    Pauchard, Vincent; Rane, Jayant P; Banerjee, Sanjoy

    2014-11-04

    In previous studies, the adsorption kinetics of asphaltenes at the water-oil interface were interpreted utilizing a Langmuir equation of state (EOS) based on droplet expansion experiments.1-3 Long-term adsorption kinetics followed random sequential adsorption (RSA) theory predictions, asymptotically reaching ∼85% limiting surface coverage, which is similar to limiting random 2D close packing of disks. To extend this work beyond this slow adsorption process, we performed rapid contractions and contraction-expansions of asphaltene-laden interfaces using the pendant drop experiment to emulate a Langmuir trough. This simulates the rapid increase in interfacial asphaltene concentration that occurs during coalescence events. For the contraction of droplets aged in asphaltene solutions, deviation from the EOS consistently occurs at a surface pressure value ∼21 mN/m corresponding to a surface coverage ∼80%. At this point droplets lose the shape required for validity of the Laplace-Young equation, indicating solidlike surface behavior. On further contraction wrinkles appear, which disappear when the droplet is held at constant volume. Surface pressure also decreases down to an equilibrium value near that measured for slow adsorption experiments. This behavior appears to be due to a transition to a glassy interface on contraction past the packing limit, followed by relaxation toward equilibrium by desorption at constant volume. This hypothesis is supported by cycling experiments around the close-packed limit where the transition to and from a solidlike state appears to be both fast and reversible, with little hysteresis. Also, the soft glass rheology model of Sollich is shown to capture previously reported shear behavior during adsorption. The results suggest that the mechanism by which asphaltenes stabilize water-in-oil emulsions is by blocking coalescence due to rapid formation of a glassy interface, in turn caused by interfacial asphaltenes rapidly increasing in

  7. 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.

  8. 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...... EoS to determine asphaltene precipitation onset conditions for various reservoir fluids but with a different modeling approach than literature approaches. A simple oil characterization technique, based on SARA analysis, is adopted which divides the C6+ fraction of the oil into “heavy component...

  9. 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

  10. 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.

  11. Simultaneous removal of asphaltenes and water from water-in-bitumen emulsion. II. Application feasibility

    Energy Technology Data Exchange (ETDEWEB)

    Zhao, Yingxian; Wei, Feng [Ningbo Institute of Technology, Zhejiang University, Ningbo, Zhejiang 315100 (China)

    2008-10-15

    Application feasibility of the accelerated deasphaltening process for simultaneous removal of asphaltenes and water from a water-in-bitumen emulsion has been examined with a pilot plant having capacity of 1.590 m3/day. The solvent (n-pentane) was injected into the emulsion from three locations with progressively increasing temperature from 423 K. The first solvent injection precipitated the asphaltenes in bitumen, the second broke the emulsion and facilitated the phase separation, and the third extracted the oil that remained in heavy asphaltenes/water phase. The effects of operation parameters such as temperature, solvent/bitumen ratio, feed rate and feedstock composition on the quality of DAO (Deasphaltening oil) were investigated. The DAO with the yield of {proportional_to} 80 wt.% and asphaltene content of < 0.5 wt.% was produced under optimal operating conditions, and the residual product was a porous solids containing 38% sulfur, 47% nitrogen, 64% MCR, and 85% metals (nickel and vanadium) of the bitumen. For a real application in oil industry, other important aspects including energy efficiency, solvent recovery and water purification have been discussed. (author)

  12. Experimental investigation of asphaltene deposition mechanism during oil flow in core samples

    Energy Technology Data Exchange (ETDEWEB)

    Papadimitriou, N.I.; Romanos, G.E.; Charalambopoulou, G.Ch.; Kainourgiakis, M.E.; Katsaros, F.K.; Stubos, A.K. [National Center for Scientific Research ' ' Demokritos' ' , Aghia Paraskevi, Attica, 15310 (Greece)

    2007-06-15

    Asphaltene deposition is an issue that has received much attention since it has been shown to be the cause of major production problems in enhanced oil recovery processes. Asphaltenes are heavy oil components which, under certain conditions, precipitate and the solid phase they form may deposit in the porous media of the oil reservoir. All proposed remediation techniques have proven costly and not highly effective, so prevention becomes the only way to counteract the problem. Revelation of the deposition mechanism and determination of the parameters they affect it are necessary in order to devise reliable prevention strategies. In this work, an experimental effort is made to investigate the deposition process in core samples, under simulant and realistic flow conditions. The main experimental tools utilized for this purpose are permeability measurements, analysis of asphaltene concentration, pore structure characterization techniques and Soxhlet extraction for the determination of the deposited asphaltenes. Both dead and reservoir oils are used as well as cores of various permeabilities and pore structure characteristics. (author)

  13. Solubility and interaction parameters as references for solution properties II: precipitation and aggregation of asphaltene in organic solvents.

    Science.gov (United States)

    Johansson, Bjarne; Friman, Rauno; Hakanpää-Laitinen, Hannele; Rosenholm, Jarl B

    2009-01-01

    The total combinatory Gibbs free energy was successfully used to model the solubility of two purified asphaltenes in pure and mixed solvents, as well as the precipitation of asphaltenes from mixed solvents. Intrinsic viscosity and aggregate size both sensitively reflected the state of the asphaltenes in homogeneous solution and were used for determining the solubility parameters of the asphaltenes. Phase separation was clearly reflected by a dramatic increase in aggregate size. The interaction parameter was subdivided into enthalpy and entropy contributions. All parameters indicate an extensive association or phase transition when the phase boundary was followed by simultaneously varying the temperature and the solubility parameter of the solvent. However, the interaction parameter is frequently derived in two ways. We show that, depending on the definition, the enthalpy and entropy contributions lead to conflicting results. These were evaluated on thermodynamic grounds.

  14. 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.

  15. 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)

  16. Adsorption of asphaltenes and resins on organic and inorganic substrates and their correlation with precipitation problems in production well tubing

    Energy Technology Data Exchange (ETDEWEB)

    Acevedo, S.; Ranaudo, M.A.; Escobar, G.; Gutierrez, L.; Ortega, P. [Universidad Central de Venezuela, Caracas (Venezuela). Centro de Quimica Organica

    1995-04-01

    The solute-solid adsorption isotherms (SSA) of asphaltenes and resins were measured using the inorganic fraction (97% SiO{sub 2}) of the deposit that plugged the tubing of a production well as an inorganic adsorbent. In other experiments, Ceuta asphaltenes and the product (HA) of heating them at 350{degree}C for 11 h were used as organic adsorbents in heptane, toluene and heptane-toluene at 26{degree}C. Ceuta and Furrial asphaltenes on the inorganic substance resulted in multilayer formation (L-3 type adsorption) whereas a Cerro Negro sample gave simple Langmuir-type adsorption. A possible correlation between these results and the tendency of the asphaltenes to precipitate from the crude oils is suggested. Saturation, multilayer formation and pore penetration were apparent in the SSA experiments for the system resins-heptane-asphaltenes. SSA results for the system resin-heptane/toluene-HA were consistent with the steric stabilization theory of colloidal dispersions. Adsorption of aggregates or micelles of asphaltenes was apparent in both the organic and the inorganic substrates. 22 refs., 6 figs., 1 tab.

  17. 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.

  18. 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.

  19. Electron spin resonance study of the kerogen/asphaltene vanadyl porphyrins: air oxidation

    Energy Technology Data Exchange (ETDEWEB)

    Premovic, P.I.; Tonsa, I.R.; Pajovic, M.T.; Lopez, L.; Monaco, S.L.; Dordevic, D.M.; Pavlovic, M.S. [University of Nis, Nis (Yugosalvia). Lab. for Geochemistry and Cosmochemistry, Dept. of Chemistry

    2001-04-01

    Thermal behavior of vanadyl porphyrins was studied by electron spin resonance during heating of the kerogens isolated from the La Luna (Venezuela), Maganik (Montenegro) and Serpiano (Switzerland) bituminous rocks at 150 and 250{degree}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 six 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 conversion of vanadyl porphyrins are observed under the same experimental conditions for the asphaltenes extracted from the La Luna and Serpiano rocks, and the floating asphalt from the Dead Sea (Israel). A comparison of the spin-Hamiltonian parameters for vandyl porphyrisn and vanadyl compounds obtained during pyrolysis of the kerogens/asphaltenes suggests that these are of non-porphyrin type. For comparison, a study was conducted on the Western Kentucky No. 9 coal enriched with vanadium (up to 800 ppm) from six mines. All coal samples show only the presence of predominant vanadyl-non-porphyrin 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. 21 refs., 2 figs.

  20. 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.

  1. 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.

  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. 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)

  4. 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

  5. On the application of NiO nanoparticles to mitigate in situ asphaltene deposition in carbonate porous matrix

    Science.gov (United States)

    Hashemi, Seyed Iman; Fazelabdolabadi, Babak; Moradi, Siyamak; Rashidi, Ali Morad; Shahrabadi, Abbas; Bagherzadeh, Hadi

    2016-01-01

    Prevention of asphaltene formation in reservoir rocks can result in resolving a severe long-lasting issue in petroleum production. The present research addresses the issue in the context of exploring the potential effect of nickel oxide (NiO) nanoparticles in destabilizing asphaltene deposition in porous media, in the presence of carbon dioxide. To ensure proper distribution within the system and to retain future field-scale applicability, the NiO nanoparticles were exposed to the in situ oil via injection gas stream, in which they had been uniformly dispersed using polydimethylsiloxane (PDMS). The experimental results, established under miscible CO2 state, indicate a considerable improvement in permeability/porosity reduction of core, as well as less asphaltene accumulation in porous media and increased oil recovery factor after applying NiO nanoparticles.

  6. 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...... during nitrogen, hydrocarbon gas mixture, and carbon dioxide injection. It is also shown how to extend the modeling approach when the reservoir fluid is split into multiple pseudocomponents. It is observed that the modeling approach using any of the three models can predict the gas injection effect......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...

  7. 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...

  8. Substances synthesis of the asphaltenes simplifying models; Sintese de substancias modelo simplificadas de asfaltenos

    Energy Technology Data Exchange (ETDEWEB)

    Romeiro, T.F.; Pereira, A. [Universidade Federal, Rio de Janeiro, RJ (Brazil); Chrisman, E.C.A.N. [Universidade Federal Rural do Rio de Janeiro, RJ (Brazil)]. E-mail: erikanunes@openlink.com.br; Seidl, P.R. [Universidade Federal Fluminense, Niteroi, RJ (Brazil)]. E-mail: pseidl@eq.ufrj.br

    2003-07-01

    The products derived from oil are essential in practically all the sectors of the modern life. The necessity of if using heavy fractions in efficient way in the production of nobler fractions, resulted in a great interest in the briefing of the molecular structure of asphaltenes, since its behavior, during the thermal processes and catalytic, it is function of its structure. In the refining, the asphaltenes increase the viscosity of the fractions submitted to the distillation and contribute for the coke formation and the poisoning and deactivation of catalyzers, used in processes as cracking, reform, etc. Therefore, a ampler knowledge of the structure of the asphaltenes and its action becomes very important to assist in the job of these fractions and to minimize the de current problems of its possible use made through substances model, suggested for the de current analyses of the separations and determination of some parameters of these substances that will be source of information for the molecular modeling. With this, from the information gotten with the extraction and the separation, it was decided to synthesize initially simpler molecules involving the formation of 4 the 5 aromatical rings, of different arrangements, involving only molecules with carbon, hydrogen and oxygen, in the form of derivatives of anthraquinones. The used methodology involved the job of reaction of aromatical electrofilic substitution using as substance phthalic anhydride reacting way Friedel-Crafts, with naphthalene and anthracene, initially, with specific methods for each isomer. Separation and purification of the products, followed of analysis and characterization of the same ones for infra-red ray and RMN. To the end, can be observed important characteristics, such as the gotten photosensibility of one of the isomer through the reaction with naphthalene. (author)

  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. Role of resins, asphaltenes and aromatics on water-oil emulsions

    Energy Technology Data Exchange (ETDEWEB)

    Jones, C.; Sermon, P.A.; Skidmore, P.G.; Collins, I.R. [Surrey Univ., Sunbury (United Kingdom). Dept. of Chemistry

    2008-07-01

    Following primary and secondary oil recovery, the remaining oil within the reservoir can be trapped by capillary forces within a network of rock pores. Tertiary oil recovery can then be based upon carbon dioxide flooding, alkaline flooding, steam injection and chemical flooding-with polymers or surfactants. However, surfactants can only be useful if they are soluble in the aqueous phase at reservoir temperature, salinity and pH. Surfactants are only modestly adsorbed on the reservoir rock and are responsible for oil-water emulsions, phase equilibria, surface tensions and viscosities. Maximum additional oil-phase displacement can be achieved when the correct surfactant blend is selected. This presentation included a table demonstrating the composition of middle phase emulsions formed with brine. GC-HPLC, phase equilibria, conductivity, optical microscopy and atomic force microscopy were used to determine how the asphaltene-resinous-aromatic content of crude oils affect the ease of formation of water-oil emulsions. The study showed that the ratio of water to oil in the emulsions formed depends on the proportion of asphaltenes and resins in the oil. This information can be used to ensure that the ratio reaches a plateau in production, thus optimizing oil production.

  12. 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)

  13. Problematic stabilizing films in petroleum emulsions: shear rheological response of viscoelastic asphaltene films and the effect on drop coalescence.

    Science.gov (United States)

    Harbottle, David; Chen, Qian; Moorthy, Krishna; Wang, Louxiang; Xu, Shengming; Liu, Qingxia; Sjoblom, Johan; Xu, Zhenghe

    2014-06-17

    Adsorption of asphaltenes at the water-oil interface contributes to the stability of petroleum emulsions by forming a networked film that can hinder drop-drop coalescence. The interfacial microstructure can either be liquid-like or solid-like, depending on (i) initial bulk concentration of asphaltenes, (ii) interfacial aging time, and (iii) solvent aromaticity. Two techniques--interfacial shear rheology and integrated thin film drainage apparatus--provided equivalent interface aging conditions, enabling direct correlation of the interfacial rheology and droplet stability. The shear rheological properties of the asphaltene film were found to be critical to the stability of contacting drops. With a viscous dominant interfacial microstructure, the coalescence time for two drops in intimate contact was rapid, on the order of seconds. However, as the elastic contribution develops and the film microstructure begins to be dominated by elasticity, the two drops in contact do not coalescence. Such step-change transition in coalescence is thought to be related to the high shear yield stress (~10(4) Pa), which is a function of the film shear yield point and the film thickness (as measured by quartz crystal microbalance), and the increased elastic stiffness of the film that prevents mobility and rupture of the asphaltene film, which when in a solid-like state provides an energy barrier against drop coalescence.

  14. 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

    Miscible and immiscible gas flooding is one of the enhanced oil recovery (EOR) techniques that has been widely used to increase the oil production. One of the critical problems with gas flooding is that it generally aggravates the asphaltene precipitation, which further creates a flow assurance...

  15. 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...

  16. 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

  17. 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

  18. 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)

  19. Multiple-sourced features of marine oils in the Tarim Basin, NW China - Geochemical evidence from occluded hydrocarbons inside asphaltenes

    Science.gov (United States)

    Tian, Yankuan; Zhao, Jing; Yang, Chupeng; Liao, Zewen; Zhang, Lühui; Zhang, Haizu

    2012-08-01

    The Tarim Basin, NW China, is a large composite basin with multiple sets of petroleum source rocks. The basin has undergone numerous episodes of hydrocarbon generation, migration and accumulation, making it difficult to assess the source rocks and oil-source correlation for the widespread marine oils in this area. Protected by the molecular structure of asphaltenes, occluded hydrocarbons can provide information about the early source rocks. In this work, the occluded hydrocarbons released from the asphaltenes by a mild chemical degradation method were compared with the crude oil maltenes and the adsorbed compounds from asphaltenes. Analysis of biomarker distribution and the carbon isotope composition of individual n-alkanes suggests that the widespread marine oils in the Tazhong Uplift, Tabei Lunnan Uplift and Halahatang Depression were contributed by Cambrian-Lower Ordovician source rocks at an early stage, and later mixed with hydrocarbons derived from Middle-Upper Ordovician source rocks. The marine oils in the Tarim Basin demonstrate extensive characteristics of having been derived from multiple source rocks.

  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. 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)

  2. Hydrogen bonding in asphaltenes and coal liquids. Quarterly report, 1 February-30 April 1981

    Energy Technology Data Exchange (ETDEWEB)

    Li, N. C.; Jones, L.; Yaggi, N. F.

    1981-01-01

    The objective of this project is to investigate the nature and strength of hydrogen bonding and other molecular interactions in coal liquids and their fractions. Determinations are made of the molecular interactions involving the preasphaltene, asphaltent and oil, together with their separated fractions, obtained from coal liquids after hydroprocessing under different processing conditions and accelerated aging. NMR, IR, GC/MS, calorimetric, GPC, ESR, viscosity methods are used to determine structural changes caused by upgrading and aging of coal liquids. The upgraded coal liquids, derived from catalytic hydroprocessing of a 30 to 70 weight percent blend of solid solvent refined coal product (SRC-I) with liquid solvent-refined coal product (SRC-II) were analyzed as a function of contact time and temperature, and the observed variations of structural parameters were correlated with the physical properties of the liquid products. The oxidative degradation of a SRC-II middle distillate, which is an oil, free of asphaltenes and benzene-insolubles, was investigated to determine the molecular types of compounds responsible for the viscosity change and postulate mechanisms. Since the middle distillate is relatively stable to oxidative degradation, copper shavings were added to accelerate the process. Results and discussion are presented in detail.

  3. Maturity trends in asphaltenes from pyrolysed source rocks and natural coals - multivariate modelling of diffuse reflectance Fourier-transform infrared spectra

    Energy Technology Data Exchange (ETDEWEB)

    Barth, T.; Seim, M.; Christy, A.A.; Kvalheim, O.M. [University of Bergen, Bergen (Norway). Dept. of Chemistry

    1995-02-01

    Drift spectra of asphaltenes have been modelled by multivariate methods to show the patterns of maturity dependent changes in chemical composition. The asphaltenes are from source rocks that have been artificially matured by hydrous pyrolysis, and cover a wide range of kerogen types and maturity levels. Asphaltenes from a set of naturally matured coal samples are modelled for comparison. The modelling results in defining a limited number of systematic trends in maturity dependent chemical changes in the spectra. The trends are comparable for similar source rocks and are interpreted as representing defunctionalisation, aromatisation and cracking reactions. However, the timing and maturity dependence of the reactions are specific for each source rock, and a general maturation model that includes all source rock types could not be established.

  4. Characterization of asphaltene molecular structures by cracking under hydrogenation conditions and prediction of the viscosity reduction from visbreaking of heavy oils

    Science.gov (United States)

    Rueda Velasquez, Rosa Imelda

    The chemical building blocks that comprise petroleum asphaltenes were determined by cracking samples under conditions that minimized alterations to aromatic and cycloalkyl groups. Hydrogenation conditions that used tetralin as hydrogen-donor solvent, with an iron-based catalyst, allowed asphaltenes from different geological regions to yield 50-60 wt% of distillates (catalytic activity, and preservation of the cycloalkyl structures. Quantitative recovery of cracking products and characterization of the distillates, by gas chromatography-field ionization--time of flight high resolution mass spectrometry, displayed remarkable similarity in molecular composition for the different asphaltenes. Paraffins and 1-3 ring aromatics were the most abundant building blocks. The diversity of molecules identified, and the high yield of paraffins were consistent with high heterogeneity and complexity of molecules, built up by smaller fragments attached to each other by bridges. The sum of material remaining as vacuum residue and coke was in the range of 35-45 wt%; this total represents the maximum amount of large clusters in asphaltenes that could not be converted to lighter compounds under the evaluated cracking conditions. These analytical data for Cold Lake asphaltenes were transformed into probability density functions that described the molecular weight distributions of the building blocks. These distributions were input for a Monte Carlo approach that allowed stochastic construction of asphaltenes and simulation of their cracking reactions to examine differences in the distributions of products associated to the molecular topology. The construction algorithm evidenced that a significant amount of asphaltenes would consist of 3-5 building blocks. The results did not show significant differences between linear and dendritic molecular architectures, but suggested that dendritic molecules would experience slower reaction rates as they required more breakages to reach a given

  5. 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.

  6. 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)

  7. 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)

  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. 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.

  10. 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)

  11. Effects of the asphaltene and resin contents of the bitumens on the water-bitumen interface properties

    Energy Technology Data Exchange (ETDEWEB)

    Jada, A.; Salou, M. [Institut de Chimie des Surfaces et Interfaces, 15 rue Jean Starcky, B.P. 2488, 68057 Mulhouse (France)

    2002-04-01

    The contact angles between various bitumen solid surfaces and aqueous solutions having pH values equal to 3, 6, 9 and 12 were measured. The objective of this work was to analyse the possible acid-base interactions at the water-bitumen interface for substrates having various asphaltenes and resins contents. In addition, the work of adhesion at a bitumen-water interface, W{sub A}, was calculated from the measured contact angle. This allows us to analyze the surface acidity and basicity of the bitumens. The results obtained indicate that the work of adhesion decreases when the bitumen asphaltenes content increases at any aqueous solution pH value. Further, the variation of the work of adhesion versus the pH for various bitumens shows the presence of acidic, basic and amphoteric groups in the surfaces of these components. The nature and the amount of acidic and basic functionalities present in the bulk bitumen were evaluated by a non-aqueous potentiometric titration method and by comparison with acid-base models compounds. No relationship was found between the acid and base contents of the bulk bitumens and the bitumen surface character determined from the work of adhesion. In order to find any correlation between the adhesion work and the stability of the bitumen aqueous dispersions, zeta potentials of the bitumen droplets dispersed in acidic aqueous solutions were measured. Stable bitumen dispersions having zeta potential values higher than 50 mV and work of adhesion values higher than 55 mJ/m{sup 2} were obtained with bitumens having high values of the resin/asphaltenes ratios. The determination of a surface's acidity and basicity by measuring the contact angles at a water-bitumen interface seems to be a more useful method than the non-aqueous potentiometric titration. Hence, a good correlation is found between the surface charge of the bitumen droplet as measured by zeta potential and the work of adhesion at water-bitumen interface.

  12. 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

  13. 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

  14. Brewster angle microscopy of Langmuir films of athabasca bitumens, n-C5 asphaltenes, and SAGD bitumen during pressure-area hysteresis.

    Science.gov (United States)

    Hua, Yujuan; Angle, Chandra W

    2013-01-08

    Bitumen films formed on water surfaces have negative consequences, both environmental and economic. CanmetENERGY has placed considerable research emphasis on understanding the structures of the bitumen films on water as a necessary step before optimization of bitumen extraction. The detailed structures of the adsorbed molecules and, especially, the role of asphaltene molecules at the interfaces are still under scrutiny and debate. In the present study, we compared bitumen and asphaltene films as they were compressed and expanded under various surface pressures in order to achieve a clearer understanding of bitumen film structures. We used a customized NIMA Langmuir trough interfaced to a Brewster angle microscope (BAM) and CCD camera (Nanofilm_ep3BAM, Accurion, previously Nanofilm Gmbh) to study images of bitumen films at the air/water interface. The bitumen film appeared uniform with high reflectivity at a surface pressure of 18 mN·m(-1) and exhibited a coarse pebblelike interface with reduced reflectivity in the liquid condensed (LC) phase at higher pressures (18-35 mN·m(-1)). During the first cycle of compression asphaltene films showed well-defined phase transitions and a uniformly smooth interface in the LC phase between 9 and 35 mN·m(-1). However, folding or buckling occurred at surface pressures from 35 to 44 mN·m(-1). On expansion, asphaltene films appeared to break into islands. The hysteresis of the pressure-area isotherm was much larger for asphaltenes than for bitumen. In both compression and expansion cycles, BAM images for bitumen films appeared to be more reproducible than those of the asphaltene films at the same surface pressures. Films for low-°API SAGD bitumen were almost identical to those for surface-mined bitumen. Films formed from partially deasphalted surface-mined bitumens showed higher compressibility and lower rigidity than the original bitumen. The BAM images illustrated significant differences between the partially deasphalted and

  15. 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.

  16. 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.

  17. Effect of various catalysts on the chemical structure of oils and asphaltenes obtained from the hydroliquefaction of a highly volatile bituminous coal

    Energy Technology Data Exchange (ETDEWEB)

    Cebolla, V.L.; Diack, M.; Oberson, M.; Bacaud, R.; Cagniant, D.; Nickel-Pepin-Donat, B. (Universite de Metz, Metz (France))

    1991-07-01

    The catalysts studied were aerosols of SiO{sub 2}, Fe{sub 2}O{sub 3}, MoO{sub 3} and Ni-Mo/Al{sub 2}O{sub 3}. The hydroliquefaction runs at 350, 400 and 430{degree}C, in the presence of tetralin and sulfur, were evaluated by solvent extractions, hydrogen consumption and structural analysis of the isolated oil and asphaltene fractions. At 350 {degree}C, a clear influence of the catalyst on the extraction yields is observed. This effect disappears at higher temperatures. Nevertheless, hydrogen consumption from gas or solvent is affected by the nature of the catalyst at a given temperature. The influence of the catalyst is also confirmed by electron spin resonance study of the stable radicals of the tetrahydrofuran insoluble fractions. After elimination of tetralin, the structural analyses were carried out by gas chromatography (oils), size exclusion chromatography (oils and asphaltenes) and extrography (raw hydroliquefaction products). The oils obtained with sulfided Fe{sub 2}O{sub 3} or MoO{sub 3} contained significantly more two-ringed aromatic compounds than oils obtained with the other catalysts or without added catalyst. No significant influence of the catalyst at a given temperature on the oils and asphaltenes is observed by size exclusion chromatography. In contrast, a large temperature effect is evidenced for each fraction, independently of the nature of the catalyst. 38 refs., 7 figs., 6 tabs.

  18. 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

  19. 3D-RISM-KH molecular theory of solvation and density functional theory investigation of the role of water in the aggregation of model asphaltenes.

    Science.gov (United States)

    da Costa, L M; Hayaki, S; Stoyanov, S R; Gusarov, S; Tan, X; Gray, M R; Stryker, J M; Tykwinski, R; Carneiro, J Walkimar de M; Sato, H; Seidl, P R; Kovalenko, A

    2012-03-21

    We applied a multiscale modeling approach that involves the statistical-mechanical three-dimensional reference interaction site model with the Kovalenko-Hirata closure approximation (3D-RISM-KH molecular theory of solvation) as well as density functional theory (DFT) of electronic structure to study the role of water in aggregation of the asphaltene model compound 4,4'-bis(2-pyren-1-yl-ethyl)-2,2'-bipyridine (PBP) [X. Tan, H. Fenniri and M. R. Gray, Energy Fuels, 2008, 22, 715]. The solvation free energy and potential of mean force predicted by 3D-RISM-KH reveal favorable pathways for disaggregation of PBP dimers in pure versus water-saturated chloroform solvent. The water density distribution functions elucidate hydrogen bonding preferences and water bridge formation between PBP monomers. The ΔG(298) values of -5 to -7 kcal mol(-1) for transfer of water molecules in chloroform to a state interacting with PBP molecules are in agreement with experimental results. Geometry optimization and thermochemistry analysis of PBP dimers with and without water bridges using WB97Xd/6-31G(d,p) predict that both PBP dimerization and dimer stabilization by water bridges are spontaneous (ΔG(298) experiment. The ΔG(298) results show that hydrogen bonding to water and water-promoted polynuclear assembly bridging is as important as π-π interactions for asphaltene aggregation.

  20. 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.

  1. 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)

  2. Optical fiber extrinsic refractometer to measure RI of samples in a high pressure and temperature systems: Application to wax and asphaltene precipitation measurements

    Energy Technology Data Exchange (ETDEWEB)

    Jimmy Castillo; Carlos Canelon; Socrates Acevedo; Herve Carrier; Jean-Luc Daridon [Universidad Central de Venezuela, Caracas (Venezuela). Facultad de Ciencias, Escuela de Quimica

    2006-10-15

    An optical fiber extrinsic sensor for measurement of changes in the refractive index of liquids confined in chambers for high pressure and temperature experiments is described. One head sensor composed by two fibers is fixed in front of a high pressure and temperature cell filled with the sample. The operation principle is based in the reflectivity dependence in the refractive index of the glass-liquid interface. Excellent results and a sensitivity of 10{sup -5} RI were obtained for pure liquids. The applicability of the sensor is demonstrated following the changes in the refractive index for pure liquids at different pressure and temperatures and by measuring the asphaltenes and wax precipitation in crude oils under pressure. The extrinsic probe designed for refractive index measurement proves to be a reliable tool for measuring heavy organics deposition in crude oils under high pressures and temperatures where the sample to be measured is not very accessible. 25 refs., 11 figs., 2 tabs.

  3. Computational study of the effect of dispersion interactions on the thermochemistry of aggregation of fused polycyclic aromatic hydrocarbons as model asphaltene compounds in solution.

    Science.gov (United States)

    Moreira da Costa, Leonardo; Stoyanov, Stanislav R; Gusarov, Sergey; Seidl, Peter R; Walkimar de M Carneiro, José; Kovalenko, Andriy

    2014-02-06

    Density functional theory (DFT), Møller-Plesset second-order perturbation theory (MP2), and semiempirical methods are employed for the geometry optimization and thermochemistry analysis of π-π stacked di-, tri-, tetra-, and pentamer aggregates of the fused polycyclic aromatic hydrocarbons (PAHs) naphthalene, anthracene, phenanthrene, tetracene, pyrene, and coronene as well as benzene. These aggregates (stabilized by dispersion interactions) are highly relevant to the intermolecular aggregation of asphaltenes, major components of heavy petroleum. The strength of π-π stacking interaction is evaluated with respect to the π-stacking distance and thermochemistry results, such as aggregation enthalpies, entropies, and Gibbs free energies (ΔG(298)). For both π-stacking interplanar distances and thermochemistry, the ωB97X-D functional with an augmented damped R(-6) dispersion correction term and MP2 are in the closest agreement with the highly accurate spin-component scaled MP2 (SCS-MP2) method that we selected as a reference. The ΔG(298) values indicate that the aggregation of coronene is spontaneous at 298 K and the formation of pyrene dimers occurs spontaneously at temperature lower than 250 K. Aggregates of smaller PAHs would be stable at even lower temperature. These findings are supported by X-ray crystallographic determination results showing that among the PAHs studied only coronene forms continuous stacked aggregates in single crystals, pyrene forms dimers, and smaller PAHs do not form π-π stacked aggregates. Thermochemistry analysis results show that PAHs containing more than four fused benzene rings would spontaneously form aggregates at 298 K. Also, round-shaped PAHs, such as phenanthrene and pyrene, form more stable aggregates than linear PAHs, such as anthracene and tetracene, due to decreased entropic penalty. These results are intended to help guide the synthesis of model asphaltene compounds for spectroscopic studies so as to help understand

  4. 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)

  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. Scalable, chromatography-free synthesis of alkyl-tethered pyrene-based materials. Application to first-generation "archipelago model" asphaltene compounds.

    Science.gov (United States)

    Diner, Colin; Scott, David E; Tykwinski, Rik R; Gray, Murray R; Stryker, Jeffrey M

    2015-02-06

    In this paper, we report a highly efficient, scalable approach to the total synthesis of conformationally unrestricted, electronically isolated arrays of alkyl-tethered polycyclic aromatic chromophores. This new class of modular molecules consists of polycyclic aromatic "islands" comprising significant structural fragments present in unrefined heavy petroleum, tethered together by short saturated alkyl chains, as represented in the "archipelago model" of asphaltene structure. The most highly branched archipelago compounds reported here share an architecture with first-generation dendrimeric constructs, making the convergent, chromatography-free synthesis described herein particularly attractive for further extensions in scope and applications to materials chemistry. The syntheses are efficient, selective, and readily adaptable to a multigram scale, requiring only inexpensive, "earth-abundant" transition-metal catalysts for cross-coupling reactions and extraction and fractional crystallization for purification. This approach avoids typical limitations in cost, scale, and operational practicality. All of the archipelago compounds and synthetic intermediates have been fully characterized spectroscopically and analytically. The solid-state structure of one archipelago model compound has been determined by X-ray crystallography.

  7. 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

    Directory of Open Access Journals (Sweden)

    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.

  8. 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)

  9. 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)

  10. 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

    Directory of Open Access Journals (Sweden)

    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

  11. 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

    Directory of Open Access Journals (Sweden)

    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.

  12. Evaluation of oil ducts wettability by measurements of contact angle. Effect of asphaltenes and naphtenic acids; Avaliacao da molhabilidade de oleodutos atraves de medidas de angulo de contato. Efeitos de asfaltenos e acidos naftenicos do petroleo

    Energy Technology Data Exchange (ETDEWEB)

    Santos, Ronaldo G. dos; Mokamed, Rahoma S. [Universidade Estadual de Campinas, SP (Brazil). Faculdade de Engenharia Quimica; Loh, Watson [Universidade Estadual de Campinas, SP (Brazil). Inst. de Quimica

    2003-07-01

    The recent interest of the petroleum companies for heavy crude oils reserves have been increased in the last decades. Rheological properties of these oils interferes with their economical production and transportation. Technologies based on the flow of lubricated oil through an aqueous film (Core Flows) represent an alternative way to improve of the flow efficiency and viability of the recovery of these heavy oils. In the systems, the pressure drop caused from the high values of viscosity can be reduced to values similar to those encounter in single aqueous flow. The progressive accumulation oil on the pipeline walls is, however, the major problem for the implementation of core flow. For oil accumulation to take place, pipeline surface would need to be oil-wet. This work examines the wettability of pipeline surfaces and the effect of oil phase polar constitute such as asphaltenes and naphtenic acids in the possible alteration of these surfaces from water-wet to oil-wet. The effect of crude oil fractions on the wettability is shown by measurements of contact angle. Commercial and carbon steel are tested. The results show that the wettability of the surfaces depend on oil composition and can be rectified by components in aqueous phase. (author)

  13. 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)

  14. 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

    Directory of Open Access Journals (Sweden)

    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

  15. 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

    Directory of Open Access Journals (Sweden)

    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.

  16. Study of asphaltene precipitation by Calorimetry

    DEFF Research Database (Denmark)

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

    2007-01-01

    of experiments showed that weak forces determine precipitation. Indeed, isothermal titration calorimetry could not detect any clear signal although this technique can detect low-energy transitions such as liquid-liquid equilibrium and rnicellization. The second series of tests proved that precipitation caused...

  17. 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

  18. 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

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

    African Journals Online (AJOL)

    MBI

    2015-12-22

    Wolf and. Alfani, 1982). ... mixture of dichloromethane: methanol (97:3 v/v) for 3 minutes and oven dried for 90 seconds at. 65oC. .... Mexican crude oils, Energy and Fuel, 23,. 1603–1609. Crek, J.L. (2005). Freedom of action in ...

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

    Indian Academy of Sciences (India)

    was demonstrated that the elemental composition of asphal- tene fractions precipitated by different solvents from ... time of analysis 105 min. 3. Results and discussion. The physical characteristics of the ..... Thomas B R 1970 Phytochemical phylogeny, chapter: modern and fossil plant resins (London: Academic Press) p. 59.

  1. 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.

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

    Indian Academy of Sciences (India)

    Administrator

    New York: Plenum Pub. Co.) Simoneit B R T, Grimalt J O, Wang T G, Cox R E, Hatcher P G and Nissenbaum A 1986 Org. Geochem. 10 877. Speight J G and Moschopedis B C 1981 Chemistry of asphalte- nes. in Advances in chemistry series No ...

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

    Energy Technology Data Exchange (ETDEWEB)

    Deo, M.D.

    2001-01-12

    The objective of this project was to identify conditions at which carbon dioxide induced precipitation occurred in crude oils. Establishing compositions of the relevant liquid and solid phases was planned. Other goals of the project were to determine if precipitation occurred in cores and to implement thermodynamic and compositional models to examine the phenomenon. Exploring kinetics of precipitation was also one of the project goals. Crude oil from the Rangely Field (eastern Colorado) was used as a prototype.

  4. 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.

  5. 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

  6. Microarray analysis of Neosartorya fischeri using different carbon sources, petroleum asphaltenes and glucose-peptone

    Directory of Open Access Journals (Sweden)

    Edna L. Hernández-López

    2015-09-01

    Here we describe experimental procedures and methods about our dataset (NCBI GEO accession number GSE68146 and describe the data analysis to identify different expression levels in N. fischeri using this recalcitrant carbon source.

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

    OpenAIRE

    Márquez, G.; Alejandre, F. J.; Bencomo, M. R.

    2006-01-01

    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 ...

  8. Configurational diffusion of asphaltenes in fresh and aged catalysts extrudates. Quarterly progress report, December 20, 1992--March 20, 1993

    Energy Technology Data Exchange (ETDEWEB)

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

    1993-07-01

    The objective of this research is to determine the relationship between the size and shape of coal and petroleum macromolecules and their diffusion rates i.e., effective diffusivities, in catalyst pore structures. That is, how do the effective intrapore diffusivities depend on molecule configuration and pore geometry. This quarter, the investigators several approaches to check the effect of external mass transfer on the diffusion rate. Theoretical analyses and experimental results showed that the external mass transfer effect can be neglected for our experimental conditions.

  9. 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.

  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. 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...... is dependent on oil composition, ice conditions and weathering degree. In open water, oil spills rapidly become “not ignitable” due to the weathering e.g. high water content and low content of residual volatile components. The slower weathering of oil spills in ice (50 and 90% ice cover) results in longer time...... (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...

  12. 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)

  13. 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.

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

    Science.gov (United States)

    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.

  15. Method for determining processability of a hydrocarbon containing feedstock

    Science.gov (United States)

    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.

  16. Distribution of vanadium and vanadylporphyrines in petroleum fractions of different chemical types

    Energy Technology Data Exchange (ETDEWEB)

    Aleshin, G.N.; Altukhova, Z.P.; Antipenko, V.R.; Marchenko, S.P.; Kam' yanov, V.F.

    Distribution of vanadium among petroleum components: tars, asphaltenes and oils from various levels of Samotlorsk fields was studied. It was shown that the predominant fraction of vanadium and vanadyl porphyrines is concentrated in petroleum tars. The highest absolute concentration of V was noted in the asphaltene fraction; however, vanadium atoms were found to be bound to heteroatomic fragments of the tarry-asphaltene compounds. Up to 98% of vanadium contained in asphaltenes and almost all V atoms in oil fractions are bound by non-porphyrinyl compounds. With increased methanization of the petroleum fractions, their V content drops rapidly. 5 references, 2 figures.

  17. Separation of petroleum residues by complex-formation with TiCl/sub 4/

    Energy Technology Data Exchange (ETDEWEB)

    Khokhlova, G.P.; Plyusnin, A.N.

    1983-01-01

    Titanium tetrachloride can be used for the quantitative separation of asphaltenes from residual oil products, for the concentration of hetero-atomic compounds of lower molecular weight, for the complete separation of nitrogen compounds of basic character and also for fractionation of resin-asphaltene substances. The action of TiCl/sub 4/ on residual oil products liberates asphaltenes as well as basic nitrogen compounds. The asphaltene recovery reaches 100%, and basic nitrogen compounds, 90-98%. Hexane is a more satisfactory solvent then benzene in this process.

  18. 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 ...

  19. 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

  20. Separating petroleum residues through complex forming with TiC/sub 4/

    Energy Technology Data Exchange (ETDEWEB)

    Khokhlova, G.P.; Plyusnin, A.N.

    1983-01-01

    It is shown that TiC/sub 4/ may be used for quantitative isolation of alphaltenes from residual petroleum products, for concentrating lower molecular heteroatomic compounds and for total isolation of nitrogen compounds of a basic nature, and for fractionation of resinous asphaltene substances. With the action of TiC/sub 4/ a joint isolation of asphaltenes and basic nitrogen compounds occurs in the residual petroleum products. The degree of asphaltene extraction reaches 100 percent and that of the basic nitrogen compound, 90 to 98 percent. Hexane in this process is a more favorable solvent than benzene.

  1. Interfacial characteristics of petroleum bitumens in contact with acid water

    Energy Technology Data Exchange (ETDEWEB)

    Salou, M.; Siffert, B.; Jada, A. [Institut de Chimie des Surfaces et Interfaces, Mulhouse (France)

    1998-03-01

    The chemical and interfacial properties of two bitumens were compared. The chemical properties were characterized by determining the asphaltene and resin contents of the bitumens. The interfacial properties were studied by wettability measurements and by determining the zeta potential of bitumen dispersions in acid water, with and without maturation of asphaltene dispersions in acid water and of bitumen dispersions in acid water containing asphaltenes. The study of the influence of the maturation at 80{degree}C for 7 h and of the addition of asphaltenes on the stability of the bitumen dispersion showed that the evolution of the interfacial properties of the bitumen depends on the resin content of the bitumen. Short communication. 15 refs., 1 figs., 2 tabs.

  2. Some studies on tar pillets at Veraval coast (Gujarat)

    Digital Repository Service at National Institute of Oceanography (India)

    Kadam, A.N.

    and high asphaltene contents revealed that the residue might have originated from residual fraction of a crude oil such as fuel oil. Its fingerprint pattern and paraffin profile did not match with those of Bombay High crude residue...

  3. A novel method for recovery of acidic sludge of used-motor oil reprocessing industries to bitumen using bentonite and SBS

    National Research Council Canada - National Science Library

    Ahmad Jonidi Jafari; malek hassanpour; Mitra Gholam; Mehdi Farzadkia

    2014-01-01

    .... The acidic sludge contains unsaturated compounds that are polar and asphaltene. The bitumen under certain conditions is produced from mixing of bentonite, polymer styrene – butadiene – styrene (SBS), and acidic sludge...

  4. 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.

  5. 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.

  6. Di- or polysulphide-bound biomarkers in sulphur-rich geomacromolecules as revealed by selective chemolysis

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Kohnen, M.E.L.; Kock-van Dalen, A.C.; Leeuw, J.W. de

    1991-01-01

    Three types of sulphur-rich, high-molecular-weight material in the alkylsulphide, the polar and the asphaltene fracions isolated from the bitumen of an immature bituminous shale from the Vena del Gesso basin (Italy) were desulphurised.

  7. 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

    OpenAIRE

    Pourabdollah K.; Zarringhalam Moghaddam A.; Kharrat R.; Mokhtari B.

    2011-01-01

    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-a...

  8. 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.

  9. 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.

  10. Screening of fungi for the biological modification of hard coal and coal derivatives

    Energy Technology Data Exchange (ETDEWEB)

    Bublitz, F.; Guenther, T.; Fritsche, W. (Friedrich-Schiller-University of Jena, Jena (Germany). Inst. of Microbiology)

    1994-11-01

    A biotechnological depolymerization of hard coal is being attempted with basidiomycetous fungi native to timber, plant residues, and soil, and with microfungi of lignite sources and contaminated soil. The coal materials such as powdered or hydrogenated hard coal (asphaltene) were aseptically exposed to fungal pure cultures in a four-step screening system. Agar surface cultures were examined for softening and erosion of the coal particles, and for alterations in the asphaltene films fixed to plastic chips and silica gel. From the shake cultures, both the culture fluid and the coal or asphaltene sediments were separately collected and processed by photospectrometry, gel permeation chromatography, combined gas chromatography-mass spectrometry, and IR spectrometry. Of the 243 fungal strains tested to date, four were reactive on coal materials and asphaltene. Two basidiomycetes ([ital Coriolus hirsutus (Wulf.) Quel.; Coprinus sclerotiger Watl.]) eroded hard coal particles, while another basidiomycetous strain ([ital Agrocybe semiorbicularis (Bull.:Fr.)]) separated the asphaltene film from its plastic carrier. The hyphomycete [ital Trichoderma spec.strain AB2] caused alterations in the IR spectrum of asphaltene. 16 refs., 2 figs.

  11. 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)

  12. Molecular Dynamics Simulation of Spontaneous Imbibition in Nanopores and Recovery of Asphaltenic Crude Oils Using Surfactants for EOR Applications Simulations de dynamique moléculaire d’imbibition spontanée dans des nanopores et pour la récupération d’huiles brutes asphalténiques en utilisant des agents tensioactifs pour des applications d’EOR

    Directory of Open Access Journals (Sweden)

    Stukan M.R.

    2012-12-01

    Full Text Available We present Molecular Dynamics (MD simulations of the imbibition process in nanopores in case of two different mechanisms of the wettability modification. We compare the imbibition of an aqueous surfactant solution into an oil-wet pore driven by surfactant adsorption onto the oil-wet rock surface (coating mechanism and the imbibition of an aqueous surfactants solution driven by surfactants removing the contaminant molecules from the originally water-wet surface (cleaning mechanism. Our results show qualitative difference in the imbibition dynamics in these two cases and indicate that MD simulation is a useful tool to investigate details of the imbibition mechanisms at the pore scale with direct implications for Enhanced Oil Recovery (EOR operations. Nous presentons des simulations de Dynamique Moleculaire (DM du processus d’imbibition dans des nanopores dans le cas de deux mecanismes differents de modification de mouillabilite. Nous comparons l’imbibition d’une solution aqueuse d’agent tensioactif dans un pore mouille d’huile entrainee par une adsorption d’agent tensioactif sur la surface de roche mouillee d’huile (mecanisme de revetement et l’imbibition d’une solution aqueuse d’agent tensioactif entrainee par des agents tensioactifs eliminant les molecules contaminantes de la surface originellement mouillee d’eau (mecanisme de nettoyage. Nos resultats montrent une difference qualitative en matiere de dynamique d’imbibition dans ces deux cas et indiquent que la simulation de DM constitue un outil utile pour etudier les mecanismes d’imbibition a l’echelle des pores avec des implications directes pour des operations de recuperation renforcee d’huile (EOR, Enhanced Oil Recovery.

  13. 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.

  14. Adsorption and molecular rearrangement of amphoteric species at oil-water interfaces.

    Science.gov (United States)

    Verruto, Vincent J; Le, Rosemary K; Kilpatrick, Peter K

    2009-10-22

    The formation of stable water-in-petroleum emulsions is a costly challenge when transporting, processing, and refining heavy crude oil and bitumen. The stability of these emulsions is attributed to interfacial films with well-documented viscoelastic properties that are known to vary with concentration, solvent quality, and asphaltene chemistry. In this study, we explore the impact of aqueous phase pH and salinity on the transient interfacial rheological properties of asphaltenic films. Using two chemically unique asphaltenes, interfacial shear rheology revealed an apparent salt-induced retardation of the interfacial consolidation processes that ultimately engender elasticity to the film. For Hondo asphaltenes at pH 7, a linear dependence of this retardation on the Debye parameter (kappa) suggested that shielding of electrostatic attraction was responsible. Further investigation with dynamic oscillating drop tensiometry at pH 3, 7, and 10 illustrated that intralayer repulsive and attractive electrostatic interactions can significantly influence the evolution of the interfacial structure. More specifically, the transient tension and dilatational modulus profiles indicated several interfacial processes were affected by the addition of salt, including (i) interfacial activity and the extent of adsorption, (ii) interfacial rearrangement and consolidation, and (iii) interfacial transport or displacement or both. Furthermore, the observed asphaltene interfacial behavior was consistent with those published for interfacial structure-forming amphoteric proteins, such as lysozyme and beta-casein.

  15. Oilfield solids and water-in-oil emulsion stability.

    Science.gov (United States)

    Sztukowski, Danuta M; Yarranton, Harvey W

    2005-05-15

    Model water-in-hydrocarbon emulsions consisting of toluene, heptane, water, asphaltenes, and native solids were used to investigate the role of native solids in the stability of oilfield emulsions. The solids were recovered from an oil-sands bitumen, a wellhead emulsion, and a refinery slop oil. The solids were clay platelets and fell into two size categories: (1) fine solids 50 to 500 nm in diameter and (2) coarse solids 1 to 10 microm in diameter. Emulsions stabilized by fine solids and asphaltenes were most stable at a 2:1 fractional area ratio of asphaltenes to solids. It appears that when the asphaltene surface coverage is high, insufficient solids remain to make an effective barrier. When the solids coverage is high, insufficient asphaltenes remain on the interface to immobilize the solids. Treatments that weaken the interface, such as toluene dilution, are recommended for emulsions stabilized by fine solids. Emulsions stabilized by coarse solids were unstable at low solids concentrations but became very stable at solids concentrations greater than 10 kg/m(3). At low concentrations, these solids may act as bridges between water droplets and promote coalescence. At high concentrations, layers of coarse solids may become trapped between water droplets and prevent coalescence. Treatments that flocculate the solids, such as heptane dilution, are recommended for emulsions stabilized by high concentrations of coarse solids. It is possible that emulsions containing both types of solids may require more than one treatment, or even process step, for effective water resolution.

  16. Greater bottoms upgrading with Albemarle's e-bed catalysts

    Energy Technology Data Exchange (ETDEWEB)

    Toshima, H.; Sedlacek, Z.; Backhouse, D.; Mayo, S.; Plantenga, F. [Albemarle Catalysts, Houston, TX (United States)

    2006-07-01

    The E-bed process is a heavy oil upgrading technology that produces near isothermal reactor conditions at a constant catalytic activity. However, E-bed conversion optimization is limited by reactor and downstream fouling problems caused by asphaltene precipitation. While asphaltene precipitation can controlled by reducing hydrogenation, high hydrogenation activity is needed for the removal of sulfur and heavy metals. This presentation described an asphaltene molecule management concept to reduce the fouling of E-bed units. Sediment reduction and high hydrogenation catalysts were used in a modified E-bed process with a variety of feeds and operating conditions. It was observed that the KF1312 catalyst achieved much higher sediment-reduction capability along with satisfactory hydrogenation activity with the different kinds of crude oil sources tested. The catalyst hydrocracked the asphaltenes into smaller molecules, which created greater asphaltene solubility. The sediment reduction capacity of the catalyst-staging technology is now being optimized. It was concluded that the technology will help to reduce fouling in E-bed processes and lead to improved conversion rates for refineries. refs., tabs., figs.

  17. Thermodynamic modeling for organic solid precipitation

    Energy Technology Data Exchange (ETDEWEB)

    Chung, T.H.

    1992-12-01

    A generalized predictive model which is based on thermodynamic principle for solid-liquid phase equilibrium has been developed for organic solid precipitation. The model takes into account the effects of temperature, composition, and activity coefficient on the solubility of wax and asphaltenes in organic solutions. The solid-liquid equilibrium K-value is expressed as a function of the heat of melting, melting point temperature, solubility parameter, and the molar volume of each component in the solution. All these parameters have been correlated with molecular weight. Thus, the model can be applied to crude oil systems. The model has been tested with experimental data for wax formation and asphaltene precipitation. The predicted wax appearance temperature is very close to the measured temperature. The model not only can match the measured asphaltene solubility data but also can be used to predict the solubility of asphaltene in organic solvents or crude oils. The model assumes that asphaltenes are dissolved in oil in a true liquid state, not in colloidal suspension, and the precipitation-dissolution process is reversible by changing thermodynamic conditions. The model is thermodynamically consistent and has no ambiguous assumptions.

  18. Cooee bitumen:

    DEFF Research Database (Denmark)

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

    2013-01-01

    We study chemical aging in “Cooee bitumen” using molecular dynamic simulations. This model bitumen is composed of four realistic molecule types: saturated hydrocarbon, resinous oil, resin, and asphaltene. The aging reaction is modelled by the chemical reaction: “2 resins → 1 asphaltene.” Molecular...... dynamic simulations of four bitumen compositions, obtained by a repeated application of the aging reaction, are performed. The stress autocorrelation function, the fluid structure, the rotational dynamics of the plane aromatic molecules, and the diffusivity of each molecule are determined for the four...... 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...

  19. Structural-group composition of resin substances of petroleums in west Siberia

    Energy Technology Data Exchange (ETDEWEB)

    Nesterenko, V.I.; Ogorodnikov, V.D.; Brodskii, E.S.; Plyusnin, A.N.

    1984-01-01

    Resin-asphaltene substances (RAS) are the most representative group of non-hydrocarbon petroleum components, which have a negative effect on catalytic processes of oil refining and on the operational indices of petroleum products. At the same time they are one of the main reserves for further increasing the extent petroleum exploitation. Therefore, an understanding of the composition and structure of resin-asphaltene substances is of considerable importance both for oil refining and the production of high-grade petroleum products. Reasonably reliable information concerning the structural-group composition of resin-asphaltene substances has only been forthcoming in recent years as a result of the development of NMR spectroscopy and high-resolution mass-spectrometry. In this study structural-group composition of petroleum resins of the Fedorov deposit (Tyumen region), was obtained using mass-spectrometry, PMR- and /sup 13/C-NMR spectroscopy, elemental analysis and molar masses. 9 references, 3 tables.

  20. Palm oil based surfactant products for petroleum industry

    Science.gov (United States)

    Permadi, P.; Fitria, R.; Hambali, E.

    2017-05-01

    In petroleum production process, many problems causing reduced production are found. These include limited oil recovery, wax deposit, asphaltene deposit, sludge deposit, and emulsion problem. Petroleum-based surfactant has been used to overcome these problems. Therefore, innovation to solve these problems using surfactant containing natural materials deserves to be developed. Palm oil-based surfactant is one of the potential alternatives for this. Various types of derivative products of palm oil-based surfactant have been developed by SBRC IPB to be used in handling problems including surfactant flooding, well stimulation, asphaltene dissolver, well cleaning, and wax removal found in oil and gas industry.

  1. 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.

  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. 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.

  4. 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.

  5. 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.

  6. 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.

  7. Molecular characterization of organically bound sulphur in crude oils. A feasibility study for the application of Raney Ni desulphurization as a new method to characterize crude oils

    NARCIS (Netherlands)

    Sinninghe Damsté, J.S.; Rijpstra, W.I.C.; Leeuw, J.W. de; Lijmbach, G.W.M.

    1994-01-01

    Five crude oils with varying sulfur contents (0.1 – 4.7%) were characterized on a molecular level for organically-bound sulfur. Aromatic fractions were analyzed by GC-(MS) and asphaltene and polar fractions were analyzed by flash pyrolysis-GC-(MS). The polar fractions were also desulfurized with

  8. 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...

  9. 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)

  10. 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

  11. Three-dimensionally printed polymer rendered electrical-resistance-based self-sensing by carbon nanofiber addition

    Science.gov (United States)

    Yadavalli, J. P. Sasankavalli

    Asphalt binder, which is the main ingredient of Asphalt Concrete (AC) pavements, is one of the products of crude oil distillation and contains an extremely large number of complex organic compounds as well as cancer-causing substances known as Polycyclic Aromatic Hydrocarbons (PAHs). This research is done to understand possible release and subsequent contamination of PAHs from the AC pavements into the surrounding environment. Molecular Dynamics (MD) simulation is used to understand the release of PAHs regarding energy loss between three PAH molecules Naphthalene, Fluoranthene, and Benzo [a] Pyrene, and two asphalt binder molecules Asphaltene Phenol and Maltene-Aromatic component Dioctyl-Cyclohexane-Naphthalene (DOCHN). Energy loss between PAHs, Asphaltene Phenol, and DOCHN is computed by MD simulation under different climate condition such as varying temperature and moisture, and mechanical conditions such as vehicle tire pressure. MD simulation between PAHs, Asphaltene Phenol, and DOCHN shows that moisture causes significant energy loss and the energy loss indicates a higher potential of releasing PAHs from the AC pavements and contaminate environment. PAHs with lower molecular weight such as Naphthalene have a higher potential to release into the environment than higher molecular weight PAHs such as Benzo [a] Pyrene. Also, it is observed that DOCHN would release more PAHs than Asphaltene Phenol. Although, vehicle tire pressure and temperature influence PAHs release from the AC pavements at various degrees but no consistency is identified. This MD simulation study supports outcomes of previous researchers' experiment completed on PAHs extraction from soil and water collected from AC pavement locations.

  12. Visible-Near Infrared (VNIR) and Shortwave Infrared (SWIR) Spectral Variability of Urban Materials

    Science.gov (United States)

    2013-03-01

    study that took into account vegetation geometry, Zhang and Qiu (2012) were able to use LiDAR data to detect individual tree crowns , then identify...cherty conglomerate (Roble et al., 1991). The asphalt mix typically consists of oil, asphaltenes, and resins (Herold, 2007). Figure 25 shows imagery from

  13. Final Report on Assessment of Crude Oil and Refined Petroleum Product Quality During Long-Term Storage.

    Science.gov (United States)

    1979-12-01

    crystalline wax, sand, clay , water and possibly asphaltenes. Emulsions at the water-oil interface have been reported after prolonged storage, and...detection of hydrogen sulfide was noted. The bitumen sediment and water inherently present in crude may contribute to this layer by settling out during

  14. 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...

  15. A Rapid Method of Crude Oil Analysis Using FT-IR Spectroscopy

    African Journals Online (AJOL)

    HP USER

    (1997). FT-IR characterization of pitches derived from Avgamasya asphaltite and Raman-Dincer heavy crude, Fuel, 76: 1389-1394. Aske, N. (2002). Characterisation of crude oil components, asphaltene aggregation and emulsion stability by means of near infrared spectroscopy and multivariate analysis. Thesis submitted to ...

  16. 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

  17. 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)

  18. The Effect of Compositional Changes of Binary Mixtures of n-alkane ...

    African Journals Online (AJOL)

    user

    Hirschberg, A., Dejong, N. J., Schipper, B. A., and. Meijer, J. G., 1984, “Influence of Temperature and Pressure on Asphaltene Flocculation”,. Society of Petroleum Engineering Journal, 24, pp. 283-291. Hu, Y. F., Li, S., Liu, N., Chu, Y. P., Park, S. J.,. Mansoori, G. A., Guo, T. M., 2004,. “Measurement and Corresponding States.

  19. 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.

  20. Relationship between the chemical properties of bitumens and their colloidal properties in water

    Energy Technology Data Exchange (ETDEWEB)

    Salou, M.; Siffert, B.; Jada, A. [Institut de Chimie des Surfaces et Interfaces, Mulhouse (France)

    1998-03-01

    The chemical properties of different bitumens were characterized by determining their asphaltene and resin contents and acid-base properties by carrying out titrations in organic media. The colloidal properties of the bitumens in water, i.e. their electrical interfacial properties, were evaluated by measuring the zeta potentials of bitumen dispersions in water. Comparison between the chemical and colloidal properties of the bitumens shows that it could be possible to predict the dispersion stability from the chemical properties of the bitumens. The resins/asphaltenes ratio can affect the dispersion stability by controlling the arrangement of the bitumens components inside the droplet and also at the interface during dispersion manufacture. Short communication. 18 refs., 2 figs., 2 tabs.

  1. Application of high-temperature simulated distillation to the residuum oil supercritical extraction process in petroleum refining

    Science.gov (United States)

    Raia; Villalanti; Subramanian; Williams

    2000-01-01

    The gas chromatographic method of high-temperature simulated distillation (HTSD) is described, and the results are presented for the application of HTSD to the characterization of petroleum refinery feed and products from solvent deasphalting operations. Results are presented for refinery residual feed, deasphalted oil, and asphaltene fractions from the residual oil supercritical extraction process. Asphaltene removal from petroleum residuum using solvent deasphalting results in the improved quality and high recovery of deasphalted oil product for use as lube oil, fluid catalytic cracking, or hydrocracker feedstocks. The HTSD procedure presented here proves valuable for characterizing the fractions from the deasphalting process to obtain the percentage yield with boiling point data over the range from approximately 36 degrees C (97 degrees F) to 733 degrees C (1352 degrees F), which covers the boiling range of n-paraffins of carbon number C5 to C108.

  2. Change in consistency and composition of trichloroethylene- and trichloroethane-treated asphalts.

    Science.gov (United States)

    Abu-Elgheit, M A; Ijam, M J

    1982-12-01

    Solvent extraction of asphalt from pavement mixtures is a technique used to study the change in asphalt during service. Rheological measurements indicate that asphalts recovered from trichloroethylene or trichloroethane are markedly hardened. Compositional studies on asphaltic fractions reveal a notable decrease in saturates, naphthenes, H, N, Ni and V, and increase in polar aromatics and asphaltenes along with incorporation of Cl in all fractions. These structural changes are responsible for the hardening of the asphalt and are interpreted in terms of cyclization of saturates, aromatization of naphthenes, coupling of free radicals with neutral species to give a high content of asphaltenes, and in terms of loss of the relatively volatile Ni and V porphyrins during the extraction-recovery process.

  3. 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.

  4. 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.

  5. Fungal attack on coal: 1. Modification of hard coal by fungi

    Energy Technology Data Exchange (ETDEWEB)

    Hofrichter, M.; Bublitz, F.; Fritsche, W. [Friedrich-Schiller-University of Jena, Jena (Germany). Inst. of Microbiology

    1997-11-01

    Within a screening program more than 750 fungal strains were tested for their ability to attack a German hard coal (Westerholt Mine). Six strains were selected, which modified the physico-chemical properties of hard coal pieces placed on the overgrown surface of Petri dishes (loss of the compact coal structure, `erosion`, increase in wettability). One of these strains, Coprinus sclerotigenis C142-1, liberated 2-hydroxybiphenyl, alkylated benzenes and polycyclic aromatic hydrocarbons (PAH) from powdered hard coal. It is presumed that most of these compounds were liberated from micropores inside of the hard coal macromolecule. Investigations using hard coal derived asphaltenes indicate that the liberation of hydroxylated biphenyl by C. sclerotigenis is due to a real cleavage of chemical bonds. The cultivation of the white-rot fungus Panus tigrinus on wood shavings coated with asphaltenes led to a decrease of the average molecular weights of these hard coal-derived hydrogenation products. 18 refs., 6 figs., 1 tab.

  6. Characterization of lignite low-severity depolymerization products

    Energy Technology Data Exchange (ETDEWEB)

    Mastral, A.M.; Cebolla, V.L.

    1985-08-01

    Oils and asphaltenes derived from direct extraction and several mild depolymerization processes have been studied. The asphaltenes have been fractionated by column adsorption chromatography (with deactivated silica gel) and benzene, THF and MeOH were used in sequence as eluothropic series. Clear chemical separation between one aromatic and two polar fractions has been obtained, giving high percentages recovery. The fractions have been characterized by VPO, FT-IR, /sup 1/H-NMR and elemental analysis. Several structural parameters of oils have been calculated. These oils can be assimilated to equivalent average hydrocarbons having between 10 and 20 carbon atoms and an aromatic carbon percentage oscillating between 47 and 66%. In general, the degree of substitution in aromatic rings is low and the presence of phenolic groups is limited. The majority of the carbons are aromatic and these rings show low degrees of condensation. 20 references.

  7. Effects of thermal treatment on colloidal chemical properties of mixtures for production of technical carbon

    Energy Technology Data Exchange (ETDEWEB)

    Svinukhov, A.G.; Kolesnikov, S.I.; Soboleva, Eh.B.; Turundaevskaya, N.E. (Moskovskii Institut Nefti i Gaza im. I.M. Gubkina (USSR))

    1990-07-01

    Evaluates thermochemical changes of petroleum-derived and coal-derived tar fractions. Mixtures studied include gasoline pyrolysis tar, anthracene fractions and gas oil residue extracts. Temperature of experiments was 200 to 300 C. Content of heptane and toluene insoluble components were factors in thermal stability. Colorimetry was applied to measure system aggregate stability. From among the initial raw materials, the anthracene fraction gave the highest asphaltene yield, but this yield decreased after treatment at 250 C together with its stability factor. Thermal treatment of pyrolysis tars sharply increased their asphaltene and carbene-carboid content but thermal stability changed slightly. Experimental results are provided in tables. The analysis shows that aggregate stability of mixtures has minima at 5, 15 and 30% of tar content. Mixtures break above 35%. Above 30%, the mixture's thermal stability and homogeneity are disturbed. 6 refs.

  8. 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

  9. The effect of moisture on the liquefaction of some Turkish coals in tetralin with microwave energy

    Energy Technology Data Exchange (ETDEWEB)

    Simsek, E.H.; Karaduman, A.; Togrul, T. [Ankara University, Ankara (Turkey). Dept. of Chemical Engineers

    2002-07-01

    The effect of the moisture content of coals, solvent/coal ratio, and the heating period by microwave energy on solubilization of Turkish coals (Bolu-Goynuk, Beypazari, Mugla-Yatagan, Tuncbilek, Aydin-Yeniceltek lignites, and Zonguldak coal) in tetralin has been investigated. The yields of tetrahydrofuran (THF) solubles and oils were increased with increasing moisture content of coals. When solvent/coal ratio increased from 2/1 to 4/1, the yield of oils increased. However, the yields of asphaltenes and preasphaltenes decreased. The yields of THF solubles and oils did not change considerably with reaction time. While the yields of asphaltenes and preasphaltenes decreased with reaction time at the value of 2/1 of solvent/coal ratio and increased with reaction time at the value of 4/1 of solvent/coal ratio, the yields are lower than at the value of 2/1 of solvent/coal ratio.

  10. Effects of molecular de-aggregation on refractive indices of petroleum-based fluids

    Energy Technology Data Exchange (ETDEWEB)

    Igor N. Evdokimov; Aleksandr P. Losev [Gubkin Russian State University of Oil and Gas, Moscow (Russian Federation). Department of Physics

    2007-10-15

    It is conventionally assumed that refractive index (RI) for a crude oil, a processed fuel or any petroleum-based solution may be evaluated in an assumption of an ideal binary mixture of non-precipitating components. However, new experimental data reveal strong non-ideality of RI in dilute oil solutions, which we attribute to de-aggregation of asphaltenes. 34 refs., 8 figs.

  11. Physico-chemical analysis of five hard bitumens : Identification of chemical species and molecular organization before and after artificial aging

    OpenAIRE

    Le Guern, Malo; Chailleux, Emmanuel; Farcas, Fabienne; DRESSEN, S; MABILLE, Isabelle

    2010-01-01

    The present paper focuses on a physico-chemical analysis of five different types of bitumens, both before and after aging. These bitumen samples were chosen based on : the original crude oil (straight-run bitumens with different asphaltene and crystallized fraction contents), mode of refining (straight-run vs. halfblown bitumen), and modifier characteristics (straight-run vs. polyphosphoric acid (PPA)-modified bitumen). The aim of this study is to determine both the aging effect on chemical s...

  12. A novel method for recovery of acidic sludge of used-motor oil reprocessing industries to bitumen using bentonite and SBS

    OpenAIRE

    Ahmad Jonidi Jafari; malek hassanpour; Mitra Gholam; Mehdi Farzadkia

    2014-01-01

    ABSTRACT Acidic sludge is a by-product from used motor oil reprocessing industries, which thousand tons of this sludge are disposed into the environment as a hazardous waste material daily. The acidic sludge contains unsaturated compounds that are polar and asphaltene. The bitumen under certain conditions is produced from mixing of bentonite, polymer styrene – butadiene – styrene (SBS), and acidic sludge. Context and purpose: The objective of this study was the recovery of acidic sludge...

  13. Viscosity Reduction and Upgrading of Athabasca Oilsands Bitumen by Natural Zeolite Cracking

    OpenAIRE

    Abu S.M. Junaid; Wei Wang; Christopher Street; Moshfiqur Rahman; Matt Gersbach; Sarah Zhou; William McCaffrey; Steven M. Kuznicki

    2010-01-01

    Oilsands bitumen is an extremely important source of energy for North America. However, due to the presence of large molecules such as asphaltenes, the density and viscosity of the bitumen recovered from these sands are much higher than those of conventional crude oil. As a result the extracted bitumen has to be diluted with expensive solvents, or thermochemically upgraded in large, capital-intensive conventional upgrading facilities prior to pipeline transport. This stud...

  14. Disjoining pressure isotherms of water-in-bitumen emulsion films.

    Science.gov (United States)

    Taylor, Shawn D; Czarnecki, Jan; Masliyah, Jacob

    2002-08-01

    In the oil sands industry, undesirable water-in-oil emulsions are often formed during the bitumen recovery process where water is used to liberate bitumen from sand grains. Nearly all of the water is removed except for a small percentage (approximately 1 to 2%), which remains in the solvent-diluted bitumen as micrometer-sized droplets. Knowledge of the colloidal forces that stabilized these water droplets would help to increase our understanding of how these emulsions are stabilized. In this study, the thin liquid film-pressure balance technique has been used to measure isotherms of disjoining pressure in water/toluene-diluted bitumen/water films at five different toluene-bitumen mass ratios. Even though a broad range of mass ratios was studied, only two isotherms are obtained, indicating a possible change in the molecular orientation of surfactant molecules at the bitumen/water interfaces. At low toluene-bitumen mass ratios, the film stability appears to be due to a strong, short-range steric repulsion created by a surfactant bilayer. Similar isotherms were obtained for water/toluene-diluted asphaltene/water films, indicating that the surface active material at the interface probably originated from the asphaltene fraction of the bitumen. However, unlike the bitumen films, films of toluene-diluted asphaltenes often formed very rigid interfaces similar to the "protective skin" described by other researcher.

  15. Roles of Various Bitumen Components in the Stability of Water-in-Diluted-Bitumen Emulsions.

    Science.gov (United States)

    Yan; Elliott; Masliyah

    1999-12-15

    An experimental study was conducted to evaluate the effectiveness of the various components of Athabasca bitumen in stabilizing water-in-diluted-bitumen emulsions. The solvent used to dilute the very viscous bitumen was a mixture of 50:50 by volume of hexane and toluene. The various bitumen components studied were asphaltenes, deasphalted bitumen, and fine solids. It was found that asphaltenes and fine solids were the main stabilizers of the water-in-diluted-bitumen emulsions. Individually, the two components can stabilize water-in-diluted-bitumen emulsions. However, when both are present the capacity of the diluted bitumen to stabilize water emulsions is greatest. Emulsion stabilization tests indicated that whole bitumen had less capacity to stabilize water emulsions than asphaltenes and solids. This would indicate that the presence of the small molecules within the whole bitumen tends to lower the emulsion stability. Deasphalted bitumen acts as a poor emulsion stabilizer. Although deasphalted bitumen led to the least emulsion stabilization capacity, interfacial tension measurements showed that diluted deasphalted bitumen gave a greater decrease in the interfacial tension of water with diluent. Copyright 1999 Academic Press.

  16. 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.

  17. 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.

  18. Relationship Between the Composition and Interfacial Tension of Former Manufactured Gas Plant Tars

    Science.gov (United States)

    Hauswirth, S.; Birak, P. S.; Miller, C. T.

    2011-12-01

    Former manufactured gas plant (FMGP) tars pose significant environmental hazards and present a challenge to regulators and industry professionals. The tars, which were produced as a byproduct of the gas manufacturing process, were frequently released into the environment through improper disposal or leaks in plant infrastructure. The interfacial tension (IFT) is a primary factor controlling the mobility of tars in porous media, and is therefore important to understand for both predicting the migration of tars and designing remediation strategies. In this study, we characterized nine field-collected FMGP tars and a commercially available coal tar by means of chemical extractions (asphaltenes, resins, acids, and bases), gas chromatography-mass spectrometry (GC-MS), and Fourier transform infrared (FTIR) spectroscopy. Additionally, the IFT and contact angle of each tar was determined for a pH range of 3-11. The IFT was found to be similar for all tars at pH 5 and 7 regardless of composition. Slight decreases in IFT at lower pH were correlated with higher concentrations of extractable bases, which consisted primarily of nitrogen-containing heterocyclic aromatic compounds. Much greater reductions of IFT were observed at high pH. These reductions were found to be associated with the presence of carbonyl or carboxyl groups in the asphaltenes. It is likely that the larger size of the asphaltene molecules (as compared to the extractable compounds) resulted in species with greater surface activity when ionized.

  19. Adsorption of bituminous components at oil/water interfaces investigated by quartz crystal microbalance: implications to the stability of water-in-oil emulsions.

    Science.gov (United States)

    Goual, Lamia; Horváth-Szabó, Géza; Masliyah, Jacob H; Xu, Zhenghe

    2005-08-30

    Silica-gel-coated QCM crystals oscillating in a thickness shear mode are used to measure adsorption of bituminous components in water-saturated heptol (1/1 vol ratio of a heptane/toluene mixture) at the oil/water interface. In addition to the viscoelasticity of the adsorbed film, the effects of the bulk liquid density and viscosity as well as the liquid trapped in interfacial cavities are taken into account for the calculation of adsorbed mass. Asphaltenes in heptol adsorb continuously at the oil/water interface, while resins (the surface-active species in maltenes) show adsorption saturation in the same solvent. For Athabasca bitumen in heptol, two adsorption regimes are observed depending on concentration. At low concentrations, a slow, non-steady-state, and irreversible adsorption takes place. At high concentrations, a steady-state adsorption with limited reversibility results in a quick adsorption saturation. The threshold concentration between these adsorption regimes is 1.5 wt % and 8 wt % for oil/water and oil/gold interfaces, respectively. The threshold concentration, the total adsorbed amount, and the flux of non-steady-state adsorption depend on the resin-to-asphaltene ratio. The threshold concentration is related to the earlier reported critical bitumen concentration characterizing the rigid-to-flexible transition of the interfacial film. We propose a new mechanism based on the change of the effective resin-to-asphaltene ratio with dilution to explain both the adsorption behavior and emulsion stability.

  20. 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.

  1. 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.

  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. Compositional analysis of heavy crude oil fractions by ultrahigh resolution FT-ICR mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Rodgers, R.; Marshall, A.G. [Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry; Florida State Univ., Tallahassee, FL (United States). National High Magnetic Field Lab; McKenna, A.M. [Florida State Univ., Tallahassee, FL (United States). Dept. of Chemistry

    2009-07-01

    The need to characterize heavy, high sulphur crudes is essential as the global oil supply of light, sweet crudes is depleted. Due to the high sulphur content in bitumen and heavy crudes, detailed compositional characterization is needed to help develop recovery strategies in the refinery. This study characterized the middle distillate fractions of Athabasca bitumen to define the structural evolution of polycyclic aromatics that may also contain nitrogen, oxygen or sulphur atoms as a function of boiling point. The higher distillate fractions were then analyzed along with vacuum resids to prove that the structural distribution in petroleum is continuous. The basic differences in solution-phase behaviour between asphaltene and maltene fractions were discussed. An argument was presented for the structural evolution of polyaromatic hydrocarbons, and the compositional boundary between asphaltene and maltene was defined. The study suggested that asphaltenes and maltenes share the same carbon number. The characterization was extended to vanadyl porphyrins by electrospray and atmospheric pressure photoionization Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). tabs., figs.

  4. 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.

  5. 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)

  6. 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)

  7. 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.

  8. Separation and characterization of vanadium and nickel organometallic compounds in heavy crudes

    Energy Technology Data Exchange (ETDEWEB)

    Nali, M.; Corana, F.; Scilingo, A.; Scotti, R. (Eniricerche S.p.A., Milan (Italy))

    1994-01-01

    A new separation scheme has been developed to concentrate nickel and vanadium complexes in selected fractions before attempting a molecular characterization of these organometallic species in heavy crude oils. It involves a combination of solubility- (n-heptane deasphalting and pyridine/water extraction of asphaltenes) and polarity- (SO[sub 3]-modified silica gel column) based steps. The proposed method has been applied to Belayim crude oil. The nature of pyridine/water extract from asphaltenes has been investigated using both preparative gel permeation chromatography (GPC) and reverse phase liquid chromatography (RP-HPLC) combined (off-line) to graphite furnace atomic absorption (GFAA). The fractions obtained after the separation of the extract on a SO[sub 3]-modified silica gel column have been submitted to a series of analytical techniques. All the analytical evidence arising from the present study, indicates that vanadium, present in pyridine/water extract obtained from asphaltenes, is mostly bound in porphyrin structures, although the coordination sphere around vanadyl species, present in the most polar fraction obtained from the extract separation by column chromatography, shows different EPR parameter. On the other hand, nickel complexes are smaller and more polar than common Ni-porphyrins, which are concentrated in deasphalted oil. 16 refs., 9 figs., 2 tabs.

  9. Multifunctional polymer composites containing inorganic nanoparticles and novel low-cost carbonaceous fillers

    Science.gov (United States)

    Wu, Hongchao

    Advanced polymer nanocomposites/composites containing inorganic nanoparticles and novel carbonaceous fillers were processed and evaluated for the multifunctional purposes. To prepare the high performance conformal coating materials for microelectronic industries, epoxy resin was incorporated with zirconium tungstate (ZrW 2O8) nanoparticles synthesized from hydrothermal reaction to alleviate the significant thermal expansion behavior. Three types of ZrW 2O8 at different loading levels were selected to study their effect of physical (morphology, particle size, surface area, etc.) and thermal (thermal expansivity) properties on the rheological, thermo-mechanical, dynamic-mechanical, and dielectric properties of epoxy resin. Epoxy resin incorporated by Type-1 ZrW2O8 exhibited the overall excellent performance. Hexagonal boron nitride (h-BN) nanoplatelets were non-covalently encapsulated by a versatile and mussel-adhesive protein polydopamine through the strong pi-pi* interaction. The high-temperature thermoset bisphenol E cyanate ester (BECy) reinforced with homogenously dispersed h-BN at different volume fractions and functionalities were processed to investigate their effect on thermo-mechanical, dynamic-mechanical, dielectric properties and thermal conductivity. Different theoretical and empirical models were also successfully applied for the prediction of CTE, thermal conductivity and dielectric constant of h-BN/BECy nanocomposites. On the basis of the improvement in dimensional stability, the enhancement in storage modulus in both glassy and rubbery regions, associated with the increment in thermal conductivity without deterioration of thermal stability, glassy transition temperature and dielectric properties, pristine h-BN/BECy nanocomposites exhibited the prospective application in microelectronic packaging industry. Polydopamine functionalized h-BN significantly increased the dielectric constant of cyanate ester at lower frequency region. Asphaltene, a

  10. 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

  11. Evaluation of Inoculum Addition To Stimulate In Situ Bioremediation of Oily-Sludge-Contaminated Soil

    Science.gov (United States)

    Mishra, Sanjeet; Jyot, Jeevan; Kuhad, Ramesh C.; Lal, Banwari

    2001-01-01

    A full-scale study evaluating an inoculum addition to stimulate in situ bioremediation of oily-sludge-contaminated soil was conducted at an oil refinery where the indigenous population of hydrocarbon-degrading bacteria in the soil was very low (103 to 104 CFU/g of soil). A feasibility study was conducted prior to the full-scale bioremediation study. In this feasibility study, out of six treatments, the application of a bacterial consortium and nutrients resulted in maximum biodegradation of total petroleum hydrocarbon (TPH) in 120 days. Therefore, this treatment was selected for the full-scale study. In the full-scale study, plots A and B were treated with a bacterial consortium and nutrients, which resulted in 92.0 and 89.7% removal of TPH, respectively, in 1 year, compared to 14.0% removal of TPH in the control plot C. In plot A, the alkane fraction of TPH was reduced by 94.2%, the aromatic fraction of TPH was reduced by 91.9%, and NSO (nitrogen-, sulfur-, and oxygen-containing compound) and asphaltene fractions of TPH were reduced by 85.2% in 1 year. Similarly, in plot B the degradation of alkane, aromatic, and NSO plus asphaltene fractions of TPH was 95.1, 94.8, and 63.5%, respectively, in 345 days. However, in plot C, removal of alkane (17.3%), aromatic (12.9%), and NSO plus asphaltene (5.8%) fractions was much less. The population of introduced Acinetobacter baumannii strains in plots A and B was stable even after 1 year. Physical and chemical properties of the soil at the bioremediation site improved significantly in 1 year. PMID:11282620

  12. 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)

  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...

  14. Natural gas hydrate formation and inhibition in gas/crude oil/aqueous systems

    DEFF Research Database (Denmark)

    Daraboina, Nagu; Pachitsas, Stylianos; von Solms, Nicolas

    2015-01-01

    in comparison with that in pure water. This observed hydrate inhibition potential shows significant variation depending on the type of crude oil. The influence of crude oil composition (saturates, aromatics, resins and asphaltenes) on this behavior was probably due to the existence of a combination of different...... inhibition mechanisms and potentially a competition among inhibition-promotion mechanisms. Moreover, the hydrate formation time has been determined at different water cuts in each crude oil and it was found that the inhibition capability increases with an increase in the oil content. The effect...... can contribute to the safe operation of sub sea pipelines in the oil and gas industry....

  15. 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.

  16. Microbial enhancement of non-Darcy flow: Theoretical consideration

    Energy Technology Data Exchange (ETDEWEB)

    Shi, Jianxin; Schneider, D.R.

    1995-12-31

    In the near well-bore region and perforations, petroleum fluids usually flow at high velocities and may exhibit non-Darcy-flow behavior. Microorganisms can increase permeability and porosity by removing paraffin or asphaltene accumulations. They can also reduce interfacial tension by producing biosurfactants. These changes can significantly affect non-Darcy flow behavior. Theoretical analysis shows that microbial activities can enhance production by decreasing the turbulence pressure drop and in some cases increasing the drag force exerted to the oil phase. This implies that the effects of microbial activities on non-Darcy flow are important and should be considered in the evaluation of microbial well stimulation and enhanced oil recovery.

  17. Characterization of oil nano-structures with monochromatic x-ray micro-tomography

    Science.gov (United States)

    Asadchikov, Victor E.; Buzmakov, Alexey V.; Osadchaya, Anna S.; Zolotov, Denis A.; Rafailov, Michael K.

    2012-10-01

    Here we report work done toward detection and characterization of micro-and nano-structures in bitumen, including mineral particles-clay and sand as well as metal-organic micro-and nano-structures containing porphyrines. X-ray micro-tomograph with monochromatic radiation has been used for detection of the structures. In order to detect and characterize nano-and micro-structures tomograph's operational wavelength has been tuned to absorption wavelength of "chemical element of interest" X-ray spectrum: whatever it is Si or porphyrine-forming metals like V, Ni, Co. Contrast between X-ray absorption of micro-structures containing specific element and average bitumen's environment absorption provides a tool for measurement of element mass concentration as well as size and mass density distributions of micro-and nano structures not only on surface but in bitumen volume. Specifically the most interest is in measurement of vanadyl porphyrines and other metal containing chemicals in asphaltene micro-structures changing per asphalten concentration due to bitumen processing.

  18. Dissolution de phases minérales MSiO3 ( M Cu, Co, Ni, Zn, Mg) imparfaitement cristallisées au contact de solutions d'agents complexants organiques (porphyrines, amino-acides, asphaltènes)

    Science.gov (United States)

    Bergaya, F.; Perruchot, A.; Van Damme, H.

    1983-05-01

    The kinetic and thermodynamic aspects of the dissolution of ill-organized ("gels") high surface area silicates of general formula MO- SiO2- nH2O( M = Cu, Co, Ni, Zn, Mg) in the presence of the following organic compounds have been investigated: meso-tetraphenylporphyrin (H 2TPP, water insoluble), mesotetra(N-methylpyridyl)porphyrin (H 3TMPyP, water soluble), glycine, and asphaltenes. Kinetic aspects were emphasised in the case of H 2TMPyP. The initial rate of the gross dissolution complexation process followed almost quantitatively (passing from one metal to another) the complexation rate of M2+ ions by H 2TMPyP in a purely homogeneous medium, suggesting that the rate limiting step of the overall process is not related to the chemical or physical processes occurring in the solid particles or at the solid-solution interface, but is simply the complexation, in the solution, of the M2+ ions released by the gel particles. Thermodynamic aspects were emphasised in the case of glycine. The total amount of metal which is extracted at equilibrium can be reasonably well predicted from a simple model which takes into account (i) the stability constant of the metal-glycine complex. (ii) the "solubility product" of the gel particles in water. The results obtained with asphaltones are closer to those obtained with glycine than to those obtained with porphyrins, suggesting that porphyrins represent only a minor population in the complexing functional groups of asphaltenes.

  19. On the stabilization of water in crude oil emulsions

    Energy Technology Data Exchange (ETDEWEB)

    Czarnecki, J. [Alberta Univ., Edmonton, AB (Canada). Dept. of Chemical and Materials Engineering

    2008-07-01

    In this study, material collected from W/O emulsion droplets from several oil samples from various geographical locations, including Athabasca bitumen was analyzed by Fourier Transform Ion Cyclotron Resonance Mass Spectrometry (FT-ICR MS). It was found to be composed of similar low molecular weight molecules containing mostly carboxylic and thiophenic groups with double bound equivalents (DBE) of the most abundant species ranging from 2 to 8. Many of the species were not even aromatic, and most were not polyaromatic. According to the mass spectral results, the surface material does not fit a conventional description of asphaltenes, being heavy, polar, polyaromatic species. Microscope observations of emulsion and rag layer samples suggest the presence of optically anisotropic species at the emulsified water droplet surfaces. Studies of phase equilibria in sodium naphthenate - toluene or heptane - water system indicate that naphthenate species can form organized phases, including liquid crystals. The author cautioned that although the nature of surface species and the exact mechanism of W/O emulsion stabilization is not fully understood, the current rule that asphaltenes or biwettable fine solids are solely responsible for water in crude oil emulsion stabilization is highly oversimplified and could hinder further progress in the field.

  20. 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.

  1. Upgrading of Orinoco Belt crude oil and its fractions by an electrochemical system in the presence of protonating agents

    Energy Technology Data Exchange (ETDEWEB)

    Ovalles, C.; Rojas, I.; Acevedo, S.; Escobar, G.; Jorge, G.; Gutierrez, L.B.; Rincon, A.; Scharifker, B. [INTEVEP, S.A., Caracas (Venezuela). Dept. of Refining

    1996-08-01

    Laboratory scale upgrading (demetallization, desulfurization, denitrogenation and increase in the H/C ratio) of Orinoco Belt crude oil and its fractions is described by an electrochemical system in the presence of protonating agents. Hamaca petroprophyrin can be efficiently demetallized (73%) and desulphurised (35%) by electrolysis at about 0.01 A cm{sup -2} in the presence of methanol as protonating agent. UV-vis spectroscopy and elemental analysis indicated that the presence of the alcohol is necessary for extensive demetallization and desulfurization. In addition, ethiovanadyl prophyrin, Hamaca asphaltene, vacuum residue (500{degree}C{sup +}), and crude oil, can be efficiently demetallized and desulfurized by electrolysis in the presence of protonating agent with relative yields for the HDM reactions of Etiovanadyl prophyrin {gt} Asphaltene {gt} residue {gt} Crude oil. For Hamaca residue (500{degree}C{sup +}), higher metal removal (approx. 81%) and lower desulfurization (11%) were obtained with a final current density of 0.02 A cm{sup -2} than that with 0.01 A cm{sup -2} indicating sensitivity to changes in the electrolysis conditions. 14 refs., 6 figs., 7 tabs.

  2. 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)

  3. 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

  4. The effect factors of the pour point of crude oil

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, Jun; Zhang, Shuichang; Zhu, Guangyou; Su, Jin; Cui, Jie [Research Institute of Petroleum Exploration and Development, PetroChina (China)], email: zhangjun506@163.com

    2010-07-01

    Crude oil does not freeze, but a freezing point is often used to describe the fluidness of crude oil, which is the highest temperature at which oil will stop flowing under specific test conditions. The freezing point of numerous samples of crude oil from the Tarim and the Junggar basins in China was measured. The freezing point is positively related to wax content for the Tarim basin samples, but negatively related to the content of resin and asphaltene. However, there are no obvious relationships between freezing point and wax, resin and asphaltene content for the Junggar samples. The results suggest that the freezing point of crude oil is mainly controlled by wax content if the wax content is not too low. Flow improvers affect the growth, modify the structure, and prevent the interlocking of wax crystals, thus enhancing the flow properties of crude oil. But when wax content is low, other factors will influence fluidness, such as the quantity and types of aromatics and heterocyclic compounds.

  5. 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.

  6. Application of the hydrophile-lipophile balance concept to the classification of demulsifiers and bituminous froth and its components

    Energy Technology Data Exchange (ETDEWEB)

    Vander Kloet, Jana; Schramm, Laurier L.; Shelfantook, Bill [Chemistry Department, University of Calgary, Calgary, Alberta (Canada)

    2002-01-18

    The hydrophile-lipophile balance (HLB) was used to characterize several naphtha-diluted bituminous froth and bitumen phases, extracted froth components, and commercial demulsifiers used to resolve the froth emulsions. The requirements for emulsification of the diluted froth and bitumen phases could be classified by the HLB system in terms of required HLB values. Although such classification was not effective in detecting gross changes in the interfacial components of the diluted froth and bitumen phases, meaningful HLB values were obtained for the water soluble natural surfactants (HLB 16{+-}1) and asphaltenes (HLB 11{+-}1) isolated from the froth. The HLB values for three commercial demulsifiers were found to change depending on the delivery medium, from 12{+-}1 if the demulsifier was dissolved in naphtha to 7{+-}1 if the demulsifier was dissolved in water. This difference in apparent HLB may arise from differences in interfacially active components in the diluent. It appears that demulsifier components delivered in naphtha and the water-soluble natural surfactants will seek to form O/W emulsions and, therefore, act to destabilize the W/O froth emulsions. Conversely, demulsifier components delivered in water and naturally occurring asphaltenes will act to stabilize the W/O froth emulsions.

  7. The distribution features of polycyclic connate hydrocarbons in Tatar oils

    Energy Technology Data Exchange (ETDEWEB)

    Kayukova, G.P.; Aref' ev, O.A.; Kurbskii, G.P.; Petrov, A.A.; Pustil' nikova, S.D.

    1982-01-01

    Using gas chromatography and chromatographic mass-spectrography, the composition of polycyclic connate hydrocarbons in saturated hydrocarbon fractions with a boiling point over 400 degrees is studied from eleven Tatar oils, which belong to a variety of Paleozoic deposits. The concentrations of tetra- and penticyclic hydrocarbons are generated by adsorption chromatography. It is demonstrated that the oils with various chemical properties are characterized by a close qualitative and quantitative composition of high-molecular polycyclic connate hydrocarbons. It is determined that these oils have a uniform nature C/sub 27/-C/sub 29/ sterane distribution composition and C/sub 27/-C/sub 33/ gopane composition which is independent of the geological growth of oil, their depth of occurence and physoichemical properties. Tatar oils are characterized by a low concentration of sterane and gopane oils having a predominance of C/sub 29/ adiantane over C/sub 30/ gopane. In thermal cracking conditions, the asphaltenes of Bavlinskaia and Mordovo-Karmal'skaia oils are formed together with isopreniod alkanes and steranes and triterpanes. The distribution of these connate hydrocarbons in thermolytic asphaltene products repeats the chemical type of the initial non-biodegraded oils and confirms the genetic uniqueness of Tatar oils.

  8. Distribution of vanadyl porphyrins in a Mexican offshore heavy crude oil

    Energy Technology Data Exchange (ETDEWEB)

    Pena, M.E.; Manjarrez, A.; Campero, A. [Mexican Petroleum Institute, Mexico City (Mexico). Geosciences Research Division

    1996-03-01

    A study was made of vanadyl porphyrins distribution of Mexican heavy crude oil from Sonda de Campeche offshore field (drilling range 4350-4371 m) in the southeast of Gulf of Mexico. Furthermore, according to planning request about future trends of refining schemes the distribution of vanadyl porphyrins was investigated in the total heavy crude oil and their distilled residue, free of the asphaltene fraction. Vanadyl-metaloporphyrins were extracted and separated by means of adsorption chromatographic schemes using adsorbents and solvents of increasing polarities. Vanadyl porphyrins were identified and characterized by ultraviolet and visible (UV-vis) spectrophotometry, high-performance liquid chromatography (HPLC) and mass spectrometry (MS). Results show that vanadyl porphyrins are present in the total crude oil and within the deasphalted residue, namely five homologues series DPEP, ETIO, THBD, BD and B with the ETIO series predominating in deasphalted residue. On the whole, data related to the distribution of vanadyl porphyrins indicates the convenience of using procedures that eliminate asphaltenes in order to remove vanadyl porphyrins and improve the efficiency of catalysts used in different catalytic refining processes. 17 refs., 7 figs., 6 tabs.

  9. Suitability of thin-layer chromatography-flame ionization detection with regard to quantitative characterization of different fossil fuel products. II. Calibration methods concerning quantitative hydrocarbon-group type analysis

    Energy Technology Data Exchange (ETDEWEB)

    Vela, J.; Membrado, L.; Cebolla, V.L.; Ferrando, A.C. [CSIC, Zaragoza (Spain). Inst. de Carboquimica, Dept. de Procesos Quimicos

    1998-10-01

    Time-consuming external standard-based calibration methods are usually performed for hydrocarbon group type analysis (HGTA) of fossil fuels, regardless of the instrumental chromatographic technique. HGTA of a broad variety of coal and petroleum products was performed using a modern thin-layer chromatography-flame ionization detection (TLC-FID) system and a rapid method based on internal normalization. Repeatability, linear intervals, and sample load ranges for quantitative application of this method are given, namely a heavy oil and its derived hydrocracked products, raw and chemically-modified petroleum asphaltenes, a coal-tar pitch, several coal extracts, and coal hydroliquefaction products. Results from external standard calibration and a normalization method (both obtained by TLC-FID) are in agreement, and they are validated using TLC-ultraviolet scanning. The use of the latter demonstrates that TLC-FID can also be applied to products such as coal extracts and hydroliquefaction products, despite these products being more volatile than petroleum asphaltenes or heavy oils. 14 refs., 3 figs., 5 tabs.

  10. Investigation of dissolution mechanisms of six Turkish coals in tetralin with microwave energy

    Energy Technology Data Exchange (ETDEWEB)

    Simsek, E.H.; Karaduman, A.; Olcay, A. [Ankara University, Ankara (Turkey). Chemical Engineering Department

    2001-12-05

    Rates of formation of oil, asphaltenes, and preasphaltenes during liquefaction of six Turkish coals in tetralin with microwave heating have been experimentally determined. Five reaction mechanisms have been proposed and tested to estimate the rates of formation of products. Proposed mechanisms are based on assumption that the reactions are irreversible and pseudo-first order with respect to the reacting species. Pseudo-first order rate constants for each of the indicated mechanistic steps have been calculated by multivariable non-linear regression analysis. The best fit between experimental data and models suggested was obtained from model 3 (this model suggests that oils, asphaltenes and preasphaltenes formed directly from coal) with Tuncbilek and Zonguldak, from model 4 (this model assumes oils to be produced directly from preasphaltenes in addition to being formed from coal according to model 3) with Mugla-Yatagan and Soma-Merkez, and from model 5 (this model describes conversion of coal tolsvent fraction products incorporating both series and parallel reactions) with Bolu-Goeynuek and Beypazari coals. The results indicated that the reaction mechanism of coal liquefaction depends on the coal type. 31 refs., 6 figs., 3 tabs.

  11. Di- or polysulphide-bound biomarkers in sulphur-rich geomacromolecules as revealed by selective chemolysis

    Science.gov (United States)

    Kohnen, Math E. l.; Sinninghe Damsté, Jaap S.; Kock-van Dalen, A. c.; Jan, W. De Leeuw

    1991-05-01

    Three types of sulphur-rich high-molecular-weight material in the alkylsulphide, the polar, and the asphaltene fractions isolated from the bitumen of an immature bituminous shale from the Vena del Gesso basin (Italy) were desulphurised using Raney Ni and were treated with MeLi/MeI, a chemical degradation method which cleaves selectively and quantitatively di- or polysulphide linkages. The products formed were characterised by gas chromatography-mass spectrometry. Raney Ni desulphurisation revealed that these S-rich macromolecules are in substantial part composed of sulphur-linked biomarkers with linear, branched, isoprenoid, steroid, hopanoid, and carotenoid carbon skeletons. MeLi/Mel treatment provided evidence that a major part of the total amount of macromolecularly bound biomarkers are linked via di- or polysulphide moieties to the macromolecular network. Since the di- or polysulphide linkages are attached at specific positions of the bound biomarkers it is proposed that they are formed by intermolecular incorporation reactions of HS x- into low-molecular-weight functionalised biological lipids during early diagenesis. The different properties (solubility and molecular weight) of the sulphur-rich macromolecules in the alkylsulphide, the resin, and the asphaltene fractions can be explained simply by differences in degree of sulphur cross-linking.

  12. 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.

  13. 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.

  14. 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)

  15. 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.

  16. Coprocessing of a Turkish lignite with a cellulosic waste material. Part 3. A statistical study on product yields and total conversion

    Energy Technology Data Exchange (ETDEWEB)

    Karaca, Fatma; Bolat, Esen; Dincer, Salih [Chemical and Metallurgical Engineering Faculty, Chemical Engineering Department, Yildiz Technical University, Davutpasa-Esenler, Istanbul (Turkey)

    2002-02-20

    The objectives of this study were to evaluate statistically the effects of coprocessing parameters on liquefaction yields, to determine the key process variables affecting the oil+gas, oil and asphaltene yields and total conversion. A statistical experimental design based on Second Order Central Composite Design was planned fixing the liquefaction period at 1 h. Parameters such as temperature, initial cold pressure, tetralin/(lignite+sawdust) and sawdust/lignite ratios coded as x{sub 1}, x{sub 2}, x{sub 3} and x{sub 4}, respectively, were used. The parameters were investigated at five levels (-2, -1, 0, 1 and 2). The effects of these factors on dependent variables, namely, oil+gas, oil and asphaltene yields and total conversion were investigated. To determine the significance of effects, the analysis of variance with 99.9% confidence limits was used. It was shown that within the experimental ranges examined, temperature and sawdust/lignite ratio were the variables of highest significance for oil+gas yields, oil yields and total conversion.

  17. Biodegradation of asphalt by Garciaella petrolearia TERIG02 for viscosity reduction of heavy oil.

    Science.gov (United States)

    Lavania, Meeta; Cheema, Simrita; Sarma, Priyangshu Manab; Mandal, Ajoy Kumar; Lal, Banwari

    2012-02-01

    Petroleum hydrocarbon is an important energy resource, but it is difficult to exploit due to the presence of dominated heavy constituents such as asphaltenes. In this study, viscosity reduction of Jodhpur heavy oil (2,637 cP at 50°C) has been carried out by the biodegradation of asphalt using a bacterial strain TERIG02. TERIG02 was isolated from sea buried oil pipeline known as Mumbai Uran trunk line (MUT) located on western coast of India and identified as Garciaella petrolearia by 16S rRNA full gene sequencing. TERIG02 showed 42% viscosity reduction when asphalt along with molasses was used as a sole carbon source compared to only asphalt (37%). The viscosity reduction by asphaltene degradation has been structurally characterized by Fourier transform infrared spectroscopy (FTIR). This strain also shows an additional preference to degrade toxic asphalt and aromatics compounds first unlike the other known strains. All these characteristics makes TERIG02 a potential candidate for enhanced oil recovery and a solution to degrading toxic aromatic compounds.

  18. Characterization of crude oil-water and solid -water interfaces and adsorption / desorption properties of crude oil fractions: The effect of low salinity water and pH

    Energy Technology Data Exchange (ETDEWEB)

    Farooq, Umer

    2010-09-15

    The reservoirs of conventional oil are rapidly depleting because of increased production and consumption of crude oil in the world. Mature and mostly depleted oil reservoirs require advanced recovery techniques to sustain the production rates. During the past years, a variety of enhanced oil recovery (EOR) methods have been developed and implemented to increase the oil recovery from mature reservoirs. Low Salinity Waterflooding (LSW) is an emerging EOR process of injecting water containing low concentrations (<4000 ppm) of total dissolved solids into the reservoir. This moderate cost process yields relatively higher incremental recoveries than other water based recovery methods. Investigation of mechanisms for increased recovery is quite challenging because this process depends upon complex crude oil/water/rock properties. This work was done to study the surface chemistry of typical reservoir surfaces where LSW can be used for EOR. The oil water and solid-water interfaces were characterised in low salinity aqueous solutions and investigated how the electrolytes and pH of solutions affect the interfacial and surface properties. The influence of low saline aqueous solution on the desorption behaviour of different fractions (acid-free oil and base-free oil) of crude oils was also explored. Reservoir minerals are sensitive to small changes in solution properties and therefore model, outcrop and reservoir particles were characterized in low salinity aqueous solutions. The extent of ionic adsorption on the mineral surfaces was found by various techniques. Particles were also characterized with respect to their elemental compositions. Asphaltene adsorption/desorption on reservoir rock surfaces play an important role in EOR processes. Various injection sequences of low saline aqueous solution of Na +, Ca2+ and sea water were considered to study the desorption of asphaltenes from silica surfaces. Composition of the aqueous phase influenced the interfacial properties of

  19. A gallery of oil components, their metals and Re-Os signatures

    Science.gov (United States)

    Stein, Holly J.; Hannah, Judith L.

    2016-04-01

    Most sediment-hosted metallic ore deposits are one degree of freedom from hydrocarbon. That is, sulfide fluid inclusions may contain vestiges of travel in tandem with hydrocarbon-bearing fluids. For metallic ore deposits of stated metamorphic and magmatic origin, the degrees of freedom are several times more or, in some cases, no relationship exists. Still, the fetish for stereotyping and classifying ore types into hardline ore deposit models (or hybrid models when the data are wildly uncooperative) impedes our ability to move toward a better understanding of source rock. Fluids in the deeper earth, fluids in the crust, and the extraterrestrial rain of metals provide the Re-Os template for oil. So, too, this combination ultimately drives the composition of many metallic ore deposits. The world of crude oil and its complex history of maturation, migration, mixing, metal-rich asphaltene precipitation, and subsequent mobility of lighter and metal-poor components, is an untapped resource for students of ore geology. In the same way that Mississippi Valley-type lead and zinc deposits are described as the outcome of two converging and mixing fluids (metal-bearing and sulfur-bearing fluids), asphaltene precipitation can be an outcome of a lighter oil meeting and mixing with a heavier one. In the petroleum industry, this can spell economic disaster if the pore-space becomes clogged with a non-producible heavy oil or solid bitumen. In ore geology, sulfide precipitation on loss of permeability may create a Pb-Zn deposit. Petroleum systems provide a gallery of successive time-integrated Re-Os results. Heavy or biodegraded oils, if intersected by lighter oil or gas, can generate asphaltite or tar mats, and release a reservoir of still lighter oil (or gas). During this process there are opportunities for separation of metal-enriched aqueous fluids that may retain an imprint of their earlier hydrocarbon history, ultimately trapped in fluid inclusions. Salinity, temperature and p

  20. Dynamics and structure of water-bitumen mixtures

    DEFF Research Database (Denmark)

    Lemarchand, Claire; Greenfield, Michael L.; Hansen, Jesper Schmidt

    2016-01-01

    Systems of Cooee bitumen and water up to 4% mass are studied by molecular dynamics simulations. The cohesive energy density of the system is shown to decrease with an increasing water content. This decrease is due mainly to an increase in the interaction energy which is not high enough...... to counterbalance the increase in volume due to the addition of water. It is not due to a decrease of interaction energy between the slightly polar asphaltene molecules. The water molecules tend to form a droplet in bitumen. The size and the distribution of sizes of the droplets are quantified, with multiple...... droplets being more stable at the highest temperature simulated. The droplet is mainly located close to the saturates molecules in bitumen. Finally, it is shown that the water dynamics is much slower in bitumen than in pure water because it is governed by the diffusion of the droplet and not of the single...

  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. 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.

  3. 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.

  4. 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.

  5. 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.

  6. Alberta bitumen : new reservoirs and new technologies

    Energy Technology Data Exchange (ETDEWEB)

    Edmunds, N. [Laricina Energy Ltd., Calgary, AB (Canada)

    2008-07-01

    In 2008, Laricina Energy Ltd. conducted cold solvent injection pilot tests at a well in the Saleski field to investigate the ability to mobilize and produce cold bitumen from the Grosmont carbonate. Cold solvent recovery from carbonates involves a cyclic solvent-assisted steam assisted gravity drainage (SAGD) process or a modified VAPEX-like process using propane and non-condensable gas. Cold solvent recovery can be applied to carbonates with dense secondary porosity networks. Laricina's well stimulation test was conducted over a 3-week period and involved a single vertical cyclic test well, propane injection followed by CO{sub 2} injection, and soak. The cold solvent test conducted on core samples from the Grosmont region revealed that oil can be mobilized and produced in bulk without the deposition of solids or asphaltenes. tabs., figs.

  7. 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.

  8. 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.

  9. 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.

  10. 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)

  11. Effect of fuel oil source on the preparation of coal-oil dispersions

    Energy Technology Data Exchange (ETDEWEB)

    Grint, A.; Veal, C.J.

    1985-08-01

    British Petroleum has devised a preparative route to stable coal-oil dispersions (COD's) which involves the fine grinding of coal in oil. This paper investigates how COD preparation and properties are affected by oil composition. COD's were prepared using a range of fuel oils from different crude sources or refineries and containing straight run or cracked components. Wide variations in sedimentation stability-milling time profiles were measured and attempts have been made to correlate these data with fuel oil analytical parameters. The tendency of the asphaltenes in the oil to flocculate is thought to be an important parameter in determining stability for a given milling time. A preliminary explanation of the observed trends is proposed. 15 references.

  12. Enhanced E-bed bottoms upgrading using latest catalytic technology

    Energy Technology Data Exchange (ETDEWEB)

    Toshima, H.; Mayo, S.; Sedlacek, Z.; Hughes, T.; De Wind, M. [Albermarle Corp., Amsterdam (Netherlands)

    2009-07-01

    The profitability of refineries depends on heavy oil upgrading in terms of price, conversion, yields and quality of the product. The Ebullated-bed process represents a solution for the effective primary upgrading of heavy oils. Since the 1970s, Albemarle has commercialized several E-bed catalysts to upgrade the bottoms in low sediment and high hydrogenation operations. Although an E-bed is used to maximize the conversion of vacuum residuum (VR), it is often limited by fouling caused by sediment in the product. In order to reduce sedimentation in the product, Albemarle developed an improved E-bed catalytic technology by characterizing the asphaltenes and sediments in order to better understand the oil chemistry and compatibility. The most recent development involves the patented catalyst-staging technology and the improved single catalyst application. Both achieve very low sediment or higher hydrodesulphurization (HDS) and Conradson carbon (CCR) removal for improved bottom upgrading. tabs., figs.

  13. 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.

  14. In memory of Yurko Duda, a physicist like few ones

    Directory of Open Access Journals (Sweden)

    2009-01-01

    Full Text Available Last February 11th, being in full summit of his career as a scientist, lamentably doctor Yurko Duda passed away. An outstanding scientist participating in the Molecular Engineering Research Program of the Mexican Institute of Petroleum (IMP, Yurko was persistently collaborating in diverse projects of basic and applied research, as well as in the formation of human resources since March 2001. His theoretical research had an important impact on the experimental design of diverse materials and products developed at IMP: foams, detergents for petroleum, coats, inhibitors-dispersants of asphaltenes, and especially on the adsorption phenomenon of polymers and particles on surfaces. This work, among others, has a direct implication in the development of anticorrosives...

  15. Compositional Simulation of In-Situ Combustion EOR: A Study of Process Characteristics

    DEFF Research Database (Denmark)

    Jain, Priyanka; Stenby, Erling Halfdan; von Solms, Nicolas

    2010-01-01

    combustion simulation is used. Preceding research work primarily focused on a kinetic model that was based on six components and incorporated four chemical reactions. However, modeling of a thermal process as complex as In-situ combustion requires in-depth understanding of detailed reaction kinetics...... and multidisciplinary process data. This paper extends the understanding of previous research done in this domain by performing the process simulations to study further the impact of oxidation reactions and combustion reactions of crude oils along with their saturate, aromatic, resin, and asphaltene (SARA) fractions....... This incorporates fourteen pseudo components and fourteen reactions (distributed amongst thermal cracking, low temperature oxidation and high temperature oxidation). The paper presents a set of derivative plots indicating that reservoir process characterization in terms of thermal behavior of oil can be well...

  16. Hydrotreating of distillates from Spanish coal liquefaction

    Energy Technology Data Exchange (ETDEWEB)

    Benito, A.M.; Martinez, M.T.; Cebolla, V.; Fernandez, I.; Miranda, J.L. (Inst. de Carboquimica, CSIC, Zaragoza (Spain))

    1993-02-01

    Distillates obtained from a first-stage Spanish coal liquefaction process have been catalytically hydrotreated in microreactor in two steps. A commercially available Harshaw HT-400 E (Co-Mo/Al[sub 2]O[sub 3]) catalyst, 10 MPa hydrogen pressure and two temperatures (400 and 425deg C) have been used. The results have been evaluated for heteroatoms removal, oils yield, boiling point distribution and aromaticity by several techniques (GC, FT-i.r., [sup 1]H n.m.r., ultrasonic extraction and liquid chromatography). At the first step of hydrotreating, preasphaltenes rather than asphaltenes have been hydrocracked to produce smaller-size polar compounds in the oil fraction but aromaticity has not varied significatively. In the second step, heteroatoms content have been considerably reduced and the product meets refinery specifications for nitrogen but does not meet sulphur refinery specifications for feedstocks. (orig.).

  17. 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)

  18. 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...

  19. Mitigating fouling in the high temperature paraffinic froth treatment process through science and serendipity

    Energy Technology Data Exchange (ETDEWEB)

    Chakrabarty, Tapantosh [Imperial Oil Resources (Canada)], email: apan.chakrabarty@esso.ca

    2010-07-01

    This work focuses on the application of high temperature paraffinic froth treatment (HT-PFT); a technique used to clean froth that results from the process of water extraction of oil sands. This technique includes the addition of a paraffinic solvent to the bitumen as a preliminary step in removing froth structures, leading to a possible fouling of the inner walls of the treatment vessels. Therefore, a fouling preventive technique consisting of three novel solutions was investigated in this work. The accumulations of fouling components were constantly monitored during the HT-PFT process using a gamma-ray densitometer. Results showed that buildups mostly consisted of inorganic solid structures held together with asphaltene. It was also shown that fluorocarbon polymer coating (FPC) proved to be the most effective additive in preventing fouling buildups, and by using fouling collectors in the vessels buildups were highly reduced downstream. In general, incorporating this preventive technique with HT-PFT was recommended.

  20. 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

  1. 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)

  2. A dielectric relaxation study of precipitation and curing of Furrial crude oil

    Energy Technology Data Exchange (ETDEWEB)

    Eric Y. Sheu; Socrates Acevedo [Vanton Research Laboratory, Incorporated, Lafayette, CA (United States)

    2006-10-15

    Low frequency dielectric spectroscopy was applied to investigate the properties of Furrial crude oil that is infamous for asphaltene precipitation during production. An experiment was conducted at ambient temperature by mixing Furrial crude oil with hexane to induce flocculation and subsequent precipitation. A drastic change in dielectric response was observed near the critical point when flocculation occured. Evolution of the dielectric loss spectra as a function of time was observed and found to closely mimic epoxy-curing process. The curing process lasted for approximately 44 h with an induction period of at least 26 h. During the induction period, the conductivity contribution to the dielectric response remains dominant. Following the induction period a structural arrest occurs signaling the onset of deposition. 16 refs., 12 figs., 2 tabs.

  3. Use of pyrogenic silicas for petroleum oil polar fraction characterisation. Fourier transform infrared spectroscopy and microelectrophoresis studies

    Energy Technology Data Exchange (ETDEWEB)

    Jada, A.; Chaou, A.A. [Inst. de Chimie des Surfaces et Interfaces, Mulhouse (France)

    2002-08-01

    In the power transformer, the presence of polar or changed species in the insulating oil can cause failure and electric discharges. Solid substrates such as silica can be used to extract the polar species and to refine the oil in order to prevent future failure in the power transformer. However, he use of silica for petroleum oil separation and refining will depend on the silica characteristics such as surface charge, surface composition, specific surface area and particle size. Various pyrogenic silicas having various specific surfaces are and particle sizes were used to extract the polar fractions from the heat transformer insulating oils (a new, NO, and used, UO{sub 2} oils). The oil covered silica samples were investigated by diffuse reflectance infrared Fourier transform (DRIFT) spectroscopy. The analysis of the DRIFT spectra for various samples indicate that the oil polar fraction resembles asphaltenes compounds. The microelectrophoresis method used to investigate the surface charge at the water/oil polar fraction covered silica interface, indicates negatively charged particles. Further, the negative charge increased with the pH, as resulting from the increase of the ionisation and/or the amount of the oil carboxylic and phenolic groups. The oil polar fraction, i.e. the asphaltene components, in contact with both the silica surface and water at high pH values rearrange, due to their amphiphilic character. Finally, the use of the silica substrates seems to be suited to extract and analyses polar species present in petroleum oil. A correlation is found between the nature of the oil, its functionalities, and the magnitude of its zeta potential value at the water/oil covered silica interface. 28 refs., 16 figs., 2 tabs.

  4. 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.

  5. 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.

  6. Compositional mapping of bitumen using local electrostatic force interactions in atomic force microscopy.

    Science.gov (United States)

    Magonov, Sergei; Alexander, John; Surtchev, Marko; Hung, Albert M; Fini, Elham H

    2017-02-01

    In recent years, many researchers have investigated bitumen surface morphology, especially the so-called bee-like structures, in an attempt to relate the chemical composition and molecular conformation to bitumen micromechanics and ultimately performance properties. Even though recent studies related surface morphology and its evolution to stiffness and stress localization, the complex chemical nature of bitumen and its time- and temperature-dependent properties still engender significant questions about the nature and origin of the observed morphological features and how they evolve due to exposure to various environmental and loading conditions. One such question is whether the observed surface features are formed from wax or from the coprecipitation of wax and asphaltene. Our prior work was mainly theoretical; it used density functional theory and showed that the coprecipitation theory may not stand, mainly because wax-asphaltene interactions are not thermodynamically favourable compared to wax-wax interactions. This paper presents a comprehensive approach based on experiments to study surface morphology of bitumen and conduct compositional mapping to shed light on the origin of the bee-like surface morphological features. We used Atomic Force Microscopy (AFM), with the main focus being on single-pass detection and mapping of local electric properties, as a novel approach to enhance existing compositional mapping techniques. This method was found to be highly effective in differentiating various domains with respect to their polarity. The results of our study favour the hypothesis that the bee-like features are mainly composed of wax, including a variety of alkanes. © 2016 The Authors Journal of Microscopy © 2016 Royal Microscopical Society.

  7. 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.

  8. 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)

  9. Diagnostic ratios for the rapid evaluation of natural attenuation of heavy fuel oil pollution along shores.

    Science.gov (United States)

    Esquinas, Noemi; Rodríguez-Valdés, Eduardo; Márquez, Gonzalo; Gallego, José Luis R

    2017-10-01

    Marine oil spills are typically followed by complex clean-up and monitoring operations of the shorelines affected. In this regard, determination of the changes in the chemical composition of the spilled product is crucial for evaluation purposes. The "GC-MS fingerprint" approach requires the identification of several key parameters in order to differentiate between weathering processes. In this context, we performed a 900-day study (eight sampling campaigns) of natural attenuation on a rocky shore affected by a heavy fuel oil spill. The residues coating the rocks were studied by extraction, separation and evaluation of SARA fractions, followed by GC-MS analysis for saturates and aromatics. The results identified a group of diagnostic ratios with irregular capabilities to differentiate between volatilization, photodegradation, and biodegradation (using n-alkanes, isoprenoids and PAHs), while a second group of primarily stable ratios (using dibenzothiphenes, tricyclics and hopanes) was also obtained. Notably, this is the first time that some of these ratios have been used for marine spill monitoring purposes. The ratios were applied not only to evaluate weathering at the study site, but also to obtain a comparison with the degradation of floating oil slicks-a demonstration that weathering of the latter was quicker than that of oil on the shore rocks. Additionally, Pyrolysis-GC-MS analysis of the asphaltene fraction of residues coating the rocks revealed moderate changes in the composition of this initially recalcitrant fraction. These changes were consistent with those found in the proportion of resins and asphaltene fractions over time. Copyright © 2017 Elsevier Ltd. All rights reserved.

  10. 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

  11. 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

  12. 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

  13. Advanced characterisation of organic matter in oil sands and tailings sands used for land reclamation by Fourier transform-ion cyclotron resonance-mass spectrometry (FT-ICR-MS)

    Science.gov (United States)

    Noah, M.; Vieth-Hillebrand, A.; Wilkes, H.

    2012-04-01

    subsequent separation into asphaltenes, aliphatic hydrocarbons, aromatic hydrocarbons, neutral nitrogen, sulphur, oxygen (NSO) compounds and carboxylic acids. The asphaltene fractions are analysed using pyrolysis-GC, all other fractions are analysed by GC-MS. Additionally Fourier transform-ion cyclotron resonance-mass spectrometry (FT-ICR-MS) is used to study the chemical composition of the samples on the molecular level using different ionisation methods.

  14. 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

  15. 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

  16. 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

  17. 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

  18. 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.

  19. Molecular archaeology: Export of Dead Sea asphalt to Canaan and Egypt in the Chalcolithic-Early Bronze Age (4th-3rd millennium BC)

    Science.gov (United States)

    Connan, Jacques; Nissenbaum, Arie; Dessort, Daniel

    1992-07-01

    Nine archaeological bitumens from excavations in Canaan, Sinai and Egypt (Tel Irani, Ein Zik, Palmahim, Tel Arad, Jerusalem, Ein Besor-Site H, Sheik Awad and Maadi), dated 3900-2200 Bc. And two natural asphalts of the Dead Sea area (Ein Gedi floating blocks and Nahal Heimar) have been compared using the following geochemical techniques: chloroform extraction and GC and GC-MS analyses of C 15+ alkanes and C 15+ aromatics, isotopic analysis (δ 13C and δD) on chloroform extracts and asphaltenes and Rock-Eval pyrolysis of the insoluble organic residue. All samples are genetically related and are different from other archaeological bitumens from Syria and Iraq. Tel Irani archaeological bitumen was found to be identical to the floating block asphalts of the Dead Sea. Other archaeological bitumens were recognized as having been weathered and biodegraded to various degrees at archaeological sites in the course of the millennia. They are regarded as counterparts of floating block asphalts altered by aging. This study is the first evidence of the trade and export of raw bitumens from the Dead Sea area within Canaan and to Egyptian trading centers on the mainland route to Egypt between 3900 and 2200 BC, prior to the extensive utilization of bitumen for mummification in ancient Egypt.

  20. 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)

  1. Adsorption and surface properties of silica with transformer insulating oils

    Energy Technology Data Exchange (ETDEWEB)

    Jada, A.; Chaou, A.A.; Bertrand, Y.; Moreau, O. [Institute de Chimie des Surfaces et Interfaces, Mulhouse (France)

    2002-06-01

    The presence of polar species in transformer insulating oil may cause degradation and electric discharges in the power transformer. Such oil polar fraction can originate either from the neat oil and/or from its oxidative degradation in the power transformer. The aim of this study is to examine the relation between the insulating oil and the electrical properties of its polar fraction in order to predict eventual failure in the power transformer. We investigate the ambient temperature the adsorption of the polar fractions of various transformers insulating oils (a new and two used oils) from the neat oils onto silica particles. The adsorbed amount was higher for the used oils as compared to the new one. Infrared spectra of the polar fraction indicate the presence of hydroxyl, aromatic and carboxyl functional groups that are found in the asphaltenes compounds. Microelectrophoresis study of the oil polar fraction covered silica particles gives negatively charged oil polar fraction. Such oil surface char depends on the pH and results from the ionisation of the oil acidic surface groups. Finally, we obtain a good correlation between the amount of the oil polar fraction and the magnitude of the zeta potential at the water/oil-silica interface. 38 refs., 3 figs., 1 tab.

  2. 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.

  3. 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%.

  4. 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.

  5. 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.

  6. Effects of simulated weathering on the toxicity of selected crude oils and their components to sea urchin embryos.

    Science.gov (United States)

    Rial, Diego; Radović, Jagoš R; Bayona, Josep M; Macrae, Kenneth; Thomas, Kevin V; Beiras, Ricardo

    2013-09-15

    Artificial weathering of Angolan crude and a Heavy Fuel Oil (HFO) was performed by evaporation and photooxidation. The aliphatic, aromatic, polar and asphaltene fractions of the fresh and weathered oils were isolated. The toxicity of the water accommodated fraction or an oil/fraction dissolved in DMSO was assessed using the sea urchin embryo test. Photooxidation was observed to decrease the aromatics content and increase polar compounds. A slight reduction in the toxicity of Angolan crude was observed following weathering for the water-accommodated fraction and the extract in DMSO, but no effect was seen for the Heavy Fuel Oil. For aliphatic compounds, the toxicity decreased in the order fresh>evaporated>photooxidated for both Angolan crude and HFO. Weathering slightly increased the toxicity of the aromatic and polar fractions of the oil. The aromatic fractions were responsible for most of the toxicity and the polar compounds were the second most important toxic components, despite having less or similar abundance than the aliphatic fraction. The toxic contribution of the aromatic compounds was higher for the HFO than for the Angolan crude. A decrease in the toxicity of Angolan crude following weathering correlated with a reduction in the toxicity of the aliphatic fraction. Copyright © 2013 Elsevier B.V. All rights reserved.

  7. Going their own way : fundamental research into froth treatment creates options for bitumen enhancement

    Energy Technology Data Exchange (ETDEWEB)

    Wells, P.

    2010-01-15

    CANMET Energy of Natural Resources Canada has been actively involved in finding new and improved ways to process bitumen. The effort has resulted in major advancements in 2 key technologies used for froth treatment. The consortium for froth treatment research was initially developed in 1993 between CANMET Energy and Syncrude. Suncor joined shortly thereafter. In 1996 Royal Dutch Shell Plc joined the consortium. Each member company also worked with CANMET Energy independent of the consortium to develop their respective approach to froth treatment. The joint effort was so successful that the researchers involved were awarded the Alberta Science and Technology award for oilsands research for the commercialization of the new froth treatment. In conventional froth treatment, naphtha is used as a solvent at a relatively low solvent-to-bitumen ratio. The separation is enhanced by addition of chemicals to destabilize the emulsion. Typical diluted bitumen products from this process contain 1 or 2 per cent water and about 0.5 per cent mineral solids, and are therefore not suitable for pipelining or refining. Heat is used to upgrade the bitumen to a synthetic crude oil. The second technology is paraffinic solvent froth treatment (PSFT ) which produces a bitumen product with lower levels of contaminants. The content of asphaltenes can also be lowered, thereby upgrading the bitumen quality. The ultimate objective was to minimize industry's energy footprint and also minimize environmental impacts. 1 ref., 5 figs.

  8. Foamed acid stimulation of old wells

    Energy Technology Data Exchange (ETDEWEB)

    Ford, W.G.F.

    1980-12-01

    As oil and gas wells age, many of them exhibit similar characteristics. One of the most obvious is reduced bottom-hole pressure that can contribute to the formation of paraffins, asphaltenes, and scales. Many old wells have had repeated acid treatments. Following conventional acid treatments, large amounts of insoluble fines such as quartz, gypsum, and feldspars may cause a reduction in fracture conductivity. All of these factors related to old wells are especially amenable to foamed acid stimulation. Treatment of wells with characteristics as outlined above with a conventional nonfoamed acid treatment probably will be beneficial. However, the high liquid content of conventional fluids may exacerbate the clay problems. Low viscosity of the spent acid may leave a large amount of insoluble fines in the well. Finally, low bottom-hole pressure may necessitate swabbing to clean up the well. Foamed acid offers characteristics to virtually eliminate the problems. First, foamed acid has a low liquid content. Less liquid contacts the formation, thereby reducing the chance for damage. Foamed acid offers high apparent viscosity. Foamed acid offers built-in gas assist. Finally, foamed acid is simply more effective than nonfoamed acid treatments in many situations.

  9. 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.

  10. Effect of polar organic components on wettability as studied by adsorption and contact angles

    Energy Technology Data Exchange (ETDEWEB)

    Standal, S.; Haavik, J.; Blokhus, A.M. [Department of Chemistry, University of Bergen, Allegaten 41, 5007 Bergen (Norway); Skauge, A. [Norsk Hydro Research Centre, Bergen (Norway)

    1999-12-01

    Adsorption of polar organic components onto the rock surface is one of the mechanisms that is believed to cause wetting alteration of a reservoir rock. Polar compounds in crude oil that are believed to be responsible for surface interactions and wetting properties include carboxylic and phenolic acids, organic bases and metal complexes. Known compounds, representative of these naturally occurring polar organic compounds in crude oil, have been chosen for adsorption and contact angle studies. Contact angles and adsorption isotherms in solid-oil-brine model systems have been examined as a function of component concentration in either water or oil and of salinity and pH of the water phase. The systems investigated consist of isooctane oil phase and water solutions of NaCl and CaCl{sub 2} as the water phase. Silicate glass and {alpha}-alumina were used as solid phases. The polar compounds were 1-naphtoic acid, 5-indanol, quinoline, vanadyl-octaethyl-porphyrin (VO OEP) and dihydrogen-octaethyl-porphyrin (H{sub 2} OEP). The compounds chosen represent functionalities that are found in polar crude oil fractions, such as asphaltenes, but still can be considered well-defined model substances. The components were adsorbed from the oil phase as well as from the water phase, both for contact angle and adsorption isotherm experiments. The results demonstrate the difference in adsorption behaviour between compounds with different functional groups of varying polarity and acidity. The importance of solid-solute interactions compared to solvent-solute interactions is demonstrated.

  11. Novel use of residue from direct coal liquefaction process

    Energy Technology Data Exchange (ETDEWEB)

    Jianli Yang; Zhaixia Wang; Zhenyu Liu; Yuzhen Zhang [Chinese Academy of Sciences, Taiyuan (China). State Key Laboratory of Coal Conversion

    2009-09-15

    Direct coal liquefaction residue (DCLR) is, commonly, designed to be used as a feed stock for gasification or combustion. Use of DCLR as a value added product is very important for improving overall economy of direct coal liquefaction processes. This study shows that the DCLR may be used as a pavement asphalt modifier. The modification ability is similar to that of Trinidad Lake Asphalt (TLA), a superior commercial modifier. Asphalts modified by two DCLRs meet the specifications of ASTM D5710 and BSI BS-3690 designated for the TLA-modified asphalts. The required addition amount for the DCLRs tested is less than that for TLA due possibly to the high content of asphaltene in DCLRs. Different compatibility was observed for the asphalts with the same penetration grade but from the different origin. Different components in the DCLR play different roles in the modification. Positive synergetic effects among the fractions were observed, which may due to the formation of the stable colloid structure. Unlike polymer-type modifier, the structure of asphalt-type modifier has a similarity with petroleum asphalts which favors the formation of a stable dispersed polar fluid (DPF) colloid structure and improves the performance of pavement asphalt. 12 refs., 1 fig., 6 tabs.

  12. High temperature ceramic membrane reactors for coal liquid upgrading

    Energy Technology Data Exchange (ETDEWEB)

    Tsotsis, T.T.

    1992-01-01

    In this project we will study a novel process concept, i.e., the use of ceramic membrane reactors in upgrading of coal model compounds and coal derived liquids. In general terms, the USC research team is responsible for constructing and operating the membrane reactor apparatus and for testing various inorganic membranes for the upgrading of coal derived asphaltenes and coal model compounds. The USC effort will involve the principal investigator of this project and two graduate research assistants. The ALCOA team is responsible for the preparation of the inorganic membranes, for construction and testing of the ceramic membrane modules, and for measurement of their transport properties. The ALCOA research effort will involve Dr. Paul K. T. Liu, who is the project manager of the ALCOA research team, an engineer and a technician. UNOCAL's contribution will be limited to overall technical assistance in catalyst preparation and the operation of the laboratory upgrading membrane reactor and for analytical back-up and expertise in oil analysis and materials characterization. UNOCAL is a no-cost contractor but will be involved in all aspects of the project, as deemed appropriate.

  13. High temperature ceramic membrane reactors for coal liquid upgrading. Quarterly report No. 10, December 21, 1991--March 20, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Tsotsis, T.T.

    1992-07-01

    In this project we will study a novel process concept, i.e., the use of ceramic membrane reactors in upgrading of coal model compounds and coal derived liquids. In general terms, the USC research team is responsible for constructing and operating the membrane reactor apparatus and for testing various inorganic membranes for the upgrading of coal derived asphaltenes and coal model compounds. The USC effort will involve the principal investigator of this project and two graduate research assistants. The ALCOA team is responsible for the preparation of the inorganic membranes, for construction and testing of the ceramic membrane modules, and for measurement of their transport properties. The ALCOA research effort will involve Dr. Paul K. T. Liu, who is the project manager of the ALCOA research team, an engineer and a technician. UNOCAL`s contribution will be limited to overall technical assistance in catalyst preparation and the operation of the laboratory upgrading membrane reactor and for analytical back-up and expertise in oil analysis and materials characterization. UNOCAL is a no-cost contractor but will be involved in all aspects of the project, as deemed appropriate.

  14. 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).

  15. raaSAFT: A framework enabling coarse-grained molecular dynamics simulations based on the SAFT- γ Mie force field

    Science.gov (United States)

    Ervik, Åsmund; Serratos, Guadalupe Jiménez; Müller, Erich A.

    2017-03-01

    We describe here raaSAFT, a Python code that enables the setup and running of coarse-grained molecular dynamics simulations in a systematic and efficient manner. The code is built on top of the popular HOOMD-blue code, and as such harnesses the computational power of GPUs. The methodology makes use of the SAFT- γ Mie force field, so the resulting coarse grained pair potentials are both closely linked to and consistent with the macroscopic thermodynamic properties of the simulated fluid. In raaSAFT both homonuclear and heteronuclear models are implemented for a wide range of compounds spanning from linear alkanes, to more complicated fluids such as water and alcohols, all the way up to nonionic surfactants and models of asphaltenes and resins. Adding new compounds as well as new features is made straightforward by the modularity of the code. To demonstrate the ease-of-use of raaSAFT, we give a detailed walkthrough of how to simulate liquid-liquid equilibrium of a hydrocarbon with water. We describe in detail how both homonuclear and heteronuclear compounds are implemented. To demonstrate the performance and versatility of raaSAFT, we simulate a large polymer-solvent mixture with 300 polystyrene molecules dissolved in 42 700 molecules of heptane, reproducing the experimentally observed temperature-dependent solubility of polystyrene. For this case we obtain a speedup of more than three orders of magnitude as compared to atomistically-detailed simulations.

  16. Performance of Surfactant Methyl Ester Sulphonate solution for Oil Well Stimulation in reservoir sandstone TJ Field

    Science.gov (United States)

    Eris, F. R.; Hambali, E.; Suryani, A.; Permadi, P.

    2017-05-01

    Asphaltene, paraffin, wax and sludge deposition, emulsion and water blocking are kinds ofprocess that results in a reduction of the fluid flow from the reservoir into formation which causes a decrease of oil wells productivity. Oil well Stimulation can be used as an alternative to solve oil well problems. Oil well stimulation technique requires applying of surfactant. Sodium Methyl Ester Sulphonate (SMES) of palm oil is an anionic surfactant derived from renewable natural resource that environmental friendly is one of potential surfactant types that can be used in oil well stimulation. This study was aimed at formulation SMES as well stimulation agent that can identify phase transitions to phase behavior in a brine-surfactant-oil system and altered the wettability of rock sandstone and limestone. Performance of SMES solution tested by thermal stability test, phase behavioral examination and rocks wettability test. The results showed that SMES solution (SMES 5% + xylene 5% in the diesel with addition of 1% NaCl at TJformation water and SMES 5% + xylene 5% in methyl ester with the addition of NaCl 1% in the TJ formation water) are surfactant that can maintain thermal stability, can mostly altered the wettability toward water-wet in sandstone reservoir, TJ Field.

  17. Producing quality synthetic crude oil from Canadian oil sands bitumen

    Energy Technology Data Exchange (ETDEWEB)

    Yui, S. [Syncrude Canada Ltd., Edmonton, AB (Canada). Edmonton Research Centre

    2008-07-01

    This study discussed the bitumen upgrading process and bitumen properties. Recent research on bitumen upgrading was reviewed, and methods of processing bitumens in conventional oil refineries were discussed. The study determined that bitumens contain large amounts of sulfur, aromatics, carbon residues, asphaltenes, and nitrogen, the majority of which is located in the last 15 per cent of the bitumen, or end cut. New upgrading processes used by Syncrude included an extraction and froth treatment plant, a diluent recovery unit (DRU) and vacuum distillation unit (VDU). Liquid products from the hydrotreaters were blended as synthetic crude oil (SCO) and shipped to refineries. The study also reviewed hydrotreating methods for gas oils; hydrocracking technologies; olefins and diolefins hydrogenation of coker naphtha; and aromatics hydrogenation. Tools to monitor the performance of commercial hydrotreaters were discussed, and the kinetics of aromatics hydrogenation were reviewed. Details of molecular structure analyses were presented. It was concluded that hydrotreating is an effective means of producing good quality SCO. 53 refs., 6 tabs., 10 figs.

  18. Role of minerals in thermal alteration of organic matter--II: a material balance.

    Science.gov (United States)

    Tannenbaum, E; Huizinga, B J; Kaplan, I R

    1986-09-01

    Pyrolysis experiments were performed on Green River and Monterey Formation kerogens (Types I and II, respectively) with and without calcite, illite, or montmorillonite at 300 degrees C for 2 to 1,000 hours under dry and hydrous conditions. Pyrolysis products were identified and quantified, and a material balance of product and reactants resulted. Significant differences were found in the products generated by pyrolysis of kerogens with and without minerals. Both illite and montmorillonite adsorb a considerable portion (up to 80%) of the generated bitumen. The adsorbed bitumen is almost exclusively composed of polar compounds and asphaltenes that crack to yield low molecular weight compounds and insoluble pyrobitumen during prolonged heating. Montmorillonite shows the most pronounced adsorptive and catalytic effects. With calcite however, the pyrolysis products are similar to those from kerogen heated alone, and bitumen adsorption is negligible. Applying these results to maturation of organic matter in natural environments, we suggest that a given type of organic matter associated with different minerals in source rocks will yield different products. Furthermore, the different adsorption capacities of minerals exert a significant influence on the migration of polar and high molecular weight compounds generated from the breakdown of kerogen. Therefore, the overall accumulated products from carbonate source rocks are mainly heavy oils with some gas, whereas light oils and gases are the main products from source rocks that contain expandable clays with catalytic and adsorptive properties.

  19. 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.

  20. 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.

  1. 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.

  2. 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)

  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. Source facies of the Paleozoic petroleum systems in the Tabei uplift, Tarim Basin, NW China: implications from aryl isoprenoids in crude oils

    Energy Technology Data Exchange (ETDEWEB)

    Yongge Sun; Shiping Xu; Hong Lu; Pingxia Cuai [Guangzhou Institute of Geochemistry, Chinese Academy of Sciences, Guangzhou (China). SKLOG

    2003-04-01

    Aryl isoprenoids have been detected for the first time in crude oils from Paleozoic petroleum systems in the Tabei uplift, Tarim Basin, northwestern China. The principal compounds possess the 1-alkyl-2,3,6-trimethyl substitution pattern characteristic of diaromatic carotenoids found in the Chlorobiaceae family of photosynthetic sulfur bacteria, with a predominance of C{sub 13} - C{sub 23} homologues in these samples. Flash pyrolysates of the asphaltene fractions isolated from crude oils show an unusual abundance of 1,2,3,4-tetramethylbenzene, an indicator for a significant contribution of diaromatic carotenoids to the source kerogen of these oils. The wide distribution of these compounds in crude oils reveals that penetration of the photic zone by sulfidic waters during deposition enabled prolific growth of photosynthetic green sulphur bacteria (Chlorobiaceae). This suggests that the source rocks for the Paleozoic petroleum systems in the Tabei uplift were likely deposited under euxinic conditions with sulfate and sulfide-rich water bodies, which doesn't support previously published conclusions of a Middle-Upper Ordovician source that marks the slope facies at the margins of structural uplifts. (author)

  5. Downhole Upgrading of Orinoco Basin Extra-Heavy Crude Oil Using Hydrogen Donors under Steam Injection Conditions. Effect of the Presence of Iron Nanocatalysts

    Directory of Open Access Journals (Sweden)

    Cesar Ovalles

    2015-03-01

    Full Text Available An extra-heavy crude oil underground upgrading concept and laboratory experiments are presented which involve the addition of a hydrogen donor (tetralin to an Orinoco Basin extra-heavy crude oil under steam injection conditions (280–315 °C and residence times of at least 24-h. Three iron-containing nanocatalysts (20 nm, 60 nm and 90 nm were used and the results showed increases of up to 8° in API gravity, 26% desulfurization and 27% reduction in the asphaltene content of the upgraded product in comparison to the control reaction using inert sand. The iron nanocatalysts were characterized by SEM, XPS, EDAX, and Mössbauer spectroscopy before and after the upgrading reactions. The results indicated the presence of hematite (Fe2O3 as the predominant iron phase. The data showed that the catalysts were deactivating by particle sintering (~20% increase in particle size and also by carbon deposition. Probable mechanisms of reactions are proposed.

  6. Inhibitory effect of aged-petroleum hydrocarbons on the survival of inoculated microorganism in a crude-oil contaminated site.

    Science.gov (United States)

    Kang, Yoon-Suk; Park, Youn Jong; Jung, Jaejoon; Park, Woojun

    2009-12-01

    We studied the effects of aged total petroleum hydrocarbons (aged TPH) on the survival of allochthonous diesel-degrading Rhodococcus sp. strain YS-7 in both laboratory and field investigations. The aged TPH extracted from a crude oil-contaminated site were fractionized by thin-layer chromatography/flame ionization detection (TLC/FID). The three fractions identified were saturated aliphatic (SA), aromatic hydrocarbon (AH), and asphaltene-resin (AR). The ratio and composition of the separated fractions in the aged TPH were quite different from the crude-oil fractions. In the aged TPH, the SA and AH fractions were reduced and the AR fraction was dramatically increased compared to crude oil. The SA and AH fractions (2 mg/L each) of the aged TPH inhibited the growth of strain YS-7. Unexpectedly, the AR fraction had no effect on the survival of strain YS-7. However, crude oil (1,000 mg/L) did not inhibit the growth of strain YS-7. When strain YS-7 was inoculated into an aged crude oil-contaminated field and its presence was monitored by fluorescent in situ hybridization (FISH), we discovered that it had disappeared on 36 days after the inoculation. For the first time, this study has demonstrated that the SA and AH fractions in aged TPH are more toxic to an allochthonous diesel-degrading strain than the AR fraction.

  7. 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.

  8. 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.)

  9. A study of the Holzener Asphaltkalk, northern Germany: observations regarding the distribution, composition and origin of organic matter in an exhumed petroleum reservoir

    Energy Technology Data Exchange (ETDEWEB)

    Horsfield, B.; Heckers, J.; Leythaeuser, D.; Littke, R.; Mann, U. (Kernforschungsanlage Juelich GmbH (Germany). Inst. fuer Chemie 5 - Erdoel und Organische Geochemie)

    1991-05-01

    The Holzener Asphalkalk deposit is located on the southwestern flank of the Hils Syncline, northern Germany. It consists of a series of Kimmeridgian-Portlandian bitumen-impregnated limestones (cumulative thickness of nearly 200 m) overlain unconformably by Neocomian claystones and underlain by older Jurassic and Triassic sediments. The most bitumen-rich limestone layers have been extensively mined with the result that there is three-dimensional access to what is probably an exhumed series of stacked petroleum reservoirs. Geochemical, petrological and petrophysical techniques were used to gain some insight into the distribution and the source of the organic matter in two of the 13 layers of the deposit. Most disseminated organic matter was found to be soluble in organic solvents and rich in non-hydrocarbons. Its distribution appears to be controlled by ooid versus carbonate matrix abundances, the occurrence of fractures and degree of impregnation. Small (meso- to micro-) pores have high bitumen saturations whereas large pores (meso- to macro-) have much lower saturations. Mature petroleum is thought to have once filled all pores, but alteration has probably removed as much as 85% of it, mainly from the large pores. Regional geochemical considerations, pyrolysis and stable carbon isotope data indicate that the original petroleum was most probably derived from the underlying Posidonia Shale (Toarcian) source rock. Asphaltene pyrolysis data indicate that an algal lacustrine co-source might have also contributed to the deposit. (author)

  10. The Use of Biobased Surfactant Obtained by Enzymatic Syntheses for Wax Deposition Inhibition and Drag Reduction in Crude Oil Pipelines

    Directory of Open Access Journals (Sweden)

    Zhihua Wang

    2016-04-01

    Full Text Available Crude oil plays an important role in providing the energy supply of the world, and pipelines have long been recognized as the safest and most efficient means of transporting oil and its products. However, the transportation process also faces the challenges of asphaltene-paraffin structural interactions, pipeline pressure losses and energy consumption. In order to determine the role of drag-reducing surfactant additives in the transportation of crude oils, experiments of wax deposition inhibition and drag reduction of different oil in pipelines with a biobased surfactant obtained by enzymatic syntheses were carried out. The results indicated that heavy oil transportation in the pipeline is remarkably enhanced by creating stable oil-in-water (O/W emulsion with the surfactant additive. The wax appearance temperature (WAT and pour point were modified, and the formation of a space-filling network of interlocking wax crystals was prevented at low temperature by adding a small concentration of the surfactant additive. A maximum viscosity reduction of 70% and a drag reduction of 40% for light crude oil flows in pipelines were obtained with the surfactant additive at a concentration of 100 mg/L. Furthermore, a successful field application of the drag-reducing surfactant in a light crude oil pipeline in Daqing Oilfield was demonstrated. Hence, the use of biobased surfactant obtained by enzymatic syntheses in oil transportation is a potential method to address the current challenges, which could result in a significant energy savings and a considerable reduction of the operating cost.

  11. 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)

  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. 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.

  14. Dust evolution, a global view: II. Top-down branching, nanoparticle fragmentation and the mystery of the diffuse interstellar band carriers.

    Science.gov (United States)

    Jones, A P

    2016-12-01

    The origin of the diffuse interstellar bands (DIBs), one of the longest-standing mysteries of the interstellar medium (ISM), is explored within the framework of The Heterogeneous dust Evolution Model for Interstellar Solids (THEMIS). The likely nature of the DIB carriers and their evolution is here explored within the framework of the structures and sub-structures inherent to doped hydrogenated amorphous carbon grains in the ISM. Based on the natural aromatic-rich moieties (asphaltenes) recovered from coal and oil, the likely structure of their interstellar analogues is investigated within the context of the diffuse band problem. It is here proposed that the top-down evolution of interstellar carbonaceous grains, and, in particular, a-C(:H) nanoparticles, is at the heart of the formation and evolution of the DIB carriers and their associations with small molecules and radicals, such as C2, C3, CH and CN. It is most probable that the DIBs are carried by dehydrogenated, ionized, hetero-cyclic, olefinic and aromatic-rich moieties that form an integral part of the contiguous structure of hetero-atom-doped hydrogenated amorphous carbon nanoparticles and their daughter fragmentation products. Within this framework, it is proposed that polyene structures in all their variants could be viable DIB carrier candidates.

  15. Group type analysis of asphalt by column liquid chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Zhang, C.; Yang, J.; Xue, Y.; Li, Y. [Chinese Academy of Science, Taiyuan (China)

    2008-07-01

    An improved analysis method for characterization of asphalt was established. The method is based on column chromatography technique. The asphalts were separated into four groups: saturates, aromatics, resins, and asphaltenes, quantitatively. About 0.1 g of sample was required in each analysis. About 20 mL of n-heptanes was used to separate out saturates first. Then about 35 mL of n-heptanes/dichloromethane (.5, v/v) mixture was used to separate out aromatics. About 30 mL of dichloromethane/tetrahydrofuran (1/3, v/v) mixture was used to separate out resin. The quality of the separation was confirmed by infrared spectra (IR) and {sup 1}H NMR analysis. The model compounds, tetracosan for saturates, dibenz(o)anthracen for aromatics, and acetanilide for resins were used for verification. The IR and {sup 1}H NMR analysis of the prepared fractions from the column liquid chromatography were in good agreement that of pure reagents.

  16. 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.

  17. 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.

  18. Theoretical Calculation of the Uv-Vis Spectral Band Locations of Pahs with Unknown Syntheses Procedures and Prospective Carcinogenic Activity

    Science.gov (United States)

    Ona-Ruales, Jorge Oswaldo; Ruiz-Morales, Yosadara

    2017-06-01

    Annellation Theory and ZINDO/S semiempirical calculations have been used for the calculation of the locations of maximum absorbance (LMA) of the Ultraviolet-Visible (UV-Vis) of 31 C_{34}H_{16} PAHs (molecular mass 424 Da) with unknown protocols of synthesis. The presence of benzo[a]pyrene bay-like regions and dibenzo[a,l]pyrene fjord-like regions in several of the structures that could be linked to an enhancement of the biological behavior and carcinogenic activity stresses the importance of C_{34}H_{16} PAHs in fields like molecular biology and cancer research. In addition, the occurrence of large PAHs in oil asphaltenes exemplifies the importance of these calculations for the characterization of complex systems. The C_{34}H_{16} PAH group is the largest molecular mass group of organic compounds analyzed so far following the Annellation Theory and ZINDO/S methodology. Future analysis using the same approach will provide evidence regarding the LMA of other high molecular mass PAHs.

  19. 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)

  20. 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)

  1. Upgrading of heavy crude oil with supported and unsupported transition metals

    Energy Technology Data Exchange (ETDEWEB)

    Nares, H.R.; Schacht-Hernandez, P.; Cabrera-Reyes, M.C.; Ramirez-Garnica, M.; Cazarez-Candia, O. [Instituto Mexicano del Petroleo, Atepehuacan (Mexico)

    2006-07-01

    Heavy crude oil presents many problems such as difficulty in transportation, low processing capacity in refineries, and low mobility through the reservoir due to high viscosity which affects the index of productivity of the wells. Because of these challenges, it is necessary to enhance heavy crude oil, both aboveground and underground. The effects of several metallic oxides used to upgrade heavy crude oil properties were examined in order to increase the mobility of reservoir oil by reducing viscosity and improving the quality of the oil. This can be accomplished by reducing the asphaltene and sulfur contents and increasing the American Petroleum Institute (API) gravity using transition metal supported in alumina and unsupported from transition metals derived from either acetylacetonate or alkylhexanoate in liquid phase homogeneously mixed with heavy crude oil as well as metal transition supported in alumina. KU-H heavy crude oil from the Golf of Mexico was studied. The results were obtained by Simulated Distillation and True Boiling Point (TBP). It was concluded that the use of crude oil thermal hydrocracking allowed the API gravity to increase and considerably reduce the viscosity. As a result, the productivity index in wells was increased. However there is a high formation of coke that could damage the conductivity of the rock and then reduce the potential of oil recovery. 27 refs., 3 tabs., 5 figs.

  2. 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)

  3. Synthesis of SO4 2-/Zr-silicalite-1 zeolite catalysts for upgrading and visbreaking of heavy oil

    Science.gov (United States)

    Su, Lu; Guan, Zhongjie; Li, Qiuye; Li, Chen; Wang, Xiaodong; Li, Xiaohong; Yang, Jianjun; Zhang, Zhijun

    2017-09-01

    Catalyst is crucially important to reduce the viscosity of heavy oil during the catalytic aquathermolysis. SO4 2--modified ZrO2-based nanoparticle catalyst is a commonly used catalyst. But less acid sites and poor hydrothermal stability limited further improving its catalytic performance and practical application. In this study, the Zr -doped silicalite zeolite catalysts with large surface area were prepared as a support matrix, and SO4 2--modified Zr-doped silicalite zeolite (denoted as SO4 2-/Zr-silicalite-1 zeolite) was used as a solid superacid catalyst to crack the heavy oil. A reference catalyst of SO4 2-/Zr-SiO2 nanoparticles (NPs) was also prepared, which has the same composition with the SO4 2-/Zr-silicalite-1 zeolite catalyst. Compared with the SO4 2-/Zr-SiO2 NP catalyst, the amount of acid sites for the SO4 2-/Zr-silicalite-1 zeolite catalyst is significantly increased and the viscosity reduction efficiency is also enhanced by 40%. More importantly, the SO4 2-/Zr-silicalite-1 zeolite catalyst exhibits a high hydrothermal stability. After catalytic aquathermolysis, the quality of the heavy oil was also ameliorated. The heavy resins and asphaltenes reduced, while the light saturated and aromatic hydrocarbon increased. The results suggest metal element-doped silicalite zeolite catalyst is a potential useful way to solving the less acid sites and poor hydrothermal stability for the SO4 2--modified nanoparticle catalyst. [Figure not available: see fulltext.

  4. Part 1. The effect of microwave receptors on the liquefaction of Turkish coals by microwave energy in a hydrogen donor solvent

    Energy Technology Data Exchange (ETDEWEB)

    Emine Yagmur; Taner Togrul [Ankara University, Ankara (Turkey). Faculty of Engineering, Department of Chemical Engineering

    2005-12-01

    The effects of microwave receptors to coal (receptor/coal) ratio and the period of heating by microwave energy on the solubilization of Turkish coals (Tuncbilek, Mugla-Yatagan, Beypazari lignites, and Zonguldak bituminous coal) in tetralin have been investigated. V{sub 2}O{sub 5} and TiO{sub 2} were used as microwave receptors. The changes of liquid product yield indicated that it depended significantly on the type and amount of receptor and the type of coal. A significant increase in the lignite conversions to oil fractions was observed by the addition of the V{sub 2}O{sub 5} receptor. The use of TiO{sub 2} receptor decreased the yield of THF soluble coal products. However, both V{sub 2}O{sub 5} and TiO{sub 2} receptors decreased the yield of preasphaltene (PAS) and asphaltene (AS) due to their catalytic effect on the coal liquefaction. 15 refs., 9 figs., 1 tab.

  5. 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.

  6. Petroleomics: advanced molecular probe for petroleum heavy ends.

    Science.gov (United States)

    Hsu, Chang S; Hendrickson, Christopher L; Rodgers, Ryan P; McKenna, Amy M; Marshall, Alan G

    2011-04-01

    To look into complex mixtures of petroleum heavy ends at the molecular level, ultra high-resolution mass spectrometry, i.e. resolving power > 50,000, is needed to resolve overlapping components for accurate determination of molecular composition of individual components. Recent progress in Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) incorporated with soft ionization techniques adaptable to liquid chromatography enables analysis of petroleum high ends, i.e., heavy oils, residua and asphaltenes. FT-ICR MS at the Future Fuels Institute of Florida State University and the National High Magnetic Field Laboratory (NHMFL) routinely provides 1,000,000 resolving power at 400 Da, with root mean square (rms) mass measurement accuracy between 30 and 500 ppb for 5000-30,000 identified species in a single mass spectrum. Phase correction of the detected ion signal increases resolving power 40-100%, improving mass accuracy up to twofold. Overlapping ionic species that differ in mass by as little as one electron mass (548 µDa) can be resolved. A database of more than 100,000 components of different elemental composition has been generated at NHMFL. Copyright © 2011 John Wiley & Sons, Ltd.

  7. 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)

  8. 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.

  9. 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)

  10. 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.

  11. 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.

  12. 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.

  13. 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.

  14. 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.

  15. Study of hydrocarbon miscible solvent slug injection process for improved recovery of heavy oil from Schrader Bluff Pool, Milne Point Unit, Alaska. Annual report, December 1, 1992--December 31, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, G.D.

    1994-01-01

    The shallow Cretaceous sands of the Schrader Bluff Reservoir occur between depths of 4,000 and 4,800 feet below surface and are estimated to contain up to 1.5 billion barrels of oil in place. The field is currently under production by primary depletion. Initial production indicated that primary recovery will fall short of earlier estimates and waterflooding will have to be employed much earlier than expected. A large portion of the oil-in-place thus would still be left behind in this reservoir after primary and secondary recovery methods have been applied. Enhanced oil recovery (EOR) techniques will be needed to recover the additional portion of remaining oil in this huge reservoir and to add significant additional reserves. Slim tube displacement studies, PVT data and asphaltene precipitation studies are needed for Schrader Bluff heavy oil to define possible hydrocarbon solvent suitable for miscible solvent slug displacement process. Such studies are essential because the API gravity of the crude in Schrader Bluff reservoir varies significantly from well to well. Coreflood experiments are also needed to determine effect of solvent slug size, WAG ratio and solvent composition on the oil recovery and solvent breakthrough. A compositional reservoir simulation study will be conducted later to evaluate the complete performance of the hydrocarbon solvent slug process and to assess the feasibility of this process for improving recovery of heavy oil from Schrader Bluff reservoir. This report contains the following: reservoir description; slim tube displacement studies; and coreflood experiments.

  16. 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.

  17. Effect of evaporative weathering and oil-sediment interaction on the fate and behavior of diluted bitumen in marine environments. Part 2. The water accommodated and particle-laden hydrocarbon species and toxicity of the aqueous phase.

    Science.gov (United States)

    Yang, Zeyu; Hua, Yujuan; Mirnaghi, Fatemeh; Hollebone, Bruce P; Jackman, Paula; Brown, Carl E; Yang, Chun; Shah, Keval; Landriault, Mike; Chan, Brian

    2018-01-01

    In this study, the water accommodated and particle-laden hydrocarbon species, and the toxicity of the aqueous phase after oil-sediment interactions by varying the weathering states of diluted bitumen (Cold Lake blend (CLB)), oil type from light to heavy, and sediment type. Compared to the original oils, the sediment-laden total petroleum hydrocarbons (TPH) contained fewer hydrocarbons in the carbon range C34 range. Sediment-laden oil amounts generally decreased with an increased viscosity and asphaltene content of the test oils, as well as with increased sediment particle size. The presence of sediments significantly decreased the oil accommodated in water due to the formation of oil particulate aggregates (OPA) after mixing and settling. Less water accommodated TPH and polycyclic aromatic hydrocarbons (PAHs) were observed for weathered CLB products. However, oil and sediment types did not clearly affect the water accommodated TPH and PAHs. Light molecular PAHs and their alkylated congeners accounted for most of the water accommodated PAH congeners. A microtoxicity test demonstrated that with or without sediment, and regardless of sediment type, the toxicity of the water phase did not change significantly. Light oil of Alberta sweet mixed blend (ASMB) had the highest toxicity, followed by fresh CLB, and then all other oils, suggesting that ASMB and fresh CLB had relatively higher levels of light toxic components dissolved in the water phase compared with the other tested oils. Copyright © 2017 Elsevier Ltd. All rights reserved.

  18. 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.

  19. You've got 'scale' : developments in well-bore remediation technology

    Energy Technology Data Exchange (ETDEWEB)

    Zemlak, Z. [Schlumberger Canada Ltd., Calgary, AB (Canada); Kortash, B. [Amoco Canada Petroleum Co. Ltd., Calgary, AB (Canada)

    2000-06-01

    The Kaybob field Beaver Hill Lake formation in Central Alberta is an aquifer driven maturing gas reservoir with high concentrations of iron sulfide scale. This scale, in combination with a time layered asphaltenes has an impact on production. Since the scale forms on tubular walls and results in corrosion of metal, it also increases risks during well intervention. Past techniques to remove the scale have not proven to be successful. This study presents a newly developed Blaster scale removal system to clean tubings. Blaster techniques use high-pressure jetting in combination with special abrasives to remove extremely hard, inert scales without damaging the tubing or completion components. Amoco Canada has been involved in the continual improvement and modification of the method since its introduction in 1998. To date, a total of 19 wells have been completed, providing valuable data about the method. It was concluded that although iron sulfide scale is common throughout the gas reservoir, the composition and solubility varies from well to well. Amoco Canada has found that Blaster techniques are a safe, low risk method of cleaning coiled tubulars to known drift parameters, in areas where scale and corrosion have been uncontrollable. 5 refs., 2 tabs., 1 fig.

  20. 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

    2017-02-22

    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.

  1. E. s. r. characterization of phenalenyl radicals in various fuel samples

    Energy Technology Data Exchange (ETDEWEB)

    Senglet, N.; Faure, D.; Courieres, T. des; Bernasconi, C.; Guilard, R. (Laboratoire de Synthese et d' Electrosynthese Organometallique, Dijon (France). Faculte des Sciences ' Gabriel' )

    1990-02-01

    Various fuel samples were studied by e.s.r. spectroscopy to identify and quantify free radicals and molecules containing unpaired electrons. The 298K spectra from various heavy fuel samples were characteristic of vanadyl porphyrins. In addition, a sharp intense peak near g 2 was assigned to the free radicals that are always observed in the asphaltenes. Two kinds of e.s.r. spectra were observed among the gas oil samples: the straight run gas oil showed a single peak close to g 2, while the light cycle oil (LCO) spectra were typical of the phenalenyl radical. The pyrolysis fuels exhibited a single resonance line attributed to an organic radical (g 2), and the mixed samples gave spectra similar to those of the heavy fuels. The data obtained by quantitative analysis of the unpaired electrons in fuel and gas oil samples are described. The concentration of phenalenyl radicals in LCO was found to decrease with time and with heating. 11 refs., 5 figs., 3 tabs.

  2. In Situ Visualization of the Phase Behavior of Oil Samples Under Refinery Process Conditions.

    Science.gov (United States)

    Laborde-Boutet, Cedric; McCaffrey, William C

    2017-02-21

    To help address production issues in refineries caused by the fouling of process units and lines, we have developed a setup as well as a method to visualize the behavior of petroleum samples under process conditions. The experimental setup relies on a custom-built micro-reactor fitted with a sapphire window at the bottom, which is placed over the objective of an inverted microscope equipped with a cross-polarizer module. Using reflection microscopy enables the visualization of opaque samples, such as petroleum vacuum residues, or asphaltenes. The combination of the sapphire window from the micro-reactor with the cross-polarizer module of the microscope on the light path allows high-contrast imaging of isotropic and anisotropic media. While observations are carried out, the micro-reactor can be heated to the temperature range of cracking reactions (up to 450 °C), can be subjected to H2 pressure relevant to hydroconversion reactions (up to 16 MPa), and can stir the sample by magnetic coupling. Observations are typically carried out by taking snapshots of the sample under cross-polarized light at regular time intervals. Image analyses may not only provide information on the temperature, pressure, and reactive conditions yielding phase separation, but may also give an estimate of the evolution of the chemical (absorption/reflection spectra) and physical (refractive index) properties of the sample before the onset of phase separation.

  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. 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.

  5. Evidence for a palaeo-oil column and alteration of residual oil in a gas-condensate field: Integrated oil inclusion and experimental results

    Science.gov (United States)

    Bourdet, Julien; Burruss, Robert C.; Chou, I.-Ming; Kempton, Richard; Liu, Keyu; Hung, Nguyen Viet

    2014-10-01

    displays a similar yellow shift when gas is added. Solid residues rarely form in mixtures with 42 °API oil. FT-IR spectra suggest that the decrease of fluorescence intensity of the original oil at short wavelengths to be due to the partitioning of low molecular weight aromatic molecules into the vapour phase and/or the new immiscible liquid phase. The decrease of fluorescence intensity at long wavelengths appears to be due to loss of high molecular weight aromatics during precipitation of solid residues by desorption of aromatics and resins from asphaltenes. Desorption of low molecular weight aromatics and resins from asphaltenes during precipitation can also increase the fluorescence intensity at short wavelengths of the residual oil. Water clearly affects the precipitation of semi-solid residues from the oil phase of the lowest API gravity oil. The change of hydrocarbon phase(s) in UV-visible fluorescence and FT-IR enclosed within the FSCCs were compared with the fluorescence patterns of natural fluid inclusions at Phuong Dong gas condensate field. The experimental results support the concept of gas-washing of residual oil and are consistent with the oil inclusion attributes from the current gas zone at Phuong Dong field. The hydrocarbon charge history of the fractured granite reservoir is interpreted to result from the trapping of residual oil after drainage of a palaeo-oil column by gas.

  6. 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

  7. 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

  8. Role of organic matter fractions in the Montney tight gas reservoir quality

    Science.gov (United States)

    Sanei, Hamed; Wood, James M.; Haeri Ardakani, Omid; Clarkson, Chris R.

    2015-04-01

    This study presents a new approach in Rock-Eval analysis to quantify various organic matter fractions in unconventional reservoirs. The results of study on core samples from the Triassic Montney Formation tight gas reservoir in the Western Canadian Sedimentary Basin show that operationally-defined S1 and S2 hydrocarbon peaks from conventional Rock-Eval analysis may not adequately characterize the organic constituents of unconventional reservoir rocks. Modification of the thermal recipe for Rock-Eval analysis, in conjunction with manual peak integration, provides important information with significance for the evaluation of reservoir quality. An adapted Rock-Eval method, herein called the extended slow heating (ESH) cycle, was developed in which the heating rate was slowed to 10°C per minute over an extended temperature range (150 to 650°C). For Montney core samples from the wet gas window, this method provided quantitative distinctions between major organic matter components of the rock. We show that the traditional S1 and S2 peaks can now be quantitatively divided into three components: (S1ESH) free light oil, (S2a ESH) condensed hydrocarbon residue (CHCR), and (S2b ESH + residual carbon) solid bitumen (refractory, consolidated bitumen/pyrobitumen). The majority of the total organic carbon (TOC) in the studied Montney core samples consists of solid bitumen that represents a former liquid oil phase which migrated into the larger paleo-intergranular pore spaces. Subsequent physicochemical changes to the oil environment led to the precipitation of asphaltene aggregates. Further diagenetic and thermal maturity processes consolidated these asphaltene aggregates into "lumps" of solid bitumen (or pyrobitumen at higher thermal maturity). Solid bitumen obstructs porosity and hinders fluid flow, and thus shows strong negative correlations with reservoir qualities such as porosity and pore throat size. We also find a strong positive correlation between the quantities of

  9. 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.

  10. Study of coal and graphite specimens by means of Raman and cathodoluminescence

    Science.gov (United States)

    Kostova, Irena; Tormo, Laura; Crespo-Feo, Elena; Garcia-Guinea, Javier

    2012-06-01

    The weak luminescence shown by coals has been attributed to accessorial minerals and poly-nuclear aromatic hydrocarbons, such as exinite, vitrinite or inertinite, while the luminescence quenching has been found in asphaltenes produced by coal hydrogenation or in pyridine extracts. Nowadays, the spatial resolution and the improved luminescence efficiency of the modern spectrometers allow some details of the luminescent emission centers to be explained. We have selected museum historical coal specimens with different rank, i.e., peat, lignite, sub-bituminous, bituminous, and anthracite to be analyzed by their spectra from cathodoluminescence probe (CL) of an environmental scanning electron microscopy (ESEM), with an energy dispersive spectrometry analyzer (EDS). Additional analytical controls were also performed by X-ray diffraction (XRD), X-ray fluorescence (XRF) and Raman spectrometries. We conclude that coals may display different luminescence emission features coming from several different sources, as follows: (i) broadband of intense luminescence from polynuclear aromatic hydrocarbons, (ii) weakly visible broadband luminescence attributed to band-tail states caused by variations in the energy gap of individual sp2 carbon clusters, which are different in size and/or shape, (iii) silicate impurities causing the common luminescence peak at 325 nm observed in coals. This peak is due to non-bridging oxygen hole centres (tbnd Sisbnd Orad ) probably generated by precursor Sisbnd Osbnd C species formed by tbnd Sisbnd Orad defects and carbon atoms; (iv) a 710 nm CL emission commonly detected also in wood and ivory, which has been correlated with hydrocarbon groups of chlorophyll or lignine. Coals are very complex rocks, composed by both organic and inorganic phases with variable and complex spectra. More analyses are necessary and carbonaceous standards of graphite, silicon carbide, stuffed carbon silica and diamond at variable experimental conditions have to be

  11. Coal liquefaction process streams characterization and evaluation. Quarterly technical progress report, January 1--March 31, 1993

    Energy Technology Data Exchange (ETDEWEB)

    Robbins, G.A.; Brandes, S.D.; Winschel, R.A.; Burke, F.P.

    1993-12-01

    Process oil samples from HRI Catalytic Two-Stage Liquefaction (CTSL) Bench Unit Run CC-16 (227-76) were analyzed to provide information on process performance. Run CC-16 was operated in December 1992 with Burning Star 2 Mine (Illinois 6 seam) coal to test and validate Akzo EXP-AO-60 Ni/Mo catalyst (1/16 in. extrudate). Results were compared with those of four previous HRI CTSL bench unit runs made with Ni/Mo catalysts. Major conclusions from this work are summarized. (1) Akzo EXP-AO-60 gave process oil characteristics in Run CC-16 similar to those of other Ni/Mo catalysts tested in Runs I-13, I-16, I-17, and I-18 (by our analytical and empirical test methods). No distinct performance advantage for any of the catalysts emerges from the process oil characteristics and plant performance. Thus, for commercial coal liquefaction, a number of equivalent catalysts are available from competitive commercial sources. The similarity of run performance and process oil characteristics indicates consistent performance of HRI`s bench unit operations over a period of several years; (2) Dominant effects on process oil properties in Run CC-16 were catalyst age and higher temperature operation in Periods 10--13 (Condition 2). Properties affected were the aromaticities and phenolic -OH concentrations of most streams and the asphaltene and preasphaltene concentrations of the pressure-filter liquid (PFL) 850{degrees}F{sup +} resid. The trends reflect decreasing hydrogenation and defunctionalization of the process streams with increasing catalyst age. Operation at higher temperature conditions seems to have partially offset the effects of catalyst age.

  12. Time-resolved fluorescence microspectroscopy for characterizing crude oils in bulk and hydrocarbon-bearing fluid inclusions.

    Science.gov (United States)

    Ryder, Alan G; Przyjalgowski, Milosz A; Feely, Martin; Szczupak, Boguslaw; Glynn, Thomas J

    2004-09-01

    Time-resolved fluorescence data was collected from a series of 23 bulk crude petroleum oils and six microscopic hydrocarbon-bearing fluid inclusions (HCFI). The data was collected using a diode laser fluorescence lifetime microscope (DLFLM) over the 460-700 nm spectral range using a 405 nm excitation source. The correlation between intensity averaged lifetimes (tau) and chemical and physical parameters was examined with a view to developing a quantitative model for predicting the gross chemical composition of hydrocarbon liquids trapped in HCFI. It was found that tau is nonlinearly correlated with the measured polar and corrected alkane concentrations and that oils can be classified on this basis. However, these correlations all show a large degree of scatter, preventing accurate quantitative prediction of gross chemical composition of the oils. Other parameters such as API gravity and asphaltene, aromatic, and sulfur concentrations do not correlate well with tau measurements. Individual HCFI were analyzed using the DLFLM, and time-resolved fluorescence measurements were compared with tau data from the bulk oils. This enabled the fluid within the inclusions to be classified as either low alkane/high polar or high alkane/low polar. Within the high alkane/low polar group, it was possible to clearly discriminate HCFI from different locales and to see differences in the trapped hydrocarbon fluids from a single geological source. This methodology offers an alternative method for classifying the hydrocarbon content of HCFI and observing small variations in the trapped fluid composition that is less sensitive to fluctuations in the measurement method than fluorescence intensity based methods.

  13. Study of agglomeration of ice particles and of trichlorofluoromethane hydrate particles suspended in a hydrocarbon phase

    Energy Technology Data Exchange (ETDEWEB)

    Colombel, E.; Palermo, T.; Barre, L.; Gateau, P. [Inst. Francais du Petrole, Rueil Malmaison (France). Dept. of Applied Chemistry and Physico-Chemistry; Gruy, F. [Ecole Nationale Superieure des Mines, Saint Etienne (France)

    2008-07-01

    Gas hydrates may lead to pipeline blockage during oil production in offshore conditions. A study was conducted to better understand the agglomeration mechanism of gas hydrate particles in water in oil emulsions. The model system chosen to study this mechanism was ice or trichlorofluoromethane (CCl{sub 3}F) hydrate particles dispersed in xylene with asphaltenes as surfactants. The system illustrated what occurs in pipelines as produced water with oil is dispersed by surfactants that are naturally present in the oil phase. Freon was selected because it models methane behaviour very well. Both methane and freon are soluble in oil and insoluble in water. CCl{sub 3}F hydrates are stable under atmospheric pressure. As such, different techniques can be applied without being limited by high pressure conditions. The agglomeration mechanism in these particles can be modelled and compared with ice crystals. This study focused on the kinetics of agglomeration formation and mechanisms of hydrate and ice particle agglomeration in a hydrocarbon phase. Two characterization techniques were implemented in this study, notably nuclear magnetic resonance (NMR) relaxometry and rheology. The different relaxation rate for solids or liquids was used to monitor in situ the ratio between the solid and total hydrogen or fluorine as a function of time with controlled shearing conditions. NMR provided information on the formation kinetics and the conversion rate of water in ice crystals. The rest of the study focused on the formation of Freon hydrate crystals. The study confirmed that the physico-chemistry of the water/oil interface has an important role in agglomeration. 9 refs., 5 tabs., 18 figs.

  14. 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.

  15. 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.

  16. Stigmastane and hopanes as conserved biomarkers for estimating oil biodegradation in a former refinery plant-contaminated soil.

    Science.gov (United States)

    Gagni, Simona; Cam, Darinn

    2007-05-01

    In the last decade, a refinery plant located in Lido Adriano, East Ravenna (Italy) has been subject to mineral oil contamination. The mineral crude oil, extracted from the offshore in Adriatic sea, consisted of 78% aliphatics, cyclic alkanes and saturated polycyclic hydrocarbons, 9% aromatics, polycyclic aromatic hydrocarbons (PAHs) and alkylated derivatives, and 13% of tars/asphaltenes. Analysis of soil after 10 years of natural attenuation revealed a complete depletion of linear (n-C(9)-C(24)), light aromatics (C1-C3/benzenes) and PAHs (C2/naphthalene, C1/phenanthrene); besides a substantial degradation of isoprenoids prystane and phytane, branched and cyclic alkanes. The remaining contaminants which withstood to natural degradation was saturated polycyclic hydrocarbons (perhydro-PAH derivatives), unsaturated polycyclic hydrocarbons (tetrahydro, dihydro-PAH derivatives), terpanes, steranes and unidentified compounds. Such residues resulted in 80% reduction of its concentration after two months of laboratory treatment. Samples were extracted by organic solvents, separated by silica/alumina gel column chromatography and analyzed by gas chromatography-mass selective detector (GC-MSD). Identification and quantification of aliphatic, cyclic alkanes, typical PAHs, terpanes and steranes were carried out to chromatograms of M/Z=85, 83, individual M/Zs, M/Z=191 and 217, respectively. The present work shows that, among numerous biomarkers present in the source oil, stigmastane and two isomers of hopane showed invariable concentrations after laboratory experiments that mimic natural biodegradation in the field, so they can be used as conserved internal biomarkers. These are very useful tools to assess alterations in less stable classes of saturated compounds contained in petroleum. Marked degradation of perhydro, tetrahydro, dihydro-PAH derivatives in the laboratory treatment has been evidenced.

  17. Investigation on the effect of phase segregation on the mechanical properties of polymer modified bitumen using analytical and morphological tools

    Directory of Open Access Journals (Sweden)

    Zainab Habib Noor

    2017-01-01

    Full Text Available The mechanical strength of polymer modified bituminous mix which is evaluated in terms of stiffness reflects the deformation behaviour of bituminous mixture. The stiffness of the binder strongly depends on its chemical composition besides aggregate structure of the bituminous mixture. Compatibility of polymer with the base bitumen is considered as major strength enhancing factor in the case of polymer modified bituminous mix. To relate the factors affecting the mechanical strength of the binder a new approach in this research study was adopted in order to relate the compatibility of 80/100 pen bitumen with polymer Polypropylene (PP using analytical and morphological tools. Morphological tools like Atomic Force Microscopy (AFM and Transmission Electron Microscope (TEM were used to study the changes due to the difference in compatibility of polymer with bitumen. It was observed that the presence of phase segregated layer as observed by AFM surface morphology was considered as the main strength enhancing factor of the bituminous mix. While the presence of lamella as observed in TEM scanned images of PP PMB revealed that addition of polymer forms localized network in the phase segregated layer which induces the stiffening effect in PMB. From the chromatographic method (SARA analytical analysis Saturate, Aromatics, Resin and Asphaltene fractionate were determined in the blend. It was observed that chemical composition of the blend also has a profound effect on the rheological properties and on the morphology of polymer modified bituminous (PMB blend. It was concluded that PP PMB gets benefited by phase segregated layer in the blend when the polymer concentration was kept below 3% as it sufficiently enhances the mechanical strength of the PMB binder as observed by dynamic creep results.

  18. 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

  19. A novel method for recovery of acidic sludge of used-motor oil reprocessing industries to bitumen using bentonite and SBS

    Directory of Open Access Journals (Sweden)

    Ahmad Jonidi Jafari

    2014-04-01

    Full Text Available ABSTRACT Acidic sludge is a by-product from used motor oil reprocessing industries, which thousand tons of this sludge are disposed into the environment as a hazardous waste material daily. The acidic sludge contains unsaturated compounds that are polar and asphaltene. The bitumen under certain conditions is produced from mixing of bentonite, polymer styrene – butadiene – styrene (SBS, and acidic sludge. Context and purpose: The objective of this study was the recovery of acidic sludge to bitumen using additives such as bentonite and SBS. Also, the effect of additives with different weight percentages (wt%(on the performance parameters of bitumen was evaluated. At first, spilled oil was separated from the acidic sludge by a centrifugal concentrator. Then, concentrated acidic sludge and additives were mixed in together. Finally, the performance tests were carried out to compare the quality of acidic sludge with the obtained products.The results indicated that performance parameters such as softening point (SP, weight loss, penetration degree, PI, Frass breaking point, and temperature susceptibility (TS were promoted from 37°C, 1.3%, 230 dmm, -0.07854, -5°C and 0.0451 to 54°C, 1%, 130 dmm, 2.7094, -11°C , 0.02721, respectively. According to the paired sample t-test analysis, a significant difference was found between the bentonite dosage and the improved performance parameters from concentrated acidic sludge and obtained products (pvalue ≤.001. The bentonite and SBS with 2 and 4 wt%, respectively were determined as the suitable additives in the recovery of acidic sludge to bitumen.

  20. 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.

  1. 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.

  2. 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)

  3. Steam pretreatment for coal liquefaction. Final report, September 26, 1990--March 18, 1995

    Energy Technology Data Exchange (ETDEWEB)

    Graff, R.A.; Balogh-Nair, V.; Ivanenko, O.; Brathwaite, C.

    1995-10-16

    The objective of this study is to demonstrate the use of subcritical steam to pretreat coal for slurry liquefaction, allowing liquefaction to be carried out at lower severity and improving product yield and quality. Samples of Illinois No. 6 coal were pretreated in 750 psia steam at 340{degree}C for 15 minutes. These samples, as well as raw coal, were liquefied at high (400{degree}C, 30 min.) and low (385{degree}C, 15 min.) severity conditions under 1500 psia hydrogen with tetralin as the donor solvent. Improved yields were obtained at both conditions. (Improved yields were not obtained at a liquefaction temperature of 350{degree}C as that put the sample into the region of retrogressive reactions). The deleterious effects of slow heating and exposure of the sample to air were demonstrated. Under low severity conditions, steam pretreatment more that doubled the oil yield, increasing it from 12.5 to 29 wt %. Tests were also conducted with aromatic ethers as model compounds. These were exposed to inert gas and steam at pretreatment conditions and in some cases to liquid water at 315{degree}C. {alpha}-Benzylnaphthyl ether and {alpha}- naphthylmethyl phenyl ether show little difference in conversion and product distribution when the thermolysis atmosphere is changed from inert gas to steam. However when these compounds were reacted in the presence of 5 {angstrom} zeolite, the yields of the thermolysis products improved. Zeolite proved effective in suppressing isomerization of the starting materials. These results suggested that zeolites might be beneficial in steam pretreatment of coal and in coal liquefaction. Pretreatment and liquefaction of mixtures of coal and zeolites increases yields of asphaltenes and preasphaltenes.

  4. 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.

  5. 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.

  6. Coal anion structure and chemistry of coal alkylation. Final report, March 1, 1979-February 29, 1980

    Energy Technology Data Exchange (ETDEWEB)

    Stock, L.M.

    1980-01-01

    In accord with Task 1, some ether cleavage reactions were carried out in two different media - potassium/naphthalene/tetrahydrofuran and potassium/ ammonia - so that the merits and demerits of the two methods could be compared. Preliminary results suggest that both systems yield the same products, and that the ammonia medium is more convenient to work with, because of the absence of by-products such as reduced naphthalenes and tetralin. Dialkyl ethers were found to be least reactive compounds while the benzyl and phenyl ethers were found to be most reactive, as would be expected. The reductive alkylation of coal was carried out in ammonia at 25/sup 0/C. The tetrahydrofuran solubility of the reaction product was surprisingly low. We have obtained additional /sup 13/C)/sup 1/H) nmr data for tetrahydrofuran-soluble butylated coal and some model compounds; obtained additional Styragel(R) chromatography data of tetrahydrofuran-soluble coal labelled with 98%-enriched butyl-1,1-d/sub 2/ iodide; and obtained /sup 2/D nmr spectra of all the deuterium-labelled, tetrahydrofuran-soluble coal products. In accord with Task 4, we have undertaken a review of the information now available concerning the nature of Illinois No. 6 coal. Also, the effects of organic additives on the exchange reactions between tetralin-d/sub 12/ and diphenyl-methane and on the thermal cleavage reactions of several model compounds in tetralin were investigated to probe the relationship between structure and reactivity. The exchange reaction can be accelerated by coal, asphaltene-preasphaltene fractions derived from coal, compounds with labile bonds, or compounds which can be reduced readily. The pyridine-insoluble coal product, acids, and bases are inactive toward the exchange reaction.

  7. 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.

  8. Large-scale reactive molecular dynamics simulation and kinetic modeling of high-temperature pyrolysis of the Gloeocapsomorphaprisca microfossils.

    Science.gov (United States)

    Zou, Chenyu; Raman, Sumathy; van Duin, Adri C T

    2014-06-12

    The ability to predict accurately the thermal conversion of complex carbonaceous materials is of value in both petroleum exploration and refining operations. Modeling the thermal cracking of kerogen under basinal heating conditions improves the predrill prediction of oil and gas yields and quality, thereby ultimately lowering the exploration risk. Modeling the chemical structure and reactivity of asphaltene from petroleum vacuum residues enables prediction of coke formation and properties in refinery processes, thereby lowering operating cost. The chemical structure-chemical yield modeling (CS-CYM) developed by Freund et al. is more rigorous, time-consuming, and requires a great deal of chemical insight into reaction network and reaction kinetics. The present work explores the applicability of a more fundamental atomistic simulation using the quantum mechanically based reactive force field to predict the product yield and overall kinetics of decomposition of two biopolymers, namely, the Kukersite and Gutternberg. Reactive molecular dynamics (RMD) simulations were performed on systems consisting of 10(4) to 10(5) atoms at different densities and temperatures to derive the overall kinetic parameters and a lumped kinetic model for pyrolysis. The kinetic parameters derived from the simulated pyrolysis of an individual component and the mixture of all four components in Guttenberg reveal the role of cross-talk between the fragments and enhanced reactivity of component A by radicals from other components. The Arrhenius extrapolation of the model yields reasonable prediction for the overall barrier for cracking. Because simulations were run at very high temperature (T > 1500 K) to study cracking within the simulation time of up to 1 ns, it, however, led to the entropically favored ethylene formation as a dominant decomposition route. Future work will focus on evaluating the applicability of accelerated reactive MD approaches to study cracking.

  9. The effect of oil spills on the bacterial diversity and catabolic function in coastal sediments: a case study on the Prestige oil spill.

    Science.gov (United States)

    Acosta-González, Alejandro; Martirani-von Abercron, Sophie-Marie; Rosselló-Móra, Ramon; Wittich, Regina-Michaela; Marqués, Silvia

    2015-10-01

    The accident of the Prestige oil tanker in 2002 contaminated approximately 900 km of the coastline along the northern Spanish shore, as well as parts of Portugal and France coast, with a mixture of heavy crude oil consisting of polycyclic aromatic hydrocarbons, alkanes, asphaltenes and resins. The capacity of the autochthonous bacterial communities to respond to the oil spill was assessed indirectly by determining the hydrocarbon profiles of weathered oil samples collected along the shore, as well as through isotope ratios of seawater-dissolved CO2, and directly by analyses of denaturing gradient gel electrophoresis fingerprints and 16S rRNA gene libraries. Overall, the results evidenced biodegradation of crude oil components mediated by natural bacterial communities, with a bias towards lighter and less substituted compounds. The changes observed in the Proteobacteria, the most abundant phylum in marine sediments, were related to the metabolic profiles of the sediment. The presence of crude oil in the supratidal and intertidal zones increased the abundance of Alpha- and Gammaproteobacteria, dominated by the groups Sphingomonadaceae, Rhodobacteraceae and Chromatiales, whilst Gamma- and Deltaproteobacteria were more relevant in subtidal zones. The phylum Actinobacteria, and particularly the genus Rhodococcus, was a key player in the microbial response to the spill, especially in the degradation of the alkane fraction. The addition of inorganic fertilizers enhanced total biodegradation rates, suggesting that, in these environments, nutrients were insufficient to support significant growth after the huge increase in carbon sources, as evidenced in other spills. The presence of bacterial communities able to respond to a massive oil input in this area was consistent with the important history of pollution of the region by crude oil.

  10. Analysis of organic sulfur and nitrogen in coal via tandem degradation methods. Final technical report, 1 September 1991--31 August 1992

    Energy Technology Data Exchange (ETDEWEB)

    Kruge, M.A.; Palmer, S.R. [Southern Illinois Univ., Carbondale, IL (United States)

    1992-12-31

    With the recent increase in concern for environmental issues and the implication of sulfur and nitrogen in coal combustion products as prime causes of acid rain, it has become clear that there is an urgent need for alternative methods for de g the nature of organic sulfur and nitrogen compounds in coal. The principal impediment to the molecular characterization of organic sulfur and nitrogen forms in coal is the polymeric nature of coal`s molecular structure, ordering coal insoluble and impossible to analyze by the necessary gas chromatographic (GC) methods. In our research, we apply mild chemical degradation techniques in order to render coal soluble in common organic solvents and thus amenable to standard GC characterization. The study also seeks to apply the degradative techniques to coal asphaltenes, since they are believed to be polymeric structures similar to the whole coal, but smaller and more readily analyzed. Of the degradation techniques used to date, oxidation by sodium dichromate provides the best chemical structural information. A variety of major sulfur compounds were detected in the dichromate oxidation products of demineralized IBC101 coal, including thiazoles (compounds which contains both sulfur and nitrogen) and a series of isomers of C{sub 2}-, C{sub 3}and C{sub 4}-alkylthiophene derivatives. Precise agreement between GC-MS and sulfur-selective GC-FPD data was obtained for these compounds, which probably originated as short alkyl chains on exterior portions of the original peat macromolecular structure that were sulfurized shortly after burial by H{sub 2}S. The results were further confirmed by the analysis of a non-Illinois Basin coal with nearly twice the organic sulfur content of IBC101.

  11. Analysis of organic sulfur and nitrogen in coal via tandem degradation methods. Final technical report, 1 September 1991--31 October 1992

    Energy Technology Data Exchange (ETDEWEB)

    Kruge, M.A.; Palmer, S.R. [Southern Illinois Univ., Carbondale, IL (United States)

    1992-12-31

    With the recent increase in concern for environmental issues and the implication of sulfur and nitrogen in coal combustion preducts as prime causes of acid rain, it has become clear that there is an urgent need for alternative methods for determining the nature of organic sulfur and nitrogen compounds in coal. The principal impediment to the molecular characterization of organic sulfur and nitrogen forms in coal is the polymeric nature of coal`s molecular structure, rendering coal insoluble and impossible to analyze by the necessary gas chromatographic (GC) methods. In our research, we apply mild chemical degradation techniques in order to render coal soluble in common organic solvents and thus amenable to standard GC characterization. The study also seeks to apply the degradative techniques to coal asphaltenes, since they are believed to be polymeric structures similar to the whole coal, but smaller and more readily analyzed. Of the degradation techniques used to date, oxidation by sodium dichromate provides the best chemical structure information. A variety of major sulfur compounds were detected in the dichromate oxidation products of demineralized IBC101 coal, including thiazoles (compounds which contains both sulfur and nitrogen) and a series of isomers of C{sub 2}-, C{sub 3}- and C{sub 4}-alkylthiophene derivatives. Precise agreement between GC-MS and sulfur-selective GC-FPD data was obtained for these compounds, which probably originated as short alkyl chains on exterior portions of the original peat macromolecular structure that were sulfurized shortly after burial by H{sub 2}S. The results were further confirmed by the analysis of a non-Illinois Basin coal with nearly twice the organic sulfur content of IBC101.

  12. The dual role of oxygen functions in coal pretreatment and liquefaction: Crosslinking and cleavage reactions. Fifth quarterly report, April 1, 1992--June 30, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Serio, M.A.; Kroo, E.; Teng, H.; Charpenay, S.; Solomon, P.R.

    1992-12-01

    Preparation of ion-exchanged (including barium, calcium and potassium) demineralized Zap and Wyodak has been completed. Both vacuum dried and moist samples were prepared, using procedures described previously. The modified samples were subjected to functional group analysis as KBr pellets with FT-IR, and programmed pyrolysis analysis with TG-FTIR. Liquefaction experiments of these samples were also performed and products were analyzed. The data show that both the pyrolytic tar and liquefaction yields decrease with the extent of ion-exchange, i.e., in the order of (demineralized) > (ion-exchanged at pH 8) > (ion-exchanged at pH 12.5). For the pyrolysis of vacuum dried samples, the tar yield was higher for the potassium-exchanged coals than the calcium and barium-exchanged samples, suggesting that bivalent cations tighten the coal structure by cross-linking coal fragments and make it more difficult for tar molecules to escape. The liquefaction results show that the potassium-exchanged samples have higher liquefaction yields (especially asphaltenes) than for the barium- and calcium-exchanged samples. This can probably be attributed to the same reason for the high pyrolytic tar yield, i.e., that bivalent cations can serve as a cross-linking agents to tighten the coal structure. Remoisturization of vacuum dried Zap and Wyodak was done in the attempt to understand if moisture uptake for low rank coals is a reversible process and to see if moisture influences the role of the cations. Preliminary results show that the moisture content can reach that of the raw samples by remoisturization for Zap, but not for Wyodak. Furthermore, the chemical structure of the coal samples seems to have been changed by remoisturization, since different C0{sub 2} evolution behaviors were observed.

  13. Distinguishing solid bitumens formed by thermochemical sulfate reduction and thermal chemical alteration

    Science.gov (United States)

    Kelemen, S.R.; Walters, C.C.; Kwiatek, P.J.; Afeworki, M.; Sansone, M.; Freund, H.; Pottorf, R.J.; Machel, H.G.; Zhang, T.; Ellis, G.S.; Tang, Y.; Peters, K.E.

    2008-01-01

    Insoluble solid bitumens are organic residues that can form by the thermal chemical alteration (TCA) or thermochemical sulfate reduction (TSR) of migrated petroleum. TCA may actually encompass several low temperature processes, such as biodegradation and asphaltene precipitation, followed by thermal alteration. TSR is an abiotic redox reaction where petroleum is oxidized by sulfate. It is difficult to distinguish solid bitumens associated with TCA of petroleum from those associated with TSR when both processes occur at relatively high temperature. The focus of the present work was to characterize solid bitumen samples associated with TCA or TSR using X-ray photoelectron spectroscopy (XPS). XPS is a surface analysis conducted on either isolated or in situ (>25 ??m diameter) solid bitumen that can provide the relative abundance and chemical speciation of carbon, organic and inorganic heteroatoms (NSO). In this study, naturally occurring solid bitumens from three locations, Nisku Fm. Brazeau River area (TSR-related), LaBarge Field Madison Fm. (TSR-related), and the Alaskan Brooks range (TCA-related), are compared to organic solids generated during laboratory simulation of the TSR and TCA processes. The abundance and chemical nature of organic nitrogen and sulfur in solid bitumens can be understood in terms of the nature of (1) petroleum precursor molecules, (2) the concentration of nitrogen by way of thermal stress and (3) the mode of sulfur incorporation. TCA solid bitumens originate from polar materials that are initially rich in sulfur and nitrogen. Aromaticity and nitrogen increase as thermal stress cleaves aliphatic moieties and condensation reactions take place. Organic sulfur in TCA organic solids remains fairly constant with increasing maturation (3.5 to ???17 sulfur per 100 carbons) into aromatic structures and to the low levels of nitrogen in their hydrocarbon precursors. Hence, XPS results provide organic chemical composition information that helps to

  14. Dependence of liquefaction behavior on coal characteristics. Part VI. Relationship of liquefaction behavior of a set of high sulfur coals to chemical structural characteristics. Final technical report, March 1981 to February 1984

    Energy Technology Data Exchange (ETDEWEB)

    Neill, P. H.; Given, P. H.

    1984-09-01

    The initial aim of this research was to use empirical mathematical relationships to formulate a better understanding of the processes involved in the liquefaction of a set of medium rank high sulfur coals. In all, just over 50 structural parameters and yields of product classes were determined. In order to gain a more complete understanding of the empirical relationships between the various properties, a number of relatively complex statistical procedures and tests were applied to the data, mostly selected from the field of multivariate analysis. These can be broken down into two groups. The first group included grouping techniques such as non-linear mapping, hierarchical and tree clustering, and linear discriminant analyses. These techniques were utilized in determining if more than one statistical population was present in the data set; it was concluded that there was not. The second group of techniques included factor analysis and stepwise multivariate linear regressions. Linear discriminant analyses were able to show that five distinct groups of coals were represented in the data set. However only seven of the properties seemed to follow this trend. The chemical property that appeared to follow the trend most closely was the aromaticity, where a series of five parallel straight lines was observed for a plot of f/sub a/ versus carbon content. The factor patterns for each of the product classes indicated that although each of the individual product classes tended to load on factors defined by specific chemical properties, the yields of the broader product classes, such as total conversion to liquids + gases and conversion to asphaltenes, tended to load largely on factors defined by rank. The variance explained and the communalities tended to be relatively low. Evidently important sources of variance have still to be found.

  15. Methods to reduce production of oil sands mature fine tailings

    Energy Technology Data Exchange (ETDEWEB)

    Ozum, B. [Apex Engineering Inc., Edmonton, AB (Canada); Scott, J.D. [Alberta Univ., Edmonton, AB (Canada)

    2010-07-01

    This paper discussed experimental findings regarding the use of alternative extraction additives in the Clark Hot Water Bitumen Extraction (CHWBE) process to improve the geotechnical characteristics of the tailings and the salinity of the recycled release water. It also discussed results regarding the production of non-segregating tailings (NST) from the blend of cyclone underflow and thickener underflow using either calcium oxide (CaO) or CaO and carbon dioxide (CO{sub 2}) as additives. Sodium hydroxide (NaOH) is currently used in CHWBE to increase extraction efficiency, but this additive also creates tailings with poor settling and consolidation properties and high salinity in the recycled release water. The use of CaO for adjusting pH, ozone (O{sub 3}) for producing surfactants from bitumen asphaltenes, and biodiesel as surfactant additives were found to increase the efficiency of the extraction process, produce tailings with friendlier geotechnical properties, and eliminate saline concentrations in the recycled release water. The use of the described alternative extraction additives and the NST production processes has the potential to reduce the environmental impacts of oil sands plants, potentially providing a solution to the problems associated with Low Temperature Extraction and Consolidated Tailings processes. The solubility of CaO and O{sub 3} as a function of temperature could potentially allow the extraction temperature to be reduced. O{sub 3} was found to work better as an oxidant to produce surfactants from bitumen when the ore-slurry is first treated with CaO. Study on a larger scale is required. 23 refs., 7 tabs., 7 figs.

  16. 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.

  17. Synthesis of catalysts supported in {gamma}-alumina; Sintese de catalisadores suportados na {gamma}-alumina

    Energy Technology Data Exchange (ETDEWEB)

    Pereira, Luiza Gabriel; Silva, A.J.N.; Santos, I.M.G.; Souza, A.G. [Paraiba Univ, Joao Pessoa, PB (Brazil). Dept. de Quimica. Lab. de Termoquimica e Materiais]. E-mail: luizagaby@yahoo.com.br; Fernandes Junior, V.J.; Araujo, A.S. [Rio Grande do Norte Univ., Natal, RN (Brazil). Dept. de Quimica. Lab. de Combustiveis

    2003-07-01

    Fuels contain a great amount of undesirable pollutants as asphaltenes, metals, sulfides and nitrogen compounds. The content of sulfur in petroleum is around 1%,. When burned, fuels liberate SO{sub x}, the greatest air pollutant . The maximum sulfur quantity in diesel is {approx}350 wppm, but in agreement to European specifications, this content will fall to 50 wppm up to 2005. To remove this sulfur a deep hydrodesulfurization is necessary, requiring high performance catalysts. This way, in this work, the following catalysts were synthesized, using Pechini method: MoO{sub 3} containing Ni and/or Co supported on {gamma}-alumina, with the formulas Co{sub x}Mo{sub 1-x}O{sub 3}/Al{sub 2}O{sub 3}, Ni{sub x}Mo{sub 1-x}O{sub 3}/Al{sub 2}O{sub 3} and Ni{sub x/2}Co{sub x/2}Mo{sub 1-x}O{sub 3}/Al{sub 2}O{sub 3} where x 0,01, 0,02 and 0,03 in mol percentage. This method was proposed, due to its high stoichiometry control, purity, reproducibility and homogeneity. All catalysts were submitted to thermal treatment at 500 deg C to 700 deg C and characterized by thermogravimetry, infrared spectroscopy, X-ray diffraction. Results indicate the stabilization of the requested composition at around 622 deg C. The X-ray diffraction results indicate that secondary phase increases with dopant amount. (author)

  18. 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.

  19. Simultaneous cleanup of soil polluted with crude oil and heavy metals

    Energy Technology Data Exchange (ETDEWEB)

    Groudeva, V.; Doycheva, A. [Sofia Univ., Faculty of Biology (Bulgaria); Groudev, S. [University of Mining and Geology, Dept. of Engineering Geoecology, Sofia (Bulgaria)

    2005-07-01

    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{sup 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.

  20. Molecular indicators for palaeoenvironmental change in a Messinian evaporitic sequence (Vena del Gesso, Italy). II: High-resolution variations in abundances and 13C contents of free and sulphur-bound carbon skeletons in a single marl bed

    Science.gov (United States)

    Kenig, F.; Damste, J. S.; Frewin, N. L.; Hayes, J. M.; De Leeuw, J. W.

    1995-01-01

    The extractable organic matter of 10 immature samples from a marl bed of one evaporitic cycle of the Vena del Gesso sediments (Gessoso-solfifera Fm., Messinian, Italy) was analyzed quantitatively for free hydrocarbons and organic sulphur compounds. Nickel boride was used as a desulphurizing agent to recover sulphur-bound lipids from the polar and asphaltene fractions. Carbon isotopic compositions (delta vs PDB) of free hydrocarbons and of S-bound hydrocarbons were also measured. Relationships between these carbon skeletons, precursor biolipids, and the organisms producing them could then be examined. Concentrations of S-bound lipids and free hydrocarbons and their delta values were plotted vs depth in the marl bed and the profiles were interpreted in terms of variations in source organisms, 13 C contents of the carbon source, and environmentally induced changes in isotopic fractionation. The overall range of delta values measured was 24.7%, from -11.6% for a component derived from green sulphur bacteria (Chlorobiaceae) to -36.3% for a lipid derived from purple sulphur bacteria (Chromatiaceae). Deconvolution of mixtures of components deriving from multiple sources (green and purple sulphur bacteria, coccolithophorids, microalgae and higher plants) was sometimes possible because both quantitative and isotopic data were available and because either the free or S-bound pool sometimes appeared to contain material from a single source. Several free n-alkanes and S-bound lipids appeared to be specific products of upper-water-column primary producers (i.e. algae and cyanobacteria). Others derived from anaerobic photoautotrophs and from heterotrophic protozoa (ciliates), which apparently fed partly on Chlorobiaceae. Four groups of n-alkanes produced by algae or cyanobacteria were also recognized based on systematic variations of abundance and isotopic composition with depth. For hydrocarbons probably derived from microalgae, isotopic variations are well correlated with

  1. Evidence and characteristics of hydrolytic disproportionation of organic matter during metasomatic processes

    Science.gov (United States)

    Price, Leigh C.; DeWitt, Ed

    2001-11-01

    Petroleum-geochemical analyses of carbonaceous regionally metamorphosed rocks, carbonaceous rocks from ore deposits, and alkalic plutonic rocks from diverse settings, demonstrated the presence of very low to moderately low concentrations of solvent-extractable organic matter, this observation in spite of the fact that some of these rocks were exposed to extremely high metamorphic temperatures. Biomarker and δ13C analyses established that the extractable organic matter originated as sedimentary-derived hydrocarbons. However, the chemistry of the extractable bitumen has been fundamentally transformed from that found in sediment bitumen and oils. Asphaltenes and resins, as defined in the normal petroleum-geochemical sense, are completely missing. The principal aromatic hydrocarbons present in oils and sediment bitumens (especially the methylated naphthalenes) are either in highly reduced concentrations or are missing altogether. Instead, aromatic hydrocarbons typical of sediment bitumens and oils are very minor, and a number of unidentified compounds and oxygen-bearing compounds are dominant. Relatively high concentrations of alkylated benzenes are typical. The polar ;resin; fraction, eluted during column chromatography, is the principal compound group, by weight, being composed of six to eight dominant peaks present in all samples, despite the great geologic diversity of the samples. These, and other, observations suggest that a strong drive towards equilibrium exists in the ;bitumen.; Gas chromatograms of the saturated hydrocarbons commonly have a pronounced hump in both the n-paraffins and naphthenes, centered near the C19 to C26 carbon numbers, and a ubiquitous minimum in the n-paraffin distribution near n-C12 to n-C14. Multiple considerations dictate that the bitumen in the samples is indigenous and did not originate from either surficial field contamination or from laboratory procedures. Our observations are consistent with the hydrolytic disproportionation of

  2. 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

  3. 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

  4. Wax deposition in crude oil pipelines

    Energy Technology Data Exchange (ETDEWEB)

    Assuncao, Pablo Morelato; Rodrigues, Lorennzo Marrochi Nolding [Universidade Federal do Espirito Santo, Sao Mateus, ES (Brazil). Centro Universitario Norte do Espirito Santo. Engenharia de Petroleo; Romero, Mao Ilich [University of Wyoming, Laramie, WY (United States). Enhanced Oil Recovery Institute], e-mail: mromerov@uwyo.edu

    2010-07-01

    Crude oil is a complex mixture of hydrocarbons which consists of aromatics, paraffins, naphthenics, resins asphaltenes, etc. When the temperature of crude oil is reduced, the heavy components, like paraffin, will precipitate and deposit on the pipe internal wall in the form of a wax-oil gel. The gel deposit consists of wax crystals that trap some amount of oil. As the temperature gets cooler, more wax will precipitate and the thickness of the wax gel will increase, causing gradual solidification of the crude and eventually the oil stop moving inside the offshore pipeline. Crude oil may not be able to be re-mobilized during re-startup. The effective diameter will be reduced with wax deposition, resulting in several problems, for example, higher pressure drop which means additional pumping energy costs, poor oil quality, use of chemical components like precipitation inhibitors or flowing facilitators, equipment failure, risk of leakage, clogging of the ducts and process equipment. Wax deposition problems can become so sever that the whole pipeline can be completely blocked. It would cost millions of dollars to remediate an offshore pipeline that is blocked by wax. Wax solubility decreases drastically with decreasing temperature. At low temperatures, as encountered in deep water production, is easy to wax precipitate. The highest temperature below which the paraffins begins to precipitate as wax crystals is defined as wax appearance temperature (WAT). Deposition process is a complex free surface problem involving thermodynamics, fluid dynamics, mass and heat transfer. In this work, a numerical analysis of wax deposition by molecular diffusion and shear dispersion mechanisms in crude oil pipeline is studied. Diffusion flux of wax toward the wall is estimated by Fick's law of diffusion, in similar way the shear dispersion; wax concentration gradient at the solid-liquid interface is obtained by the volume fraction conservation equation; and since the wax deposition

  5. 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

  6. 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

  7. Fate and Transport of Organic Contaminants in Coastal Marsh Sediments Resulting from the 2010 Gulf Oil Spill

    Science.gov (United States)

    Natter, M.; Keevan, J.; Lee, M.; Keimowitz, A.; Savrda, C.; Son, A.; Okeke, B.; Wang, Y.

    2011-12-01

    The devastating explosion and subsequent sinking of the oil platform Deepwater Horizon at the British Petroleum Macondo-1 well in the Northern Gulf of Mexico on April 20, 2010, released approximately 4.9 million barrels of crude oil into the Gulf before the well was capped on July 15, 2010. Although most light compounds of oil may be easily degraded by natural microbes on the short term, saturated heavy oil (e.g., asphaltenes, resins, polycyclic aromatics, etc.) and those adsorbed by sediments could persist in the environment for decades. The long-term effects of high levels of persistent oil compounds on biogeochemical evolution and ecosystems of salt marshes remain unclear. This research investigates the spatial range and changes in levels of oil and their biogeochemical impacts. A total of ten marsh sampling sites that varied from pristine, non-effected marshes (e.g., Weeks Bay and Wolf Bay, Alabama) to heavily oiled wetlands (e.g., Bay Jimmy and Bayou Dulac, Louisiana) were utilized for this study. Sediment cores, bulk sediments, surface water samples, degraded oil, oiled dead marsh grass, and live marsh grass were collected from these sites in an attempt to study the source, distribution, and evolution of organic compounds and oil present in sediments and pore-waters. Geochemical analyses show alarmingly high organic carbon loads in pore-waters and sediments at heavily contaminated sites months after the influx of oil ceased. Very high levels (10-28%) of total organic carbon (TOC) within the heavily oiled sediments (down to 30 cm) are clearly distinguished from those found in pristine wetland sediments (generally marsh sediments due to their higher density with respect to freshwater. TOC and DOC data clearly indicate that not all the spilled oil rose to the water surface and washed on-shore. Plumes of partially degraded oil could be spreading at various levels of the water column and feeding the underlying sediments. Geochemical biomarkers and stable isotopes

  8. 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

  9. 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

  10. Geochemical Features of Shale Hydrocarbons of the Central Part of Volga-Ural Oil and Gas Province

    Science.gov (United States)

    Nosova, Fidania F.; Pronin, Nikita V.; Plotnikova, Irina N.; Nosova, Julia G.

    2014-05-01

    This report contains the results of the studies of shale hydrocarbons from carbonate-siliceous rocks on the territory of South-Tatar arch of Volga-Ural oil and gas province of the East European Platform. The assessment of the prospects of shale hydrocarbon in Tatarstan primarily involves finding of low permeable, poor-porous shale strata that would be rich in organic matter. Basing on the analysis of the geological structure of the sedimentary cover, we can distinguish three main objects that can be considered as promising targets for the study from the point of the possible presence of shale hydrocarbons: sedimentary deposits Riphean- Vendian; Domanicoid high-carbon rocks of Devonian time; sedimentary strata in central and side areas of Kama-Kinel deflection system. The main object of this study is Domanicoid high-carbon rocks of Devonian time. They are mainly represented by dark gray, almost black bituminous limestones that are interbedded with calcareous siliceous shales and cherts. Complex studies include the following: extraction of bitumen from the rock, determination of organic carbon content, determination of the group and elemental composition of the bitumen, gas chromatographic studies of the alkanoic lube fractions of bitumoid and oil, gas chromato-mass spectrometry of the naphthenic lube fractions of bitumoid and oil, pyrolysis studies of the rock using the Rock -Eval method (before and after extraction), study of trace-element composition of the rocks and petrologen, comparison in terms of adsorbed gas and studying of the composition of adsorbed gases. Group and elemental analyses showed that hydrocarbons scattered in the samples contain mainly resinous- and asphaltene components, the share lube fraction is smaller. The terms sediment genesis changed from weakly to strongly reducing. According to the results of gas chromatography, no biodegradation processes were observed. According to biomarker indicators in the samples studied there is some certain

  11. 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)

  12. 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)

  13. 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

  14. 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.

  15. Changes of Properties of Bitumen Binders by Additives Application

    Science.gov (United States)

    Remišová, Eva; Holý, Michal

    2017-10-01

    Requirements for properties of bituminous binders are determined in the European standards. The physico-chemical behaviour of bitumen depends on its colloidal structure (asphaltenes dispersed into an oily matrix constituted by saturates, aromatics and resins) that depends primarily on its crude source and processing. Bitumen properties are evaluated by group composition, elementary analysis, but more often conventional or functional tests. Bitumen for road uses is assessed according to the physical characteristics. For the purpose of improving the qualitative properties of bitumen and asphalts the additives are applied e.g. to increase elasticity, improving the heat stability, improving adhesion to aggregate, to decrease viscosity, increasing the resistance to aging, to prevent binder drainage from the aggregate surface, etc. The objective of presented paper is to assess and compare effect of additives on properties of bitumen binders. In paper, the results of bitumen properties, penetration, softening point, and dynamic viscosity of two paving grade bitumen 35/50, 50/70 and polymer modified bitumen PmB 45/80-75 are analyzed and also the changes of these properties by the application of selected additives (Sasobit, Licomont BS100, Wetfix BE and CWM) to improve adhesion to aggregate and improve workability. Measurements of properties have been performed according to the relevant European standards. The laboratory tests showed significantly increasing the softening point of paving grade bitumen 50/70 and 35/50 by 13 to 45°C. The effect of various additives on bitumen softening point is different. Penetration varies according to type of bitumen and type of used additive. The penetration values of modified bitumen PmB 45/80-75 with additives Sasobit and Licomont BS100 show increase of bitumen stiffness of 16 0.1mm and a shift in the gradation. The changes in penetration and in softening point significantly shown when calculating on Penetration index as a parameter of

  16. 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

  17. Caracterisation et transformation par hydroviscoreduction du brut lourd de Doba/Tchad: Strategie de pompage par pipeline

    Science.gov (United States)

    Dehkissia, Soumaine

    Le projet de la these est defini par rapport a la recente exploitation commerciale du brut lourd de Doba, une region du Tchad, pays enclave d'ou le brut ainsi produit doit etre achemine par pipeline. Le but dans ce travail est de caracteriser ce brut et de determiner une strategie thermique de transformation en vue de reduire de la facon la plus economique, la viscosite du brut pour permettre son transport par pipeline. Concernant la partie caracterisation, nous avons utilise entre autres, un rheometre rotatif et des analyseurs (LECO CHN-2000 & LECO S-144DR Elemental Analyzers) pour evaluer respectivement la viscosite et les elements tels que C, H, N, O, S. Sur la base des methodes de transformation disponibles, nous avons determine une strategie simple de transformation thermique par hydroviscoreduction , strategie dans laquelle, la fraction legere du brut comme le naphta (80--180°C), pourrait constituer la source d'hydrogene a utiliser. Le brut de Doba, a une faible teneur en soufre (0.14%) et sa densite specifique de 0.940 a 15.6°C, soit 18.8° API, le classe parmi les bruts lourds. Outre le point initial se situant a 85°C, la distillation du brut a revele que la fraction distillant avant 250°C ne represente que 10% (v/v) et que le craquage thermique du substrat debute a 300°C. Par ailleurs, outre son caractere Newtonien, les densites specifiques de la fraction lourde de l'essence (100--200°C) et de la fraction distillant au-dessus 350°C, etant respectivement de 0.813 (0.813 > 0.800) et de 0.951 (0.930 vieillissement meme apres deux mois, ce qui correspond au temps de sejour du brut dans le pipeline. L'etude montre aussi que les asphaltenes du brut traite en absence d'un catalyseur sont moins aromatiques que ceux du brut non-traite.

  18. 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

  19. MTS-MD of Biomolecules Steered with 3D-RISM-KH Mean Solvation Forces Accelerated with Generalized Solvation Force Extrapolation.

    Science.gov (United States)

    Omelyan, Igor; Kovalenko, Andriy

    2015-04-14

    We developed a generalized solvation force extrapolation (GSFE) approach to speed up multiple time step molecular dynamics (MTS-MD) of biomolecules steered with mean solvation forces obtained from the 3D-RISM-KH molecular theory of solvation (three-dimensional reference interaction site model with the Kovalenko-Hirata closure). GSFE is based on a set of techniques including the non-Eckart-like transformation of coordinate space separately for each solute atom, extension of the force-coordinate pair basis set followed by selection of the best subset, balancing the normal equations by modified least-squares minimization of deviations, and incremental increase of outer time step in motion integration. Mean solvation forces acting on the biomolecule atoms in conformations at successive inner time steps are extrapolated using a relatively small number of best (closest) solute atomic coordinates and corresponding mean solvation forces obtained at previous outer time steps by converging the 3D-RISM-KH integral equations. The MTS-MD evolution steered with GSFE of 3D-RISM-KH mean solvation forces is efficiently stabilized with our optimized isokinetic Nosé-Hoover chain (OIN) thermostat. We validated the hybrid MTS-MD/OIN/GSFE/3D-RISM-KH integrator on solvated organic and biomolecules of different stiffness and complexity: asphaltene dimer in toluene solvent, hydrated alanine dipeptide, miniprotein 1L2Y, and protein G. The GSFE accuracy and the OIN efficiency allowed us to enlarge outer time steps up to huge values of 1-4 ps while accurately reproducing conformational properties. Quasidynamics steered with 3D-RISM-KH mean solvation forces achieves time scale compression of conformational changes coupled with solvent exchange, resulting in further significant acceleration of protein conformational sampling with respect to real time dynamics. Overall, this provided a 50- to 1000-fold effective speedup of conformational sampling for these systems, compared to conventional MD

  20. 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.

  1. Evidence and characteristics of hydrolytic disproportionation of organic matter during metasomatic processes

    Science.gov (United States)

    Price, L.C.; Dewitt, E.

    2001-01-01

    Petroleum-geochemical analyses of carbonaceous regionally metamorphosed rocks, carbonaceous rocks from ore deposits, and alkalic plutonic rocks from diverse settings, demonstrated the presence of very low to moderately low concentrations of solvent-extractable organic matter, this observation in spite of the fact that some of these rocks were exposed to extremely high metamorphic temperatures. Biomarker and ??13C analyses established that the extractable organic matter originated as sedimentary-derived hydrocarbons. However, the chemistry of the extractable bitumen has been fundamentally transformed from that found in sediment bitumen and oils. Asphaltenes and resins, as defined in the normal petroleum-geochemical sense, are completely missing. The principal aromatic hydrocarbons present in oils and sediment bitumens (especially the methylated naphthalenes) are either in highly reduced concentrations or are missing altogether, Instead, aromatic hydrocarbons typical of sediment bitumens and oils are very minor, and a number of unidentified compounds and oxygen-bearing compounds are dominant. Relatively high concentrations of alkylated benzenes are typical. The polar "resin" fraction, eluted during column chromatography, is the principal compound group, by weight, being composed of six to eight dominant peaks present in all samples, despite the great geologic diversity of the samples. These, and other, observations suggest that a strong drive towards equilibrium exists in the "bitumen." Gas chromatograms of the saturated hydrocarbons commonly have a pronounced hump in both the n-paraffins and naphthenes, centered near the C19 to C26 carbon numbers, and a ubiquitos minimum in the n-paraffin distribution near n-C12 to n-C14. Multiple considerations dictate that the bitumen in the samples is indigenous and did not originate from either surficial field contamination or from laboratory procedures. Our observations are consistent with the hydrolytic disproportion of

  2. 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

  3. 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, components for a full comprehensive model are still missing. Prior to this work, research efforts were focused on flowing hydrate particles with relatively little research on hydrate accumulation, leaving hydrate deposition in multiphase flow an unexplored subject. The focus of this thesis was to better understand hydrate deposition as a form of accumu- lation in pipelines. To incorporate the multiphase flow effect, hydrate formation experiments were carried out at varying water cut (WC) from 15 to 100 vol.%, liquid loading (LL) from 50 to 85 vol.%, mixture velocity (vmix) from 0.75 to 3 m/s, for three fluids systems (100 % WC, water in Conroe crude oil emulsions and King Ranch condensate + water) on the ExxonMobil flowloop (4 in. nominal size and 314 ft. long) at Friendswood, TX. For the 100 % WC flowloop tests, hydrate particle distribution transitions beyond a critical hydrate volume concentration, observed values were between 8.2 to 29.4 vol.%, causing a sudden increase in pressure drop (DP). A revised correlation of the transition as a function of Reynolds number and liquid loading was developed. For Conroe emulsions, DP starts increasing at higher hydrate concentrations than King Ranch condensate, many times at 10 vol.%. Experiments with King Ranch show higher relative DP (10 to 25) than Conroe (2 to 10) performed at the same vmix and LL. Cohesive force measurements between cyclopentane hydrate particles were reduced from a value of 3.32 mN/m to 1.26 mN/m when 6 wt.% Conroe was used and to 0.41 mN/m when 5 wt.% Caratinga crude oil was used; similar values were obtained when extracted asphaltenes were used. King Ranch condensate (11 wt.%) did not significantly change the

  4. Organic geochemistry and petrology of subsurface Paleocene-Eocene Wilcox and Claiborne Group coal beds, Zavala County, Maverick Basin, Texas, USA

    Science.gov (United States)

    Hackley, Paul C.; Warwick, Peter D.; Hook, Robert W.; Alimi, Hossein; Mastalerz, Maria; Swanson, Sharon M.

    2012-01-01

    degradation at the beginning and end of Indio mire development. Fluorescence spectra of sporinite and resinite are consistent and distinctly different from each other, attributed to the presence of a greater proportion of complex asphaltene and polar molecules in resinite. Gas chromatography of resinite-rich coal shows sesquiterpenoid and diterpenoid peaks in the C14–17 range, which are not present in resinite-poor coal. Quantities of extracts suggest bitumen concentration below the threshold for effective source rocks [30–50 mg hydrocarbon/g total organic carbon (HC/g TOC)]. Saturate/aromatic and pristane/phytane (Pr/Ph) ratios are different from values for nearby Tertiary-reservoired crude oil, suggesting that the Indio coals are too immature to source liquid hydrocarbons in the area. However, moderately high HI values (200–400 mg HC/g rock) may suggest some potential for naphthenic–paraffinic oil generation where buried more deeply down stratigraphic/structural dip. Extractable phenols and C20+ alkanes are suggested as possible intermediates for acetate fermentation in microbial methanogenesis which may, however, be limited by poor nutrient supply related to low rainfall and meteoric recharge rate or high local sulfate concentration.

  5. Comportement en vapocraquage de molécules modèles et de distillats sous vide hydrotraités. Première partie : potentialité de craquage, réacteur à profil de température rectangulaire et à court temps de séjour Steam-Cracking Behavior of Model Molecules and Hydrotreated Vacuum Distillates

    Directory of Open Access Journals (Sweden)

    Berthelin M.

    2006-11-01

    to determine a scale of cracking potential, so that the performances of a pretreatment catalyst could be oriented, i. e. optimization of hydrogen consumption and better upgrading of heavy feedstocks during steam cracking. Thanks to the rectangular temperature profile of the micropilot plant, very great improvements in ethylene production and very low asphaltene production were revealed by the pyrolysis of hydrotreated vacuum distillates. The primordial importance of temperature in the temperature/residence-time pair was confirmed.

  6. Solubility of crude oil in methane as a function of pressure and temperature

    Science.gov (United States)

    Price, L.C.; Wenger, L.M.; Ging, T.; Blount, C.W.

    1983-01-01

    solubility, as does the presence of fine grained rocks. The n-paraffin distributions (as well as the overall composition) of the solute condensates are controlled by the temperature and pressure of solution and exsolution, as well as by the composition of the original starting material. It appears quite possible that primary migration by gaseous solution could 'strip' a source rock of crude-oil like components leaving behind a bitumen totally unlike the migrated crude oil. The data of this study demonstrate previous criticisms of primary petroleum migration by gas solution are invalid; that primary migration by gaseous solution cannot occur because methane cannot dissolve sufficient volumes of crude oil or cannot dissolve the highest molecular weight components of petroleum (tars and asphaltenes). ?? 1983.

  7. Joint Industry-Funded R and D Projects in Exploration and Production

    Energy Technology Data Exchange (ETDEWEB)

    Guerillot, D.; Eschard, R.; Malla, M.; Van Buchem, F.; Baghbani, D.; Granjeon, D.; Wolf, S.; Callot, J.P.; Jardin, A.; Kirkwood, D.; Rodriguez, S.; Abadi, A.; Roure, F.; Ghandriche, F.; Prinzhofer, A.; Moretti, I.; Le Melinaire, P.; Vizika, O.; Bekri, S.; Zinszner, B.; Lucet, N.; Rasologosaon, P.; Duquet, B.; Tonellot, T.; Nivlet, P.; Le Ravalec, M.; Bennis, C.; Barroux, C.; Hu, L.Y.; Doligez, B.; Vidal-Gilbert, S.; Zabalza-Mezghani, I.; Caillabet, Y.; Sarda, S.; Ricois, O.; Mouchel, R.; Behar, E.; Nabzar, L.; Zaitoun, A.; Audibert-Hayet, A.; Sauvant, V.; Chauchot, P.; Ropital, F.; Sinquin, A.; Decarre, S.; Larsen, R.; Biolley, F.; Brucy, F.; Charron, Y.; Averbuch, D.; Perrin, G.; Falcimaigne, J.; Roux, P.; Paen, D.; Broutin, P.; Renard, G.; Egermann, P.; Lombard, J.M.; Le Thiez, P.; Fries, G.

    2005-07-01

    and Monitoring: Hybrid LGR: Hybrid Local Grid Refinement, Mick: Lumping and De-lumping Algorithms in Reservoir Simulation, Condor: History Matching Using a Gradual Deformation Method, Calfrac: Calibration of Faulted and Fractured Reservoir Models, Pab 4D: Stratigraphic Architecture of Turbiditic Fans in the PAB Sandstone Outcrop, 4Demon: 4D Deformation Monitoring, Monitor II: Use of Time Lapse Seismic to Update, Constrain and Improve Reservoir Simulation Model, Cougar II: Quantification of Uncertainties in Reservoir Simulation; - Session 4, Reservoir Characterization, Simulation and Monitoring: Industrial JIP: Fraca ++ with Beicip-Franlab: The Next Generation Tools for Fracture Modeling and Characterization, Industrial JIP: First with Beicip-Franlab: A New Generation of Reservoir Simulation Platform; - Session 5, Oil and Gas Production: Padoc: Precipitation of Asphaltenes in Deep Offshore Conditions, Prowide: Optimization of Water Reinjection Scheme, Stargel: Size-Controlled Micro-gels for Water Shut-off, SandCoat: Sand Consolidation by Polymer/Gel Treatment, Waoe: Well Abandonment, Tideep with Ifremer: Thermal Insulation of Deep Sea Flow-lines, Hypip: Hydrogen Permeation in Pipe-in-Pipe, Hydis: Hydrate Plug Dissociation, Thyssi with Sintef: Transportation of Hydrates in Slurry, Hilm: Comprehension, Prediction and Modeling of Heave Induced Lateral Motions of Steel Catenary Risers; - Session 6, Oil and Gas Production: Cold Start: Crude Oil Flow Restartability at Low Temperatures, Icare: Internal Coating for Pressure Loss Reduction, Famus with DNV: Flow Assurance by Management of Uncertainties and Simulation, Charpy X100: Fracture Assessment of X100 Steel for Gas Pipelines, Pearl with DB Guinard Pumps: Production of Energy and Additional Recovery of Liquid, Industrial JIP: Platina with RSI: The Solution for Engineering and Process Analysis from Near Well Bore to Export; - Session 7, Environmental Protection: Acacia: Acid Alteration of Cement and Interface, Castor with

  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 planted by 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 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 ~16

  9. Effects of silica-based nanostructures with raspberry-like morphology and surfactant on the interfacial behavior of light, medium, and heavy crude oils at oil-aqueous interfaces

    Science.gov (United States)

    Bai, Lingyun; Li, Chunyan; Korte, Caroline; Huibers, Britta M. J.; Pales, Ashley R.; Liang, Wei-zhen; Ladner, David; Daigle, Hugh; Darnault, Christophe J. G.

    2017-11-01

    were ranked as follows: (1) Prudhoe Bay > (2) Lloydminster > and (3) West Texas Intermediate. The level of asphaltenes and resins in these crude oil samples reflected these rankings. A decrease in the IFT also indicated the potential of the SiO2 NPs to decrease capillary pressure and induce the movement and recovery of oil in original water-wet reservoirs. Conversely, an increase in IFT indicated the potential of SiO2 NPs to increase capillary pressure and oil recovery in reservoirs subject to wettability reversal under water-wet conditions. Raspberry-like morphology particles were discovered in 5 wt% brine-surfactant-SiO2 nanofluid-oil systems. The development of raspberry-like particles material with high surface area, high salt stability, and high capability of interfaces alteration and therefore wettability changes offers a wide range of applications in the fields of applied nanoscience, environmental engineering, and petroleum engineering.

  10. Evaluating Re-Os systematics in organic-rich sedimentary rocks in response to petroleum generation using hydrous pyrolysis experiments

    Science.gov (United States)

    Rooney, A.D.; Selby, D.; Lewan, M.D.; Lillis, P.G.; Houzay, J.-P.

    2012-01-01

    Successful application of the 187Re–187Os geochronometer has enabled the determination of accurate and precise depositional ages for organic-rich sedimentary rocks (ORS) as well as establishing timing constraints of petroleum generation. However, we do not fully understand the systematics and transfer behaviour of Re and Os between ORS and petroleum products (e.g., bitumen and oil). To more fully understand the behaviour of Re–Os systematics in both source rocks and petroleum products we apply hydrous pyrolysis to two immature hydrocarbon source rocks: the Permian Phosphoria Formation (TOC = 17.4%; Type II-S kerogen) and the Jurassic Staffin Formation (TOC = 2.5%; Type III kerogen). The laboratory-based hydrous pyrolysis experiments were carried out for 72 h at 250, 300, 325 and 350 °C. These experiments provided us with whole rock, extracted rock and bitumen and in some cases expelled oil and asphaltene for evaluation of Re–Os isotopic and elemental abundance. The data from these experiments demonstrate that the majority (>95%) of Re and Os are housed within extracted rock and that thermal maturation does not result in significant transfer of Re or Os from the extracted rock into organic phases. Based on existing thermodynamic data our findings suggest that organic chelating sites have a greater affinity for the quadravalent states of Re and Os than sulphides. Across the temperature range of the hydrous pyrolysis experiments both whole rock and extracted rock 187Re/188Os ratios show small variations (3.3% and 4.7%, for Staffin, respectively and 6.3% and 4.9% for Phosphoria, respectively). Similarly, the 187Os/188Os ratios show only minor variations for the Staffin and Phosphoria whole rock and extracted rock samples (0.6% and 1.4% and 1.3% and 2.2%). These isotopic data strongly suggest that crude oil generation through hydrous pyrolysis experiments does not disturb the Re–Os systematics in ORS as supported by various studies on natural systems. The

  11. Hydroprocessing Catalysts. Utilization and Regeneration Schemes Catalyseurs d'hydrotraitement. Schémas d'utilisation et de régénération

    Directory of Open Access Journals (Sweden)

    Furimsky E.

    2006-11-01

    Full Text Available The catalyst reactor inventory represents an important part of the cost of hydroprocessing operation. The selection of a suitable catalyst and reactor is influenced by feedstock properties. Processes ensuring an uninterrupted operation during catalyst addition and withdrawal are preferred for processing high asphaltene and metal content feedstocks. The spent catalyst can be regenerated and returned to the operation if the extent of its deactivation is not high. The regeneration may be performed either in-situ or off-site. The former is suitable for fixed bed reactors whereas the catalyst from ebullated bed reactors must be regenerated off -site. The regeneration of spent catalysts heavily loaded with metals such as V, Ni and Fe may not be economic. Such catalysts may be suitable for metal reclamation. An environmentally safe method for catalyst disposal must be found if neither regeneration nor metal reclamation from spent catalysts can be performed. La quantité de catalyseurs utilisée représente une part importante du coût d'une opération d'hydrotraitement. Le choix d'un réacteur et d'un catalyseur approprié dépend des propriétés de la charge. On préfère utiliser les procédés permettant un fonctionnement continu pendant le chargement et le soutirage du catalyseur lorsqu'il s'agit de traiter des charges à haute teneur en asphaltène et en métaux. Le catalyseur usé peut être régénéré et remis en fonctionnement s'il n'est pas trop désactivé. La régénération peut être réalisée in situ ou hors du site. La première solution convient pour les réacteurs à lit fixe, tandis que le catalyseur de réacteurs à lit bouillonnant doit être régénéré hors du site. La régénération de catalyseurs usés fortement chargés en métaux tels que le vanadium, le nickel et le fer n'apparaît pas économique. De tels catalyseurs peuvent convenir pour la récupération des métaux. On doit trouver une méthode sans danger pour l

  12. Analyse géochimique de la matiére organique extraite des roches sédimentaires. IV. Extraction des roches en faible quantités Geochemical Analysis of Organic Matter Extracted from Sedimentary Rocks Iv. Exraction from Small Amounts of Rock

    Directory of Open Access Journals (Sweden)

    Monin J. C.

    2006-11-01

    extraction medium. The nature of the solvent is not critical provided that a very poor solvent for hydrocabbues is not chosen. Extractability actually depends more on the desorbing power vis-à-vis the rock thon the solving power. For resins and asphaltenes, interpreting the results is a delicote job because there is no clearcut boundary between simply dissolved products, solvolysis products and neoformation products produced by solvent/organic motter/mineral motter interaction. Hence there is no ultimately recommendable extraction procedure. Everything depends on the analytical requirements as well as on laboratory practices. The procedure retained et Institut Français du Pétrole (IFP is a beaker extraction process with magnetic stirring for 20 min in chloroform at 50 'C (approximately. The procedure for evaporation of the solvent and recovery of the extract is also described and should be studied carefully on account of the small amounts.

  13. Fluid Sampling under Adverse Conditions Echantillonnage des fluides en conditions difficiles

    Directory of Open Access Journals (Sweden)

    Williams J. M.

    2006-12-01

    Full Text Available Valid samples are essential to the proper description of reservoir fluids; if the samples are not representative, all measurements on them will be invalid. This paper discusses the principal challenges facing fluid sampling including gas condensate reservoirs, compositional gradients, water content of hydrocarbon fluids, asphaltene deposition, wax formation, oil base mud contamination, and reactive components. It also reports the major technological advances recently made in this field. It reviews developments in sampling techniques such as MDT-type tools, new DST sampling tools, coiled tubing sampling, and isokinetic techniques, and it highlights common limitations. The value of making proper use of existing technology is emphasized, both with traditional techniques and new developments, with reference to correct well conditioning, interpretation of field data, and especially to optimum handling of samples. The paper emphasizes the need for better exchange of sampling knowledge between organizations, and highlights the lack of up-to-date industry standards with respect to fluid sampling. A solution is proposed in the form of a joint industry project to identify and document best practices. Des échantillons valables sont essentiels pour bien caractériser les fluides de gisements. Si les échantillons ne sont pas représentatifs, toutes les mesures ultérieures seront entachées d'erreurs. Cet article discute les principaux défis en matière d'échantillonnage, en particulier les réservoirs de gaz à condensats, les gradients compositionnels, la teneur en eau des fluides hydrocarbonés, les dépôts d'asphaltènes, les dépôts de paraffines, la contamination par les boues à base d'huile, et les constituants réactifs. Il relate également les principaux progrès technologiques récemment réalisés dans ce domaine et passe en revue les développements des techniques d'échantillonnage telles que les outils de type MDT, les nouveaux outils d

  14. Turbulent Flow of Saudi Non-Newtonian Crude Oils in a Pipeline Écoulement turbulent de bruts non-newtoniens séoudiens dans une canalisation

    Directory of Open Access Journals (Sweden)

    Hemeidia A. M.

    2006-11-01

    Full Text Available Rheological properties of Saudi Arab-Light, Arab-Berri and Arab-Heavy crude oils were measured with Brookfield Viscometer (LVT Model at temperatures 10, 15, 20, 25, 38, 55 and 70°C. Saudi Arab-Light and Arab-Heavy exhibit non-Newtonian behavior at temperature less than or equal to 20°C, while Saudi Arab-Berri behaves as a non-Newtonian fluid at all temperatures. The main reason for this rheological behavior can be attributed to the thermal and shear histories; the relative amounts of wax and asphaltene content in Saudi crude oils as well. Therefore, Statistical Analysis (t-test was used to check the variability of the change in rheological behavior of Saudi non-Newtonian crude oils at a confidence level of 95%. The evaluation ensured that, all non-Newtonian data were statistically not different and were correlated with power-law model. Under turbulent flow conditions the pipeline design calculations were carried out through a computer program. Les propriétés rhéologiques des bruts séoudiens Arab-Light, Arab-Berri et Arab-Heavy ont été mesurées à l'aide d'un viscomètre Brookfield (modèle LVT à des températures de 10, 15, 20, 25, 38, 55 et 70°C. Les Saudi Arab-Light et Arab-Heavy présentent un comportement non newtonien à des températures égales ou inférieures à 20°C, tandis que le Saudi Arab-Berri se comporte comme un fluide non newtonien à toutes les températures. Ce comportement rhéologique est principalement dû aux historiques thermiques et de cisaillement, de même qu'aux quantités relatives de paraffine et à la teneur en asphaltène des bruts séoudiens. Une analyse statistique (essai t a donc été menée pour vérifier la variabilité des changements de comportement rhéologique des bruts séoudiens non newtoniens à un degré de fiabilité de 95%. Il en est ressorti que toutes les données non newtoniennes étaient statistiquement non différentes et étaient en corrélation avec le modèle de la loi des

  15. Tin-polymetallic sulfide deposits in the eastern part of the Dachang tin field (South China) and the role of black shales in their origin

    Science.gov (United States)

    Pašava, Jan; Kříbek, Bohdan; Dobeš, Petr; Vavřín, Ivan; Žák, Karel; Delian, Fan; Tao, Zhang; Boiron, Marie-Christine

    2003-01-01

    The Dafulou and Huile vein and stratabound cassiterite-sulfide deposits and sheeted ore veins at the Kangma cassiterite-sulfide deposit are located in the eastern part of the Dachang tin field. These deposits are hosted in a sedimentary sequence containing significant concentrations of organic matter in the form of Lower Devonian calcareous black shales and hornfels. These rocks together with the younger intrusion of Longxianggai granite (91±2 Ma) actively participated in the formation of Sn-polymetallic deposits. The following three major stages have been distinguished in stratiform and vein-type orebodies at Dafulou, Huile and Kangma: stage I (cassiterite, pyrrhotite, arsenopyrite, tourmaline, carbonate), stage II - main sulfide stage (quartz, cassiterite, arsenopyrite, pyrrhotite, sphalerite, stannite, pyrite, carbonates) and stage III (native Bi, galena, electrum, sulfosalts). Stage IV (post-ore), recognized at Huile is represented by barren carbonates and zeolites. Whole rock geochemistry has revealed that at Dafulou, Bi and Cu correlate strongly with S, whereas V and Pb correlate well with Corg (organic carbon). The similar distribution patterns of selected elements in average slightly mineralized low-Ca black shales indicate a fluid composition similar for all deposits studied. Studies of graphitization of the organic matter in black shales adjacent to orebodies indicate that d(002) and FWHM (full width in half maximum)/peak height values gradually decrease in the following sequence: Dafulou deposit → Kangma deposit → Huile deposit. The pyrolysate of wall rocks at the Dafulou deposit is relatively enriched in asphaltenes and maltenes (55.6-72.0% of the pyrolysate) comparable with pyrolysate obtained from more distal black shales (19.2-28.5%). Typical GC-MS spectra of pyrolysate from distal black shales are dominated by alkanes in the n-C15 to n-C25 range, aromatic molecules being represented mostly by alkyl-naphthalenes. In contrast, only traces of

  16. DETERMINACIÓN DE LAS FRACCIONES SARA DE ASFALTOS COLOMBIANOS ENVEJECIDOS AL MEDIO AMBIENTE EMPLEANDO CROMATOGRAFÍA LÍQUIDA EN COLUMNA DETERMINAÇÃO DAS FRAÇÕES SARA DE ASFALTOS COLOMBIANOS ENVELHECIDOS AO MÉDIO AMBIENTE EMPREGANDO CROMATOGRAFIA LÍQUIDA EM COLUNA DETERMINATION OF SARA FRACTIONS OF ENVIRONMENTALLY AGED COLOMBIAN ASPHALTS USING LIQUID CHROMATOGRAPHY COLUMN

    Directory of Open Access Journals (Sweden)

    Fredy Alberto Reyes

    2012-06-01

    ôde ser responsável pelo endurecimento observado nos asfaltos, que apresentaram uma consistência dura e quebradiça, o que está de acordo com a obtenção de índices coloidais elevados. O método empregado permitiu estabelecer correlações entre a composição química do asfalto e suas propriedades mecânicas.In this paper, we present a method based on liquid chromatography column to quantify the chemical composition of asphalt cements manufactured in Colombia, under the environment by determining the SARA fractions. The method was applied to thin layers of asphalt 60/70 and 80/100 to determine changes in the chemical composition of the material after exposure for 12 months in the weather conditions in the city of Bogotá; SARA tests were performed to the original asphalt, 1, 3, 6, 9 and 12 months aged respectively. SARA trials showed that aging caused a decrease in the fraction of aromatics and asphaltenes increased compared to non-aged asphalt. The reduction of aromatics and resins could be responsible for the hardening observed in the asphalt, which had a stiff and brittle consistency; that leads to obtaining higher colloidal index. The performed method established possible correlations between the chemical composition of asphalt and its mechanical properties.

  17. Observations on the Primary Migration of Oil in the la Luna Source Rocks of the Maracaibo Basin, Venezuela Observations de la migration primaire de l'huile dans les roches mères de la Formation de La Luna dans le bassin de Maracaïbo, Venezuela

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    Talukdar S.

    2006-11-01

    Full Text Available In the present work, an integrated approach has been made to understand the primary migration of oil in the organic-rich, oil prone, predominantly carbonate source rocks of the La Luna Formation of the Maracaibo Basin. Geochemical data on source rock extracts and the simulation of oil generation by hydrous-pyrolysis experiments indicate that the primary migration and expulsion of oil began at an early stage of thermal maturity and that the bulk oil expulsion at peak generation could have been as high as 75%. Fluorescence and transmitted light petrography of the source rocks at different maturity levels show the dominant mode of oil expulsion through microfractures. It is interpreted from the geochemical and geological data that the primary migration of oil in the La Luna source rocks took place as a separate oil phase through microfractures caused by the excess fluid pressure due to hydrocarbon generation. The oils expelled from the La Luna source are enriched in saturated hydrocarbons and depleted in resins + asphaltenes compared to the La Luna rock extracts. However the distributions of n-alkanes, in the oils and the rock extracts are very similar, which suggest that fractionation of the n-alkanes did not occur during the primary migration. In the Maracaibo Basin, updip lateral primary migration of oil within the La Luna source system seem to have occurred for a considerable distance. Local internal migration has been observed at a relatively early stage of maturity. Cette étude consiste en une approche intégrée cherchant à comprendre la migration primaire de l'huile dans les roches mères de la Formation de La Luna dans le bassin de Maracaïbo, riches en matière organique, génératrices d'huile et à dominante carbonatée. Les données géochimiques sur des extraits de roches mères et la simulation de genèse d'huile par des expériences de pyrolyse en présence d'eau indiquent que la migration primaire et l'expulsion de l'huile ont

  18. Thermal Evolution of Crude Oils in Sedimentary Basins: Experimental Simulation in a Confined System and Kinetic Modeling Evolution thermique des huiles dans les bassins sédimentaires : simulation expérimentale par pyrolyse en milieu confiné et modélisation cinétique

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    Behar F.

    2006-11-01

    Full Text Available A detailed knowledge of the cracking mechanisms of crude oils should highly improve the understanding of geochemical reactions involved in hydrocarbon degradation into lighter oil and gas and consequently the applicability of kinetic models currently used for prediction of gas formation. Although the mechanisms of cracking are well known for several model compounds or simple mixtures, there is, to date, no available method to model complex mixtures, especially when they contain heavy compounds, except by using empirical approaches. During thermal cracking, oil will produce both lighter and heavier molecules than those present in the initial sample. Thus, the pyrolysate will be a mixture of both new compounds and compounds not yet degraded. In order to discriminate between reactants and products, we have chosen to fractionate each oil into two classes : the first one (distillate 300- comprising light hydrocarbons ranging from C6 to C16 the second one (residue 300+ comprising both hydrocarbons and polar compounds. For simulation of thermal evolution of crude oils, about 100 experiments were carried out on two oils (Boscan and Pematang, in a closed pyrolysis system, over a wide range of heating times (few minutes to 1 month and temperatures (335 to 500°C. The pyrolysate is represented by 10 chemical fractions (C1, C2, C3-C5, C6-C13 saturates, benzene + toluene + xylenes + naphthalene, C9-C13 alkyl aromatics, C14+ saturates, C14+ condensed aromatics, C14+ alkyl and/or naphtheno aromatics + resins + asphaltenes and coke. For kinetic modeling, the degradation of each fraction, except for C1, C6-C13 aromatic mixture comprising benzene, toluene, xylenes and naphthalene, and coke considered as stable compounds, is described by a balanced elementary reaction governed by first order kinetics and obeying Arrhenius law. For a given oil, the kinetic parameters of the model (apparent activation energies Ei, preexponential factor A and stoichiometric

  19. Ignition et oxydation des particules de combustible solide pulvérisé Ignition and Oxidation of Pulverized Solid Fuel

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    De Soete G. G.

    2006-11-01

    the rate of heterogeneous combustion can reach its normal steady state, which is practically the same as that of char. At temperatures between the ignition temperature of the solid fuel and the extinction temperature of residual char, combustion is incomplete and extinction occurs at a devolatilization degree that is all the greater as the temperature is high. This phenomenon can be qualitively explained by the standard thermal ignition theory when it is applied to the specific case of pyrolyzable solid fuels. Ignition temperatures as well as ignition delays have been determined for a great many lower- and higher-rank solid fuels (coals, cokes, asphaltenes, soot, wood, graphite. An analysis of the experimental rate of heterogeneous combustion, and especially of the apparent activation temperature, and its dependency with regard to particle size and oxygen concentration, shows that this combustion is controlled under test conditions by CO desorption and that it occurs mainly in the mixed kinetico-diffusional regime. Investigations of the dependency of ignition delays with regard to temperature, to particle size and to oxygen partial pressure suggest that reactions occur in a pure kinetic regime during such delays and that the desorption reaction product is mainly CO.

  20. Solubilisation des hydrocarbures dans les solutions micellaires Influence de la structure et de la masse moléculaire Solubilization of Hydrocarbons in Micellar Solutions Influence of Structure and Molecular Weight

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    Baviere M.

    2006-11-01

    ideal behavior disappears for hydrocarbon mixtures. The different effects of alcohol on the phase behavior of micellar systems, due to its partitioning among the different phases, have been confirmed, and in particular the effect on solubilization. This solubilization is all the weaker as the alcohol concentration is great. The solubilization of crude oils depends strongly on their chemical composition. It may vary from single to double for crudes having exactly the same equivalent alkane, i. e. having similar molecular weights. Oil from Daqing has very weak solubilization, even though the interfacial tensions between the micellar phase and the excess oil are relatively low. According to tests of fractions extracted from the crude oil, resins might be responsible for such a behavior in an environment with high molecular weights. To achieve better control over the formulation of micellar fluids, further research will have to be done to determine the effect of heavy constituents (paraffins, resins and asphaltenes on the interfacial properties of water/hydrocarbon/surfactant systems. Likewise, the interactions occurring between the hydrocarbon constituents and the surfactant raise problems concerning the choice of the surfactant. The use of surfactants having varying structures, mainly with regard to the lipophilic part (branching, aromaticity, etc. , should make it possible to indicate to what extent this structure can be adapted to the composition of the oil to make formulations as efficient as possible.