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Sample records for asphaltene

  1. Model molecules mimicking asphaltenes.

    Science.gov (United States)

    Sjöblom, Johan; Simon, Sébastien; Xu, Zhenghe

    2015-04-01

    Asphalthenes are typically defined as the fraction of petroleum insoluble in n-alkanes (typically heptane, but also hexane or pentane) but soluble in toluene. This fraction causes problems of emulsion formation and deposition/precipitation during crude oil production, processing and transport. From the definition it follows that asphaltenes are not a homogeneous fraction but is composed of molecules polydisperse in molecular weight, structure and functionalities. Their complexity makes the understanding of their properties difficult. Proper model molecules with well-defined structures which can resemble the properties of real asphaltenes can help to improve this understanding. Over the last ten years different research groups have proposed different asphaltene model molecules and studied them to determine how well they can mimic the properties of asphaltenes and determine the mechanisms behind the properties of asphaltenes. This article reviews the properties of the different classes of model compounds proposed and present their properties by comparison with fractionated asphaltenes. After presenting the interest of developing model asphaltenes, the composition and properties of asphaltenes are presented, followed by the presentation of approaches and accomplishments of different schools working on asphaltene model compounds. The presentation of bulk and interfacial properties of perylene-based model asphaltene compounds developed by Sjöblom et al. is the subject of the next part. Finally the emulsion-stabilization properties of fractionated asphaltenes and model asphaltene compounds is presented and discussed.

  2. The fractal aggregation of asphaltenes.

    Science.gov (United States)

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

    2013-07-16

    This paper discusses time-resolved small-angle neutron scattering results that were used to investigate asphaltene structure and stability with and without a precipitant added in both crude oil and model oil. A novel approach was used to isolate the scattering from asphaltenes that are insoluble and in the process of aggregating from those that are soluble. It was found that both soluble and insoluble asphaltenes form fractal clusters in crude oil and the fractal dimension of the insoluble asphaltene clusters is higher than that of the soluble clusters. Adding heptane also increases the size of soluble asphaltene clusters without modifying the fractal dimension. Understanding the process of insoluble asphaltenes forming fractals with higher fractal dimensions will potentially reveal the microscopic asphaltene destabilization mechanism (i.e., how a precipitant modifies asphaltene-asphaltene interactions). It was concluded that because of the polydisperse nature of asphaltenes, no well-defined asphaltene phase stability envelope exists and small amounts of asphaltenes precipitated even at dilute precipitant concentrations. Asphaltenes that are stable in a crude oil-precipitant mixture are dispersed on the nanometer length scale. An asphaltene precipitation mechanism is proposed that is consistent with the experimental findings. Additionally, it was found that the heptane-insoluble asphaltene fraction is the dominant source of small-angle scattering in crude oil and the previously unobtainable asphaltene solubility at low heptane concentrations was measured.

  3. Athabasca asphaltene structures

    Energy Technology Data Exchange (ETDEWEB)

    Dettman, H.; Salmon, S.; Zinz, D. [National Centre for Upgrading Technology, Devon, AB (Canada)

    2009-07-01

    In order to model petroleum behaviour during production and refining processes, it is important to understand the molecular character of oil components. Gas chromatography can be used to separate components with boiling points less than 524 degrees C. However, since asphaltenes have a higher boiling point, gel permeation chromatography (GPC) must be used to separate species before analysis. Analysis of Athabasca asphaltene GPC fractions has shown that asphaltenes consist of 2 types of species, notably crunchy species that are graphitic in appearance, and oily species. The molecular weights range from 400 to 2000 g/mole as measured by low resolution mass spectrometry. This poster described the ongoing effort to separate the asphaltenes by polarity. Athabasca asphaltenes were subfractioned into 4 parts according to differential solubility in pentane and centrifugation. Acidic species were isolated from the asphaltenes using adsorption chromatography. The 4 polarity fractions and acid species have been characterized with particular reference to elemental and metals content. Analyses were performed by Fourier transform infrared (FTIR) and nuclear magnetic resonance (NMR) carbon type analyses. This poster provided comparisons of their elution profiles by GPC. tabs., figs.

  4. 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.

  5. Asphaltene based photovoltaic devices

    Energy Technology Data Exchange (ETDEWEB)

    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.

  6. Methods of making carbon fiber from asphaltenes

    Energy Technology Data Exchange (ETDEWEB)

    Bohnert, George; Bowen, III, Daniel E.

    2017-02-28

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

  7. Kinetics of asphaltene precipitation from crude oils

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

  8. Revisiting the flocculation kinetics of destabilized asphaltenes.

    Science.gov (United States)

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

    2016-07-07

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

  9. Waxes and asphaltenes in crude oils

    Energy Technology Data Exchange (ETDEWEB)

    Thanh, N.X. [Branch of Vietnam Petroleum Institute, Ho Chi Min City (Viet Nam). Dept. of Geochemistry; Hsieh, M.; Philp, R.P. [University of Oklahoma, Norman, OK (United States). School of Geology and Geophysics

    1999-07-01

    High molecular weight (HMW) hydrocarbons (> C{sub 40}) and asphaltenes are important constituents of petroleum, and can cause problems related to crystallization and deposition of paraffin waxes during production and transportation, as well as in the formation of tar mats. However, traditional methods to isolate asphaltene fractions, by adding 40 volumes in excess of low boiling point solvents such as pentane, hexane or heptane, can produce asphaltene fractions which are contaminated with a significant amount of microcrystalline waxes (> C{sub 40}). The presence of these microcrystalline waxes in the asphaltene fractions has the potential to provide misleading and ambiguous results in modeling and treatment programs. The sub-surface phase behaviour of an asphaltene fraction will be quite different from that of a wax-contaminated asphaltene fraction. Similarly accurate modelling of wax drop-out requires information on pure wax fractions and not asphaltene-dominated fractions. Hence the aim of this paper is to describe a novel method for the preparation of wax-free asphaltene fractions. In addition, this method provides a quantitative subdivision of the wax fraction into pentane soluble and insoluble waxes which, when correlated with physical properties of crude oil such as viscosity, pour point, cloud point, etc., may help explain causes of wax deposition during production, transportation and storage of petroleum. (author)

  10. 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.

  11. Petroleum asphaltenes: Part 1. Asphaltenes, resins and the structure of petroleum; Les asphaltenes, composes petroliers. Partie 1: asphaltenes, resines et structure du petrole

    Energy Technology Data Exchange (ETDEWEB)

    Speight, J.G. [CD and W Inc., Laramine, Wyoming (United States)

    2004-07-01

    The definition of the nonvolatile constituents of petroleum (i.e., the asphaltene constituents, the resin constituents, and, to some extent, part of the oils fraction insofar as nonvolatile oils occur in residua and other heavy feedstocks) is an operational aid. It is difficult to base such separations on chemical or structural features. This is particularly true for the asphaltene constituents and the resin constituents, for which the separation procedure not only dictates the yield but can also dictate the quality of the fraction. For example, the use of different hydrocarbon liquids influences the yield by a considerable factor. The technique employed also dictates whether or not the asphaltene contains coprecipitated resins. This is based on the general definition that asphaltene constituents are insoluble in n -pentane (or in n-heptane) but resins are soluble n -pentane (or in n-heptane). The results of structural studies of asphaltene constituents are moving away from the older ideas that asphaltene constituents contained large polynuclear aromatic systems and there are a variety of functional types that also play a role in asphaltene behavior. The stability of petroleum is dependent upon the molecular relationships of the asphaltene and resin constituents and the balance with the other constituents of petroleum. Thus, the stability of petroleum can be represented by a three-phase system in which the asphaltene constituents, the aromatic fraction (including the resin constituents), and the saturate fraction are in a delicately balanced harmony. Various factors, such as oxidation, can have an adverse effect on the system, leading to instability or incompatibility as a result of changing the polarity, and bonding arrangements, of the species in crude oil. (author)

  12. 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)

  13. 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...

  14. Asphaltene Precipitation inHeavy-Oil Systems

    OpenAIRE

    Verås, Tor Jørgen

    2011-01-01

    Vapor-Assisted Petroleum Extraction (VAPEX) is a relatively new and promising method for recovering heavy crude oils in Canada. The technique upgrades the oil in-situ through asphaltene precipitation, but it may also cause damage to the formation by clogging its pore throats. This thesis brings some clarity to what asphaltenes are and how they form from mixes of bitumen and solvent, depending on the type and amount of solvent used. This was investigated through a series of laboratory experime...

  15. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1997-02-01

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

  17. Carbonized asphaltene-based carbon-carbon fiber composites

    Energy Technology Data Exchange (ETDEWEB)

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

    2016-12-27

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

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

    DEFF Research Database (Denmark)

    Khvostichenko, Daria S; Andersen, Simon Ivar

    2010-01-01

    transients recorded during electrodeposition tests indicated that the current was transported by the dissolved asphaltene fraction rather than the solid asphaltene particles and a sharp increase in conductivity was observed upon transition from systems with asphaltene deposition to systems without deposition....

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

  20. Hydrogen bonding in asphaltenes and coal

    Energy Technology Data Exchange (ETDEWEB)

    Li, N.C.; Tewari, K.C.

    1978-04-01

    The objective of this program is to investigate and to determine the nature of hydrogen bonding and other molecular interactions that occur in asphaltene and coal liquids, and to seek possible correlations between the interactions and the viscosity. The asphaltene components of samples of centrifuged liquid product, CLP, and solvent-refined coal, SRC, supplied by the Pittsburgh Energy Research Center, are isolated by solvent fractionation. The compositions of the asphaltenes are obtained by elemental analysis and the molecular weights by vapor pressure osmometry. The acid/neutral and base components of the asphaltenes are separated and again elemental analysis and molecular weights are obtained. The magnetic resonance, infrared and calorimetric methods are used to determine the strength of hydrogen-bond and other molecular interactions in the fractions isolated. Investigations on the toluene-insoluble and heavy-oil fractions are also carried out. In addition, extensive proton magnetic resonance, near infrared and calorimetric studies are carried out for o-phenylphenol and quinoline, which serve as model compounds for the aromatic phenols and the heteronuclear aromatic base nitrogens, respectively, found in coal liquefaction products. This is the final report, giving a summary of activities under the Contract for the entire period.

  1. 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...

  2. 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 pe...

  3. 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...

  4. 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.

  5. 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...

  6. 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.)

  7. Pyrolysis of petroleum asphaltenes from different geological origins and use of methylnaphthalenes and methylphenanthrenes as maturity indicators for asphaltenes

    Indian Academy of Sciences (India)

    Manoj Kumar Sarmah; Arun Borthakur; Aradhana Dutta

    2010-08-01

    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 alkylphenanthrenes. Both the asphaltenes produced aliphatic as well as aromatic compound classes. Alkylnaphthalenes and alkylphenanthrenes were identified by using reference chromatograms and literature data and the distributions were used to assess thermal maturity of the asphaltenes. The ratios of -substituted to α-substituted isomers of both alkylnaphthalenes and alkylphenanthrenes revealed higher maturity of the JN asphaltenes than the DK asphaltenes. For both the asphaltenes the abundance of 1-methylphenanthrene dominated over that of 9-methylphenanthrene showing the terrestrial nature of the organic matter.

  8. Pyrolysis of petroleum asphaltenes from different geological origins and use of methylnaphthalenes and methylphenanthrenes as maturity indicators for asphaltenes

    Indian Academy of Sciences (India)

    Manoj Kumar Sarmah; Arun Borthakur; Aradhana Dutta

    2013-04-01

    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 alkylphenanthrenes. Both the asphaltenes produce aliphatic as well as aromatic compound classes. Alkylnaphthalenes and alkylphenanthrenes were identified by using reference chromatograms and literature data and the distributions used to assess thermalmaturity of the asphaltenes. The ratios of -substituted to -substituted isomers of both alkylnaphthalenes and alkylphenanthrenes revealed higher maturity of the JN asphaltenes than the DK asphaltenes. For both the asphaltenes, the abundance of 1-methylphenanthrene dominates over that of 9-methylphenanthrene showing the terrestrial nature of the organic matter.

  9. Characterisation of the non-asphaltene products of mild chemical degradation of asphaltenes

    Energy Technology Data Exchange (ETDEWEB)

    Ekweozor, C.M.

    1986-01-01

    The major steranes of the non-asphaltene fraction of Nigerian tar sand bitumen (maltene) are the C{sub 27-29} and C{sub 28-29} regular steranes. The reducing-metal reaction products of the corresponding asphaltenes (maltene-I) contain mainly C{sub 27-29} regular steranes with the 14{beta}(H),17{beta}(H);20R+S and 14{alpha}(H),17{alpha}(H);20R+S configurations as well as the corresponding diasteranes having the 13{beta}(H),17{alpha}(H);20R+S configuration. These sterane distributions suggest that maltene-I corresponds to an unaltered oil while the maltene is equivalent to the product of severe biodegradation of maltene-I. This is consistent with maltene-I being the remnant of original oil trapped within the asphaltene matrix and protected from the effect of in-reservoir biodegradation. Degradation of Nigerian asphaltenes by refluxing with ferric chloride-acetic anhydride or methanolic potassium hydroxide also releases soluble reaction products having the characteristics of unaltered oil such as the presence of n-alkanes having an unbiased distribution. These methods appear to be milder and more suitable than reducing-metal reactions for releasing hydrocarbons occluded by asphaltenes. 15 refs., 3 figs., 2 tabs.

  10. Characterization of the non-asphaltene products of mild chemical degradation of asphaltenes

    Energy Technology Data Exchange (ETDEWEB)

    Ekweozor, C.M.

    1986-01-01

    The major steranes of the non-asphaltene fraction of Nigerian tar sand bitumen (maltene) are the C/sub 27/-C/sub 29/ diasteranes (13..beta.. (H),17..cap alpha.. (H); 20 R + S) and C/sub 28/-C/sub 29/ regular steranes (14..beta.. (H),17..beta.. (H); 20S). The reducing metal reaction products of the corresponding asphaltenes (maltene-I) contain mainly C/sub 27/-C/sub 29/ regular steranes with the 14..beta.. (H),17..beta.. (H); 20R + S and 14..cap alpha.. (H),17..cap alpha.. (H); 20R + S configurations as well as the corresponding diasteranes having the 13..beta.. (H),17..cap alpha.. (H); 20R + S configuration. These sterane distributions suggest that maltene-I corresponds to an unaltered oil whilst the maltene is equivalent to the product of severe biodegradation of maltene-I. This is consistent with maltene-I being the remnant of original oil trapped within the asphaltene matrix and protected from the effect of in-reservoir biodegradation. Degradation of Nigerian asphaltenes by refluxing with ferric chloride-acetic anhydride or methanolic potassium hydroxide also releases soluble reaction products having the characteristics of unaltered oil such as the presence of n-alkanes having an unbiased distribution. These methods appear to be milder and more suitable than reducing metal reactions for releasing hydrocarbons occluded by asphaltenes.

  11. 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....

  12. Pyrolysis of asphaltenes from lignite semicoking tar

    Energy Technology Data Exchange (ETDEWEB)

    Platonov, V.V.; Ryl' tsova, S.V.; Rozental, D.A.; Proskuryakov, V.A.; Polovetskaya, O.S.

    2000-07-01

    Pyrolysis of asphaltenes from lignite semicoking tar in the range 750-900{degree}C at a contact time within 0.5-6.0 s was studied. The yields of pyrocarbons, pyrolysis gas, and liquid products and the group composition of the liquid products were determined. The total analysis of the major groups of compounds present in the liquid products was performed, and the optimal conditions of pyrolysis, from the viewpoint of preparation of particular compounds, were recommended.

  13. Asphaltene and solids-stabilized water-in-oil emulsions

    Science.gov (United States)

    Sztukowski, Danuta M.

    Water-in-crude oil emulsions are a problem in crude oil production, transportation, and processing. Many of these emulsions are stabilized by asphaltenes and native oilfield solids adsorbed at the oil-water interface. Design of effective emulsion treatments is hampered because there is a lack of understanding of the role asphaltenes and solids play in stabilizing these emulsions. In this work, the structural, compositional and rheological properties of water/hydrocarbon interfaces were determined for model emulsions consisting of water, toluene, heptane, asphaltenes and native oilfield solids. The characteristics of the interface were related to the properties of asphaltenes and native solids. Emulsion stability was correlated to interfacial rheology. A combination of vapour pressure osmometry, interfacial tension and emulsion gravimetric studies indicated that asphaltenes initially adsorb at the interface as a monolayer of self-associated molecular aggregates. It was demonstrated why it is necessary to account for asphaltene self-association when interpreting interfacial measurements. The interfacial area of Athabasca asphaltenes was found to be approximately 1.5 nm2 and did not vary with concentration or asphaltene self-association. Hence, more self-associated asphaltenes simply formed a thicker monolayer. The interfacial monolayer observed in this work varied from 2 to 9 nm in thickness. The asphaltene monolayer was shown to adsorb reversibly only at short interface aging times. The film gradually reorganizes at the interface to form a rigid, irreversibly adsorbed network. The elastic and viscous moduli can be modeled using the Lucassen-van den Tempel (LVDT) model when the aging time is less than 10 minutes. An increase in film rigidity can be detected with an increase in the total elastic modulus. Increased film rigidity was shown to reduce the rate of coalescence in an emulsion and increase overall emulsion stability (reduce free water resolution). The rate of

  14. 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

  15. 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

  16. 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

  17. Nature of hydrogen bonding in coal-derived asphaltenes

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, S.R.; Li, N.C.

    1978-02-01

    Reports are presented on near-infrared and proton magneti resonance studies of hydrogen bonding between the hydroxyl group of o-phenylphenol (OPP) and two coal derived asphaltenes, and their acid and base components. The asphaltenes were prepared from bituminous coal under the same conditions except that one was prepared using a CoMo catalyst. The results of the studies show that the use of the CoMo catalyst leads to a base asphaltene component of lower molecular weight and higher hydrogen-bond acceptor strength.

  18. Petroleum asphaltenes Part 2. The effect of asphaltenes and resin constituents on recovery and refining processes; Les asphaltenes, composes petroliers - partie 2: l'effet des asphaltenes et des resines sur les procedes de recuperation et de raffinage

    Energy Technology Data Exchange (ETDEWEB)

    Speight, J.G. [CD and W Inc., Laramine, Wyoming (United States)

    2004-07-01

    Petroleum is a complex but delicately balanced system that depends upon the relationship of the constituent fractions to each other and the relationships are dictated by molecular interactions. Thus, some aspects of recovery and refining chemistry, especially the chemistry of the deposition of asphaltenic material (degradation or reaction products of the asphaltene constituents and the resin constituents), can be proposed by virtue of the studies that have led further knowledge of the nature of asphaltene constituents and the resin constituents and particularly the nature of their interaction in crude oil. (author)

  19. 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.

  20. Interfacial properties of asphaltenes at toluene-water interfaces.

    Science.gov (United States)

    Zarkar, Sharli; Pauchard, Vincent; Farooq, Umer; Couzis, Alexander; Banerjee, Sanjoy

    2015-05-05

    Asphaltenes are "n-alkane insoluble" species in crude oil that stabilize water-in-oil emulsions. To understand asphaltene adsorption mechanisms at oil-water interfaces and coalescence blockage, we first studied the behavior in aliphatic oil-water systems in which asphaltenes are almost insoluble. They adsorbed as monomers, giving a unique master curve relating interfacial tension (IFT) to interfacial coverage through a Langmuir equation of state (EoS). The long-time surface coverage was independent of asphaltene bulk concentration and asymptotically approached the 2-D packing limit for polydisperse disks. On coalescence, the surface coverage exceeded the 2-D limit and the asphaltene film appeared to become solidlike, apparently undergoing a transition to a soft glassy material and blocking further coalescence. However, real systems consist of mixtures of aliphatic and aromatic components in which asphaltenes may be quite soluble. To understand solubility effects, we focus here on how the increased bulk solubility of asphaltenes affects their interfacial properties in comparison to aliphatic oil-water systems. Unlike the "almost irreversible" adsorption of asphaltenes where the asymptotic interfacial coverage was independent of the bulk concentration, an equilibrium surface pressure, dependent on bulk concentration, was obtained for toluene-water systems because of adsorption being balanced by desorption. The equilibrium surface coverage could be obtained from the short- and long-term Ward-Tordai approximations. The behavior of the equilibrium surface pressure with the equilibrium surface coverage was then derived. These data for various asphaltene concentrations were used to determine the EoS, which for toluene-water could also be fitted by the Langmuir EoS with Γ∞ = 3.3 molecule/nm(2), the same value as that found for these asphaltenes in aliphatic media. Asphaltene solubility in the bulk phase only appears to affect the adsorption isotherm but not the Eo

  1. HINDERED DIFFUSION OF ASPHALTENES AT ELEVATED TEMPERATURE AND PRESSURE

    Energy Technology Data Exchange (ETDEWEB)

    James A. Guin; Ganesh Ramakrishnan

    1999-10-07

    During this time period, experiments were performed to study the diffusion controlled uptake of quinoline and a coal asphaltene into porous carbon catalyst pellets. Cyclohexane and toluene were used as solvents for quinoline and the coal asphaltene respectively. The experiments were performed at 27 C and 75 C, at a pressure of 250 psi (inert gas) for the quinoline/cyclohexane system. For the coal asphaltene/toluene system, experiments were performed at 27 C, also at a pressure of 250 psi. These experiments were performed in a 20 cm{sup 3} microautoclave, the use of which is advantageous since it is economical from both a chemical procurement and waste disposal standpoint due to the small quantities of solvents and catalysts used. A C++ program was written to simulate data using a mathematical model which incorporated both diffusional and adsorption mechanisms. The simulation results showed that the mathematical model satisfactorily fitted the adsorptive diffusion of quinoline and the coal asphaltene onto a porous activated carbon. For the quinoline/cyclohexane system, the adsorption constant decreased with an increase in temperature. The adsorption constant for the coal asphaltene/toluene system at 27 C was found to be much higher than that of the quinoline/cyclohexane system at the same temperature. Apparently the coal asphaltenes have a much greater affinity for the surface of the carbon catalyst than is evidenced by the quinoline molecule.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1994-09-10

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

  3. Multiscale scattering investigations of asphaltene cluster breakup, nanoaggregate dissociation, and molecular ordering.

    Science.gov (United States)

    Hoepfner, Michael P; Fogler, H Scott

    2013-12-10

    Small-angle X-ray and neutron scattering (SAXS/SANS) by asphaltenes in various solvents (toluene, tetrahydrofuran, and 1-methylnaphthalene) at dilute concentrations of asphaltenes are presented and discussed. As asphaltenes are diluted, it was found that the cluster size decreases and follows a fractal scaling law. This observation reveals that asphaltene clusters persist to dilute concentrations and maintain fractal characteristics, regardless of concentration. For the first time, the fraction of asphaltenes that exist in nanoaggregates compared to those molecularly dispersed was estimated from the scattering intensity. Significant dissociation was detected at concentrations similar to the previously reported critical nanoaggregate concentration (CNAC); however, the dissociation was observed to occur gradually as the asphaltene concentration was lowered. Complete dissociation was not detected, and aggregates persisted down to asphaltene concentrations as low as 15 mg/L (0.00125 vol. %). A simplified thermodynamic aggregation model was applied to the measurements, and the free energy change of association per asphaltene-asphaltene interaction was calculated to be approximately -31 kJ/mol. Finally, novel solvent-corrected WAXS results of asphaltene in a liquid environment are presented and reveal three distinct separation distances, in contrast to the two separation distances observed in diffraction studies of solid phase asphaltenes. Significant differences in the WAXS peak positions and shapes between aromatic and nonaromatic solvents suggests that there may be large differences between the solvation shell or conformation of the asphaltene alkyl shell depending on the surrounding liquid environment.

  4. Change of asphaltene and resin properties after catalytic aquathermolysis

    Institute of Scientific and Technical Information of China (English)

    Yi Yufeng; Li Shuyuan; Ding Fuchen; Yu Hang

    2009-01-01

    Resin and asphaltene were separated from Liaohe heavy oil.Catalytic aquathermolysis of asphaltene and resin was investigated by using water soluble catalysts (NiSO4 and FeSO4) and oil soluble catalysts (nickel naphthenate and iron naphthenate).Before and after aquathermolysis, the properties of the resin and asphaltene was compared by means of ultimate analysis, vapor pressure osmometer (VPO) average molecular weight, X-ray diffraction (XRD), 13C and 1H nuclear magnetic resonance (NMR).The conversion sequence was as follows: No-catalystasphaltene and resin increased after reaction without catalyst.But the catalysts restrained this trend.The H/C ratio of asphaitene and resin decreased after reaction.From the results of average structural parameters and molecular weight, it was found that asphaltene and resin were partly aggregated after aquathermolysis.

  5. 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.

  6. Thin film pyrolysis of oil sands asphaltenes for structural analysis

    Energy Technology Data Exchange (ETDEWEB)

    Karimi, Arash; Gray, Murray R [Department of Chemical and Materials Engineering, University of Alberta (Canada); Qian, Kuangnan; Olmstead, William N.; Freund, Howard [ExxonMobil Research and Engineering (United States)], email: murray.gray@ualberta.ca

    2010-07-01

    Current methods to extract asphaltene building blocks only produce small sample quantities per batch for analysis. To reach sample quantities sufficient for several analytical methods on each batch, the following method was investigated in a preliminary study. Asphaltenes from Alberta bitumen were spray coated as thin films on alloy plates to be used in controlled pyrolysis. Each batch of six plates reacted around 1 g of asphaltenes in the furnace. Reaction products were purged from the reaction chamber with cold nitrogen, then cooled in a cold trap. Gases were collected and analysed using gas chromatography. Liquid products were condensed in a cold trap, rinsed with solvent, and evaporated overnight. The coke was also recovered from the plates and analysed. The method yielded mass balances greater than 90%. Products analysis revealed molecular fragment sizes ranging from C10 to C100. Lighter components (C5-C10) were not detected, having probably evaporated during solvent removal.

  7. Cooee bitumen II: Stability of linear asphaltene nanoaggregates

    CERN Document Server

    Lemarchand, Claire A; Dyre, Jeppe C; Hansen, Jesper S

    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 chose first to consider the simple case where only asphaltene molecules are counted in a nanoaggregate. We used a master equation approach and a related statistical mechanics model. The linear asphaltene nanoaggregates behave as a rigid linear chain. The most complicated case where all aromatic molecules are counted in a nanoaggregate is then discussed. The linear aggregates where all aromatic molecules are counted seem ...

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

    Energy Technology Data Exchange (ETDEWEB)

    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.

  9. Precipitation, fractionation and characterization of asphaltenes from heavy and light crude oils

    Energy Technology Data Exchange (ETDEWEB)

    F. Trejo; G. Centeno; J. Ancheyta [Instituto Mexicano del Petroleo, Mexico (Mexico). Programa de Tratamiento de Crudo Maya

    2004-11-01

    Asphaltenes of Maya and Isthmus crude oils were precipitated, fractionated and characterized in this work. Isolation of asphaltenes was performed by following the ASTM D3279 method, which uses n-heptane for solvent precipitation. Asphaltenes were separated into three fractions by Soxhlet extraction with a binary solvent system of toluene and n-heptane. C, H, O, N, S, and Ni and V contents were determined in asphaltenes and in their fractions by elemental analysis and atomic absorption, respectively. VPO aggregate weight and NMR measurements were also performed in all samples. Important differences in properties of unfractionated asphaltenes and asphaltenes fractions were observed. Some of these differences were attributed to impurities in the unfractionated asphaltenes. 26 refs., 5 figs., 2 tabs.

  10. The effect of asphaltene particle size and distribution on the temporal advancement of the asphaltene deposition profile in the well column

    Science.gov (United States)

    Zeinali Hasanvand, Mahdi; Mosayebi Behbahani, Reza; Feyzi, Farzaneh; Ali Mousavi Dehghani, Seyed

    2016-05-01

    Asphaltene deposition in oil wells is an inconvenient production problem. Generating a precise deposition model for the well column is essential for optimal well design and prevention/reduction of deposition-associated difficulties. The goal of this study is to determine the effects of various parameters on the deposition process. These parameters include oil viscosity, temperature, flow velocity, well diameter and asphaltene particle size and particle size distribution. The first five parameters are analyzed using Escobedo and Mansoori (2010), Cleaver and Yates (1975) and Friedlander and Johnstone (1957) asphaltene deposition models. The last parameter (asphaltene particle size distribution) is not directly included in the asphaltene deposition models. Therefore, a dynamic well column model is generated by combining transport phenomena (mass, heat and momentum transfer) equations with thermodynamic models. The model is fine-tuned and verified based on field data from an Iranian producing oil well with frequent asphaltene deposition problem and subsequently used for predicting the time-dependent development of the asphaltene deposition profile in the well column for a series of asphaltene particle size distributions. The results show the effect of the said parameters depends on how the buffer layer and Brownian motion are defined. The Escobedo and Mansoori (2010) model is found to make better predictions of deposited asphaltene in the studied well.

  11. Effect of asphaltene structure on association and aggregation using molecular dynamics.

    Science.gov (United States)

    Sedghi, Mohammad; Goual, Lamia; Welch, William; Kubelka, Jan

    2013-05-01

    The aggregation of asphaltenes has been established for decades by numerous experimental techniques; however, very few studies have been performed on the association free energy and asphaltene aggregation in solvents. The lack of reliable and coherent data on the free energy of association and aggregation size of asphaltene has imposed severe limitations on the thermodynamic modeling of asphaltene phase behavior. Current thermodynamic models either consider asphaltenes as non-associating components or use fitting parameters to characterize the association. In this work, the relations between Gibbs free energy of asphaltene association and asphaltene molecular structure are studied using molecular dynamics (MD). The free energy of association is computed from the potential of mean force profile along the separation distance between the centers of mass of two asphaltene molecules using the umbrella sampling technique in the GROMACS simulation package. The average aggregation number for asphaltene nanoaggregates and clusters is also calculated through MD simulations of 36 asphaltene molecules in toluene and heptane in order to estimate the effects of association free energy and steric repulsion on the aggregation behavior of asphaltenes. Our simulation results confirm that the interactions between aromatic cores of asphaltene molecules are the major driving force for association as the energy of association increases substantially with the number of aromatic rings. Moreover, heteroatoms attached to the aromatic cores have much more influence on the association free energy than to ones attached to the aliphatic chains. The length and number of aliphatic chains do not seem to have a noticeable effect on asphaltene dimerization; however, they have a profound effect on asphaltene aggregation size since steric repulsion can prevent asphaltenes from forming T-shape configurations and therefore decrease the aggregation size of asphaltenes significantly. Our MD simulation

  12. Aggregation of model asphaltenes: a molecular dynamics study

    Science.gov (United States)

    Costa, J. L. L. F. S.; Simionesie, D.; Zhang, Z. J.; Mulheran, P. A.

    2016-10-01

    Natural asphaltenes are defined as polyaromatic compounds whose chemical composition and structure are dependent on their geological origin and production history, hence are regarded as complex molecules with aromatic cores and aliphatic tails that occur in the heaviest fraction of crude oil. The aggregation of asphaltenes presents a range of technical challenges to the production and processing of oil. In this work we study the behaviour of the model asphaltene-like molecule hexa-tert-butylhexa-peri-hexabenzocoronene (HTBHBC) using molecular dynamics simulation. It was found that the regular arrangement of the tert-butyl side chains prevents the formation of strongly-bound dimers by severely restricting the configurational space of the aggregation pathway. In contrast, a modified molecule with only 3 side chains is readily able to form dimers. This work therefore confirms the influence of the molecular structure of polyaromatic compounds on their aggregation mechanism, and reveals the unexpected design rules required for model systems that can mimic the behavior of asphaltenes.

  13. Kinetic features of pyrolysis of asphaltenes from lignite semicoking tar

    Energy Technology Data Exchange (ETDEWEB)

    Platonov, V.V.; Ryl' tsova, S.V.; Rozental, D.A.; Proskuryakov, V.A.; Polovetskaya, O.S.

    2000-07-01

    The kinetic features of accumulation of the main gaseous and some liquid products in pyrolysis of asphaltenes from lignite semicoking tar at 750-900{degree}C (contact time 0.5-6.0 s) were studied. The overall reaction order of accumulation of certain compounds was determined, and possible pathways for their formation were suggested.

  14. 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 activi...

  15. 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...

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

    Science.gov (United States)

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

    2009-04-01

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

  17. 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.

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

    OpenAIRE

    Edna L. Hernández-López; Ramírez-Puebla, Shamayim T.; Rafael Vazquez-Duhalt

    2015-01-01

    Asphaltenes are considered as the most recalcitrant petroleum fraction and represent a big problem for the recovery, separation and processing of heavy oils and bitumens. Neosartorya fischeri is a saprophytic fungus that is able to grow using asphaltenes as the sole carbon source [1]. We performed transcription profiling using a custom designed microarray with the complete genome from N. fischeri NRRL 181 in order to identify genes related to the transformation of asphaltenes [1]. Data ana...

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

    Directory of Open Access Journals (Sweden)

    Silas R. Ferreira

    2016-01-01

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

  20. 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.

  1. 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

  2. Molecular dynamic simulation of asphaltene co-aggregation with humic acid during oil spill.

    Science.gov (United States)

    Zhu, Xinzhe; Chen, Daoyi; Wu, Guozhong

    2015-11-01

    Humic acid in water and sediment plays a key role in the fate and transport of the spilled oil, but little is known about its influence on the aggregation of heavy oil asphaltenes which is adverse for remediation. Molecular dynamic simulation was performed to characterize the co-aggregation of asphaltenes (continental model and Violanthrone-79 model) with Leonardite humic acid (LHA) at the toluene-water interface and in bulk water, respectively, to simulate the transport of asphaltenes from oil to water. At the toluene-water interface, a LHA layer tended to form and bind to the water by hydrogen bonding which provided a surface for the accumulation of asphaltenes by parallel or T-shape stacking. After entering the bulk water, asphaltene aggregates stacked in parallel were tightly sequestrated inside the inner cavity of LHA aggregates following surface adsorption and structure deformation. Asphaltene aggregation in water was 2-fold higher than at the toluene-water interface. The presence of LHA increased the intensity of asphaltene aggregation by up to 83% in bulk water while relatively less influence was observed at the toluene-water interface. Overall results suggested that the co-aggregation of asphaltene with humic acid should be incorporated to the current oil spill models for better interpreting the overall environmental risks of oil spill.

  3. 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.

  4. 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.

  5. 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

    Asphaltenes precipitated from pressure-preserve bottomhole oil samples have been obtained for three oils at different pressures, using a bulk high-pressure filtration apparatus. The precipitates captured on the filter were recovered, the asphaltenes defined by the n-heptane insolubility were extr...

  6. 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

    The self-association of asphaltenes in toluene is believed to occur step-wise, rather than by the formation of micelles. A number of step-wise models have been used to fit the calorimetric titration of asphaltenes in dried toluene solutions, with excellent results. All the models are based on che...

  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. Adsorption and wettability study of methyl ester sulphonate on precipitated asphaltene

    Science.gov (United States)

    Okafor, H. E.; Sukirman, Y.; Gholami, R.

    2016-03-01

    Asphaltene precipitation from crude oil and its subsequent aggregation forms solid, which preferentially deposit on rock surfaces causing formation damage and wettability changes leading to loss of crude oil production. To resolve this problem, asphaltene inhibitor has been injected into the formation to prevent the precipitation of asphaltene. Asphaltene inhibitors that are usually employed are generally toxic and non-biodegradable. This paper presents a new environmentally friendly asphaltene inhibitor (methyl ester sulphonate), an anionic surfactant, which has excellent sorption on formation rock surfaces. Result from adsorption study validated by Langmuir and Freundlich models indicate a favourable adsorption. At low volumes injected, methyl ester sulphonate is capable of reverting oil-wet sandstone surface to water-wet surface. Biodegradability test profile shows that for concentrations of 100-5000ppm it is biodegradable by 65-80%.

  9. 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)

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

    Directory of Open Access Journals (Sweden)

    G. E. Oliveira

    2013-06-01

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

  11. 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.

  12. First evidence of mineralization of petroleum asphaltenes by a strain of Neosartorya fischeri

    Science.gov (United States)

    Uribe‐Alvarez, Cristina; Ayala, Marcela; Perezgasga, Lucia; Naranjo, Leopoldo; Urbina, Héctor; Vazquez‐Duhalt, Rafael

    2011-01-01

    Summary A fungal strain isolated from a microbial consortium growing in a natural asphalt lake is able to grow in purified asphaltenes as the only source of carbon and energy. The asphaltenes were rigorously purified in order to avoid contamination from other petroleum fractions. In addition, most of petroporphyrins were removed. The 18S rRNA and β‐tubulin genomic sequences, as well as some morphologic characteristics, indicate that the isolate is Neosartorya fischeri. After 11 weeks of growth, the fungus is able to metabolize 15.5% of the asphaltenic carbon, including 13.2% transformed to CO2. In a medium containing asphaltenes as the sole source of carbon and energy, the fungal isolate produces extracellular laccase activity, which is not detected when the fungus grow in a rich medium. The results obtained in this work clearly demonstrate that there are microorganisms able to metabolize and mineralize asphaltenes, which is considered the most recalcitrant petroleum fraction. PMID:21624102

  13. Hydrogen bonding in asphaltenes and coal. Quarterly Report for July 1, 1978 - September 30, 1978

    Energy Technology Data Exchange (ETDEWEB)

    Li, N.C.; Tewari, K.C.

    1978-09-29

    Two coal liquid products derived from the same Kentucky hvAb coal have been separated into toluene-insoluble, asphaltene, and pentane-soluble heavy oil fractions. Viscosity and calorimetric studies are reported of the interaction between heavy oil and asphaltene(A) and its acid/neutral(AA) and base(BA) components in solvent benzene. The increase in viscosity and molar enthalpy of interaction, {Delta}H{sup 0}, in the order BA>A>AA, correlate well with the proton magnetic resonance downfield chemical shift of the OH signal of o-phenylphenol, as a function of added asphaltene (A, AA, BA) concentration in solvent CS{sub 2}· The results suggest that when asphaltene .and heavy oil are present together, hydrogen-bonding involving largely phenolic OH, is one of the mechanisms by which asphaltene-heavy oil interactions are achieved and, in part, is responsible for the viscosity increase of coal liquids.

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

    Energy Technology Data Exchange (ETDEWEB)

    Rajagopal, K.; Silva, S.M.C. [Universidade Federal, Rio de Janeiro, RJ (Brazil). Escola de Engenharia. Dept. de Engenharia Quimica]. E-mail: raja@eq.ufrj.br

    2004-12-01

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

  15. The effect of asphaltene-paraffin interactions on crude oil stability

    Energy Technology Data Exchange (ETDEWEB)

    Garcia, M.C. del; Carbogani, L. [PDVSA, Caracas (Venezuela)

    2000-08-01

    The effect of asphaltene-paraffin complexes on crude oil stability, in terms of wax crystallization and asphaltene deposits solubility, was studied. The influence of flocculated asphaltenes on the wax crystallization tendency of a paraffinic crude oil was evaluated by means of Polarized Light Microscopy. Heavy linear paraffins (nC24+ paraffins) were added to the crude oil in a controlled fashion in order to evaluate its effect on the cloud point and the effectiveness of a maleic anhydride copolymer derivative paraffin inhibitor. Experiments done in the presence and absence of asphaltene fraction allowed to demonstrate that flocculated asphaltenes provide wax crystallization sites whose presence increases the cloud point of crude oil and also interferes with crystal inhibition mechanism. The existence of asphaltene-paraffins complexes and some structural effects were further assessed by HPLC kinetic dissolution studies of composite materials formed by combinations of such hydrocarbon types. Commercial macrocrystalline and microcrystalline waxes were used in these experiments. Different types of asphaltenes were probed as well, covering varying ranges of aromaticities and stability. (au)

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2012-02-07

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

  17. Heavy Oil Process Monitor: Automated On-Column Asphaltene Precipitation and Re-Dissolution

    Energy Technology Data Exchange (ETDEWEB)

    John F. Schabron; Joseph F. Rovani; Mark Sanderson

    2007-03-31

    An automated separation technique was developed that provides a new approach to measuring the distribution profiles of the most polar, or asphaltenic components of an oil, using a continuous flow system to precipitate and re-dissolve asphaltenes from the oil. Methods of analysis based on this new technique were explored. One method based on the new technique involves precipitation of a portion of residua sample in heptane on a polytetrafluoroethylene-packed (PTFE) column. The precipitated material is re-dissolved in three steps using solvents of increasing polarity: cyclohexane, toluene, and methylene chloride. The amount of asphaltenes that dissolve in cyclohexane is a useful diagnostic of the thermal history of oil, and its proximity to coke formation. For example, about 40 % (w/w) of the heptane asphaltenes from unpyrolyzed residua dissolves in cyclohexane. As pyrolysis progresses, this number decrease to below 15% as coke and toluene insoluble pre-coke materials appear. Currently, the procedure for the isolation of heptane asphaltenes and the determination of the amount of asphaltenes soluble in cyclohexane spans three days. The automated procedure takes one hour. Another method uses a single solvent, methylene chloride, to re-dissolve the material that precipitates on heptane on the PTFE-packed column. The area of this second peak can be used to calculate a value which correlates with gravimetric asphaltene content. Currently the gravimetric procedure to determine asphaltenes takes about 24 hours. The automated procedure takes 30 minutes. Results for four series of original and pyrolyzed residua were compared with data from the gravimetric methods. Methods based on the new on-column precipitation and re-dissolution technique provide significantly more detail about the polar constituent's oils than the gravimetric determination of asphaltenes.

  18. 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.

  19. Investigating molecular interactions and surface morphology of wax-doped asphaltenes.

    Science.gov (United States)

    Pahlavan, Farideh; Mousavi, Masoumeh; Hung, Albert; Fini, Ellie H

    2016-04-07

    The nature and origin of bee-like microstructures (bees) in asphalt binders and their impact on asphalt oxidation have been the subject of extensive discussions in recent years. While several studies refer to the bees as solely surface features, some others consider them to be bulk microcrystalline components that are formed due to co-precipitation of wax and asphaltene molecules. In this study, we use a rigorous theoretical and experimental approach to investigate the interplay of asphalt components (mainly asphaltene and wax) and their impact on bee formation. In the theoretical section, quantum-mechanical calculations using density functional theory (DFT) are used to evaluate the strength of interactions between asphaltene unit sheets in the presence and absence of a wax component, as well as the mutual interactions between asphaltene molecules (monomers and dimers) and paraffin wax. The results of this section reveal that paraffin waxes not only do not reinforce the interaction between the asphaltene unit sheets, they destabilize asphaltene assembly and dimerization. AIM (Atom in Molecules) analysis shows the destabilizing effect of wax on asphaltene assembly as a reduction in the number of cage and bond critical points between asphaltenes. This destabilization effect among interacting systems (asphaltene-asphaltene and wax-asphaltene) does not support the hypothesis that interaction between paraffin waxes and non-wax components, such as asphaltene, is responsible for their co-precipitation and bee formation. To further examine the effect of wax component on asphalt microstructure experimentally, we used atomic force microscopy (AFM) to study the surface morphology of an asphalt sample doped with 1% to 25% paraffin wax. In agreement with the conclusions drawn from the DFT approach, our experiments indicate that paraffin wax tends to crystallize separately and form lamellar paraffin wax crystal inclusions with 10 nm thickness. Moreover, the addition of 3% wax

  20. Pyrolysis mechanisms of thiophene and methylthiophene in asphaltenes.

    Science.gov (United States)

    Song, Xinli; Parish, Carol A

    2011-04-07

    The pyrolysis mechanisms of thiophene in asphaltenes have been investigated theoretically using density functional and ab initio quantum chemical techniques. All of the possible reaction pathways were explored using B3LYP, MP2, and CBS-QB3 models. A comparison of the calculated heats of reaction with the available experimental values indicates that the CBS-QB3 level of theory is quantitatively reliable for calculating the energetic reaction paths of the title reactions. The pyrolysis process is initiated via four different types of hydrogen migrations. According to the reaction barrier heights, the dominant 1,2-H shift mechanism involves two competitive product channels, namely, C(2)H(2) + CH(2)CS and CS + CH(3)CCH. The minor channels include the formation of CS + CH(2)CCH(2), H(2)S + C(4)H(2), HCS + CH(2)CCH, CS + CH(2)CHCH, H + C(4)H(3)S, and HS + C(4)H(3). The methyl substitution effect was investigated with the pyrolysis of 2-methylthiophene and 3-methylthiophene. The energetics of such systems were very similar to that for unsubstituted thiophene, suggesting that thiophene alkylation may not play a significant role in the pyrolysis of asphaltene compounds.

  1. 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.

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

    Directory of Open Access Journals (Sweden)

    Eshagh Rezaee Nezhad

    2013-01-01

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

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

    DEFF Research Database (Denmark)

    Garcia, Daniel Merino; Andersen, Simon Ivar

    2005-01-01

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

  4. First evidence of mineralization of petroleum asphaltenes by a strain of Neosartorya fischeri

    OpenAIRE

    Uribe‐Alvarez, Cristina; Ayala, Marcela; Perezgasga, Lucia; Naranjo, Leopoldo; Urbina, Héctor; Vazquez‐Duhalt, Rafael

    2011-01-01

    Summary A fungal strain isolated from a microbial consortium growing in a natural asphalt lake is able to grow in purified asphaltenes as the only source of carbon and energy. The asphaltenes were rigorously purified in order to avoid contamination from other petroleum fractions. In addition, most of petroporphyrins were removed. The 18S rRNA and β‐tubulin genomic sequences, as well as some morphologic characteristics, indicate that the isolate is Neosartorya fischeri. After 11 weeks of growt...

  5. Preparation and characterization of a composite membrane based on the asphaltene component of coal

    Institute of Scientific and Technical Information of China (English)

    Zhang Liying; Qin Zhihong; Li Xinyan; Chen Juan; Liu Peng; Wang Xiaoyan

    2011-01-01

    Asphaltene-ceramic composite membranes were fabricated from ceramic supports and an asphaltene component,which was obtained from the separation of coal to give a kind of new carbonaceous precursor material.Using SEM and thermogravimetric analysis to measure the microstructure and properties of the asphaltene component allowed the porosity,permeability,and retention ratios to be determined.The results show that the asphaltene component can be regarded as a good carbon membrane precursor material because of its high carbon content and strong bonding capacity.When ceramic supports are impregnated with asphaltene colloid the asphaltene easily combines with the support surface and forms a good carbonaceous film after carbonization.Little of the asphaltene component permeates into the internal pores of the ceramic support.Although the number of coats applied to the substrate had little affect on the porosity of the asphaltene-ceramic composite membranes the permeability varied depending upon the number of times the substrate was treated.The way bubbles escape from the film.and the phenomenon of coalescence,as affected by different film thicknesses also seem closely related to the number of coats.A composite membrane carbonized at a final temperature of 600 ℃ is relatively dense and the permeability of Fe(OH)3 colloid through it is very low.A membrane fired at 800 ℃ is porous and its permeability and retention of Fe(OH)3 colloid are 88 L/(m2 h MPa) and 85.3%,respectively when the trans-membrane pressure is 0.22 MPa.

  6. 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.

  7. 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.

  8. Kinetic studies on the pyrolysis of asphaltenes from differenttypes of kerogens

    Institute of Scientific and Technical Information of China (English)

    2000-01-01

    The pyrolysis kinetics of a series of asphaltenes, from different types of kerogens, are studied in this work. The results indicate that the distributions of activation energy are over a wide range for the asphaltenes from type I kerogens. There is still a large potential of hydrocarbon generation in case the activation energy is above 350 kJ·mol-1. While the distributions of activation energy are comparatively over a narrow range for the asphaltenes from type II and II kerogens,there is a little or almost no potential of hydrocarbon generation with the activation energy above 350 kJ·mol-1 respectively. For the asphaltenes from some specific type of kerogens, the pyrolysis kinetics can be applied to marking their maturity. Furthermore, based on detailed discussions of the kinetics parameter frequency factor, the asphaltenes from type I kerogens are considered to be of great potential to regenerate oils, while the asphaltenes' potential for oil-to-gas conversion tends to go down in order of primitive kerogen types of Ⅲ II and I.

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

    Directory of Open Access Journals (Sweden)

    Yong-Jun Liu

    2015-01-01

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

  10. Interaction Mechanism of Oil-in-Water Emulsions with Asphaltenes Determined Using Droplet Probe AFM.

    Science.gov (United States)

    Shi, Chen; Zhang, Ling; Xie, Lei; Lu, Xi; Liu, Qingxia; Mantilla, Cesar A; van den Berg, Frans G A; Zeng, Hongbo

    2016-03-15

    Emulsions with interface-active components at the oil/water interface have long been of fundamental and practical interest in many fields. In this work, the interaction forces between two oil droplets in water in the absence/presence of asphaltenes were directly measured using droplet probe atomic force microscopy (AFM) and analyzed using a theoretical model based on Reynolds lubrication theory and the augmented Young-Laplace equation by including the effects of disjoining pressure. It was revealed that the interaction forces measured between two pristine oil droplets (i.e., toluene) could be well described by the classical Derjaguin-Landau-Verwey-Overbeek (DLVO) theory, while an additional steric interaction should be included in the presence of asphaltenes in the oil. The surface interaction and the stability of oil droplets in aqueous solution were demonstrated to be significantly influenced by the asphaltenes concentration in oil, salt concentration, pH, and presence of divalent ions (Ca(2+)) in water. Adsorbed asphaltenes at the oil/water interface led to more negative surface potential of the oil/water interface and also induced steric repulsion between oil droplets, inhibiting the drop coalescence and stabilizing the oil-in-water emulsion. Lower pH of aqueous solution could lead to less negative surface potential and weaken the repulsion between oil droplets. Addition of divalent ions (Ca(2+)) was found to disrupt the protecting effects of adsorbed asphaltenes at oil/water interface and induce coalescence of oil droplets. Our results provide a useful methodology for quantifying the interaction forces and investigating the properties of asphaltenes at the oil/water interfaces and provide insights into the stabilization mechanism of oil-in-water emulsions due to asphaltenes in oil production and water treatment.

  11. Surface chemistry and spectroscopy of UG8 asphaltene Langmuir film, part 2.

    Science.gov (United States)

    Orbulescu, Jhony; Mullins, Oliver C; Leblanc, Roger M

    2010-10-05

    While there has been much focus on asphaltenes in toluene, there has been much less focus on asphaltenes in other solvents. It is important to quantify characteristics of asphaltenes in solvents besides toluene in order to better assess their molecular architecture as well as their fundamental aggregation characteristics. The present work focuses on the investigation of UG8 asphaltene Langmuir films at the air-water interface using chloroform as spreading solvent. The results are compared to the results recently obtained using toluene as spreading solvent. Surface pressure-area isotherms and UV-vis spectroscopy indicate that asphaltenes form smaller nanoaggregates in chloroform than in toluene in similar concentration ranges. Still these nanoaggreates share common features with those in toluene. From the surface pressure-area and compression-decompression isotherms, Brewster angle microscopy, and p-polarized infrared reflection-absorption spectroscopy, it was concluded that small size aggregates are spread on the water surface and the compression of the film leads to formation of large aggregates. The films (Langmuir-Schaefer and Langmuir-Blodgett) studied by atomic force microscopy reveal the existence of nanoaggregates spread on the water surface that coexist with large aggregates formed during compression. In addition to these findings, the spreading solvent, chloroform, allows the determination of asphaltene absorption bands using in situ UV-vis spectroscopy at the air-water interface after 15 min waiting time period. The absorbance data carried out after waiting a time period of 1 h shows similar features with the ones carried out after only 15 min; therefore, there is no need to wait 1 h as in the case when toluene is used as spreading solvent. A comparison of the data obtained from chloroform and toluene shows that smaller aggregate sizes are obtained from chloroform as suggested from the surface pressure-area isotherm, in situ UV-vis spectroscopy, and

  12. 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 Mice...

  13. 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.

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

    Directory of Open Access Journals (Sweden)

    Alireza Fazlali

    2010-01-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1996-11-01

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

  16. 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.

  17. 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......The interaction of two model asphaltene molecules from the Athabasca sand oil with a water molecule in a toluene solution was studied by means of molecular mechanics calculations. It was found that water forms bridging H bonds between the heteroatoms of asphaltenes with a considerable span...... in energies. The stronger H bond found has energies higher than those corresponding to the stacking of the aromatic areas of the same asphaltene molecules. This shows that the water molecule may generate additional mechanisms of aggregation of asphaltenes in toluene solution, as found experimentally. The H...

  18. HINDERED DIFFUSION OF ASPHALTENES AT ELEVATED TEMPERATURE AND PRESSURE

    Energy Technology Data Exchange (ETDEWEB)

    James A. Guin; Zachery Emerson

    2001-10-01

    During this final time period of the project, work was carried out in two areas. A major amount of effort was devoted to preparation of the final technical report for the project. The data taken on the project were organized and the asphaltenes, solvents, and catalysts used in the diffusional uptake experiments were organized into various systems. Since a large portion of the time for this report was spent on the preparation of the final technical report itself, the executive summary of the final technical report has been included in this semi-annual report as indicative of the effort during this time period. In addition to work on the final technical report for the project, a limited experimental study of dye adsorption into active carbon particles was performed by an undergraduate student in chemical engineering, Mr. Zachery Emerson. The objective of this study was to compare the diffusional uptake performance in two different types of vessels, a stirred glass cell and the tubing microreactor, for a simple dye-water-carbon diffusional uptake system. Due to time limitations, only qualitative conclusions were drawn from this study.

  19. Small angle neutron scattering (SANS and V-SANS) study of asphaltene aggregates in crude oil.

    Science.gov (United States)

    Headen, Thomas F; Boek, Edo S; Stellbrink, Jörg; Scheven, Ulrich M

    2009-01-06

    We report small angle neutron scattering (SANS) experiments on two crude oils. Analysis of the high-Q SANS region has probed the asphaltene aggregates in the nanometer length scale. We find that the radius of gyration decreases with increasing temperature. We show that SANS measurements on crude oils give similar aggregate sizes to those found from SANS measurements of asphaltenes redispersed in deuterated toluene. The combined use of SANS and V-SANS on crude oil samples has allowed the determination of the radius of gyration of large scale asphaltene aggregates of approximately 0.45 microm. This has been achieved by the fitting of Beaucage functions over two size regimes. Analysis of the fitted Beaucage functions at very low-Q has shown that the large scale aggregates are not simply made by aggregation of all the smaller nanoaggregates. Instead, they are two different aggregates coexisting.

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

    Science.gov (United States)

    Hernández-López, Edna L.; Ramírez-Puebla, Shamayim T.; Vazquez-Duhalt, Rafael

    2015-01-01

    Asphaltenes are considered as the most recalcitrant petroleum fraction and represent a big problem for the recovery, separation and processing of heavy oils and bitumens. Neosartorya fischeri is a saprophytic fungus that is able to grow using asphaltenes as the sole carbon source [1]. We performed transcription profiling using a custom designed microarray with the complete genome from N. fischeri NRRL 181 in order to identify genes related to the transformation of asphaltenes [1]. Data analysis was performed using the genArise software. Results showed that 287 genes were up-regulated and 118 were down-regulated. 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. PMID:26484261

  1. 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)

  2. Using the biomarker bonded on the asphaltenes for biodegraded oil-source correlation

    Institute of Scientific and Technical Information of China (English)

    2003-01-01

    Ruthenium-ion-catalyzed oxidation (RICO) has been used to investigate asphaltenes from three oils with the same origin in the Juquan Basin and three oils with the same origin but with different degree of biodegradation in the Turpan Basin, Northwest China. The preliminary results showed that the biomarkers bonded on the asphaltenes with the same origin is similar and is correlated with the free biomarker in saturates. The bonded biomarkers have no relationship with the biodegradation. An application on the severely biodegraded oils is reported here. The biomarker and benzenecarboxylic methyl esters reflecting the structure of the asphaltenes after RICO should provide a new way for oil-source correlation and it should be specially useful for severely biodegraded oil-source correlation.

  3. 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

  4. Interfacial rheology of asphaltenes at oil-water interfaces and interpretation of the equation of state.

    Science.gov (United States)

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

    2013-04-16

    In an earlier study, oil-water interfacial tension was measured by the pendant drop technique for a range of oil-phase asphaltene concentrations and viscosities. The interfacial tension was found to be related to the relative surface coverage during droplet expansion. The relationship was independent of aging time and bulk asphaltenes concentration, suggesting that cross-linking did not occur at the interface and that only asphaltene monomers were adsorbed. The present study extends this work to measurements of interfacial rheology with the same fluids. Dilatation moduli have been measured using the pulsating droplet technique at different frequencies, different concentrations (below and above CNAC), and different aging times. Care was taken to apply the technique in conditions where viscous and inertial effects are small. The elastic modulus increases with frequency and then plateaus to an asymptotic value. The asymptotic or instantaneous elasticity has been plotted against the interfacial tension, indicating the existence of a unique relationship, between them, independent of adsorption conditions. The relationship between interfacial tension and surface coverage is analyzed with a Langmuir equation of state. The equation of state also enabled the prediction of the observed relationship between the instantaneous elasticity and interfacial tension. The fit by a simple Langmuir equation of state (EOS) suggests minimal effects of aging and of nanoaggregates or gel formation at the interface. Only one parameter is involved in the fit, which is the surface excess coverage Γ∞ = 3.2 molecules/nm(2) (31.25 Å(2)/molecule). This value appears to agree with flat-on adsorption of monomeric asphaltene structures consisting of aromatic cores composed of an average of six fused rings and supports the hypothesis that nanoaggregates do not adsorb on the interface. The observed interfacial effects of the adsorbed asphaltenes, correlated by the Langmuir EOS, are consistent with

  5. Asphaltene Erosion Process in Air Plasma: Emission Spectroscopy and Surface Analysis for Air-Plasma Reactions

    Institute of Scientific and Technical Information of China (English)

    H. MARTINEZ; O. FLORES; J. C. POVEDA; B. CAMPILLO

    2012-01-01

    Optical emission spectroscopy (OES) was applied for plasma characterization during the erosion of asphaltene substrates. An amount of 100 mg of asphaltene was carefully applied to an electrode and exposed to air-plasma glow discharge at a pressure of 1.0 Torr. The plasma was generated in a stainless steel discharge chamber by an ac generator at a frequency of 60 Hz, output power of 50 W and a gas flow rate of 1.8 L/min. The electron temperature and ion density were estimated to be 2.15±0.11 eV and (1.24±0.05)× 10^16 m^-3, respectively, using a double Langmuir probe. OES was employed to observe the emission from the asphaltene exposed to air plasma. Both molecular band emission from N2, N2+, OH, CH, NH, O2 as well as CN, and atomic light emission from V and Hγ were observed and used to monitor the evolution of asphaltene erosion. The asphaltene erosion was analyzed with the aid of a scanning electron microscope (SEM) equipped with an energy dispersive X-ray (EDX) detector. The EDX analysis showed that the time evolution of elements C, O, S and V were similar and the chemical composition of the exposed asphaltenes remained constant. Particle size evolution was measured, showing a maximum size of 2307 μm after 60 min. This behavior is most likely related to particle agglomeration as a function of time.

  6. 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.

  7. Ionic Liquids: Novel Solvents for Petroleum Asphaltenes%离子液体:石油沥青质的新型溶剂

    Institute of Scientific and Technical Information of China (English)

    刘艳升; 胡玉峰; 王海波; 徐春明; 纪德军; 孙研; 郭天民

    2005-01-01

    The dissolution of petroleum asphaltenes with ionic liquids is studied for the first time. The results show that the ionic liquids could be used as novel solvents for asphaltenes. The important parameters governing the ability of ionic liquids for dissolution of asphaltenes are discussed. It is found that, the ionic liquids based on the cations containing a conjugated aromatic core or the anions which are strong hydrogen bond acceptors are most for asphaltenes. Increase in the effective anion charge density enhances the ability of ionic liquids to break the extensive asphaltene associations and thus enhances the solubility of asphaltenes in the ionic liquid. The dissolution ability of ionic liquid decreases apparently with increasing the substituted alkyl chain length of its cationic head ring. Temperature is found to play an important role on dissolution of asphaltenes, and the dissolution can be significantly improved by microwave heating.

  8. 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

  9. Hydrogen bonding in asphaltenes and coal. Comprehensive progress report, December 1975--Februray 1977. [13 references

    Energy Technology Data Exchange (ETDEWEB)

    Li, N.C.

    1977-01-01

    Proton magnetic resonance (PMR) studies are reported of hydrogen bonding between the OH proton of o-phenylphenol (OPP) and the nitrogen electron donor of quinoline (Qu). Data are also reported on the hydrogen bonding of a coal-derived asphaltene and its acid and base components with OPP. Determination was made of the equilibrium constants of the 1:1 complex between OPP and Qu at 39, 32, 1, and -18/sup 0/C from the PMR studies. Qualitative results are reported for the interaction between the base fraction of asphaltene and OPP at 32, 1, and -26/sup 0/C.

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

    DEFF Research Database (Denmark)

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

    2012-01-01

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

  11. Resins and asphaltenes: evolution as a function of organic-matter type and burial

    Energy Technology Data Exchange (ETDEWEB)

    Castex, H. (Institut Francais du Petrole, 92 - Rueil-Malmaison (France))

    Elemental analysis was used to investigate 151 resins and 175 asphaltenes extracted from rocks from several basins. It was shown that: resins have higher mean carbon and hydrogen values as well as a lower C/H ratio than asphaltenes. Resins thus have a more aliphatic and or more alicyclic structure. On the other hand, asphaltenes contain more sulfur, oxygen and nitrogen. Different types of organic matter are revealed by an H/C, O/C diagram. Their chemical evolution with burial is characterized by a decrease in hydrogen, oxygen and sulfur contents. Proton nuclear magnetic resonance (NMR) and infrared spectroscopy (IRS) were used to follow the structural evolution of resins and asphaltenes coming from different types of organic matter (algal, marine and terrestrial) buried at increasing depths. NMR can be used to compute several structural parameters such as Fsub(A) aromaticity and the degree of sigma substitution of the aromatic system. These data were completed by infrared spectroscopy. Variations in the intensity of bands: decrease of aliphatic C-H and of C = O fonctions; increase of aromatic C-H and C = C are related to both the type of organic matter and its catagenesis.

  12. 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

    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...

  13. 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...

  14. Biomarker distributions in asphaltenes and kerogens analyzed by flash pyrolysis-gas chromatograph-mass spectrometry

    Energy Technology Data Exchange (ETDEWEB)

    Van Graas, G.

    1986-01-01

    Biomarker distributions in a suite of asphaltenes and kerogens have been analyzed by flash pyrolysis directly coupled to a GCMS system. Attention has been focussed on biomarkers of the sterane and triterpane types. The sample suite under investigation consists of sediments with different kerogen types and some crude oils. Biomarker distributions in the pyrolysates have been compared with the free biomarkers in the corresponding saturated hydrocarbon fractions. The analyses show significant differences between the distributions of the free biomarkers and those in the pyrolysates. The latter have lower amounts of steranes while diasteranes are absent or present at low concentrations only. In the triterpane traces a shift of maximum intensity from C/sub 30/ (free compounds) to C/sub 27//C/sub 29/ is observed. Furthermore, the pyrolysates contain a set of triterpanes that are present in the saturated hydrocarbon fractions. The observed differences between pyrolysates and free hydrocarbons can be explained partly by the processes occurring during pyrolysis such as bond rupture and subsequent stabilization of primary pyrolysis products. To a certain extent these differences also show that maturation processes occurring in sediments have effects on free biomarker molecules different from those on molecules that are enclosed in a macromolecular matrix (kerogen or asphaltenes). Differences between biomarker distributions of asphaltene and kerogen pyrolysates are relatively small. A comparison with the pyrolysates from extracted whole sediments suggests that these differences are mainly caused by interactions between the organic material and the mineral matrix during pyrolysis. Oil asphaltenes behave differently from sediment asphaltenes as their pyrolysates are more similar to the corresponding saturated hydrocarbon fractions, i.e. the differences described above are observed to a much smaller extent.

  15. An FTIR method for the analysis of crude and heavy fuel oil asphaltenes to assist in oil fingerprinting.

    Science.gov (United States)

    Riley, Brenden J; Lennard, Chris; Fuller, Stephen; Spikmans, Val

    2016-09-01

    A proof-of-concept spectroscopic method for crude and heavy fuel oil asphaltenes was developed to complement existing methods for source determination of oil spills. Current methods rely on the analysis of the volatile fraction of oils by Gas Chromatography (GC), whilst the non-volatile fraction, including asphaltenes, is discarded. By discarding the non-volatile fraction, important oil fingerprinting information is potentially lost. Ten oil samples representing various geographical regions were used in this study. The asphaltene fraction was precipitated from the oils using excess n-pentane, and analysed by Attenuated Total Reflectance Fourier Transform Infrared Spectroscopy (ATR-FTIR). Based on visual interpretation of FTIR spectra along with peak height ratio comparisons, all ten oil samples could be differentiated from one another. Furthermore, ATR-FTIR was not able to differentiate a weathered crude oil sample from its source sample, demonstrating significant potential for the application of asphaltenes in oil fingerprinting.

  16. 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)

  17. 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.

  18. 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.

  19. Evaluation of hydrotreating reaction time of Furrial crude oil for improvement of asphaltene and their fractions in p-nitrophenol

    Energy Technology Data Exchange (ETDEWEB)

    Luis, M.A. [Univ. de Carabobo, Estado Carabobo (Venezuela, Bolivarian Republic of). Dept. de Quimica, Laboratorio de Catalisis y Metales de Transicion; Villasana, Y. [Univ. de Carabobo, Estado Carabobo (Venezuela, Bolivarian Republic of). Dept. de Quimica, Laboratorio de Catalisis y Metales de Transicion; Univ. de Carabobo, Estado Carabobo (Venezuela, Bolivarian Republic of). Dept. de Quimica, Grupo de Petroleo, Hidrocarburo y Derivados; Labrador, H. [Univ. de Carabobo, Estado Carabobo (Venezuela, Bolivarian Republic of). Dept. de Quimica, Grupo de Petroleo, Hidrocarburo y Derivados

    2008-07-01

    This study evaluated the hydrotreating (HDT) reaction time of Furrial crude oil using NiMoS/g- Al2O3 as a catalyst. The objective was to improve asphaltene and their fractions obtained by the p-nitrophenol method. The reaction conditions in terms of temperature, pressure and stirring times in the batch reactor were presented. Two hydrotreating reactions were conducted without catalysts at 6 and 8 hours under the same conditions in order to compare the effect of the catalyst on the asphaltene. In addition, 2 other reactions were conducted in which the catalysts were varied. The hydrotreated asphaltene was precipitated with n-heptane, and was later fractionated using the p-nitrophenol method (PNP). Two fractions were obtained. One was insoluble in toluene, while the other was a soluble fraction. Nuclear magnetic resonance and elemental analysis of C, H, N and S were used to characterize the asphaltene obtained in each reaction along with their fractions. The optimum reaction time was 6 hours. The asphaltene was as stable as the original and was predominantly aliphatic with less nitrogen and sulphur content. The hydrotreating reactions without a catalyst did not improve the asphaltene characteristic.

  20. On the determination of molecular weight distributions of asphaltenes and their aggregates in laser desorption ionization experiments

    Energy Technology Data Exchange (ETDEWEB)

    Hortal, A.R.; Martinez-Haya, B.; Lobato, M.D.; Pedrosa, J.M.; Lago, S. [University of Pablo Olavide, Seville (Spain)

    2006-07-15

    Molecular weight distributions (MWD) of asphaltenes and their aggregates have been investigated in laser desorption ionization (LDI) mass spectrometric experiments. A systematic investigation of the dependence of the measured MIND on the asphaltene sample density and on the laser pulse energy allows the assignment of most probable molecular weights within 300-500 amu and average molecular weights of 800-1000 amu for the monomeric asphaltenes, as well as for the estimation of the contribution from asphaltene clusters in typical LDI measurements. The results serve to reconcile the existing controversy between earlier mass spectrometric characterizations of asphaltenes based on laser desorption techniques by different groups. Furthermore, the MWD measurements performed on particularly dense samples yield an additional differentiated broad band peaking around 9000-10,000 amu and extending over 20,000 amu, not observed previously in LDI experiments, thereby revealing a strong propensity of the asphaltenes to form clusters with specific aggregation numbers, which is in qualitative agreement with previous theoretical predictions and with the interpretation of measurements performed with other techniques.

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

    Science.gov (United States)

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

    2007-07-01

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

  2. Composting and vermicomposting experiences in the treatment and bioconversion of asphaltens from the Prestige oil spill.

    Science.gov (United States)

    Martín-Gil, Jesús; Navas-Gracia, Luís Manuel; Gómez-Sobrino, Ernesto; Correa-Guimaraes, Adriana; Hernández-Navarro, Salvador; Sánchez-Báscones, Mercedes; del Carmen Ramos-Sánchez, María

    2008-04-01

    This work illustrates the effectiveness of composting and vermicomposting in degrading fuel-in-water emulsions from oil spills (chapapote), and the isolation of potentially useful microorganisms for its biodegradation. Firstly, an alternative to the biodegradation of asphaltens from the Prestige oil spill (still present in some chapapote rafts in the Cantabrian coast) by means of the application of composting techniques to a microbial partnership acclimated to fuel-oil is offered. Our aim is that, after a relatively short period of time, the microorganisms can obtain its source of carbon and energy from asphaltens. The addition of metabolic co-substrates, like cow bed and potato peelings, allows the fragmentation of complex compounds into smaller structures, susceptible to further degradation. Afterwards, a maturation of the compost by means of a treatment with earthworms (Eisenia foetida) is necessary. Thus, through the vermicomposting it will be possible to obtain a valued product, useful in the processes of ground amendment, with little presence of asphaltens and occluded polycyclic aromatic hydrocarbons, rich in humus, and with an important bacterial flora of Bacillus genera, so that it can be typical of co-activators and accelerating products in composting processes. Along with this article, we show some parameters that control the evolution of the compost products (evolved gases, acidity, temperature and humidity); the chemical and microbiological analytical results; and the germination assays of vermicomposting. Results reveal that by using microorganisms living in either earthworm intestines (Stenotrophomonas maltophilia) or vermiculture substrates (Scedosporium apiospermium), it is possible to degrade and to eliminate the polycyclic asphaltens into CO(2) and H(2)O, helped by evaporation, dissolution and/or photo-oxidation processes. The obtained end product has contents of interesting vegetal nutrients and, mainly, it displays very high germination indices.

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

    Energy Technology Data Exchange (ETDEWEB)

    Aske, Narve

    2002-06-01

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

  4. Chemistry and structure of coal-derived asphaltenes, Phase III. Quarterly progress report, April--June 1978

    Energy Technology Data Exchange (ETDEWEB)

    Yen, T. F.

    1978-01-01

    Solubility parameters may be calculated for coal liquid derived products by use of a semi-empirical relationship between solubility parameter and refractive index. Thermal treatment of Synthoil coal liquid oil + resin solvent fraction at 235 to 300/sup 0/C resulted in the transformation of oil and resin into asphaltene. Further support of structural characterizations was obtained by use of a combined x-ray and NMR structural characterization procedure which relies on the important x-ray structural parameter L/sub a/ (average layer diameter of the aromatic sheet). L/sub a/ values of approx. = 8 to 10 A for asphaltenes, approx. = 13.4 to 14 A for carbenes, and approx. = 14 to 16.5 A for carboids were obtained by the x-ray procedure. These data were used to calculate C/sub Au/ (aromatic carbons per structural unit) and N (number of structural units per molecule) values. For asphaltenes the results agree with those previously deduced from NMR and other techniques. The C/sub Au/ values are generally close to 14 which is the number of aromatic carbons present in a 3-ring kata-system such as anthracene or phenanthrene. The number of structural units per molecule is close to two for all the asphaltenes. Additional data were used to improve the correlation equation between weight percent OH, determined by the silylation method, and the absorbance of the monomeric OH infrared stretching band at 3600 cm/sup -1/ for asphaltenes. A similar correlation between weight percent NH, from elemental analysis of asphaltene samples containing essentially all nitrogen as pyrrolic N-H, and the infrared absorbance of the N-H stretching band at 3470 cm/sup -1/ was developed for asphaltenes.

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

    Science.gov (United States)

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

    2016-06-01

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

  6. 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.

  7. Biological marker distribution in coexisting kerogen, bitumen and asphaltenes in Monterey Formation diatomite, California

    Science.gov (United States)

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

    1986-01-01

    Organic-rich (18.2%) Monterey Formation diatomite from California was studied. The organic matter consist of 94% bitumen and 6% kerogen. Biological markers from the bitumen and from pyrolysates of the coexisting asphaltenes and kerogen were analyzed in order to elucidate the relationship between the various fractions of the organic matter. While 17 alpha(H), 18 alpha(H), 21 alpha(H)-28,30-bisnorhopane was present in the bitumen and in the pryolysate of the asphaltenes, it was not detected in the pyrolysates of the kerogen. A C40-isoprenoid with "head to head" linkage, however, was present in pyrolysates of both kerogen and asphaltenes, but not in the bitumen from the diatomite. The maturation level of the bitumen, based on the extent of isomerization of steranes and hopanes, was that of a mature oil, whereas the pyrolysate from the kerogen showed a considerably lower maturation level. These relationships indicate that the bitumen may not be indigenous to the diatomite and that it is a mature oil that migrated into the rock. We consider the possibility, however, that some of the 28,30-bisnorhopane-rich Monterey Formation oils have not been generated through thermal degradation of kerogen, but have been expelled from the source rock at an early stage of diagenesis.

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

    Directory of Open Access Journals (Sweden)

    Omer El-Amin Ahmed Adam

    2013-01-01

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

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

    DEFF Research Database (Denmark)

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

    2016-01-01

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

  10. Colloidal analysis of the asphaltene and their fractions with p-nitrophenol (PNP) of the Furrial crude oil for effect of the hydrotreating to different pressures

    Energy Technology Data Exchange (ETDEWEB)

    Labrador-Sanchez, H. [Univ. de Carabobo, Estado Carabobo (Venezuela, Bolivarian Republic of). Dept. de Quimica, Grupo de Petroleo, Hidrocarburo y Derivados; Lindarte, L. [Univ. de Carabobo, Estado Carabobo (Venezuela, Bolivarian Republic of). Dept. de Quimica, Grupo de Petroleo, Hidrocarburo y Derivados; Univ. de Carabobo, Estado Carabobo (Venezuela, Bolivarian Republic of). Dept. de Quimica, Laboratorio de Catalisis y Metales de Transicion; Luis, M.A. [Univ. de Carabobo, Estado Carabobo (Venezuela, Bolivarian Republic of). Dept. de Quimica, Laboratorio de Catalisis y Metales de Transicion

    2008-07-01

    A study was conducted to investigate the effect of hydrotreating Furrial crude oil on asphaltene and its fractions (A1 and A2) obtained by the p-Nitrophenol (PNP) method. A batch reactor was used at different pressures of hydrogen to perform 8 hydrotreating reactions on the Furrial crude oil. Asphaltenes were separated from the oil and fractioned with PNP to obtain A1 and A2. The asphaltene and their fractions were characterized for flocculation threshold, percentage of total sulfur, nuclear magnetic resonance of 13C and elemental composition. The study showed that hydrotreating influenced the colloidal behaviour of the asphaltene and that the catalyst promoted the conversion of asphaltene, its stability, and its desulfurization. Hydrotreating had a greater affect on the A2 fraction than the A1 fraction. 2 refs.

  11. 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

    dependency upon the saturates, aromatics, resins, and asphaltenes (SARA) analysis or molecular weight (MW) of asphaltene is also analyzed. In addition, a unique characteristic of the model for the given stock tank oil (STO) is identified, which does not change with different types and amounts of gas...... injections and also remains the same at upper and lower onset pressure boundaries. On the basis of this unique characteristic, a simple procedure to predict asphaltene phase envelope (APE) for the reservoir oil with relatively simple and few experimental data, performed on STO with n......-pentane/n-heptane as a precipitant, is proposed. This proposed procedure avoids the need of high-pressure measurements of upper onset pressure (UOP)....

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2001-07-01

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

  13. Investigation of some solvents for asphalten-wax-paraffin depositions formed on the oil refinery equipment

    Directory of Open Access Journals (Sweden)

    О. В. Тертишна

    2013-07-01

    Full Text Available Тhe methods of asphalten - wax- paraffin depositions removal from the oil refinery equipment were studied. The effectiveness of solvents were estimated by mass losses of samples wrapped up in filter paper after exposition in different reagents, such as once-run petrol, benzene, toluene, hexane and some mixtures of these substances. The best results were obtained in the hexane - benzene mixture with volume ratio 1:1. The maximal level of dissolution was achieved at 30-35 °С

  14. COMPATIBILITY STUDIES ON POLYMER/WAX AND POLYMER/RESIN-ASPHALTENE BY VISCOMETRY AND PHOTOMICROGRAPHY

    Institute of Scientific and Technical Information of China (English)

    QIAN Jinwen; QI Guorong; DING Xinzhe; YANG Shiling

    1997-01-01

    The compatibility of mixtures of polymeric pour point depressants, i.e. poly(ethylene-co-vinylacetate) (EVA), poly(EVA-graft-octadecylacrylate) (EVA-g-POA), poly(ethylene-co-octadecylacrylate) (EOA) and poly(ethylene oxide-co-propylene oxide) (EO-co-PO) with wax or resin-asphaltene from crude oil have been studied by means of dilute-solution viscometry. It was found that each mixture pair is incompatible, but the degrees of incompatibility are quite different, which are in good agreement with the results from photomicrography.

  15. Carbon isotopic compositions of 1,2,3,4-tetramethylbenzene in marine oil asphaltenes from the Tarim Basin: Evidence for the source formed in a strongly reducing environment

    Institute of Scientific and Technical Information of China (English)

    JIA WangLu; PENG PingAn; XIAO ZhongYao

    2008-01-01

    Although 1-alkyl-2,3,6-trimethylbenzenes and a high relative amount of 1,2,3,4-tetramethylbenzene have been detected in marine oils and oil asphaltenes from Tabei uplift in the Tarim Basin, their biological sources are not determined. This paper deals with the molecular characteristics of typical marine oil asphaltenes from Tabei and Tazhong uplift in the Tarim Basin and the stable carbon isotopic signatures of individual compounds in the pyrolysates of these asphaltenes using flash pyrolysis-gas chromatograph-mass spectrometer (PY-GC-MS) and gas chromatograph-stable isotope ratio mass spectrometer (GC-C-IRMS), respectively. Relatively abundant 1,2,3,4-tetramethylbenzene is detected in the pyrolysates of these marine oil asphaltenes from the Tarim Basin. δ13C values of 1,2,3,4-tetramethylbenzene in the pyrolysates of oil asphaltenes vary from -19.6‰ to -24.0‰, while those of n-alkanes in the pyrolysates show a range from -33.2‰ to -35.1‰. The 1,2,3,4-tetramethylbenzene in the pyrolysates of oil asphaltenes proves to be significantly enriched in 13C relative to n-alkanes in the pyrolysates and oil asphaltenes by 10.8‰-15.2%. and 8.4‰-13.4‰, respectively. This result indicates a contribution from photosynthetic green sulfur bacteria Chlorobiaceae to relatively abundant 1,2,3,4-tetramethylbenzene in marine oil asphaltenes from the Tarim Basin. Hence, it can be speculated that the source of most marine oil asphaltenes from the Tarim Basin was formed in a strongly reducing water body enriched in H2S under euxinic conditions.

  16. 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

  17. Hydrogen bonding in asphaltenes and coal. Progress report, April 1, 1978--June 30, 1978

    Energy Technology Data Exchange (ETDEWEB)

    Li, N.C.; Tewari, K.C.

    1978-06-01

    A direct calorimetric method has been used to determine simultaneously the molar enthalpy, ..delta..H/sup 0/, and equilibrium constant, K, for quinoline (QU) interaction with coal-derived asphaltenes (A), acid/neutral (AA) and base (BA) components of A, silylated asphaltenes (A(TMS)) and heavy oil (HO) fractions in solvent C/sub 6/H/sub 6/. Solvent fractionated A and HO fractions were from three centrifuged liquid product (CLP) samples prepared in the 450 kg (/sup 1///sub 2/ ton) per-day Process Development Unit at Pittsburgh Energy Research Center, at different process conditions from the same feed coal, Kentucky hvAb. For a given system, Qu-A (AA or BA), Qu-HO, the almost constant value of K and linear variation of ..delta..H/sup 0/ with the phenolic oxygen content of coal liquid fractions, have been attributed to the dominance of hydrogen-bonding effects, involving phenolic OH, over other types of molecular interactions in solution. In Qu-A(TMS) system, -..delta..H/sup 0/ values increase with decrease in molecular weight of A(TMS), while -..delta..S/sup 0/ values increase with increase in aromaticity of A fraction. The degree of complexation, in absence of OH groups, is much smaller than Qu-A system and largely depends upon some unusual entropy effects.

  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. Enthalpies of hydrogen bonding of quinoline with o-phenylphenol and of hydrogen-bonding reactions involving the acid and base components of a coal-derived asphaltene

    Energy Technology Data Exchange (ETDEWEB)

    Dietz, A.G.; Blaha, C.; Li, N.C.

    1977-01-01

    Calorimetric studies are reported of hydrogen bonding between quinoline (Qu) and o-phenylphenol (OPP). The enthalpies of hydrogen-bonding of the acid and base components of a coal-derived asphaltene with OPP and Qu are also reported. The results provide strong evidence that the acid and base components of asphaltene function substantially as hydrogen donor and acceptor, respectively. 1 figure, 1 table.

  20. Study of the chemical structure of petroleum asphaltenes by spectral methods

    Energy Technology Data Exchange (ETDEWEB)

    Posadov, I.A.; Pokonova, Yu.V.; Khusidman, M.B.; Gitlin, I.G.; Proskuryakov, V.A.

    1977-03-01

    Results of nuclear magnetic resonance (NMR), ultraviolet (UV), and infrared (IR) spectroscopy studies of the chemical and supermolecular structure of asphaltene concentrates isolated from petroleum residues are reported. Considerable intensity of a characteristic series of absorption bands at 750, 810, 870, 1560, 1600, and 3030 cm/sup -1/ is interpreted as indicative of aromatic structures; while the bands at 870 and 810 cm/sup -1/ are taken as evidence of the predominant presence of highly substituted aromatic rings which are apparently included in alicyclic structures but do not form polynuclear condensed aromatic systems. The bathochromic shift of the electronic absorption spectrum in the region of 250-600 nm and the weak inflection at 300-310 nm are attributed to the partial condensation of the aromatic rings with predominance of fragments of the bi- and tricyclic types. The percentage content of various organic groups, the degree of polycondensation, the degree of potential for substitution, and the elementary composition are reported.

  1. Surface chemistry and spectroscopy of UG8 asphaltene Langmuir film, part 1.

    Science.gov (United States)

    Orbulescu, Jhony; Mullins, Oliver C; Leblanc, Roger M

    2010-10-05

    This research focuses on a systematic investigation of UG8 asphaltene Langmuir films at the air-water interface using toluene as the spreading solvent. From the surface pressure-area isotherms, it was concluded that small-sized aggregates are spread on the water surface and the compression of the film leads to formation of large aggregates. Our methods provide a stringent test and confirmation for the formation of corresponding asphaltene nanoaggregates that have recently been proposed for bulk solutions. These results were confirmed by compression-decompression isotherms, Brewster angle microscopy, and p-polarized infrared reflection-absorption spectroscopy. The transfer of a single layer using both the Langmuir-Schaefer and Langmuir-Blodgett deposition techniques shows different aggregate shapes depending on the technique used as imaged using atomic force microscopy. The films reveal the existence of nanoaggregates spread on the water surface that coexist with large aggregates formed during compression. For the nanoaggregate, the thickness of the Langmuir-Schaefer and Langmuir-Blodgett films determined by AFM is consistent with small aggregation numbers of nanoaggregates determined by Langmuir film compression. In addition to these findings, the spreading solvent, toluene, was found to be trapped within the aggregates as confirmed by in situ UV-vis spectroscopy at the air-water interface. This result was possible only after waiting a time period of 1 h to allow the complete evaporation of the spreading solvent. This is the only study that reveals the presence of the in situ toluene within the UG8 aggregates directly at the air-water interface.

  2. Hydrogen-bonding studies of pyridine and 0-phenylphenol with coal asphaltenes by multi-nuclei magnetic resonance

    Energy Technology Data Exchange (ETDEWEB)

    Schweighardt, F.K.; Friedel, R.A.; Retcofsky, H.L.

    1976-01-01

    Proton, carbon, and nitrogen-14 nuclear magnetic resonance studies are reported of hydrogen bonding between the OH proton of o-phenylphenol (OPP) and the nitrogen electron donor of pyridine (Py). Data are also reported on the hydrogen bonding of the acid and base components of coal-derived asphaltenes with the model system. Determination was made of the equilibrium constant of the 1:1 complex between OPP and Py from the proton NMR studies. Qualitative results are reported from the /sup 13/C and /sup 14/N studies of the model system (OPP-Py) with the individual asphaltene fractions. Because of the recent renewed interest in coal liquefaction this investigation may provide a starting point for future research. 7 figures.

  3. Comparative Morphological Study of Asphaltenes in Cuban Crude Using N-Pentane and N-Hexane as Precipitating Agent

    Directory of Open Access Journals (Sweden)

    Doramis de la Caridad Vega Torres

    2015-07-01

    Full Text Available The components of petroleum are grouped into four organic classes such as: Saturated, Aromatic,Resins and Asphaltenes. Asphaltenes are compounds with a complex structure and high molecularweight, made up by carbon rings linked to alkyl chains and cycloalkanes in addition to heterocycliccompounds with. Nitrogen, Sulphur, and Oxygen. Their precipitation of compounds is associated withprocess of production, transportation and refining of crude oil. Recent studies have proved that asphalteneprecipitates vary depending on the precipitating agent used. The research objective in this study isdeveloping a comparative morphological evaluation to asphaltene samples in crude oils from Seboruco,Santa Cruz, Cabaña and Pina. The asphalting precipitations were obtained employed ASTMD-6560-00,using n-pentane and n-hexane as precipitation agents. It was characterized through the use of a ScanningElectron Microscope using 20 KV acceleration. Solids made up by overlapping flakes linked toform agglomerates were obtained with n-hexane and solids with a higher porosity were obtained withn-pentane. Such behavior is attributed to the occupied spaces where resins were initially. The quantityof precipitate that was obtained with n-pentane is higher than the one obtained with the use of n-hexane.

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

    Energy Technology Data Exchange (ETDEWEB)

    Guin, J.A.

    1998-12-31

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

  5. 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.

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

    Directory of Open Access Journals (Sweden)

    Szewczyk V.

    2006-11-01

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

  7. Asphalts and asphaltenes: Macromolecular structure, precipitation properties, and flow in porous media

    Science.gov (United States)

    Rassamdana, Hossein

    Depending on rock and fluid properties, more than 50% of reservoir oil in place is normally produced by enhanced oil recovery (EOR) methods. Among the EOR techniques, miscible flooding is one of the most efficient and widely-used methods. However, this method can suffer from the formation and precipitation of asphalt aggregates. In addition, asphalt deposition is also a major hindrance to heavy oil production, and even primary recovery operations. Asphalt deposition can alter the reservoir rock properties, fluid saturation distribution, fluid flow properties, and eventually the ultimate oil recovery. The shortage of studies on the macromolecular structure and growth mechanisms of asphalt particles is the main reason for the unsuccessful modeling of their precipitation properties. The equivocal behavior of asphalt under some specific conditions could be the other reason. In this research we look at the problem of asphalt formation, flow, and precipitation from three different angles. We analyze extensive small-angle X-ray and neutron scattering data, precipitation data, and molecular weight distribution measurements, and show that they all suggest conclusively that asphalts and asphaltenes are fractal aggregates, and their growth mechanisms are diffusion-limited particle (DLP) and diffusion-limited cluster-cluster (DLCC) aggregation processes. These results lead us to development of a scaling equation of state for predicting asphalt precipitation properties, such as its onset and amount of precipitation. Another result of our study is an analytical equation for modeling the molecular weight distribution of asphalt and asphaltene aggregates. In addition, asphalt phase behavior in miscible and immiscible injections is studied. The effect of the governing thermodynamic factors, such as the pressure, temperature, and composition of the oil and precipitation agents, on the asphalt aggregation and disaggregation processes are investigated. Finally, a model is developed to

  8. 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)

  9. 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 (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 yield of distillates. Thermal cracking of asphaltenes in heavy oils and bitumens can

  10. Hydrogen bonding study of quinoline and coal-derived asphaltene components with o-phenylphenol by proton magnetic resonance. [9 references

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, S.R.; Galya, L.G.; Brown, B.J.; Li, N.C.

    1976-01-01

    Proton magnetic resonance (PMR) studies are reported of hydrogen bonding between the OH proton of o-phenylphenol (OPP) and the nitrogen electron donor of quinoline (Qu). Data are also reported on the hydrogen bonding of a coal-derived asphaltene and its acid and base components with OPP. Determination was made of the equilibrium constants of the 1 : 1 complex between OPP and Qu at 39, 32, 1, and -18/sup 0/C from the PMR studies. Qualitative results are reported for the interaction between the base fraction of asphaltene and OPP at 32, 1, and -26/sup 0/C.

  11. Hydrogen bonding study of quinoline and coal-derived asphaltene components with o-phenylphenol by proton magnetic resonance. [9 refs

    Energy Technology Data Exchange (ETDEWEB)

    Taylor, S.C.; Galya, L.G.; Brown, B.J.; Li, N.C.

    1976-01-01

    Proton magnetic resonance (PMR) studies are reported of hydrogen bonding between the OH proton of o-phenylphenol (OPP) and the nitrogen electron donor of quinoline (Qu). Data are also reported on the hydrogen bonding of a coal-derived asphaltene and its acid and base components with OPP. Determination was made of the equilibrium constants of the 1:1 complex between OPP and Qu at 39, 32, 1, and -18/sup 0/C from the PMR studies. Qualitative results are reported for the interaction between the base fraction of asphaltene and OPP at 32, 1, and -26/sup 0/C.

  12. Carbon isotopic compositions of 1,2,3,4-tetramethylbenzene in marine oil asphaltenes from the Tarim Basin:Evidence for the source formed in a strongly reducing environment

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    Although 1-alkyl-2,3,6-trimethylbenzenes and a high relative amount of 1,2,3,4-tetramethylbenzene have been detected in marine oils and oil asphaltenes from Tabei uplift in the Tarim Basin, their bio-logical sources are not determined. This paper deals with the molecular characteristics of typical ma-rine oil asphaltenes from Tabei and Tazhong uplift in the Tarim Basin and the stable carbon isotopic signatures of individual compounds in the pyrolysates of these asphaltenes using flash pyrolysis-gas chromatograph-mass spectrometer (PY-GC-MS) and gas chromatograph-stable isotope ratio mass spectrometer (GC-C-IRMS), respectively. Relatively abundant 1,2,3,4-tetramethylbenzene is detected in the pyrolysates of these marine oil asphaltenes from the Tarim Basin. δ 13C values of 1,2,3,4-tetrame-thylbenzene in the pyrolysates of oil asphaltenes vary from-19.6‰ to-24.0‰, while those of n-alkanes in the pyrolysates show a range from-33.2‰ to-35.1‰. The 1,2,3,4-tetramethylbenzene in the pyro-lysates of oil asphaltenes proves to be significantly enriched in 13C relative to n-alkanes in the pyro-lysates and oil asphaltenes by 10.8‰―15.2‰ and 8.4‰―13.4‰, respectively. This result indicates a contribution from photosynthetic green sulfur bacteria Chlorobiaceae to relatively abundant 1,2,3,4-tetramethylbenzene in marine oil asphaltenes from the Tarim Basin. Hence, it can be speculated that the source of most marine oil asphaltenes from the Tarim Basin was formed in a strongly reducing water body enriched in H2S under euxinic conditions.

  13. 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.

  14. 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)

  15. Exploring the structure-solubility relationship of asphaltene models in toluene, heptane, and amphiphiles using a molecular dynamic atomistic methodology.

    Science.gov (United States)

    Aray, Yosslen; Hernández-Bravo, Raiza; Parra, José G; Rodríguez, Jesús; Coll, David S

    2011-10-27

    The solubility parameters, δ, of several asphaltene models were calculated by mean of an atomistic NPT ensemble. Continental and archipelago models were explored. A relationship between the solubility parameter and the molecule structure was determined. In general, increase of the fused-rings number forming the aromatic core and the numbers of heteroatoms such as oxygen, nitrogen, and sulfur produces an increase of the solubility parameter, while increases of the numbers and length of the aliphatic chains yield a systematic decrease of this parameter. Molecules with large total carbon atom number at the tails, n(c), and small aromatic ring number, n(r), exhibit the biggest values of δ, while molecules with small n(c) and large n(r) show the smallest δ values. A good polynomial correlation δ = 5.967(n(r)/n(c)) - 3.062(n(r)/n(c))(2) + 0.507(n(r)/n(c))(3) + 16.593 with R(2) = 0.965 was found. The solubilities of the asphaltene models in toluene, heptane, and amphiphiles were studied using the Scatchard-Hildebrand and the Hansen sphere methodologies. Generally, there is a large affinity between the archipelago model and amphiphiles containing large aliphatic tails and no aromatic rings, while continental models show high affinity for amphiphiles containing an aromatic ring and small aliphatic chains.

  16. Far- and mid-infrared spectroscopy of complex organic matter of astrochemical interest: coal, heavy petroleum fractions, and asphaltenes

    CERN Document Server

    Cataldo, F; Manchado, A

    2012-01-01

    The coexistence of a large variety of molecular species (i.e., aromatic, cycloaliphatic and aliphatic) in several astrophysical environments suggests that unidentified IR emission (UIE) occurs from small solid particles containing a mix of aromatic and aliphatic structures (e.g., coal, petroleum, etc.), renewing the astronomical interest on this type of materials. A series of heavy petroleum fractions namely DAE, RAE, BQ-1, and asphaltenes derived from BQ-1 were used together with anthracite coal and bitumen as model compounds in matching the band pattern of the emission features of proto-planetary nebulae (PPNe). All the model materials were examined in the mid-infrared (2.5-16.7 um) and for the first time in the far-infrared (16.7-200 um), and the IR bands were compared with the UIE from PPNe. The best match of the PPNe band pattern is offered by the BQ-1 heavy aromatic oil fraction and by its asphaltenes fraction. Particularly interesting is the ability of BQ-1 to match the band pattern of the aromatic-ali...

  17. 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)

  18. 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.

  19. 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.

  20. Structure characterization of asphaltene from medium and low temperature coal tar%中低温煤焦油沥青烯的结构表征

    Institute of Scientific and Technical Information of China (English)

    杜庆阳; 张晶晶; 牛京超; 尚宁波; 孙智慧; 田盼盼; 李稳宏; 李冬

    2014-01-01

    The asphaltene of medium and low temperature coal tar from Shanbei was isolated.The composition and structure of asphaltene from coal tar were characterized by elemental analysis,average relative molecular mass determination,Fourier transform infrared (FTIR)spectroscopy technique and proton nuclear magnetic resonance (1 H-NMR),etc.The results show that the average relative molecular mass of the asphaltene is 652,with its average molecule formula of C39.12H31.3N1.26O7.34S0.51.The asphaltene mainly consists of highly condensed aromatic rings with aliphatic side chains and contains amounts of heteroatoms.The average alkyl chain length is 4 and methyl side chains are major substituents in the asphaltene sample.%采用甲苯溶解-正庚烷沉淀的方法从陕北中低温煤焦油中分离出沥青质,通过元素分析、平均相对分子质量、红外光谱分析、1 H-NMR等方法对其进行了分子结构研究。结果表明:该沥青质的平均相对分子质量为652,平均分子式为C39.12H31.3N1.26O7.34S0.51,其主要结构是多环稠合芳香烃并富含杂原子,且芳环上存在链长不一的烷基取代基,平均链长约为4个碳原子,甲基侧链相对较多。

  1. Far- and mid-infrared spectroscopy of complex organic matter of astrochemical interest: coal, heavy petroleum fractions and asphaltenes

    Science.gov (United States)

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

    2013-03-01

    The coexistence of a large variety of molecular species (i.e. aromatic, cycloaliphatic and aliphatic) in several astrophysical environments suggests that unidentified infrared emission (UIE) occurs from small solid particles containing a mix of aromatic and aliphatic structures (e.g. coal, petroleum, etc.), renewing the astronomical interest on this type of materials. A series of heavy petroleum fractions namely `distillate aromatic extract', `Residual Aromatic Extract', heavy aromatic fraction (BQ-1) and asphaltenes derived from BQ-1 were used together with anthracite coal and bitumen as model compounds in matching the band pattern of the emission features of proto-planetary nebulae (PPNe). All the model materials were examined in the mid-infrared (2.5-16.66 μm) and for the first time in the far-infrared (16.66-200 μm), and the infrared bands were compared with the UIE from PPNe. The best match of the PPNe band pattern is offered by the BQ-1 heavy aromatic oil fraction and by its asphaltenes fraction. Particularly interesting is the ability of BQ-1 to match the band pattern of the aromatic-aliphatic C-H stretching bands of certain PPNe, a result which is not achieved neither by the coal model nor by the other petroleum fractions considered here. This study shows that a new interesting molecular model of the emission features of PPNe is asphaltene molecules which are composed by an aromatic core containing three to four condensed aromatic rings surrounded by cycloaliphatic (naphtenic) and aliphatic alkyl chains. Instead, the weakness of the model involving a mixture of polycyclic aromatic hydrocarbons (PAHs) for modelling the aromatic infrared emission bands (AIBs) is shown. The laboratory spectra of these complex organic compounds represent a unique data set of high value for the astronomical community, e.g. they may be compared with the Herschel Space Observatory spectra (˜51-220 μm) of several astrophysical environments such as (proto-) planetary nebulae, H

  2. Influence of Hydrotreating Time on Hydrotreated Asphaltene Structure%加氢反应时间对塔河沥青质结构组成的影响

    Institute of Scientific and Technical Information of China (English)

    孙昱东; 杨朝合; 韩忠祥

    2015-01-01

    采用高压釜反应器进行塔河常压渣油正庚烷沥青质加氢反应,考察反应时间对加氢后沥青质结构组成的影响。结果表明,加氢后沥青质缔合体的平均相对分子质量、 nH/nC 、结构单元数 n以及芳香环系缩合度参数H AU/CA均减小,芳碳分率升高,沥青质在加氢反应过程中发生了明显的烷基侧链和环烷环脱除反应及缩合反应,使次生沥青质的缩合度增加。加氢后沥青质中Hα和Hγ所占总氢原子的比例减小, Hβ和HA 的比例增加,表明不仅沥青质分子中长的烷基侧链可以脱除,像甲基、乙基类的短烷基侧链也可以发生氢解反应。与原生沥青质相比,次生沥青质单元薄片的总环数和平均相对分子质量增大,说明单元薄片间可以发生脱氢缩合反应。随反应时间的延长,沥青质结构参数的变化幅度逐渐减小,沥青质的加氢转化反应时间以控制在2h左右为宜,过长的反应时间无益于反应的进一步进行。%T he influence of hydrotreating time on the structure parameters of hydrotreated asphaltene was studied in an autoclave .The results showed that the molecular mass ,nH/nC ,number of structural unit , HAU/CA of hydrotreated asphaltene decreased ,but the aromatic‐carbon ratio increased , compared to the original asphaltene .T he condensation degree of hydrotreated asphaltene increased due to the dealkylation and dehydrogenative condensation reactions during asphaltene hydrotreating ,in w hich the ratios of Hα and Hγ decreased but the ratios of Hβ and HA increased ,indicating that not only the long alkyl side chains ,but also the short alkyl side chains (such as methyl and ethyl) in asphaltenemolecule can be removed . The total number of rings and the relative mass of the structural unit in hydrotreated asphaltene increased . It is proved that the dehydrogenative condensation reactions occurred among asphaltene units in hydrotreating

  3. 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

  4. 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

  5. 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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-03-31

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

  7. 影响煤焦油沥青质测定量的工艺参数%Effect of process parameters on determination of asphaltene from coal tar

    Institute of Scientific and Technical Information of China (English)

    田盼盼; 郗小明; 李冬; 孙智慧; 李稳宏

    2014-01-01

    Solvent analysis is a method for quantitative separation of coal tar into toluene insoluble, asphaltene (toluene soluble,pentane insoluble),and oil (pentane soluble). The prime objective was to identify the variables in the procedure,including aromatic solvent type,extraction method,amount of toluene solution concentrate (degree of toluene boil-off) ,alkane solvent type,and ratio of n-heptane to toluene solution concentrate that affected the precipitate obtained for asphaltene content. Substitution of toluene with benzene and extraction method did not have a large effect on the precipitate reported for asphaltene. Heptane was chosen as alkane solvent instead of pentane. However amount of toluene solution concentrate and ratio of n-heptane to toluene solution concentrate did have a large effect on the precipitate reported as asphaltene. Coal tar from northern Shaanxi province was tested. With the suitable time of ultrasonic extraction for 3 hours,toluene solution concentrate of 9mL,a 20-fold of n-heptane over toluene solution concentrate,the asphaltene precipitate determined was 13.4%. The separation conditions of asphaltene determination should be indicated when studying the properties and structure of asphaltene from coal tar,since the coal tar separation technique have a large effect on asphaltene precipitated.%煤焦油通过溶剂分析可定量分离为三部分:甲苯不溶物、沥青质和油相。本文主要研究了煤焦油在此分离过程中芳烃溶剂类型、萃取方法、甲苯溶液浓缩量、烷烃溶剂类型和正庚烷溶剂与甲苯溶液浓缩量的添加比例对煤焦油沥青质沉淀量的影响。结果表明,甲苯溶液浓缩量、正庚烷与甲苯溶液浓缩量的添加比例对沥青质沉淀量的影响较大,萃取方法次之,将苯替换成甲苯影响最小。当选择甲苯溶解煤焦油,超声萃取3h,甲苯溶液浓缩量9mL,正庚烷与甲苯溶液浓缩液的添加比例为20∶1时,煤焦

  8. 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.

  9. Determination of the functional chemical structure of sulphur in asphaltenes using quantum mechanical ab-initio modelling and infra-red techniques

    Energy Technology Data Exchange (ETDEWEB)

    Hovell, Ian; Monte, Marisa de Mello; Coelho, Roberto Rodrigues [Centro de Tecnologia Mineral (CETEM), Rio de Janeiro, RJ (Brazil); Souza, Andre Lopes de [Universidade Federal do Rio de Janeiro (UFRJ), RJ (Brazil). Escola de Quimica

    2004-07-01

    In this work a proposed methodology of the characterization of organic sulphur compounds is proposed in agreement with its functionality for the elucidation of asphaltenic structures that contain sulphur. Theoretical Infrared spectra of organic sulphur compounds were modelled using quantum mechanical ab initio Hartree-Fock calculations. Using these spectra it is possible to identify the frequency corresponding to the vibrational transition of the C-S bond of the organic sulphur compounds studied. The experimental IR spectra were studied, of these same compounds, and their respective C-S bond frequencies were obtained. A good comparison was obtained when the theoretical vibrational frequencies when compared with the experimental vibrational frequencies. Finally, this proposed methodology was applied to the experimental deconvoluted DRIFTS, and theoretical spectra of an asphaltene from Brazilian VR's, with the elucidation of the organic sulphur that is present in the average molecule. (author)

  10. Linkage of Aromatic Ring Structures in Saturates, Aromatics, Resins and Asphaltenes Fractions of Vacuum Residues Determined by Collision-Induced Dissociation Technology

    Institute of Scientific and Technical Information of China (English)

    Wang Wei; Liu Yingrong; Liu Zelong; Hou Huandi; Tian Songbai

    2016-01-01

    The linkage of aromatic ring structures in vacuum residues was important for the reifning process. The Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) combined with collision-induced dissociation (CID) is a powerful method to characterize the molecular structure of petroleum fractions. In this work, model compounds with differ-ent aromatic ring structures were measured by CID FT-ICR MS. The cracking of the parent ions and the generated fragment ions were able to distinguish different linkage of the model compounds. Then, vacuum residues were separated into saturates, aromat-ics, resins and asphaltenes fractions (SARA), and each fraction was characterized by CID technology. According to the experi-mental results, the aromatic rings in saturates and aromatics fractions were mainly of the island-type structures, while the aromatic rings in resins and asphaltenes fractions had a signiifcant amount of archipelago-type structures.

  11. Ruthenium-ion-catalyzed oxidation of asphaltenes and oil-source correlation of heavy oils from the Lunnan and Tahe oilfields in the Tarim Basin, NW China

    Institute of Scientific and Technical Information of China (English)

    MA Anlai; ZHANG Shuichang; ZHANG Dajiang; JIN Zhijun; MA Xiaojuan; CHEN Qingtang

    2005-01-01

    The identification of marine source rocks in the Tarim Basin is debated vigorously. The intention of this paper is to investigate the asphaltenes in heavy oils from the Lunnan and Tahe oilfields and Well TD2 with ruthenium-ions-catalyzed oxidation technique (RICO), in order to explore its role in oil-oil and oil-source correlations. The RICO products included n-alkanoic acids, α, ω-di-n-alkanoic acids, branched alkanoic acids, tricyclic terpanoic acids, hopanoic acids, gammacerane carboxylic acid , regular sterane carboxylic acids and 4-methylsterane carboxylic acids. The n-alkyl chains and biomarkers bounded on the asphaltenes were of unsusceptibility to biodegradation. The distribution and absolute concentrations of n-alkanoic acids in the RICO products of heavy oils from the Lunnan and Tahe oilfields are different from those of Well TD2. The biomarkers bounded on the asphaltenes, especially steranes, have a distribution trend similar to that of the counterparts in saturates. The sterane carboxylic acids and 4-methylsterane carboxylic acids in the RICO products of heavy oils from the Lunnan and Tahe oilfields, dominated by C30 sterane and C31 4-methylsterane carboxylic acids, respectively, are significantly different from those of the heavy oils of Well TD2, whose dominating sterane and 4-methylsterane carboxylic acids are C2s sterane and C29 4-methylsterane acids, respectively. The RICO products of the asphaltenes further indicate that the Middle-Upper Ordovician may be the main source rocks for heavy oils from the Lunnan and Tahe oilfields.

  12. Observation of vanadyl porphyrins and sulfur-containing vanadyl porphyrins in a petroleum asphaltene by atmospheric pressure photonionization Fourier transform ion cyclotron resonance mass spectrometry.

    Science.gov (United States)

    Qian, Kuangnan; Mennito, Anthony S; Edwards, Kathleen E; Ferrughelli, Dave T

    2008-07-01

    Vanadyl (VO) porphyrins and sulfur-containing vanadyl (VOS) porphyrins of a wide carbon number range (C(26) to C(52)) and Z-number range (-28 to -54) were detected and identified in a petroleum asphaltene by atmospheric pressure photonionization (APPI) and Fourier transform ion cyclotron resonance mass spectrometry (FTICR-MS). APPI provides soft ionization of asphaltene molecules (including VO and VOS porphyrins), generating primarily molecular ions (M(+.)). The ultra-high mass resolving power (m/Delta m(FWHM) approximately 500 K) of FTICR-MS enabled resolution and positive identification of elemental formulae for the entire family of VO and VOS porphyrins in a complicated asphaltene matrix. Deocophylerythro-etioporphyrin (DPEP) is found to be the most prevalent structure, followed by etioporphyrins (etio)- and rhodo (benzo)-DPEP. The characteristic Z-distribution of VO porphyrins suggests benzene and naphthene increment in the growth of porphyrin ring structures. Bimodal carbon number distributions of VO porphyrins suggest possible different origins of low and high molecular weight species. To our knowledge, the observation of VOS porphyrins in a petroleum product has not previously been reported. The work is also the first direct identification of the entire vanadyl porphyrin family by ultra-high resolution mass spectrometry without chromatographic separation or demetallation.

  13. 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.

  14. 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

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

    Science.gov (United States)

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

    2013-07-01

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

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

    Science.gov (United States)

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

    2013-07-01

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

  17. 沥青质临氢热裂化转化规律初步研究%Preliminary Investigation on Behaviors of Thermal Conversion of Asphaltene in the Presence of Hydrogen and Catalyst

    Institute of Scientific and Technical Information of China (English)

    董明; 龙军; 王子军; 侯焕娣; 王威

    2015-01-01

    The asphaltene structure of Tahe VR was studied by using APPI + FT-ICR MS ,XPS et al .The behaviors of thermal conversion of Tahe VR asphaltene in the presence of hydrogen and catalyst were investigated .The results showed that the thermal conversion process was dominated by thermal cracking ,and the catalyst inhibited the condensation of asphaltene and hydrogenate aromatic rings to promote the conversion of asphaltene . In the appropriate conditions , the asphaltene conversion rate of Tahe VR reached 85.8% ,and cracking rate 78.2% .The conversion of secondary asphaltene was the key for the conversion of asphaltene . It is difficult for the condensed aromatics and N-heterocycle aromatics in the secondary asphaltene of Tahe VR to convert ,and conversion difficulties of HC (aromatic) ,N1 (N-heterocycle containing one N atom ) , N2 (N-heterocycle containing two N atoms) decreased in turn .The components of asphaltene with sulfur and two or more than two different heteroatoms were easier to convert .The hydrogenation reaction is the key for asphaltene upgrading .%运用APPI+结合FT-ICR MS、XPS等方法分析塔河沥青质结构。以塔河减压渣油为原料研究沥青质的临氢热裂化转化规律。结果表明,沥青质临氢热裂化过程中的裂化反应以热裂化为主,催化剂可以抑制沥青质的缩合反应,并对沥青质中芳环结构加氢以促进其转化。在合适的条件下,塔河减压渣油沥青质转化率可以达到85.8%,裂化率达到78.2%。次生沥青质的转化是沥青质转化的关键,次生沥青质中最难转化的是稠环芳烃结构和氮稠环结构,其转化难度按从难到易的顺序为 HC(芳烃结构)、N1(含1个氮原子的芳香性氮化物结构)、N2(含2个氮原子的芳香性氮化物结构)。含硫结构以及含有2种或多于2种杂原子的沥青质结构的转化率较高。加氢反应是沥青质轻质化的关键。

  18. 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.

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

    Directory of Open Access Journals (Sweden)

    Barre L.

    2006-12-01

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2013-06-05

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

  1. 轻质油油井沥青质沉淀清除作业%Cleanup operation of asphaltene precipitation in light oil wells

    Institute of Scientific and Technical Information of China (English)

    董涛; 王海涛; 高巧娟

    2015-01-01

    两伊边界轻质油油田主力产层A油组在生产过程中,沥青质在井筒析出、沉淀的现象很严重,是无水开采阶段影响油井生产时率的主要因素之一。A油组异常高压,地层原油中高含硫化氢,所以整个作业过程,油管和油套环空之间不允许建立循环,这些都给井筒沥青质沉淀清除工作带来了很大困难。本次施工先采用泵车小排量控压、分段挤入、分段浸泡以及分段返排的工艺,挤入过程中井筒被沥青沉淀堵死,之后改用连续油管通洗井和泵车小排量控压挤入与浸泡相结合的工艺,顺利完成作业,使油井恢复正常生产。本次作业历时5 d,现场施工过程艰难复杂,通过作业认识到高效的沥青质沉淀溶剂、连续油管通洗、泵车控压控排量挤入、浸泡时间和浸泡深度几方面紧密配合是保证施工成功的关键。%During production of the major productive zone-Oil Reservoir A in light oil oilifeld close to Iran and Iraq borders, asphaltene precipitation and settling in wellbore is a severe problems and is one of the factors which affect the production time efifciency of oil wells in water-free production period. The Oil Reservoir A has anomalously high pressure and formation crude oil contains large amount of hydrogen sulphide (H2S), so no circulation should be established between the tubing and casing annulus during the operation process. All these factors pose great dififculty for removing the asphaltene precipitation on wellbore. In this job, the pumping unit was ifrstly used to control the pressure with small displacement, squeeze in lfuid in stages and soak in stages and lfow back in stages. During squeezing, the wellbore was fully blocked by asphaltene precipitation.Then coiled tubing was used to drift and wash the well in conjunction with controlling the pressure by pumping unit with small displacement and soaking. The job was completed successfully and the

  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. 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)

  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. 沥青质裂解反应选择性分析%Analysis for the Selectivity of Asphaltene Cracking Reactions

    Institute of Scientific and Technical Information of China (English)

    赵迎宪; 危凤; 李达

    2011-01-01

    A pentane-insoluble asphaltene was processed by thermal cracking, thermal hydrocracking and catalytic hydrocracking over NiMo/γ-Al2O3 at 703 K, respectively. Analysis of selectivity showed that at the same level of asphaltene conversion and according to the selectivity of liquid products from high to low the three cracking reactions were in the order of catalytic hydrocracking, thermal hydrocracking, thermal cracking, while according to the selectivity of coke from high to low, the three cracking reactions were in the opposite order. In thermal cracking, a large amount of sulfur converted from the feed into coke, and in thermal hydrocracking, molecular hydrogen played a certain degree role in inhibiting formation of coke with high sulfur content, and in catalytic hydrocracking the catalyst effectively activated hydrogen molecules to hydrogenate the reactant and middle products, leading to a significant reduction of coke formation and remarkable improvement of liquid stability, selectivity and quality (lower average relative molecular mass and sulfur content).%在703K下,考察了1种正戊烷不溶的沥青质的热裂解、临氢热裂解和NiMo/y-Al2O3存在时的临氢催化裂解反应.结果表明,在相同的反应物转化率水平下,3种裂解反应按液体产物选择性从大到小的排列顺序为临氢催化裂解、临氢热裂解、热裂解反应,而按焦炭的选择性的排列顺序则相反.在热裂解反应中,沥青质中大量的硫被转化生成高硫焦炭;在临氢热裂解反应中,氢气分子对高硫焦炭的生成只起到有限的抑制作用;在临氢催化裂解反应中,催化剂充分激活氢气分子,使其有效地对沥青质及中间产物发生“加氢”(氢化)作用,显著地抑制了焦炭的生成,提高了液体产物的稳定性、选择性和品质(低相对分子质量和低硫含量).

  6. 稠油沥青质的基本化学组成结构与缔合性研究%STUDY ON CASIC CHE MICAL STRUCTURE AND ASSOCIATION OF ASPHALTENE IN HEAVY OIL

    Institute of Scientific and Technical Information of China (English)

    张庆; 邓文安; 李传; 吴乐乐

    2014-01-01

    从4种不同稠油中分离沉淀出正戊烷沥青质,用红外光谱表征了其官能团结构,用1 H-N MR 结合相对分子质量及元素分析测定了沥青质的基本结构参数,并得出了沥青质的平均分子式,同时测定了沥青质的偶极矩来表征其极性。研究结果表明:稠油沥青质分子中杂原子的存在使其含有较多的极性基团,沥青质具有较大极性。杂原子含量越高,其极性越大,缔合性越强,缔合数越高。此外,用两种方法计算了沥青质的分子直径,结果表明:相对分子质量越大时,沥青质分子尺寸越大,但特性黏度法测得的分子直径与其选用的溶剂有关,且关联出的分子直径偏大,而相对密度和相对分子质量法能较好地反映分子颗粒尺寸。%Four kinds of asphaltenes were obtained from four different heavy oils with n-pentane as solvent.Their functional structures were characterized by FTIR spectroscopy,and the basic structural parameters of the asphaltenes were determined by 1 H-NMR,then the average molecular formula of the asphaltene were given by molecular weight and element content.The dipole moments were also meas-ured to indicate the polarities of the asphaltene molecules.The results show that the presence of het-eroatom in asphaltene makes the asphalt form the polar groups with high polarity,and the higher the content of impurity atoms,the greater the polarity,the stronger the association,the higher the associa-tion numbers.In addition,molecular diameters were measured by two methods:intrinsic viscosity method,and relative density and relative molecular mass method.With the increase of relative molecu-lar mass,the molecular size of asphaltene becomes larger.However,the molecular diameter measured by viscosity method is related to the selected solvents and usually is larger than the size obtained by rela-tive density and relative molecular mass method,and the latter method can well reflect

  7. Study of Characteristics and Kinetics of Catalytic Degradation o f Asphaltene%沥青质催化降解特征及动力学研究

    Institute of Scientific and Technical Information of China (English)

    李术元; 郭绍辉; 沈润梅

    2001-01-01

    采用热解气相色谱仪(Py—GC),对东营凹陷烃源岩可溶有机质中的沥青质进行了热解模拟实验。考察了蒙脱石和K2CO3介质对沥青质催化降解过程的影响,求得了沥青质的催化降解动力学参数。结果表明,在K2CO3介质存在下,沥青质热解生成气态烃、轻烃和重烃的收率均有明显的提高,模拟温度下总检测烃收率提高了约20%;在蒙脱石介质存在下,除重烃收率下降外,气态烃和轻烃收率均有所提高,模拟温度下总检测烃收率提高了约10 %。与之相对应,除蒙脱石存在下重烃的生成活化能有所增加外,介质的存在均不同程度地降低了其它各热解产物的生成活化能。最后,对沥青质的催化降解机理进行了初步的探讨。%The thermal simulation experiments on the catalytic degra dation of Dongying asphaltene have been carried out by using pyrolysis gas chrom atography at the presence of mineral and salt. The isothermal experimental data are used to develop a kinetic model of the generation of the pyrolysates including g as hydrocarbon, light hydrocarbon and heavy hydrocarbon. It is found that K2CO 3 acts as a catalyst to promote the generation of all pyrolysates. At the temperat ure of 570 ℃, the yield of total hydrocarbons is increased by about 20% in the prese nce of K2CO3. Montmorillonite increases the yeild of gas and light hydrocarb on b ut decreases the yield of heavy hydrocarbon. At the temperature of 570 ℃, the yield of total hydrocarbons is increased by about 10% in the presence of montmoril lon ite. The higher activation energy is obtained for the generation of heavy hydro carbon in the presence of montmorillonite while the lower activation energies are calculated for other pyrolysates. Finally, the mechanism of catalytic degra da tion of asphaltene is tentatively investigated.

  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. 二氧化碳驱油藏沥青质沉淀量测量装置的实验研究%Experimental Study on Measuring Asphaltene Precipitation Volume in Carbon Dioxide Flooding Reservoir

    Institute of Scientific and Technical Information of China (English)

    胡杰; 何岩峰; 李栋; 王红梅; 李华明; 李森林

    2011-01-01

    设计了一套二氧化碳驱油藏沥青质沉淀量测量装置,该装置采用全密闭流程,借助计算机实现控制并做数据采集,对产出的气体进行同步气相色谱分析.使用该装置对某油田的二氧化碳驱进行实验分析,最终得出了地层温度、驱替压力对二氧化碳驱沥青质沉淀的影响关系.%A device boasting of a fully-enclosed process, and computer control and data acquisition was designed to measure asphaltene precipitation volume in carbon dioxide flooding reservoir and analyze the gas with gas chromatography. The designed device can withstand high pressures and temperatures and acid. The experimental analysis shows that this device helps obtain effects of both ground temperature and displacement pressure on the asphaltene precipitation in carbon dioxide flooding reservoir.

  10. 沥青质引发的蜡油体系结蜡层分层现象及分层规律%Stratification phenomenon and laws of wax deposits of waxy oil triggered by asphaltene addition

    Institute of Scientific and Technical Information of China (English)

    李传宪; 蔡金洋; 程梁; 杨飞; 张皓若; 张莹

    2016-01-01

    Stratification phenomenon and laws of wax deposits were studied for oil samples 1 (without asphaltene) and 2 (0.75%(mass) asphaltene) with the same wax content using the Couette wax deposition device. In the study of stratification phenomenon of wax deposits, the macroscopic morphology, DSC curves, amount of precipitated wax and wax crystal microcosmic morphology of the outer and inner deposits of oil samples 1 and 2 were analyzed. It was found that the deposit of oil sample 1 had no obvious stratification while that of oil sample 2 had obvious stratification, proving that the asphaltene led to the stratification of wax deposit. Compared with outer deposit, the WAT, amount of precipitated wax and asphaltene content of inner deposit of oil sample 2 increased significantly. It was found in the study of stratification laws of wax deposits that the outer wax deposition mass decreased with the increase of the temperature of wax deposition barrel, the temperature difference of oil and wax deposition barrel and the rotate speed of oil sample barrel, while the inner one deceased with the increase of the temperature of wax deposition barrel and increased with the temperature difference of oil and wax deposition barrel and the rotate speed of oil sample barrel. The total wax deposition mass deceased with the increase of the temperature of wax deposition barrel and the rotate speed of oil sample barrel, and increased firstly then decreased with the increase of the temperature difference of oil and wax deposition barrel.%利用自主研发的Couette结蜡装置,对蜡含量相同的油样1(不含沥青质)和油样2[含0.75%(质量分数)沥青质]进行结蜡实验,并研究其结蜡层的分层现象和分层规律。通过对油样1和油样2结蜡表层和底层的宏观形貌、DSC放热、析蜡量、蜡晶微观形貌的分析发现:油样1结蜡层无明显分层现象,而油样2结蜡层分层现象明显,沥青质的加入导致了结蜡层的分

  11. 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)

  12. 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

  13. 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.

  14. 煤/煤焦油/沥青质的热等离子体裂解特性比较分析%Comparison of pyrolysis performances of coal/coal tar/asphaltene in thermal plasmas

    Institute of Scientific and Technical Information of China (English)

    程炎; 颜彬航; 李天阳; 金涌; 程易

    2015-01-01

    针对化石资源劣质化和大宗低价值化工中间产品的反应工程新问题,提出利用热等离子体超高温特性实现极端条件下难利用原料的高效清洁转化,重点探讨并比较了煤化工中的原煤、煤焦油和石油化工中的沥青质的热等离子体裂解特性。通过热等离子体裂解实验室小试装置考察了3种典型原料的裂解行为,结果表明,煤焦油和沥青质具有高于煤的转化率和乙炔收率;建立了基于热力学的热等离子体裂解反应过程的能量平衡分析方法,模拟计算了不同操作条件下各原料在兆瓦级中试装置上的裂解结果,给出了相同等离子体能量注入的条件下不同原料裂解过程的物流和能流关系;并进一步模拟分析了原料间混合裂解的混料配比对裂解气的影响,为热等离子体裂解过程的工业原料筛选和原料混合裂解提供了科学依据。%The chemical reaction engineering nowadays is facing the new challenge from the degraded feedstocks of heavy fossil resources and low-value intermediate chemical products. Thermal plasma technique operated at extreme conditions (e.g., ultra-high temperature) is proposed as a potential means to realize the clean and efficient conversion of materials that are difficult to be handled using the conventional technologies. This work aims to study the pyrolysis performances of representative coal, coal tar and asphaltene materials in thermal plasmas. Experimental investigations were carried out on a lab-scale device to evaluate the pyrolysis characteristics of the feedstocks. The results showed that higher conversion and acetylene yield than coal can be achieved by using coal tar and asphaltene as the feeds. A model to describe the material and energy balances was established based on thermodynamics and the thermal effects in the thermal plasma process. The simulations on 2 MW pilot-plant scales were performed to compare the pyrolysis

  15. 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

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

    Directory of Open Access Journals (Sweden)

    Briant J.

    2006-11-01

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

  17. 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)

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

    Directory of Open Access Journals (Sweden)

    Minssieux L.

    2006-12-01

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

  19. Characteristics of Surface Functional Groups From Coal Tar Asphaltene and Its Influence on the Selection of Assistants in Slurry-Bed Hydrocracking%煤焦油沥青质的表面官能团特性及对悬浮床加氢裂化助剂选择的影响

    Institute of Scientific and Technical Information of China (English)

    邓文安; 吴乐乐; 王晓杰; 芦静; 李传

    2015-01-01

    以煤焦油常压渣油(T‐AR)为原料,分离出了正庚烷沥青质(T‐AR‐HI),通过元素分析、XPS、FT‐IR手段对该沥青质的表面官能团进行了表征,同时考察了不同助剂作用下T‐AR悬浮床加氢裂化反应过程中的生焦行为,进而分析了不同助剂对T‐AR沥青质的稳定作用机理。结果表明, T‐AR‐HI表面官能团以C—C、C— H、C—O为主;杂原子中O含量最高,杂原子官能团以含O官能团为主,其中醚类结构(C—O—C )占大多数;含N官能团主要为吡啶、吡咯和胺类,此外含有少量亚砜等含S官能团。表面官能团中,中性官能团总相对浓度为7.9%,酸性官能团为0.01%,碱性官能团为1.47%,沥青质表面呈弱碱性。SDBS、OA、CTAB 3种助剂对T‐AR沥青质的稳定作用依次降低,稳定作用主要取决于沥青质表面官能团与助剂之间的酸碱作用和氢键作用,其中酸碱作用影响较大。宜选取具有酸性基团的阴离子型双亲分子作为T‐AR悬浮床加氢裂化的助剂。%n‐Heptane asphaltene(HI) was isolated from coal tar atmospheric residue (T‐AR) .Its surface functional groups characteristics were studied by Element analysis ,XPS and FT‐IR .The coke formation in slurry bed hydrocracking of T‐AR in the presence of assistant and the mechanism of the stabilization of T‐AR asphaltene by different assistants were investigated simultaneously . The results indicated that the main surface functional groups of T‐AR‐HI were C—C ,C— H and C—O ,and the O content was highest in heteroatom contents .In addition ,O‐containing groups were the main part of heteroatom functional groups and appeared mainly as ethers structure (C—O—C) .N‐containing groups were mainly pyridine ,pyrrole and amine .Sulfoxides was detected as the main S‐containing functional group with the smallest content in the total heteroatom functional group contents .In the

  20. 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.

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

    Directory of Open Access Journals (Sweden)

    Monin J. C.

    2006-11-01

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

  2. 硝酸氧化对沥青烯基有序介孔炭电化学性能的影响%The influence of nitric acid oxidation on the electrochemical performance of asphaltene-based ordered mesoporous carbon

    Institute of Scientific and Technical Information of China (English)

    王六平; 周颖; 邱介山

    2011-01-01

    采用硝酸对沥青烯基有序介孔炭(Ordered mesoporous carbon,OMC)进行氧化处理,在硝酸浓度为5mol/L、40℃~100℃下,考察了氧化温度对沥青烯基OMC的孔结构和电化学性能的影响,讨论了不同表面化学氛围的OMC孔道内电解液离子的传输过程.OMC的结构表征和性能测试采用XRD、物理吸附仪和电化学工作站等技术.结果表明:适度的硝酸氧化处理可以有效地改善OMC的电化学性能,低温氧化处理在化学改性OMC表面的同时,仍能保持其规则的孔道结构,比表面积和孔容基本不变;60℃氧化处理时,OMC表现出良好的双电层电化学行为和频率响应特性,电容器可以保持较快的充放电速率,时间常数约为6s;在5mV·s-1的扫描速率下其质量比电容值和能量密度分别为138F·g-1和3.9Wh·kg-1,较改性前分别提高了57%和63%.%Asphaltene-based ordered mesoporous carbon ( OMC) was oxidized with 5 mol/L nitric acid at 40-100 ℃ . The influence of nitric acid oxidation treatment on its textural properties and electrochemical performance as a supercapacitor electrode material was investigated and the ionic transport behavior in relation to surface chemical structure was discussed. The pore structures and electrochemical performance were examined using XRD, nitrogen adsorption and an electrochemical workstation. Results indicate that electrochemical performance can be improved with nitric acid treatment under mild conditions. The regular mesostructure can be retained, and the surface areas and pore volumes vary slightly when oxidation temperature is below 60 ℃ . A capacitor assembled with the OMC sample oxidized at 60℃ exhibits excellent electric double layer behavior, improved frequency response characteristics and a fast charge-discharge rate with a time constant of 6s. The gravimetric specific capacitance and energy density of OMC oxidized at 60 ℃ are 138 F·g-1 and 3. 9 Wh.kg-1 respectively at a scanning rate of 5 m

  3. 煤液化重质产物的催化加氢裂解研究%Study of catalytic hydrocracking of asphaltenes from heavy products of coal liquefaction

    Institute of Scientific and Technical Information of China (English)

    康士刚; 宗志敏; 水恒福; 王知彩; 魏贤勇

    2011-01-01

    为了使煤直接液化的重质产物转化为轻质油类,利用管式高压反应釜,以四氢萘为溶剂、FeS和S为催化剂,对沥青烯进行了加氢裂解研究.考察了催化剂种类及加入量、反应温度和反应压力等因素对沥青烯加氢液化的转化率和产物分布的影响.利用FTIR与元素分析仪对原料沥青烯及残余沥青烯进行了结构表征.结果表明:在一定实验条件下,FeS加硫后使原料的转化率由30.76%增加至53.94%,油+气的产率也由6.01%增至38.39%,而逆向缩合程度减少了9%;两种催化体系下原料的液化转化率均随着温度的升高而增加,但不加硫时增加的幅度为15.20%,明显小于加硫时的23.83%;随着压力的增加,两种催化条件下原料的转化率均增加,而逆向缩合程度在不加硫时随着压力的增加而增加(16.17%,6~30.54%),加硫时则相反.%In order to upgrading the heavy products from Xiaolongtan lignite liquefaction, the hydrocracking experiments of asphaltenes (AS) were carried out with tetralin as solvent and FeS or sulfur as catalyst in a batch micro-autoclave. The effects of types and amount of catalyst, reaction temperature and hydrogen pressure on the distribution of liquefied products were investigated. The elementary and FTIR analyses were used to illustrate the structural characteristics of feedstock AS and residue ASs. The results indicate that under specific conditions,the addition of sulfur into FeS catalyst increases the conversion of feedstock AS from 30. 76 %to 53.94% with the yield of oil+gas from 6.01% to 38.39%. The retrogressive condensation is reduced by 9%. In the two cases, both the conversions of feedstock AS increase with the increasing of reaction temperature. The conversion increment of 15.20% without sulfur addition is distinctly lower than that of 23.83% with sulfur addition. With the increasing of initial H2 pressure, the conversions of feedstock AS increase in the two cases, where

  4. 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...

  5. 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

  6. 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

  7. HINDERED DIFFUSION OF ASPHALTENES AT EVALUATED TEMPERATURE AND PRESSURE

    Energy Technology Data Exchange (ETDEWEB)

    James A. Guin; Surya Vadlamani

    1999-04-01

    During this time period, we performed experiments to examine the effects of solvent composition on the diffusion controlled uptake of quinoline into alumina catalyst pellets. Of particular interest was the effect of solvent aromaticity on the diffusive uptake process. The uptake experiments were performed at a temperature of 300 C for the adsorptive diffusion of quinoline in a solvent mixture of mineral oil and 1-methyl naphthalene onto alumina catalyst pellets. These experiments were conducted in a 40 cm{sup 3} microautoclave, the use of which is more economical from both a purchasing and waste disposal standpoint due to the small quantities of solvents and catalysts utilized, and is also significantly safer at the higher temperatures. In order to study the effect of aromaticity of the solvent on the hindered diffusion-adsorption process, the experiments were performed at different volume fractions of 1-methyl naphthalene. Detailed calculations were made to estimate the effects of aromaticity, i. e., as reflected by the percentage of 1-methyl naphthalene in the solvent, on the diffusive properties of the solute. Model simulation results were then performed which showed that the mathematical model incorporating diffusion and adsorption mechanisms satisfactorily fitted the adsorptive diffusion of quinoline onto the alumina catalyst at 300 C with various solvent aromaticities. The logarithm of the adsorption constant at a particular volume fraction of 1-methyl naphthalene, obtained by simulating the experimental data with the model solution, was found to be linearly dependent on an aromaticity factor.

  8. 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.

  9. Influence of Heat Treatment Temperature on the Structure and Electrochemical Performance of Asphaltene-Based B/N Co-Doped Porous Carbons%热处理温度对沥青基硼氮共掺杂多孔炭结构与电化学性能的影响

    Institute of Scientific and Technical Information of China (English)

    周颖; 王道龙; 肖南; 侯雨辰; 邱介山

    2014-01-01

    B/N co-doped porous carbons have been synthesized by heat treatment at different temperatures using asphaltene from coal liquefaction residue as a carbon precursor, nitric acid as a nitrogen source, H3BO3 as a boron source and a pore-forming agent. The influence of the heat treatment temperature on the pore-structure and surface chemical properties was investigated, and the electrochemical performance in relation to the pore-structure and surface chemical properties was discussed. The crystal structure, morphology, pore-structure, composition and electrochemical performance were examined using X-ray diffraction (XRD), Raman spectroscopy, scanning electron microscopy (SEM), transmission electron microscopy (TEM), nitrogen adsorption, element analysis, inductively coupled plasma-atomic emission spectroscopy (ICP-AES), X-ray photoelectron spectroscopy (XPS), and an electrochemical workstation. The results of these analyses indicated that the crystal structure, pore-structure and surface properties were influenced significantly by the heat treatment process. Increases in the heat treatment temperature led to improvements in the degree of graphitization, as wel as gradual increases in the boron content. In contrast, the nitrogen content decreased and the specific surface area and total pore volume increases gradual y and then decline. The electrochemical performance was found to be dependent on the pore-structure and suitable surface chemical properties. The sample synthesized at 900 °C had a specific surface area of 1103 m2∙g-1, pore volume of 0.921 cm3∙g-1, nitrogen content of 5.256%(w), boron content of 1.703%(w), and a maximal specific capacitance of 349 F∙g-1 at 100 mA∙g-1 in 6 mol∙L-1 aqueous solution of KOH. The sample subjected to a heat treatment at 1000 °C had the best rate capability, with a capacity retention of 75%when the current density increased from 100 mA∙g-1 to 10 A∙g-1.%以煤液化沥青质为碳源、硝酸为氮源、硼酸为

  10. 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.

  11. 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.

  12. Hydrogen bonding in asphaltenes and coal liquids. Quarterly report, November 1, 1980-January 31, 1981

    Energy Technology Data Exchange (ETDEWEB)

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

    1981-01-01

    The aging characteristics of 30/70 (wt. %) blend of SRC I and SRC II and of a SRC II Middle Distillate (boiling point range 450 to 565/sup 0/K), have been studied. Viscometric, electron spin resonance, ultimate analysis, solvent separations, gel permeation chromatography, and 600-MHz measurements have been used to monitor the aging properties of the SRC liquids under various conditions. The viscosity of the blend increases significantly in ten days with oxygen bubbling at 335/sup 0/K. However, copper, in addition to oxygen, is necessary to significantly change the viscosity of the Middle Distillate. For the blend, there is a linear increase in the logarithm of viscosity with increasing wt. % of toluene-insolubles formed during oxygen-aging. There is also a linear decrease in the logarithm of viscosity with decreasing content of toluene-insolubles resulting from hydroprocessing of the blend with Ni-Mo catalyst. These observations indicate that under conditions of oxidative degradation the formation and content of larger molecular-size toluene-insolubles are mainly responsible for the increased viscosity of the blend. The middle distillate does not contain toluene-insolubles, and oxygen-aging occurs only in the presence of copper. Oxidative coupling of phenols is proposed as an aging mechanism for both the blend and the middle distillate.

  13. Hydrogen bonding in asphaltenes and coal liquids. Quarterly report, August 1, 1980-October 31, 1980

    Energy Technology Data Exchange (ETDEWEB)

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

    1980-01-01

    A coal-derived liquid (SRC-II) and its fractions have been characterized by 600 MHz /sup 1/H NMR spectrometer. Saturate fraction, being 8.1% by weight of unfractionated coal-liquid, is mainly composed of n-alkanes of high carbon numbers and the content of cycloalkanes is negligible. Aromatic fraction (49.0%) contains a considerable amount of partially hydrogenated polynuclear compounds. Double resonance techniques have been used for chemical shift identification of ..beta..-CH/sub 2/ and ..cap alpha..-CH/sub 2/ protons attached to aromatic ring structures. The decoupled signals may be used for quantitative analysis of donor hydrogens, which are known to be effective in hydrogen-transfer phenomenon in coal-liquefaction processes. The aromatic fraction contains larger amounts of CH/sub 3/ group attached to condensed aromatic ring structures, which appear as singlets in the region of 2.4 to 2.7 ppM, whereas in acidic fractions almost all benzylic CH/sub 3/ groups are attached to mono-aromatic ring structure (chemical-shift range of 2.2 to 2.3 ppM). The relatively strong acidic fraction, Acid-II (15.0%), can be recovered from anion-exchange resin by the elution with CO/sub 2/ saturated methanol after the elution with benzene. Acid-II is substantially composed of alkyl substituted mono-aromatic phenols and 75% of the fraction boil in the narrow boiling-point range of 461 to 516 K (370 to 470 F).

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

    Directory of Open Access Journals (Sweden)

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

    2016-11-01

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

  15. New caffeine bonded phase for separation of polyaromatic hydrocarbons and petroleum asphaltenes by high-performance liquid chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Felix, G.; Bertrand, C.; Gastel, F. van

    1985-03-01

    The preparation of a new caffeine phase for HPLC is described. The capacity ratios (k') of about ten polyaromatic hydrocarbons have been determined. It has been shown that the aromatics were eluted according the number of rings, only slightly influenced by the substituents. The performance of the stationary phase is demonstrated with separations of petroleum asphalts and residues and aromatic mixtures.

  16. Hydrogen bonding in asphaltenes and coal. Progress report, July 1, 1976--December 31, 1976. [Between quinoline and o-phenylphenol

    Energy Technology Data Exchange (ETDEWEB)

    Li, N.C.

    1977-01-04

    Calorimetric studies of hydrogen bonding between quinoline and o-phenylphenol were carried out because they represent the nitrogenous heteronuclear aromatic bases and aromatic bases, respectively, found in the liquefaction products from coal. Further experiments are planned to try to resolve discrepancies observed between experimental and calculated values. (EJH)

  17. 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.

  18. 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)

  19. Hydrogen bonding in asphaltenes and coal liquids. Quarterly report, May 1, 1981-July 31, 1981. [Effects of phenols or anisole on aging of SRC blends

    Energy Technology Data Exchange (ETDEWEB)

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

    1981-01-01

    Coal-derived liquids are very susceptible to oxidative degradation. Oxygen and temperature exert a dramatic effect on enhancing the viscosity of coal-derived fuels, and a free-radical mechanism is an obvious choice for the mechanism of this noted oxidative degradation. In the present study, several different phenols were added to blends consisting of two different ratios of SRC I and SRC II middle distillate: 20/80 and 30/70 by weight. The objective of this research is to study the effect of phenols on the aging of the SRC blends. It has been found that upon the addition of phenol itself, the original hydrogen bonding between the acidic and basic functional groups in the coal-derived liquids is apparently disrupted because the added phenol can now interact with the proton-accepting species in liquids, thus, leading to a lower viscosity. When anisole (which contains no hydroxyl group) is added instead of phenol, the effect of slowing down the aging process is much smaller. o-Phenylphenol is a hindered phenol, and the effect on the aging process is intermediate between anisole and phenol.

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

    DEFF Research Database (Denmark)

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

    2012-01-01

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

  1. 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.

  2. 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.

  3. 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.

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

    Directory of Open Access Journals (Sweden)

    Claudete Bernardo Henriques

    2011-01-01

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

  5. 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

    OpenAIRE

    Castex H.

    2006-01-01

    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 différencie...

  6. 状态方程法用于原油沥青质沉淀的计算%CALCULATION OF ASPHALTENE PRECIPITATION FROM CRUDE OIL USING PENG-ROBINSON EQUATION OF STATE

    Institute of Scientific and Technical Information of China (English)

    林雄森; 胡玉峰; 马昌峰; 杨继涛

    1999-01-01

    应用Peng-Robinson(PR)状态方程代替目前广泛使用的活度系数模型,对原油中沥青质的沉淀点及沉淀量进行了计算.利用实验数据反算原油中重组分的特征化参数,以解决目前原油重组分特征化较差的问题.计算结果表明,沥青质沉淀点的计算值与实验数据基本相符,但沉淀量计算结果尚不能令人满意.与常规特征化方法相比,PR状态方程法有了较大改进.

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

    Science.gov (United States)

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

    2014-01-14

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

  8. Viscosity, calorimetric, and proton magnetic resonance studies on coal liquid fractions in solution

    Energy Technology Data Exchange (ETDEWEB)

    Tewari, K.C.; Kan, N.; Susco, D.M.; Li, N.C.

    1979-02-01

    Two coal liquid products derived from the same Kentucky hvAb coal have been separated into toluene-insoluble, asphaltene, and pentane-soluble heavy oil fractions. Viscosity and calorimetric studies are reported of the interaction between heavy oil and asphaltene (A) and its acid/neutral (AA) and base (BA) components in solvent benzene. The increase in viscosity and molar enthalpy of interaction, ..delta..H/sup 0/, in the order BA > A > AA, correlates well with the proton magnetic resonance downfield chemical shift of the OH signal of o-phenylphenol, as a function of added asphaltene (A, AA, BA) concentration in solvent CS/sub 2/. The results suggest that when asphaltene and heavy oil are present together, hydrogen-bonding involving largely phenolic OH, is one of the mechanisms by which asphaltene-heavy oil interactions are achieved and, in part, is responsible for the viscosity increase of coal liquids. 4 figures, 3 tables.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1995-12-31

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

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-07-01

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

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

    Directory of Open Access Journals (Sweden)

    João Batista V. S. Ramalho

    2010-01-01

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

  12. 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.

  13. 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.

  14. 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.

  15. 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.

  16. 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)

  17. 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.

  18. 超声波处理对加氢反应前后沥青质单元分子结构的影响%Effect of ultrasonic treatment on the unit structure of pre-and post-hydrotreating asphaltenes

    Institute of Scientific and Technical Information of China (English)

    张强; 孙昱东; 杨朝合; 王雪

    2014-01-01

    以胜利减渣和沙轻减渣为原料,研究了超声波处理对加氢反应前后沥青质单元分子结构的影响,并结合1H-NMR数据、沥青质单元分子参数变化和红外光谱分析等结果,用Chem Bio Draw Ultra 2012模拟出不同条件下两种沥青质单元分子的结构.结果表明,超声波处理减少了沥青质的缔合数,使沥青质单元分子发生开环反应和脱烷基侧链反应加剧,改变了沥青质单元分子的结构,对加氢后沥青质单元分子的结构和组成产生重要影响.沥青质单元分子模型可形象体现超声波处理对加氢反应前后沥青质单元分子化学结构的影响,有助于在分子水平上解释超声波处理影响沥青质单元分子的原因.

  19. 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.

  20. Probing Intermolecular Interactions in Polycyclic Aromatic Hydrocarbons with 2D IR Spectroscopy

    Science.gov (United States)

    Krummel, Amber

    2014-03-01

    Polycyclic aromatic hydrocarbons (PAHs) are ubiquitous in the environment and impact geochemical processes that are critical to sustainable energy resources. For example, asphaltenes exist naturally in geologic formations and their aggregates heavily impact the petroleum economy. Unfortunately, the chemical dynamics that drive asphaltene nanoaggregation processes are still poorly understood. Solvent dynamics and intermolecular interactions such as π-stacking interactions play integral roles in asphaltene nanoaggregation. Linear and nonlinear vibrational spectroscopy including two-dimensional infrared spectroscopy (2DIR), are well suited to explore these fundamental interactions. Teasing apart the vibrational characteristics in PAHs that model asphaltenic compounds represents an important step towards utilizing 2D IR spectroscopy to understand the intermolecular interactions that are prevalent in asphaltene nanoaggregation. A solar dye, N,N'-Dioctyl-3,4,9,10-perylenedicarboximide, is used in this work to model aphaltenes. Carbonyl and ring vibrations are used to probe the nanoaggregates of the model compounds. However, the characteristics of these normal modes change as a function of the size of the conjugated ring system. Thus, in order to fully understand the nature of these normal modes, we include a systematic study of a series of quinones. Our investigation employs a combination of 2DIR spectroscopy and electronic structure calculations to explore vibrational coupling in quinones and PAHs. We compare the calculated vibrational characteristics to those extracted from 2DIR spectra. ATK acknowledges the Donors of the American Chemical Society Petroleum Research Fund for support of this research.

  1. Simple statistical model for branched aggregates

    DEFF Research Database (Denmark)

    Lemarchand, Claire; Hansen, Jesper Schmidt

    2015-01-01

    , given that it already has bonds with others. The model is applied here to asphaltene nanoaggregates observed in molecular dynamics simulations of Cooee bitumen. The variation with temperature of the probabilities deduced from this model is discussed in terms of statistical mechanics arguments......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....... The relevance of the statistical model in the case of asphaltene nanoaggregates is checked by comparing the predicted value of the probability for one molecule to have exactly i bonds with the same probability directly measured in the molecular dynamics simulations. The agreement is satisfactory...

  2. Properties of Tahe crude oil and influence of separation components on crude oil viscosity

    Energy Technology Data Exchange (ETDEWEB)

    Chaogang, Chen; Hongjun, Deng [Northwest Oilfield Branch Engineering and Technology Institute of Sinopec (China); Jixiang, Guo; Heyi, Wang; Meiqin, Lin [Enhanced Oil Recovery Research Center, China University of Petroleum (China)], email: guojx002@163.com

    2010-07-01

    The Tahe oil field in Xinjiang produces oil from depths of 5500m to 7000m whose temperatures range from 128 to 140 Celsius. The formation waters have a high salinity. To determine the major factors that contribute to the viscosity of the oil, such as saturate, aromatic resin, and asphaltene, a variety of techniques were used. Measurements were done using IR, scanning electron microscopy, energy spectrum analysis (EDX), elemental analysis, and ICP techniques. It was found, as predicted, that the viscosity of the crude oil decreased with increase of the temperature. However, different types of crude oil have various levels of temperature-sensitive turning points. The Tahe oil fields have a higher turning point due to the asphaltene and resins. To conduct the experiment the Tahe crude AD11 was separated into oil fractions using toluene as the solvent. It was concluded that the asphaltene has the greatest impact on viscosity.

  3. Use of X-ray diffraction in assessing the aging pattern of asphalt fractions

    Energy Technology Data Exchange (ETDEWEB)

    Siddiqui, M.N.; Ali, M.F.; Shirokoff, J. [King Fahd University of Petroleum and Minerals, Dhahran (Saudi Arabia). Dept. of Chemistry and The Research Institute

    2002-01-01

    The X-ray diffraction (XRD) method was employed to investigate and compare some of the crystallite parameters and aromaticity of asphaltenes obtained from fresh and aged Arabian asphalts, procured from Ras Tanura (RT) and Kuwait (KW) refineries. A new crystallite parameters in the polar aromatics, naphthene aromatics and saturate fractions of these Arabian asphalts were also determined. The results obtained by XRD method for both the types of asphaltenes and other fractions were evaluated and compared. Significant differences were observed between the structure and the aging patterns of fresh and aged asphaltenes of RT and KW asphalt. The results indicate that the source and chemistry of asphalt are responsible for the aging behavior of its components. The rolling thin-film oven and the pressurized aging vessels tests were used to simulate asphalt aging in this research. 21 refs., 5 figs., 4 tabs.

  4. COOEE bitumen: chemical aging

    CERN Document Server

    Lemarchand, Claire A; Dyre, Jeppe C; Hansen, Jesper S

    2013-01-01

    We study chemical aging in "COOEE bitumen" using molecular dynamic simulations. The 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 $\\rightarrow$ 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 is given.

  5. Mobilization and micellar solubilization of NAPL contaminants in aquifer rocks

    Science.gov (United States)

    Javanbakht, Gina; Goual, Lamia

    2016-02-01

    Surfactant-enhanced aquifer remediation is often performed to overcome the capillary forces that keep residual NAPL phases trapped within contaminated aquifers. The surfactant selection and displacement mechanism usually depend on the nature of NAPL constituents. For example, micellar solubilization is often used to cleanup DNAPLs from aquifers whereas mobilization is desirable in aquifers contaminated by LNAPLs. Although the majority of crude oils are LNAPLs, they often contain heavy organic macromolecules such as asphaltenes that are classified as DNAPLs. Asphaltenes contain surface-active components that tend to adsorb on rocks, altering their wettability. Previous studies revealed that surfactants that formed Winsor type III microemulsions could promote both mobilization and solubilization. However the extent by which these two mechanisms occur is still unclear, particularly in oil-contaminated aquifers. In this study we investigated the remediation of oil-contaminated aquifers using an environmentally friendly surfactant such as n-Dodecyl β-D-maltoside. Focus was given on asphaltenes to better understand the mechanisms of surfactant cleanup. Through phase behavior, spontaneous imbibition, dynamic interfacial tension and contact angle measurements, we showed that microemulsions formed by this surfactant are able to mobilize bulk NAPL (containing 9 wt.% asphaltenes) in the porous rock and solubilize DNAPL (i.e., 4-6 wt.% adsorbed asphaltenes) from the rock surface. Spontaneous imbibition tests, in particular, indicated that the ratio of mobilized to solubilized NAPL is about 6:1. Furthermore, aging the cores in NAPL beyond 3 days allowed for more NAPL to be trapped in the large pores of the rock but did not alter the amount of asphaltenes adsorbed on the mineral surface.

  6. 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.

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

    Directory of Open Access Journals (Sweden)

    Lyzette Gonçalves Moraes de Moura

    2011-01-01

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

  8. 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.

  9. 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.

  10. 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...

  11. Modification on coal- tar- pitch by additives%添加剂对煤沥青筑路油改质作用

    Institute of Scientific and Technical Information of China (English)

    朱静; 欧阳林; 刘忠安

    2001-01-01

    利用组成分析与热失重分析方法研究了不同添加剂对煤沥青筑路油的改质影响。不同添加剂改质后使沥青中软沥青和甲苯不溶物减少,沥青质增加。沥青质热失重动力学分析说明改质后的沥青质是由添加剂、原沥青质以及其它组分组成的复杂混合物,分子间靠范德华力与氢键力结合在一起。橡胶类添加剂对煤沥青的改质作用显著。%The modification on coal- tar- pitch by additives was investigated by composition and thermogravimetry. After modification the content of heptene soluble and toluene insoluble was decreased ,the content of asphaltene was increased. The kinetic analysis of thermogravimetry indicated that asphaltene modified consisted of additives, original asphaltene and others compositions.There were the forces of Van der Walls and hydrogen bonding among asphaltene modecules. The effect modified was remarkable to additiving rubbers.

  12. 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.

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

    Science.gov (United States)

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

    2015-01-01

    Organic-rich shales are populated by methanogenic consortia that are able to degrade the fossilized organic matter into methane gas. To identify the organic fraction effectively degraded, we have sequentially depleted two types of organic-rich sedimentary rocks, shale, and coal, at two different maturities, by successive solvent extractions to remove the most soluble fractions (maltenes and asphaltenes) and isolate kerogen. We show the ability of the consortia to produce methane from all rock samples, including those containing the most refractory organic matter, i.e., the kerogen. Shales yielded higher methane production than lignite and coal. Mature rocks yielded more methane than immature rocks. Surprisingly, the efficiency of the consortia was not influenced by the removal of the easily biodegradable fractions contained in the maltenes and asphaltenes. This suggests that one of the limitations of organic matter degradation in situ may be the accessibility to the carbon and energy source. Indeed, bitumen has a colloidal structure that may prevent the microbial consortia from reaching the asphaltenes in the bulk rock. Solvent extractions might favor the access to asphaltenes and kerogen by modifying the spatial organization of the molecules in the rock matrix. PMID:26136731

  14. Thermal treatment of Lloydminster heavy oil: yield and product separation by adsorption chromatography

    Energy Technology Data Exchange (ETDEWEB)

    Tiwari, P.K.; Sastre, H.; Chornet, E.; Kotlyar, L.S.; Ripmeester, J.A.; Overend, R.P. (University of Sherbrooke, Quebec (Canada). Dept. of Chemical Engineering)

    1989-09-01

    The effect of thermal treatment on Lloydminster heavy oil has been studied under pyrolytic, catalytic and non-catalytic hydropyrolysis and hydrogen donor solvent (tetralin) regimes using a batch autoclave. Product yields are reported for each type of reaction regime in terms of gases, maltenes, asphaltenes and toluene insoluble organic matter (coke). The maltene fraction was further separated by column chromatography into four chemical compound types namely: saturates, mono- and di-aromatics, polyaromatics and polars. The asphaltene fraction was also separated in four fractions by column chromatography by elution with solvents of increasing polarity. These fractions were characterized by FTIR and {sup 1}{sup 3}C NMR. The evolution of these fractions was studied as a function of the treatment. Tetralin was found to be effective in eliminating coke and increasing the maltene content relative to other treatments. It has been observed that the decrease of polyaromatic and polar species in the maltenes results in a corresponding increase of saturates. The asphaltene yield also decreases with thermal treatment. In all treatments the asphaltene fractions rich in polar and highly functional groups decrease drastically. 34 refs., 7 figs., 2 tabs.

  15. Surfactant-assisted liquefaction of particulate carbonaceous substances

    Science.gov (United States)

    Hsu, G. C. (Inventor)

    1978-01-01

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

  16. 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 Ran

  17. Organosulphur compounds in coals as determined by reaction with Raney nickel and microscale pyrolysis techniques. Quarterly report, January 1, 1995--March 31, 1995

    Energy Technology Data Exchange (ETDEWEB)

    Philp, R.P.; Stalker, L.

    1995-09-01

    This report briefly descibes a method for cleaving organosulfur compounds from coal, kerogens and asphaltenes. The technique utilized nickel chloride and sodium borohydride. Experiments were performed on Illinois No. 6 coal. The method was also used in a deuterium labelling technique for investigating sulfur bonds.

  18. The factors controlling the abundance and migration of heavy versus light oils, as constrained by data from the Gulf of Suez. Part 1. The effect of expelled petroleum composition, PVT properties and petroleum system geometry

    Energy Technology Data Exchange (ETDEWEB)

    Khavari-Khorasani, G. [PETEC, Stavanger (Norway); Dolson, J.C. [GUPCO, Cairo (Egypt); Michelsen, J.K. [STATOIL, Stavanger (Norway)

    1998-12-31

    In the Gulf of Suez (GOS) petroleum systems the main factors which control the abundance and migration of heavy vs light oils are (a) the composition and PVT properties of the expelled fluids, (b) the geometry of the petroleum systems and (c) reservoir flow processes. Compositional and PVT modeling of the expelled petroleum fluids from the Brown Limestone and the Thebes Formation carbonate source rocks show the following. The fluids expelled below a transformation ratio of 0.5 are heavy oils (stock tank API gravity = 10-20{sup o}), have a low GOR, and contain 20-25% asphaltenes. These fluids are formed from source rocks which have mainly low to intermediate sulfur content and normal thermal stability. The further expelled fluids, up to a transformation ratio of around 0.97, are bubble point behaving fluids (oils) with stock tank API from > 20-50{sup o}, and GOR {approx} 300-800 scf/bbl, and display a progressive decrease in asphaltene content. The latest {approx} 3% expelled fluids represent dew point behaving fluids (gas condensates). The heavy, low GOR oils expelled below a transformation ratio of 0.5, have a very low saturation pressure and are not prone to asphaltene precipitation, unless they are mixed with higher GOR fluids. Geometrically imposed mixing of fluids with large maturity-induced compositional differences, and reservoir flow processes have a significant effect on the PVT behavior of the migrating fluids, on asphaltene precipitation, and on the distribution of heavy vs light oils. (author)

  19. THE STUDY OF THE STRUCTURAL CHARACTERISTICS AND RHEOLOGICAL PROPERTIES OF OIL AND THE SOUTH -INZYREYSKOGO USINSK DEPOSIT

    Directory of Open Access Journals (Sweden)

    Shiryaeva R.N.

    2013-03-01

    Full Text Available By means of IR-spectrometry general structural fragments of high-viscous oils resins and asphaltenes isolated from oils are stadied. It was determined that differ significantly on content alkil, hydroxide and carbonil groups. Developed reagent OKN allows to improve significantly reological deseription of South- Inzyreyskoy and Usinsk oil and may be recommended for use in oil industry

  20. Rapid method for characterization of heavy petroleum fractions. [Gel permeation chromatography for molecular weight distribution

    Energy Technology Data Exchange (ETDEWEB)

    Hodgin, J. C.; Kaiser, M. A.; Lubkowitz, J. A.; Rogers, L. B.

    1977-03-01

    The use of LiChrospher and LiChrosorb to obtain profiles of molecular weight distributions is shown for some petroleum crudes, pitches, and asphaltenes. The elution time was less than thirty minutes, and data were obtained on less than 16 ..mu..g of sample.

  1. 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)

  2. 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...

  3. 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)

  4. 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.

  5. Effects of Ultrasonic Treatment on Residue Properties

    Institute of Scientific and Technical Information of China (English)

    Sun Yudong; Zhang Qiang; Shi Honghong; Wang Xue; Liu Bo

    2013-01-01

    The changes in properties and structural parameters of four vacuum residue samples before and after ultrasonic treatment were analyzed. Ultrasonic treatment could increase the carbon residue value, decrease the average molecular weight and viscosity, which can barely inlfuence the density of vacuum residue. Meanwhile the constitution of residue can be varied including the decrease in the content of saturates, aromatics and asphaltenes, while the increase in the content of resins can lead to an increase in the total content of asphaltenes and resins. Among the four kinds of residue samples, there is a common trend that the more the content of asphaltenes in feedstock is, the more the increase in the content of resins, the more signiifcant decrease in the aromatic content and the less decrease in the saturates content after ultrasonic treatment of residue would be. Changes in the structure and content of asphaltenes caused by ultrasonic treatment have a signiifcant impact on the changes in residue properties. Ultrasonic treatment has changed the structural parameters of residue such as decrease in the total carbon number of average molecule (CTotal), the total number of rings (RT), the aromatic carbon number (CA),the aromatic rings number (RA) and the naphthenic rings number (RN) , and increase of characterization factor (KH). The study has indicated that ultrasonic treatment of vacuum residue can change the average structure of residue, and the changes in the content and structure of asphaltenes are the main cause leading to property changes. The results of residue hydrotreat-ing revealed that coke yield decreased, whereas the gas and light oil yield and conversion increased after ultrasonic treat-ment of vacuum residue.

  6. 二氧化碳非混相驱油藏沥青质沉淀规律研究

    Institute of Scientific and Technical Information of China (English)

    何岩峰; 李栋; 胡杰; 郭立春

    2011-01-01

    为研究二氧化碳驱油藏中原油沥青质沉淀量预测方法,设计了二氧化碳非混相驱沥青质沉淀动态岩心驱替实验装置,采用正交实验分析方法研究了非混相驱条件下驱替压力、温度、岩心初始渗透率、原油中的沥青质含量和驱替速度等因素对驱替后岩心中原油沥青质沉淀量的影响,分析了作用机理,回归出了二氧化碳非混相驱过程中原油沥青质沉淀量预测公式并用实验结果进行了验证.验证结果表明,该预测公式可直接用于二氧化碳非混相驱原油沥青质沉淀量预测.%Oilfield practices indicate that carbon dioxide flooding may cause the precipitation of asphaltene, which will decrease the permeability of reservoir,the productivity of oil well and the result of reservoir development. Therefore,it is very important to understand the rules of asphaltene precipitation during carbon dioxide flooding. The effects of displacement pressure,temperature,original core permeability,original asphaltene content in crude oil and displacement rate on the precipitation amount of asphaltene are studied by self-designed experimental device and by means of orthogonal experiment method. The regression formula for calculating the precipitation a-mount of asphaltene is obtained,and it is verified by experimental results. The verified result shows that the regression formula can be used for predicting the precipitation amount of asphaltene in the immiscible displacement of carbon dioxide.

  7. Effects of Different Heavy Crude Oil Fractions on the Stability of Oil-in-Water Emulsion—Ⅲ. Effects of pH on the interfacial properties of heavy crude functional fractions and water system

    Institute of Scientific and Technical Information of China (English)

    FanWeiyu; NanGuozhi; LiShuiping; SongYuanming

    2005-01-01

    In this paper, effects of pH on the interracial properties of heavy crude functional fractions and water system are investigated. The influence ofpH on π-A isotherms of acid fraction, basic fraction, amphoteric fraction and asphaltene is great. The interracial pressure of fractions increases in strongly basic conditions. The ζ(-80mv) of acid fraction is the largest under basic conditions (pH=11-12), with the result to show that the interfacial activity of the acid fraction is superior to that of other fractions. The results of model emulsions show that strongly basic conolition (pH≥ 11) is beneficial to oil-inwater emulsion stability. The interfacial activity of acid fraction and asphaltene is superior to that of other crude fractions.

  8. Hindered diffusion of coal liquids. Quarterly report No. 12, June 18, 1995--September 17, 1995

    Energy Technology Data Exchange (ETDEWEB)

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

    1995-12-31

    The design of industrial catalysts requires that the diffusivity of the reacting species within the catalyst be accurately known. Nowhere is this more important than in the area of coal liquefaction and upgrading of coal liquids. In this area one is faced with the task of processing a number of heavy oils, containing metals and other contaminants, in a variety of process dependent solvents. It is important, therefore, on the basis of predicting catalyst activity, selectivity, and optimizing reactor performance, that the diffusivities of these oil species be accurately known. It is the purpose of the project described here to provide such a correct concept of coal asphaltenes by careful and detailed investigations of asphaltene transport through porous systems under realistic process temperature and pressure conditions. The experimental studies will be coupled with detailed, in-depth statistical and molecular dynamics models intended to provide a fundamental understanding of the overall transport mechanisms.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    1996-10-28

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

  10. Aquathermolysis of conventional heavy oil with superheated steam

    Institute of Scientific and Technical Information of China (English)

    Song Guangshou; Zhou Tiyao; Cheng Linsong; Wang Yunxian; Tian Guoqing; Pi Jian; Zhang Zheng

    2009-01-01

    This paper presents a new aquathermolysis study of conventional heavy oil in superheated steam. A new high temperature autoclave was designed, where volume and pressure could be adjusted. Aquathermolysis was studied on two different conventional heavy oil samples under different reaction times and temperatures. Experimental results show that aquathermolysis does take place for conventional heavy oil. As reaction time increases, the oil viscosity reduces. However, the reaction will reach equilibrium after a certain period of time and won't be sensitive to any further reaction time any more. Analysis shows that, while resin and asphaltenes decrease, saturated hydrocarbons and the H/C ratio increase after reaction. The main mechanism of aquathermolysis includes hydrogenization, desulfuration reaction of resin and asphaltenes, etc.

  11. Research on Organic Matter of Hydrogenation Liquefaction Residue%加氢残渣中有机质的性质及研究

    Institute of Scientific and Technical Information of China (English)

    张瑞; 李峰

    2015-01-01

    The separation of organic matter and ash content in coal tar hydrogenation residue was introduced. And the basic properties of the asphaltenes were analyzed. It was found that the coal tar hydrogenation residue had high asphaltene content and high hydrocarbon ratio. It was suitable for the preparation of mesophase pitch. The mesophase pitch was prepared by thermal conversion and characterized.%对煤焦油加氢残渣中的有机质和灰分进行分离,并对其基本性质进行分析,发现其中沥青质含量很高,碳氢比高,适宜于制备碳素材料前驱体——中间相沥青.采用热转化法制备中间相沥青,并对其进行表征.

  12. 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

  13. Hindered diffusion of coal liquids. Quarterly report No. 3, March 18, 1993--June 17, 1993

    Energy Technology Data Exchange (ETDEWEB)

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

    1993-11-01

    The design of industrial catalysts requires that the diffusivity of the reacting species within the catalyst be accurately known. Nowhere is this more important than in the area of coal liquefaction and upgrading of coal liquids. In this area one is faced with the task of processing a number of heavy oils, containing metals and other contaminants, in a variety of process dependent solvents. It is important, therefore, on the basis of predicting catalyst activity, selectivity, and optimizing reactor performance, that the diffusivities of these oil species be accurately known. It is the purpose of this project to provide a correct concept of coal asphaltenes by careful and detailed investigations of asphaltene transport through porous systems under realistic process temperature and pressure conditions. The experimental studies will be coupled with detailed, in-depth statistical and molecular dynamics models intended to provide a fundamental understanding of the overall transport mechanisms.

  14. Effect of Components on the Performance of Asphalt Modiifed by Waste Packaging Polyethylene

    Institute of Scientific and Technical Information of China (English)

    ZHANG Maorong; FANG Changqing; ZHOU Shisheng; CHENG Youliang; YU Ruien; LIU Shaolong; LIU Xiaolong; SU Jian

    2016-01-01

    Waste packaging polyethylene (WPE) was used to modify raw asphalt by melt blending the components at 190℃ for 1 h in a simple mixer and subsequently machining them at 120℃ for 1 h in a high-speed shearing machine. The effect of modiifcation on the degree of the penetration, the softening point and the ductility of the asphalt was studied using lfuorescent microscopy, infrared spectrometry, component changes and various other techniques. The experimental results showed that no chemical reactions took place in the components themselves (saturate, aromatic, asphaltene and resin) during the modifications. The softening point and penetration of the asphalt were found to be closely related to the resulting contents of the asphaltene, saturate and resin components. In addition, aromatics were identified as having the greatest impact on the ductility of the asphalt.

  15. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2011-07-01

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

  17. Detection of Oil in Water Column: Sensor Design

    Science.gov (United States)

    2013-02-01

    Subsurface Injection of Corexit 9500 (undated PowerPoint presentation). Lee, K., Nedwed, T., & Prince, R.C. (2011). Lab Tests on the Biodegradation ...refined oil products are primarily composed of saturated and aromatic hydrocarbons, resins, and asphaltenes. Polyaromatic hydrocarbons ( PAHs ) are chemical...compounds comprised of fused rings containing strong unsaturated bonds. Due to the structural arrangement of PAHs , they tend to fluoresce in

  18. 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...

  19. Structural Description of Polyaromatic Nucleus in Residue

    Institute of Scientific and Technical Information of China (English)

    Zhang Huicheng; Yan Yongjie; Sun Wanfu; Wang Jifeng

    2007-01-01

    The proton nuclear magnetic resonance spectroscopy(1H-NMR),the synchronous fluorescence spectrometry(SFS)and the rutheniam ions catalyzed oxidation(RICO)method wen used to determine the chemical structure of polyaromatic nucleus in Oman residue fractions.The results of1H-NMR analyses showed that the average numbers of aromatic rings in the aromatics,resins and asphaltenes units were 3.2,5.6 and 8.2.respectively.SFS was used to investigate the distribution of aromatic tings in residue fractions,the main distribution range of aromatic rings in aromatics,resins and asphaltenes were 3-4 rings,3-5 rings and more than 5 tings,respectively.The aromatic network in residue fractions was oxidized to produce numerous carboxylic acids.The types and content of benzenepolycarboxylic acids,such as phthalic acid,benzenetricarboxylic acids,benzenetetracarbOxylic acids,benzenepentacarboxylic acid and benzenehexacarboxylic acid disclosed the condensed types of aromatic nuclei in the core.The biphenyl fraction(BIPH),the cata-condensed fraction(CATA),the peri-condensed fraction(PERI)and the condensed index(BCI)were calculated based on the benzenepolycarboxylic acids formed.The results implied that there was less biphenyl type structures in all residue fractions.The aromatics fraction was almost composed of the cata-condensed type system,and the asphaltenes fraction was wholly composed of the peri-condensed type system,while in the resins fraction co-existed the two types,herein the peri-condensed type Was predominant over the cata-condensed type.Based on the analytical results obtained in the study,the components-aromatics,resins and asphaltenes-were given the likely structural models.

  20. Formation, prevention and breaking of sea water in crude oil emulsions, chocolate mousses

    Energy Technology Data Exchange (ETDEWEB)

    Bridie, A.L.; Wanders, T.H.; Zegveld, W.; Van Der Hiejde, H.B.

    1980-12-01

    During the combating of oil spills, the handling of stable sea water in crude oil emulsions called chocolate mousses is often a major problem. A recent laboratory study of the formation and properties of such emulsions revealed the key roles played by asphaltenes and crystallized wax in their stability. A chemical additive, designated LA 1834, was found to be effective in preventing the formation of mousses.

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

    OpenAIRE

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

    2015-01-01

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

  2. Lignin Peroxidase Oxidation of Aromatic Compounds in Systems Containing Organic Solvents

    OpenAIRE

    Vazquez-Duhalt, Rafael; Westlake, Donald W. S.; Fedorak, Phillip M.

    1994-01-01

    Lignin peroxidase from Phanerochaete chrysosporium was used to study the oxidation of aromatic compounds, including polycyclic aromatic hydrocarbons and heterocyclic compounds, that are models of moieties of asphaltene molecules. The oxidations were done in systems containing water-miscible organic solvents, including methanol, isopropanol, N, N-dimethylformamide, acetonitrile, and tetrahydrofuran. Of the 20 aromatic compounds tested, 9 were oxidized by lignin peroxidase in the presence of hy...

  3. 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.

  4. 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)

  5. Literature survey and documentation on organic solid deposition problem. Status report

    Energy Technology Data Exchange (ETDEWEB)

    Chung, Ting-Horng

    1993-12-01

    Organic solid deposition is often a major problem in petroleum production and processing. Recently, this problem has attracted more attention because operating costs have become more critical to the profit of oil production. Also, in miscible gas flooding, asphaltene deposition often occurs in the wellbore region after gas breakthrough and causes plugging. The organic deposition problem is particularly serious in offshore oil production. Cooling of crude oil when it flows through long-distance pipelines under sea water may cause organic deposition in the pipeline and result in plugging. NIPER`s Gas EOR Research Project has been devoted to the study of the organic solid deposition problem for three years. NIPER has received many requests for technical support. Recently, the DeepStar project committee on thermo-technology development and standardization has asked NIPER to provide them with NIPER`s expertise and experience. To assist the oil industry, NIPER is preparing a state-of-the-art review on the technical development for the organic deposition problem. In the first quarter, this project has completed a literature survey and documentation. total of 258 publications (114 for wax, 124 for asphaltene, and 20 for related subjects) were collected and categorized. This literature survey was focused on the two subjects: wax and asphaltene. The subjects of bitumen, asphalt, and heavy oil are not included. Also, the collected publications are mostly related to production problems.

  6. Geochemical Characteristics and Origin of Tar Mats from the Yaha Field in Tarim Basin,China

    Institute of Scientific and Technical Information of China (English)

    张敏; 张俊; 等

    1999-01-01

    Tar mats were firstly discovered and determined accurately in terrestrial oil and gas reservoirs associated with Lower Tertiary sandstone reservoirs in the Yaha field of the Tarim Basin,China,by thin-layer chromatography-flame ionization detector(TLC-FID)and Rock-Eval analysis.The relative content of asphaltene in gross composition of tar mat extracts accounts for more than 30%,that in the corresponding oil leg less than 20%.In the geochemical description profile of oil gas reservoirs,drastic changes in asphaltene contents between tar mats and oil legs could be discovered.This in an important marker to determine tar mats.Distribution characteristics of saturated and aromaic hydrocarbons from reservoir core extracts and crude oils in the Yaha oil and gas reservoirs in the Tarim Basin are described systematically in this paper,and the results show there are similarities among n-alkane distribution characteristics,biomarker distribution characteristics and their combined characteristics of saturated hydrocarbons,and the geochemical characteristics of aromatic hydrocarbons for tar mats.oil leg,asphaltic sand and crude oil.These characteristics suggest the hydrocarbons in these samples were originated from the common source rocks.However,the geochemical characteristics of tar mats reveales that the mechanism of formation of tar mats is the precipitation of asphaltene from crude oils in petroleum reservoirs caused by increased dissolved gas in oil legs(gas injection).

  7. Molecular interactions and thermal instability of coal derived liquids

    Energy Technology Data Exchange (ETDEWEB)

    Galya, L.G.

    1983-01-01

    The purpose of the first part of this research was to investigate interactions between the acid/neutral and base fractions of coal derived asphaltenes. These interactions are thought to cause high viscosities in coal derived liquids which are obtained from catalytic processes. The asphaltenes were obtained from Synthoil and separated into acid/neutral and base fractions. The interactions of model compounds, o-phenylphenol and quinoline, and the acid/neutral and base fractions with these model compounds were studied by proton nuclear magnetic resonance spectroscopy and solution colorimetry. The results indicate that interactions between the acid/neutral and base fractions of the asphaltenes are partially responsible for high viscosities in these synthetic fuels. The purpose of the second part of this research was to investigate the causes and mechanism of formation of deposits from SRC II naphtha in heat exchangers. Formation of these deposits causes plugging and results in pilot plant shutdowns. A deposit obtained from a hydrogenation reactor was examined, and the deposit precursors were concentrated through distillation and ion exchange chromatography. The results indicate that phenols and alkylated nitrogenous bases are responsible for deposit formation. Phenols react through coupling reactions to give arylethers and water. Alkylated nitrogenous bases react by pyrolysis to produce free radicals which crosslink to produce carbonaceous deposits. These reactons have been followed using thermogravimetric analysis, Fourier transform infrared spectroscopy and gas chromatography in the temperature range of 250-400/sup 0/C.

  8. Hindered diffusion of coal liquids. Quarterly report No. 4, June 18, 1993--September 17, 1993

    Energy Technology Data Exchange (ETDEWEB)

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

    1993-12-31

    The design of industrial catalysts requires that the diffusivity of the reacting species within the catalyst be accurately known. Nowhere is this more important than in the area of coal liquefaction and upgrading of coal liquids. In this area one is faced with the task of processing a number of heavy oils, containing metals and other contaminants, in a variety of process dependent solvents. It is important, therefore, on the basis of predicting catalyst activity, selectivity, and optimizing reactor performance, that the diffusivities of these oil species by accurately known. It is the purpose of this project to provide a correct concept of coal asphaltenes by careful and detailed investigations of asphaltene transport through porous systems under realistic process temperature and pressure conditions. The experimental studies will be coupled with detailed, in-depth statistical and molecular dynamics models intended to provide a fundamental understanding of the overall transport mechanisms. The project is of both experimental and theoretical nature and is divided into a number of tasks. Experimental tasks cover measuring asphaltene diffusivity in: model catalysts under realistic temperature and pressure conditions; sol-gel ceramic membranes; and model and real membranes under reactive conditions. Theoretical tasks include: study of hindered transport in a single pore; transport and reaction in networks of interconnected pores; Monte Carlo and molecular dynamics simulations; dilute simulations; low density diffusion with adsorption desorption; role of intramolecular, intermolecular and surface forces-accounting for aggregation and delamination phenomena; and molecular dynamics simulations.

  9. 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.

  10. 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)

  11. Evaluation of Reservoir Wettability and its Effect on Oil Recovery.

    Energy Technology Data Exchange (ETDEWEB)

    Buckley, J.S.

    1998-01-15

    We report on the first year of the project, `Evaluation of Reservoir Wettability and its Effect on Oil Recovery.` The objectives of this five-year project are (1) to achieve improved understanding of the surface and interfacial properties of crude oils and their interactions with mineral surfaces, (2) to apply the results of surface studies to improve predictions of oil production from laboratory measurements, and (3) to use the results of this research to recommend ways to improve oil recovery by waterflooding. During the first year of this project we have focused on understanding the interactions between crude oils and mineral surfaces that establish wetting in porous media. As background, mixed-wetting and our current understanding of the influence of stable and unstable brine films are reviewed. The components that are likely to adsorb and alter wetting are divided into two groups: those containing polar heteroatoms, especially organic acids and bases; and the asphaltenes, large molecules that aggregate in solution and precipitate upon addition of n-pentane and similar agents. Finally, the test procedures used to assess the extent of wetting alteration-tests of adhesion and adsorption on smooth surfaces and spontaneous imbibition into porous media are introduced. In Part 1, we report on studies aimed at characterizing both the acid/base and asphaltene components. Standard acid and base number procedures were modified and 22 crude oil samples were tested. Our approach to characterizing the asphaltenes is to focus on their solvent environment. We quantify solvent properties by refractive index measurements and report the onset of asphaltene precipitation at ambient conditions for nine oil samples. Four distinct categories of interaction mechanisms have been identified that can be demonstrated to occur when crude oils contact solid surfaces: polar interactions can occur on dry surfaces, surface precipitation is important if the oil is a poor solvent for its

  12. Influence of crude oil composition on wax deposition on tubing wall%原油组成对原油管道结蜡规律的影响

    Institute of Scientific and Technical Information of China (English)

    李传宪; 白帆; 王燕

    2014-01-01

    The wax deposition was studied for man-made crude oil with various compositions (different contents of resin, asphaltene and wax) under various conditions in a rotary wax deposition facility. The influence of the compositions was explored by sediment sampling from tubing wall, analyzing with the differential scanning calorimetry (DSC) and using four components method. Combined with mechanism of the wax deposition initiated by resin and asphaltene, it was found that lower content resin and asphaltene in crude oil could have a synergistic effect with paraffin molecules on the wax deposition, while for higher content resin and asphaltene they were attached to the pipe wall in the form of paste, although the existence of resin and asphaltene could weaken the driving force for paraffin molecule migration and impede deposition of paraffin molecules. The results obtained from studying on the effect of various wax contents on wax deposition showed that higher average carbon number of paraffin molecules in man-made crude oil was, less content of wax in the wax layer deposited. But the paraffin molecules with more carbon number could take place eutectic roles with resin and asphaltene easily, due to they were of longer carbon chain, leading to they was easier to deposit on the pipe wall with resin and asphaltene together.%利用旋转式动态结蜡装置,对不同组成的人工油样(胶质和沥青质含量不同或蜡含量不同)进行了不同条件下的实验研究。通过对管壁沉积物取样并利用差式扫描量热法(DSC)和四组分法进行分析,探究了不同原油组成对结蜡的影响规律。结合胶质和沥青质在结蜡过程中的作用机理,发现胶质和沥青质的存在虽然总会削弱蜡分子的迁移动力,阻碍蜡分子的沉积,但在含量较小时会协同蜡分子的沉积作用,而当含量较大时会以粘壁的形式附着于管壁。对蜡含量不同原油的结蜡规律研究发现:原油所含

  13. 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

  14. 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)

  15. 原油组分对石英表面润湿性的影响与表征方法%Effects of crude fractions on quartz surface wettability and characterization method

    Institute of Scientific and Technical Information of China (English)

    王业飞; 徐怀民; 齐自远; 徐晓丽; 宋新旺

    2012-01-01

    采用石油酸、沥青质和原油对石英片表面进行处理,用动态板法和悬滴法分别评价处理前后石英表面的润湿性,获得水湿、中性润湿和油湿3种不同润湿性的石英表面,分析石英表面润湿性改变机制.结果表明:经过铬酸洗液处理后,石英表面亲水性增强;用石油酸甲苯溶液处理后,石英表面变为弱水湿状态;沥青质甲苯溶液使石英表面变为中性润湿性;用20%正庚烷原油混合体系处理得到油湿性的表面,沥青质的吸附和沉积是导致石英表面润湿性反转的主要因素.%The quartz plates were treated by petroleum acid, asphaltene and crud oil respectively. The wettability of the surface was evaluated by dynamic plate and sessile drop method separately, and the quartz surfaces with different wettabilities were obtained and the wettability alteration mechanism was also studied. The experimental results suggest that the quartz surface is strongly water wet after soaked in chromic acid, and weakly water wet surface is obtained after soaked in petroleum acid toluene solution. The quartz surface becomes internediately wet in asphaltene toluene solution and oil wet in 20% heptane-crude oil mixture. The adsorption and deposition of asphaltene is the major reason for wettability alteration.

  16. Determination of molecular parameters in asphalts; Determinacao de parametros moleculares em asfaltos

    Energy Technology Data Exchange (ETDEWEB)

    Carvalho, C.C.V. [Universidade Federal, Rio de Janeiro, RJ (Brazil); Guilherme, H.C.N.; Goncalves, L.C.; 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 asphalts, materials of dark color, are constituted of complex mixtures of not volatile hydrocarbons and of raised molecular mass. These are gotten from the oil, that are submitted to the process of distillation in the which light fractions (gasoline, kerosene and gasoleum) are separate of asphalt for vaporization, fractionation and condensation. The product gotten in the deep one of the tower, after the removal of the light components of oil, is called asphalt cement of oil (CAP), which the ambient temperature is half - solid. In this work six different CAP's, called A, B, C, D, E and F had been analyzed, how much its composition and structure of its fraction of asphaltenes, using as extraction method the IP-143. The concern in the analysis of this fraction if bases on the fact of if believing that this is one of the responsible ones for the use of this substance as asphalt blanket. Being thus, the determination of possible pertaining structures to this fraction can allow one better agreement of its commercial application. The texts of asphaltenes gotten in this CAP's had varied of 6 to 12%, with some sufficiently similar results in asphaltene text terms however with well differentiated molecular characteristics defined through analysis for RMN of proton and carbon 13. These different analyses had allowed to correlate the CAP's and esteem given molecular important for posterior studies of molecular modeling. Between them we can showed groups of similarities in the CAP's A, B, and C, and in CAP's D, E and F how much to the text of aliphatic and aromatical totals hydrogens, not observed in the carbon study, where, in some cases, we find distinct similarities only the observed ones for the study of RMN of proton. (author)

  17. Organosulphur compounds in coals as determined by reaction with Raney nickel and microscale pyrolysis techniques. Quarterly report, 1 July 1995--31 October 1995

    Energy Technology Data Exchange (ETDEWEB)

    Stalker, L.; Philp, R.P.

    1995-12-31

    As well as studying coal samples from Oklahoma and Missouri States, we have now completed the preliminary part of a study of a well known high organosulphur containing coal, Illinois No. 6. As a number of other research groups have used Illinois No. 6 for study, we thought it wise to also analyse this coal for comparison of our method with existing data reported in the literature. To date, analyses of the aliphatic fractions of the free maltene components and the aliphatic hydrocarbons isolated following desulphurization of the free maltene polar fraction, asphaltenes and pre-extracted coal matrix have been performed in duplicate. So far, most of these samples have been analysed by GC and subsequently quantified using n-C{sub 24}D{sub 50}. As Figures 1 and 2 show, the duplicates for the desulphurized products (e.g. Figure 2a and 2b of desulphurized asphaltenes) while showing broad similarities, do not appear to be identical. This is emphasized by differences in the yields of n-alkanes generated, quantified in Table 1. Abundance of corresponding n-alkanes are often quite variable for duplicate analyses, which have been normalized to the quantity of original starting material. While inhomogeneity of sampling can easily explain the variation in abundance of products generated for the asphaltenes and coal matrix, the same cannot be said for the free polar compounds, which dissolve easily in the methanol/tetrahydrofuran solvent system used in the desulphurization process. It would therefore appear that desulphurization experiments should be performed at the very least, in duplicate to gain a clear impression of the distribution and abundance of aliphatic products cleaved from organosulphur compounds. The GC analysis also appears to show that there are different organosulphur compound precursors trapped in the different fractions of the coals.

  18. Structural analysis of bio-oils from pyrolysis and steam pyrolysis of cottonseed cake

    Energy Technology Data Exchange (ETDEWEB)

    Oezbay, N. [Anadolu University, Career School of Bozueyuek, Bilecik (Turkey); Puetuen, A.E.; Puetuen, E. [Department of Chemical Engineering, Faculty of Engineering and Architecture, Anadolu University, Iki Eyluel Campus, 26470, Eskisehir (Turkey)

    2001-06-01

    Structural analysis and the effect of the water vapour on the structure of the products obtained by low temperature thermal destruction of biomass at atmospheric pressure has been investigated. The liquid products were fractionated into pentane solubles and insolubles (Asphaltenes). Pentane solubles were then solvent fractionated into pentane, toluene, ether and methanol subfractions by fractionated column chromatograpy. The aliphatic subfractions of the oils were then analysed by capillary column gas-liquid chromatography and GC/MS. For further structural analysis, the pyrolysis oils and aromatic and polar subfractions were conducted using FTIR and 1H-NMR spectra.

  19. Molecular mass ranges of coal tar pitch fractions by mass spectrometry and size-exclusion chromatography.

    Science.gov (United States)

    Karaca, F; Morgan, T J; George, A; Bull, I D; Herod, A A; Millan, M; Kandiyoti, R

    2009-07-01

    A coal tar pitch was fractionated by solvent solubility into heptane-solubles, heptane-insoluble/toluene-solubles (asphaltenes), and toluene-insolubles (preasphaltenes). The aim of the work was to compare the mass ranges of the different fractions by several different techniques. Thermogravimetric analysis, size-exclusion chromatography (SEC) and UV-fluorescence spectroscopy showed distinct differences between the three fractions in terms of volatility, molecular size ranges and the aromatic chromophore sizes present. The mass spectrometric methods used were gas chromatography/mass spectrometry (GC/MS), pyrolysis/GC/MS, electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry (ESI-FTICRMS) and laser desorption time-of-flight mass spectrometry (LD-TOFMS). The first three techniques gave good mass spectra only for the heptane-soluble fraction. Only LDMS gave signals from the toluene-insolubles, indicating that the molecules were too involatile for GC and too complex to pyrolyze into small molecules during pyrolysis/GC/MS. ESI-FTICRMS gave no signal for toluene-insolubles probably because the fraction was insoluble in the methanol or acetonitrile, water and formic acid mixture used as solvent to the ESI source. LDMS was able to generate ions from each of the fractions. Fractionation of complex samples is necessary to separate smaller molecules to allow the use of higher laser fluences for the larger molecules and suppress the formation of ionized molecular clusters. The upper mass limit of the pitch was determined as between 5000 and 10,000 u. The pitch asphaltenes showed a peak of maximum intensity in the LDMS spectra at around m/z 400, in broad agreement with the estimate from SEC. The mass ranges of the toluene-insoluble fraction found by LDMS and SEC (400-10,000 u with maximum intensity around 2000 u by LDMS and 100-9320 u with maximum intensity around 740 u by SEC) are higher than those for the asphaltene fraction (200-4000 u with

  20. Synthesis and Properties of Depressators Based on Sopolymers in the Presence of Gossypol Pitch

    Directory of Open Access Journals (Sweden)

    R. S. Turemuratov

    2015-09-01

    Full Text Available Nowadays search of ways of obtainment new, more effective depressants for base oils is especially actual. Action of pour-point depressants is reduced to their influence on processes of crystallisation and structurizations of firm, first of all, paraffin hydrocarbons. In the given work we investigated depressants influence on some physical and chemical properties of oil distillates of the Kumkol deposit on the basis of the oil waste and a waste of oil-fatty industries. Concentration of entered additives and efficiency of their action depend on temperature of input of an additive, structure and quantity of paraffinic hydrocarbons, the asphaltenes and pitches maintenance, and also their ratio.

  1. Application of TLC and LA ICP SF MS for speciation of S, Ni and V in petroleum samples.

    Science.gov (United States)

    Vorapalawut, Nopparat; Martinez Labrador, Mauro; Pohl, Pawel; Caetano, Manuel; Chirinos, Jose; Arnaudguilhem, Carine; Bouyssiere, Brice; Shiowatana, Juwadee; Lobinski, Ryszard

    2012-08-15

    A coupling of thin layer chromatography with laser ablation ICP SF MS was developed for the fractionation of Ni, V, Fe and S in crude oil and its fractions (saturate, aromatic, resin and asphaltene). The detection limits were 18 ng g(-1) and 23 ng g(-1) for nickel and vanadium, respectively, and a sample could be characterized in terms of the metal distribution as a function of species polarity within 10 min. The method was used to characterize the metal distribution in crude oils of different origins and their different fractions.

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

    DEFF Research Database (Denmark)

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

    2013-01-01

    , the model is based on SARA representation of a petroleum mixture (saturates–aromatics–resins–asphaltenes), which may react differently with oxygen and produce other components (for example, light oils and coke). In total, the model contains 14 components, which may undergo 15 chemical reactions. The set...... of reactions in the original model of M.R. Kristensen has been modified in order to account for secondary combustion of the light oil fraction. The results of the model implementation are applied to the four heavy oil systems and qualitatively compared to the results of previous experimental studies. A new...

  3. Identification of nitrogen compounds and amides from spent hydroprocessing catalyst

    Energy Technology Data Exchange (ETDEWEB)

    Choi, J.H.K.; Gray, M.R. (University of Alberta, Edmonton, AB (Canada). Dept. of Chemical Engineering)

    1991-06-01

    A spent commercial naphtha hydrotreating catalyst was analyzed to identify compounds which had accumulated on the catalyst surface during its active life. The catalyst was extracted with methylene chloride, methanol and pyridine to remove adsorbed organic material, which was rich in nitrogen and oxygen. A series of quinolones were identified in the methanol extract after enrichment with HCl-modified silica gel adsorption and subsequent silica gel chromatography. Tetra- and hexahydroquinolones with alkyl substituents up to C{sub 3} were identified. Similar amides have been identified in asphaltenes, and are very resistant to hydrogenation. Tetrahydroquinolines and piperidines were detected in the pyridine extract. 36 refs., 8 figs., 2 tabs.

  4. Association models for petroleum applications

    DEFF Research Database (Denmark)

    Kontogeorgis, Georgios

    2013-01-01

    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.......g., for gas hydrate related systems, CO2/H2S mixtures, water/hydrocarbons and others. This review highlights both the major advantages of these association models and some of their limitations, which we believe should be discussed in the future....

  5. De-emulsifiers for water-in-crude oil-emulsions

    Energy Technology Data Exchange (ETDEWEB)

    Zaki, N. [Egyptian Petroleum Research Inst. (EPRI), Cairo (Egypt); Al-Sabagh, A. [Egyptian Petroleum Research Inst. (EPRI), Cairo (Egypt)

    1997-01-01

    The efficiency of 18 different polyalkylphenols-polyalkylene-polyamines-formaldehyde ethoxylates (PAPAFE) in the deemulsification of water-in-crude oil-emulsion were studied. In this respect, two naturally occurring Egyptian water-in-curde oil-emulsions were used to test the investigated de-emulsifiers. The effect of the variation in the molecular structure of the (PAPAFE) on their de-emulsification potency is investigated. The investigation reveals that de-emulsifiers containing nonyl phenol reduce crude oil-water interfacial tension (IFT) and are more efficient than those containing dodecyl phenol. PAPAFE containing more amino groups are found to have better emulsion breaking ability. This is attributed to their enhanced ability to solubilize asphaltenes, which are the prime motivators for crude oil-water emulsion stability. They drag asphaltenes crosslinked at the water-crude oil interface and consequently, resulting in a substantial decrease in emulsion stability. There exists an optimum hydrophilic-lipophilic balance (HLB) for the investigated PAPAFE, ranging from 12 to 13.5 at which their maximum de-emulsification ability is attained. All studied PAPAFE showed increased de-emulsification performance by increasing the temperature from 50 to 70 C. Increasing the temperature reduces the viscosity of the crude oil continuous phase and increases the rate of diffusion of both the surfactant molecules and the dispersed water droplets. This will cause an increase in the rate of coalescence of the water droplets. (orig.) [Deutsch] Es wurde die Wirkung von 18 verschiedenen Polyalkylphenolpolyalkylenpolyamine-formaldehydethoxylaten (PAPAFE) bei der Demulgierung von Wasser-in-Rohoel-Emulsionen untersucht. Zwei in Aegypten natuerlich vorkommende Wasser-in-Rohoel-Emulsionen wurden fuer die Versuche eingesetzt, dabei wurde der Einfluss der molekularen Struktur der PAPAFEs auf das Demulgiervermoegen untersucht. Es zeigte sich, dass Demulgatoren mit Nonylphenol die

  6. Composition, stabilisation and cleavage of crude oil emulsions. Pt. 1. Mechanism of stabilization and cleavage of crude oil emulsions. Aufbau, Stabilisierung und Spaltung von Rohoelemulsionen. T. 1. Mechanismus der Stabilisierung und Spaltung von Rohoelemulsionen

    Energy Technology Data Exchange (ETDEWEB)

    Oetter, G. (BASF AG, Ludwigshafen am Rhein (Germany). Forschungsabteilung); Oppenlaender, K. (BASF AG, Ludwigshafen am Rhein (Germany). Forschungsabteilung)

    Asphaltenes and resins, two chemically and structurally different colloid fractions, are responsible for the stability of crude oil emulsions. Their aggregation behavior and interfacial properties are studied. The crude oil stability is mainly governed by the shear viscosity and elasticity of the interfacial film and less by the interfacial tension. The mechanism of emulsion destabilization by chemical demulsifiers as well as coagulation and coalescence of the water droplets are discussed. The effectiveness of the demulsifier can be monitored by physicochemical parameters of the interfacial film. (orig.)

  7. Immature condensate from southeastern Mediterranean coastal plain, Israel

    Energy Technology Data Exchange (ETDEWEB)

    Nissenbaum, A.; Aizenshtat, Z.; Goldberg, M.

    1985-06-01

    A highly unsaturated, sulfur-rich, naphthenic condensate was discovered in association with dry biogenic gas in the upper Tertiary of the southeastern Mediterranean coastal plain of Israel. Geologic and geochemical evidence suggests that this condensate was generated in thermally immature rocks. Similar material has been reported from the upper Tertiary of the western Mediterranean. We suggest that the immature condensates were formed from resin-rich, terrestrially derived organic matter. Under an equivalent thermal regime, marine material derived primarily from algae and bacteria will produce heavy crude, rich in asphaltenes.

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

    Energy Technology Data Exchange (ETDEWEB)

    Ferrari, M.D.; Neirotti, E.; Albornoz, C.; Mostazo, M.R.; Cozzo, M. [Administracion Nacional de Combustibles, Alcohol y Portland Pando, Canelones (Uruguay). Centro de Investigaciones Tecnologicas

    1996-11-01

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

  9. 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.

  10. 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.

  11. The Relationship between the Viscosity and Fraction Characteristcs of the Heavy Oil of Shengli Oil Field%胜利油田稠油黏度与其组分性质的关系研究

    Institute of Scientific and Technical Information of China (English)

    盖平原

    2011-01-01

    选取黏度分别属于普通稠油、特稠油、超稠油、特超稠油的GD排15-0、GD排13-10、单56-16-10、56-9-11、单113-P1、郑411系列、坨826系列等13个胜利油田稠油样品,利用液相色谱法将其分离成饱和分、芳香分、胶质、沥青质四个组分;采用VPO法分别测定各组分的平均相对分子质量;采用元素分析仪和原子吸收光谱仪测定其元素组成与金属含量.研究结果表明,沥青质含量是影响稠油黏度的主要因素,胶质含量对原油黏度也有重要影响,稠油黏度随胶质、沥青质总量增大而增加;胶质沥青质组分的高相对分子质量是其影响体系黏度的主要原因;组分杂原子含量和金属元素含量对稠油黏度均有一定影响.%The 13 samples including CD Pail 5-0, CD Pail 3-10, Shan 56-16-10, 56-9-11, Shan 113-P1, Zheng 411 and Tuo 826, which were classified into ordinary heavy oil, heavy oil, extra heavy oil and super-heavy oil, were fractioned into four components of saturates, aromatics, resins, and asphaltenes by liquid chromatogram.The relative molecular mass of fractions was measured by VPO method, and the element composition and the mental content of fractions were measured by elemental analysis and atomic absorption spectrometry.It could be concluded that the content of asphaltenes and resins played a decisive role in the viscosity of heavy oil.The viscosity of the heavy oil would be great if the content of resins and asphaltenes was high.The high relative molecular mass was the main reason for the resins and asphaltenes impacting the viscosity of the samples.The viscosity of heavy oil was also affected by the content of heteroatom or metals of fraction.

  12. EPR and EOM studies in well samples from some Venezuelan oil fields: possible mechanisms of magnetic authigenesis

    Science.gov (United States)

    Aldana, M.; Díaz, M.; Costanzo-Alvarez, V.; Jiménez, S. M.; Sequera, P.

    2003-04-01

    In the last few years we have conducted Electron Paramagnetic Resonance (EPR) and Magnetic Susceptibility (MS) studies in drilling fines, from near-surface levels, from producer and non-producer wells. These studies were aimed at examining a possible causal relationship between magnetic contrasts and underlying hydrocarbons. In this work we have extended these studies to some new wells, trying to identify the possible origin (microbial and/or thermochemical) of the observed anomalies. Together with EPR and MS studies, quantification of extractable organic matter (EOM) has been also performed. The samples were pulverized and split into two aliquots. One aliquot was treated with chloroform in order to separate de EOM and obtain the sample without EOM and the EOM itself. The other aliquot was not solvent extracted. The EOM was quantified and EPR measurements were performed on both aliquots in order to determine the organic matter free radical concentration (OMFRC). The treatments performed allow identifying whether the OMFRC belongs to the EOM or to the total organic matter (TOM). Asphaltenes tend to be the major components in highly biodegraded crude oils. Then the presence of OMFRC belonging to the TOM or to the EOM could indicate a possible microbial or thermochemical origin, respectively, of the detected MS anomalies. We have found OMFRC and EOM anomalies only at the producer wells, in the same zone where MS anomalies, associated with the presence of spherical aggregates of magnetic minerals, were observed. For some of these wells our results indicate the solely presence of free radicals of kerogen at OMFRC anomalous level. In fact, the EOM of these wells has no EPR signal and precipitation of asphaltene in n-heptane was not observed. In other instances, free radicals of kerogen and asphaltenes and precipitation of asphaltene from the EOM in n-heptane was observed. In the former case we suggest the existence of a reducing zone where thermochemical conditions are

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

    Directory of Open Access Journals (Sweden)

    Y.M. Polishchuk, I.G. Yashchenko

    2011-07-01

    Full Text Available 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.

  14. 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.

  15. [Rapid quantitative analysis of hydrocarbon composition of furfural extract oils using attenuated total reflection infrared spectroscopy].

    Science.gov (United States)

    Li, Na; Yuan, Hong-Fu; Hu, Ai-Qin; Liu, Wei; Song, Chun-Feng; Li, Xiao-Yu; Song, Yi-Chang; He, Qi-Jun; Liu, Sha; Xu, Xiao-Xuan

    2014-07-01

    A set of rapid analysis system for hydrocarbon composition of heavy oils was designed using attenuated total reflection FTIR spectrometer and chemometrics to determine the hydrocarbon composition of furfural extract oils. Sixty two extract oil samples were collected and their saturates and aromatics content data were determined according to the standard NB/SH/T0509-2010, then the total contents of resins plus asphaltenes were calculated by the subtraction method in the percentage of weight. Based on the partial least squares (PLS), calibration models for saturates, aromatics, and resin+asphaltene contents were established using attenuated total reflection FTIR spectroscopy, with their SEC, 1.43%, 0.91% and 1.61%, SEP, 1.56%, 1.24% and 1.81%, respectively, meeting the accuracy and repeatability required for the standard. Compared to the present standard method, the efficiency of hydrocarbon composition analysis for furfural extract oils is significantly improved by the new method which is rapid and simple. The system could also be used for other heavy oil analysis, with excellent extension and application foreground.

  16. Degradative capacities of bacteria and fungi isolated from a fuel-contaminated soil. Capacites degradatives de bacteries et de champignons isoles d'un sol contamine par un fuel

    Energy Technology Data Exchange (ETDEWEB)

    Oudot, J.; Fusey, P.; Abdelouahid, D.E.; Haloui, S.; Roquebert, M.F. (Museum national d' histoire naturelle, Cedex (France))

    1987-01-01

    The long-term influence of a fuel spill on the bacterial and fungal communities of an agricultural soil was studied. Three years after the contamination, biodegradation of the fuel in the soil was achieved and after 5 years the residual compounds had no significant effect on the density and the specific composition of the microbial populations of the soil. Hydrocarbon-oxidizing bacteria Corynebacterium and Nocardia spp. were isolated. Most of the active fungi were Aspergillus and Penicillium spp., but strains of Paecilomyces, Acremonium, Fusarium, and Gliocladium were also identified. In laboratory experiments, the biodegration rate of a reference crude oil by pure cultures of oil-degrading strains was nearly the same as in mixed cultures. The biodegradation potential of the strains isolated from the control plot was as high as strains isolated from the oiled plot. In the soil, as in laboratory cultures, the saturate hydrocarbons were more degraded than the aromatics, whereas the resins and asphaltenes were resistant to microbial attack, as were polycyclic alkanes, steranes and triterpanes. Nocardia degraded preferentially the aromatics and attacked significantly the asphaltenes, as did Fusarium oxysporum. Aspergillus niger, Aspergillus flavus, and Fusarium oxysporum degraded part of the resins. The spectrum of the initial degradation of petroleum by the most active fungi and bacteria was identical, and it appears that the enzymatic equipment necessary to oxidize hydrocarbons is quite complete in these strains. 21 refs., 9 figs., 5 tabs.

  17. Study on the mechanism of coal liquefaction reaction and a new process concept

    Institute of Scientific and Technical Information of China (English)

    SHI Shi-dong; LI Wen-bo; WANG Yong; GUO Zhi; LI Ke-jian

    2008-01-01

    The coal hydrogenation reaction process is simply considered as three steps. In the first step, the smaller molecules associated with coal structure units are released as some gases and water in the condition of solvent and heating. In this step, some weaker bonds of the coal structure units are ruptured to form free radicals. The radicals are stabi-lized by hydrogen atoms from donor solvent and/or H2. In the second step, chain reaction occurs quickly. In the process of chain reaction, the covalent bonds of coal structure units are attacked by the radicals to form some asphaltenes. In the third step, asphaltenes are hydrogenated form more liquids and some gases. In coal liquefaction, the second step of coal hydrogenation reaction should be controlled to avoid integration of radicals, and the third step of coal hydrogenation should be accelerated to increase the coal conversion and the oil yield. A new concept of coal liquefaction process named as China direct coal lique-faction (CDCL) process is presented based on the mechanism study of coal liquefaction.

  18. Etude par simulation en laboratoire de l'opération de viscoréduction Laboratory Simulation of the Visbreaking Process

    Directory of Open Access Journals (Sweden)

    Favre A.

    2006-11-01

    Full Text Available Une simulation par pyrolyse du traitement de viscoréduction est mise au point afin de comprendre le comportement individuel des quatre grandes classes de composés formant les résidus lourds. Après détermination des conditions opératoires, chaque famille (hydrocarbures aliphatiques et aromatiques, résines et asphaltènes est pyrolysée et son pyrolysat est analysé. Cette démarche permet de mettre en évidence l'origine des constituants de la recette de viscoréduction (hydrocarbures légers de conversion, oléfines, asphaltènes, coke,. . . et de déterminer la frontière entre les produits valorisables et les produits nocifs lors de la viscoréduction. A pyrolysis simulation of the visbreaking process has been developed to understand the individual behavior of the four major classes of compounds of heavy residues. After the operating conditions have been determined, each class (aliphatic and aromatic hydrocarbons, resins and asphaltenes is pyrolyzed, and its pyrolyzate is analyzed. This procedure reveals the origin of each fraction of the viabreaking product (light conversion hydrocarbons, olefins, asphaltenes, coke, etc. and indicates the limit between upgradable products and prejudicial products during visbreaking.

  19. 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.

  20. Potential of fungal co-culturing for accelerated biodegradation of petroleum hydrocarbons in soil.

    Science.gov (United States)

    Yanto, Dede Heri Yuli; Tachibana, Sanro

    2014-08-15

    The potential of fungal co-culture of the filamentous Pestalotiopsis sp. NG007 with four different basidiomycetes--Trametes versicolor U97, Pleurotus ostreatus PL1, Cerena sp. F0607, and Polyporus sp. S133--for accelerating biodegradation of petroleum hydrocarbons (PHCs) was studied using three different physicochemical characteristic PHCs in soil. All the combinations showed a mutual intermingling mycelial interaction on the agar plates. However, only NG007/S133 (50/50) exhibited an optimum growth rate and enzymatic activities that supported the degradation of asphalt in soil. The co-culture also degraded all fractions at even higher concentrations of the different PHCs. In addition, asphaltene, which is a difficult fraction for a single microorganism to degrade, was markedly degraded by the co-culture, which indicated that the simultaneous biodegradation of aliphatic, aromatic, resin, and asphaltene fractions had occurred in the co-culture. An examination of in-vitro degradation by the crude enzymes and the retrieval fungal culture from the soil after the experiment confirmed the accelerated biodegradation due to enhanced enzyme activities in the co-culture. The addition of piperonyl butoxide or AgNO3 inhibited biodegradation by 81-99%, which demonstrated the important role of P450 monooxygenases and/or dioxygenases in the initial degradation of the aliphatic and aromatic fractions in PHCs.

  1. 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.

  2. 离子液体介质中沥青砂内重组分降解过程%CATALYTIC DEGRADATION OF MACROMOLECULAR CONSTITUENTS OF ASPHALTIC SANDS IN IONIC LIQUIDS

    Institute of Scientific and Technical Information of China (English)

    邹长军; 刘超; 黄志宇; 罗平亚

    2004-01-01

    This paper illustrates the reaction pattern of catalytic degradation of macromolecules in asphaltic sands. Such parameters as ionic liquid catalyst system and H+ proton donor, that affect the change of the organic phase and the mass of organic matter in residual phase of asphaltic sands, were investigated. It was found that chloroaluminate (Ⅲ) ionic liquid/H3PO4 systems as reaction medium was an effective catalyst system for asphaltic sands degradation. The catalytic degradation of asphaltic sand swas related to the kinds of chloroaluminate (Ⅲ) ionic liquids and H+ proton donor. In [BMIM] [AlCl4]/H3PO4 reaction catalytic medium, the degradation of asphaltenes in the organic phase reached 16.44 %, the degradation of asphaltenes in the residual phase reached 30.74%. TLC-FID analysis of asphaltic sands showed that the main degradation products were saturates and aromatics, and resin fractions as well. At a temperature close to oil-bearing formation and with absense of oxygen, the yield of H2S reached 74%,which indicated that catalytic degradation of sulphur-containing compounds was easier.

  3. 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)

  4. 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)

  5. Enhanced biodegradation of asphalt in the presence of Tween surfactants, Mn(2+) and H2O2 by Pestalotiopsis sp. in liquid medium and soil.

    Science.gov (United States)

    Yanto, Dede Heri Yuli; Tachibana, Sanro

    2014-05-01

    Asphalt and fractions thereof can contaminate water and soil environments. Forming as residues in distillation products in crude oil refineries, asphalts consist mostly of asphaltene instead of aliphatics, aromatics, and resins. The high asphaltene content might be responsible for the decrease in bioavailability to microorganisms and therefore reduce the biodegradability of asphalt in the environment. In this study, the effect on asphalt biodegradation by Pestalotiopsis sp. in liquid medium and soil of nonionic Tween surfactants in the presence of Mn2+ and H2O2 was examined. The degradation was enhanced by Tween 40 or Tween 80 (0.1%) in the presence of Mn2+ (1 mM) and H2O2 (0.05 mM). A Tween surfactant, Mn2+, and H2O2 can overcome bioavailability-mediated constraints and increase ligninolytic activities, particularly manganese peroxidase and laccase activities. The study is significant for the bioremediation of asphalt and/or viscous-crude oil-contaminated environments.

  6. 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.

  7. 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.

  8. Effect of Dodecylbenzene Sulfonic Acid Used as Additive on Residue Hydrotreating

    Institute of Scientific and Technical Information of China (English)

    Sun Yudong; Yang Chaohe

    2015-01-01

    The effect of additive—dodecylbenzene sulfonic acid (DBSA)—on residue hydrotreating was studied in the au-toclave. The results showed that the additive improved stabilization of the colloid system of residue, which could delay the aggregation and coke formation from asphaltenes on the catalyst, and make heavy components transformed into light oil. The residue conversion in the presence of this additive increased by 1.94%, and the yield of light oil increased by 1.53% when the reaction time was 90 min. The surface properties of the catalyst in the presence of this additive were better than that of the blank test within a very short time (30 min) and deteriorated rapidly after a longer reaction time due to higher conversion and coke deposition. Compared with the blank test, the case using the said additive had shown that the structure of hydrotreated asphaltene units was smaller and the condensation degrees were higher. The test results indicated that the additive could improve the hydrotreating reactivity of residue via permeation and depolymerization, the heavier components could be transformed into light oil more easily, and the light oil yield and residue conversion were higher for the case using the said additive in residue hydrotreating process.

  9. Aminated Copolymers as Flow Improvers for Super-viscous Crude Oils

    Institute of Scientific and Technical Information of China (English)

    Zhang Hong; Shen Benxian

    2007-01-01

    The new flow improvers for super-viscous crude oils were developed via esterification of polybasic high carbon alcohol with methacrylate and copolymerization of monomers followed by amination of copolymers.The structure of the synthesized polymer flow improver additive was confirmed by IR spectroscopy and the crystal structure of the flow improver additives were determined by X-ray diffraction analysis.The structure of wax crystals was also studied at the same time.The results showed that the wax crystal structure was closely related with the crystal structure of the flow improver,which could change the pour point depression and viscosity reduction behavior of the crude oil.When the wax crystal structure matched well with that of the additive,the Wax crystals were dispersed satisfactorily,resulting in favorable effects in terms of pour point depression and viscosity reduction.The new synthesized aminated polymer flow improver additive was most efficient for treating super-viscous crude oils.The super-viscous crude oil had a high content of resins and asphaltenes,which might aggregate onto the surface of wax crystals to form blocks to limit the crude oil fluidity.However,amination of copolymers having similar structure with the resins and asphaltenes contained in crude oil could dissolve the huge polar groups to make the deposit formation difficult.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2004-07-01

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

  11. Mousse photochemistry formation; Formacao fotoquimica de mousse

    Energy Technology Data Exchange (ETDEWEB)

    Rangel, George W.M.; Nicodem, David E. [Universidade Federal, Rio de Janeiro, RJ (Brazil). Inst. de Quimica]. E-mail: gwallace_iq@yahoo.com.br; nicodem@iq.ufrj.br

    2003-07-01

    The petroleum, when spilled in the sea it forms an emulsion of water in oil could contain up to 90% of water. This emulsion, called Mousse of Chocolate, it can be very stable, taking to the increase of the environmental impact and impeding the microbiological degradation. It was observed that the petroleum, when irradiated with solar light, it forms Mousse more easily. However, same being known about the importance of the action of the light in the formation of Mousse, little it is known regarding the processes and conditions involved in the formation of Mousse. This project proposes the study of the process of formation of Mousse, in function of the suffered transformations for petroleum after solar irradiation. We will study the relationship between the stability and formation of Mousse and the present amount of asphaltenes in the petroleum as a result of the irradiation. We will develop a methodology for analysis of emulsions of water in petroleum, in way we know her/it the stability of the emulsion in function of the time and the amount of water in the same. We will study the behavior of a sample of Brazilian petroleum of Campos' Basin, already used in other photochemistry studies. We will analyze the effect of the time of irradiation in the asphaltenes formation and Mousse. We will also analyze other types of petroleum, for us to compare results with obtained them in the Brazilian petroleum. (author)

  12. Laboratory research on rheological behavior and characterization of ultraviolet aged asphalt

    Institute of Scientific and Technical Information of China (English)

    吴少鹏; 朱国军; 陈筝; 刘至飞

    2008-01-01

    The influence of aging on the evolution of structural,morphological and rheological properties of neat asphalt was investigated by Fourier transform infrared(FTIR),atomic force microscopy(AFM) and dynamic shear rheometer(DSR),respectively.Asphalt was suffered under 20 W/m2 of UV radiant intensity and under the condition of aging time(0,48,96 and 144 h) with film thickness of 100 μm and film thickness of 50,100,200 and 500 μm after aging for 120 h,respectively,at certain UV radiant intensity 20 W/m2.Rheological results tested by DSR exhibit higher the complex shear(stiffness) modulus(G*) and lower phase angle(δ),compared to the virgin at the same test condition.The compositions analysis of asphalt before and after aging show an increase of carbonyl and sulfoxides,while a decrease of aromatic functional groups.With the increase of the component of asphaltene,obvious agglomerates of asphalten appear in neat asphalt surfaces after aging.

  13. 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.

  14. Interaction of oil components and clay minerals in reservoir sandstones

    Energy Technology Data Exchange (ETDEWEB)

    Changchun Pan; Linping Yu; Guoying Sheng; Jiamo Fu [Chinese Academy of Sciences, State Key Lab. of Organic Geochemistry, Wushan, Guangzhou (China); Jianhui Feng; Yuming Tian [Chinese Academy of Sciences, State Key Lab. of Organic Geochemistry, Wushan, Guangzhou (China); Zhongyuan Oil Field Co., Puyang, Henan (China); Xiaoping Luo [Zhongyuan Oil Field Co., Puyang, Henan (China)

    2005-04-15

    The free oil (first Soxhlet extract) and adsorbed oil (Soxhlet extract after the removal of minerals) obtained from the clay minerals in the <2 {mu}m size fraction as separated from eight hydrocarbon reservoir sandstone samples, and oil inclusions obtained from the grains of seven of these eight samples were studied via GC, GC-MS and elemental analyses. The free oil is dominated by saturated hydrocarbons (61.4-87.5%) with a low content of resins and asphaltenes (6.0-22.0% in total) while the adsorbed oil is dominated by resins and asphaltenes (84.8-98.5% in total) with a low content of saturated hydrocarbons (0.6-9.5%). The inclusion oil is similar to the adsorbed oil in gross composition, but contains relatively more saturated hydrocarbons (16.87-31.88%) and less resins and asphaltenes (62.30-78.01% in total) as compared to the latter. Although the amounts of both free and adsorbed oils per gram of clay minerals varies substantially, the residual organic carbon content in the clay minerals of the eight samples, after the free oil extraction, is in a narrow range between 0.537% and 1.614%. From the decrease of the percentage of the extractable to the total of this residual organic matter of the clay minerals with burial depth it can be inferred that polymerization of the adsorbed polar components occurs with the increase of the reservoir temperature. The terpane and sterane compositions indicate that the oil adsorbed onto the clay surfaces appears to be more representative of the initial oil charging the reservoir than do the oil inclusions. This phenomenon could possibly demonstrate that the first oil charge preferentially interacts with the clay minerals occurring in the pores and as coatings around the grains. Although the variation of biomarker parameters between the free and adsorbed oils could be ascribed to the compositional changes of oil charges during the filling process and/or the differential maturation behaviors of these two types of oils after oil

  15. Analysis of chemical composition of high viscous oils

    Directory of Open Access Journals (Sweden)

    Irina Germanovna Yashchenko

    2014-07-01

    Full Text Available The spatial distribution of viscous oils which are considered as an important reserve for oil-production in future were studied on base of information from global database on oil physical and chemical properties. Changes in chemical composition of viscous oils in different basins and continents were analyzed as well. It is shown, on average, viscous oils are sulfur-bearing, low paraffin, highly resinous oils with an average content of asphaltenes and low content of the fraction boiling at 200 C. Study results of viscous oils peculiarities of Canada, Russia and Venezuela are given. The analysis results can be used to determine the optimal layouts and conditions of oil transportation, to improve the search methods of geochemical exploration, and to solve other problems in the oil chemistry.

  16. Rheology and microstructure of MDI PEG reactive prepolymer-modified bitumen

    Science.gov (United States)

    Navarro, F. J.; Partal, P.; Martínez-Boza, F.; Gallegos, C.; Bordado, J. C. M.; Diogo, A. C.

    2006-12-01

    This paper deals with the use of a new bitumen modifier, a reactive prepolymer, based on the reaction of 4,4‧-diphenylmethane diisocyanate (MDI) and a low molecular weight polyethylene glycol (PEG). The rheological and thermal behaviours of modified bitumen containing a low MDI PEG concentration, as well as its morphology, have been studied. A relatively low amount of MDI PEG (0.5 to 1.5% wt.) yields a significant improvement in the modified bitumen rheological properties, mainly in the high in-service temperature region. In this range of temperature, the rheological properties are clearly affected by curing time at room temperature. These results indicate that chemical changes, due to the reaction of MDI isocyanate groups with the most polar groups ( OH; NH) of asphaltenes and resins, are produced. Thus, new chemical structures, non-visible by optical microscopy, slowly develop in MDI PEG modified bitumen when samples are cured at room temperature.

  17. ADVANCE IN FCC TECHNOLOGY FOR RESID UPGRADING

    Institute of Scientific and Technical Information of China (English)

    2001-01-01

    In order to treat residual oil in conventional FCC units, various aspects of catalyst improvement must be considered, such as how to get effective bottoms crackbility, lower selectivity of dry gas/coke or higher metals tolerance. Because residual oil contains many kinds of metals (Ni, V, Na), Conrandson carbon residue and asphaltene or basic nitrogen compunds, there are a lot of problems in FCC operation.   A new catalyst has been developed by means of modifying zeolite or matrix in our laboratory. The developed catalyst has a excellent bottoms crackbility, lower hydrogen / coke selectivity and higher metal tolerance. The features of the catalyst and the actual performance in our commercial units will be shown in this paper. The liquid product yield has been improved and the catalyst consumption has reduced.

  18. Hydrocarbon group type analysis of petroleum heavy fractions using the TLC-FID technique

    Energy Technology Data Exchange (ETDEWEB)

    Sharma, B.K.; Sarowha, S.L.S.; Bhagat, S.D. [Indian Institute of Petroleum, Dehradun (India); Tiwari, R.K.; Gupta, S.K.; Venkataramani, P.S. [Defence Materials and Stores, Research and Development, Establishment, Kanpur (India)

    1998-03-01

    Hydrocarbon group type analysis is important in all conversion processes and in preparation of feed for these conversion processes so as to learn the selectivity of the different type of catalysts for product yield and quality. The use of the Mark 5 Iatroscan detector and the method reported here allowed for a rapid and quantitative hydrocarbon group type analysis of petroleum residues without prior separation of asphaltenes. SARA type analyses of petroleum residues have been performed by a three stage development using n-hexane, toluene and DCM (95%):MeOH (5%). The standard deviation and coefficient of variation in repeated measurements by this method were as low as 0.65 wt% or less and 3.5 wt% or less, respectively. The time required for analysis of 10 samples could be as short as 90 min. (orig.) With 2 figs., 6 tabs., 21 refs.

  19. 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...

  20. Group-type separation and simulated distillation: a niche for SFC

    Energy Technology Data Exchange (ETDEWEB)

    Thiebaut, D.R.P. [Ecole Superieure de Physique et Chimie Industrielles, 75 - Paris (France). Lab. Environnement et Chimie Analytique; Robert, E.C. [Institut Francais du Petrole (IFP), 92 - Rueil-Malmaison (France)

    1999-10-01

    Recent advances in supercritical-fluid chromatography (SFC) of petroleum fractions are reviewed. Simulated distillation (Simdis) still requires some improvements of the hardware so that routine analysis of heavy fraction can be performed. Compared to gas-chromatography Simdis, SFC Simdis extends the range of this application up to C{sub 140} hydrocarbons while multi-detection would allow the differentiation of aromatic and non-aromatic hydrocarbons. SFC has been registered by ASTM for hydrocarbon group-type analysis using carbon dioxide. It enables fast separation of aromatic and non-aromatic fractions, sub-fractionation of aromatics and easier quantitation than in liquid chromatography. Resins and asphaltenes of heavier samples can be back flushed from the column. The method could be further improved for better resolution and quantitation via multiple detection and more selective stationary and mobile detection and more selective stationary and mobile phases (CO{sub 2}-SF{sub 6} mixtures for example). (authors)

  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 New Type of Exposed Oil Sand Mine

    Institute of Scientific and Technical Information of China (English)

    2002-01-01

    With several means of analysis, the unique organic compound component and distribution of exposed oil sand existing in Qinghai, north-west China, is revealed. Qinghhai oil sand has great content of light components with high saturated hydrocarbon content up to approximately 50%, while its heavy components of colloid and asphaltene is rather low (<38%); straight-chain alkane has a regular distribution concentrating mainly around C28; it has a very high atom ratio of H/C. The physical parameters of the oil sand mine are within the range of common heavy oils. Such chemical composition and distribution obviously differs from that of other known exposed oil sand mines. This particular property of the oil sand is formed due to the unique geographical and geological environment. Therefore, it is intended to exploit the mine with a new combined method, i.e., first drill horizontal wells and then opencut.

  3. Dust evolution, a global view I. Nanoparticles, nascence, nitrogen and natural selection … joining the dots

    Science.gov (United States)

    Jones, A. P.

    2016-12-01

    The role and importance of nanoparticles for interstellar chemistry and beyond is explored within the framework of The Heterogeneous dust Evolution Model for Interstellar Solids (THEMIS), focusing on their active surface chemistry, the effects of nitrogen doping and the natural selection of interesting nanoparticle sub-structures. Nanoparticle-driven chemistry, and in particular the role of intrinsic epoxide-type structures, could provide a viable route to the observed gas phase OH in tenuous interstellar clouds en route to becoming molecular clouds. The aromatic-rich moieties present in asphaltenes probably provide a viable model for the structures present within aromatic-rich interstellar carbonaceous grains. The observed doping of such nanoparticle structures with nitrogen, if also prevalent in interstellar dust, could perhaps have important and observable consequences for surface chemistry and the formation of precursor pre-biotic species.

  4. WETTABILITY AND PREDICTION OF OIL RECOVERY FROM RESERVOIRS DEVELOPED WITH MODERN DRILLING AND COMPLETION FLUIDS

    Energy Technology Data Exchange (ETDEWEB)

    Jill S. Buckley; Norman R. Morrow

    2004-05-01

    We report on progress in three areas. In part one, the wetting effects of synthetic base oils are reported. Part two reports progress in understanding the effects of surfactants of known chemical structures, and part three integrates the results from surface and core tests that show the wetting effects of commercial surfactant products used in synthetic and traditional oil-based drilling fluids. An important difference between synthetic and traditional oil-based muds (SBM and OBM, respectively) is the elimination of aromatics from the base oil to meet environmental regulations. The base oils used include dearomatized mineral oils, linear alpha-olefins, internal olefins, and esters. We show in part one that all of these materials except the esters can, at sufficiently high concentrations, destabilize asphaltenes. The effects of asphaltenes on wetting are in part related to their stability. Although asphaltenes have some tendency to adsorb on solid surfaces from a good solvent, that tendency can be much increased near the onset of asphaltene instability. Tests in Berea sandstone cores demonstrate wetting alteration toward less water-wet conditions that occurs when a crude oil is displaced by paraffinic and olefinic SBM base oils, whereas exposure to the ester products has little effect on wetting properties of the cores. Microscopic observations with atomic forces microscopy (AFM) and macroscopic contact angle measurements have been used in part 2 to explore the effects on wetting of mica surfaces using oil-soluble polyethoxylated amine surfactants with varying hydrocarbon chain lengths and extent of ethoxylation. In the absence of water, only weak adsorption occurs. Much stronger, pH-dependent adsorption was observed when water was present. Varying hydrocarbon chain length had little or no effect on adsorption, whereas varying extent of ethoxylation had a much more significant impact, reducing contact angles at nearly all conditions tested. Preequilibration of

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2008-07-01

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

  6. Investigation of products of low-temperature catalytic hydrogenization of Donbas coals

    Energy Technology Data Exchange (ETDEWEB)

    Osipov, A.M.; Osipov, K.D.; Chernyshova, M.I.; Petrik, G.K.

    1980-11-01

    The relationship of the composition and properties of primary products of low-temperature hydrogenation is presented in relation to the nature of the coal, of catalysts, and of the conditions of hydrogenation. Temperature, the nature of the catalysts and of the type of coal used were directly related to the content of methane, ethane, propane, and CO/sub 2/, and of hydrogen sulphide in the case of brown gaseous coals, as well as the dissolving of hydrogenates and asphaltene content. The structural composition of components dissolved in methylene chloride was determined by proton magnetic resonance. Results of the experiments indicated that lead chloride was the most promising catalyst for low-temperature hydrogenation.

  7. 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

  8. Visbreaking of heavy petroleum oil catalyzed by SO42-/ZrO2 solid super-acid doped with Ni2+ or Sn2+

    Institute of Scientific and Technical Information of China (English)

    2008-01-01

    SO42-/ZrO2 solid super-acid catalysts (SZ)doped with Ni2+ or Sn2+ (Ni2+/SZ,Sn2+/SZ) were prepared for catalytic visbreaking of heavy petroleum oil from Shengli oil field.The visbreaking reactions were carried out at 240℃ and 3-4 MPa for 24 h using a heavy petroleum oil to catalyst mass ratio of 100 :0.05.The effect of water content on viscosity of heavy petroleum oil was also investigated.Both catalysts can promote thermolysis of heavy petroleum oil and the viscosity was reduced for (Sn2+/SZ) with visbreaking rates of 57.7% and 48.9%,respectively.After visbreaking,the saturated hydrocarbon content increased while aromatics,resin,asphaltene,sulfur and nitrogen content decreased.The presence of water was disadvantageous to visbreaking of heavy petroleum oil.

  9. Rheological properties of crude oils in Yaregskoye and Yaraktinskoye oil fields

    Science.gov (United States)

    Manzhai, V. N.; Le Grand Monkam Monkam, Clovis; Terre, D. A.

    2016-09-01

    Rotary viscometer tests of crude oil with a high content of resins and asphaltenes (Yaregskoye oil field) and crude oil with high paraffin content (Yaraktinskoye oil field) have been conducted. The typical flow curves for these oil types have been plotted. It has been detected that these oils are non-Newtonian fluids, viscosity of which is dependent on shear rate. Based on Arrhenius-Eyring equation, calculations of viscous flow activation energy and complex structural unit (CSU) sizes have been performed. It has been stated that there is a tenfold reduction in CSU size in asphaltic crude oil with the increase in shear rate in a rotary viscometer, while particle size in paraffinic crude oil does not essentially change under the same hydrodynamic conditions.

  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. 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.

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

    Energy Technology Data Exchange (ETDEWEB)

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

    2010-07-01

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

  13. 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.

  14. Northwest Australia's Saladin crude assayed

    Energy Technology Data Exchange (ETDEWEB)

    Rhodes, A.K.

    1993-10-18

    High-quality Saladin crude oil from offshore Western Australia has been assayed. The 48.2[degree] API, 0.02 wt % sulfur crude's characteristics--determined in 1990--are presented here for the first time. The estimated 30--40 million bbl field, south of Barrow Island, is produced from two platforms in 58 ft of water in block TP 3. Production began in late 1989 from three platforms with three wells each and from two wells drilled directionally from Thevenard Island. The paper lists data on the following properties: API gravity, density, sulfur content, pour point, flash point, viscosity, salinity, heat of combustion, ash content, asphaltene content, wax content, and metal content for the whole crude and various fractions.

  15. 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.

  16. 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.

  17. 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.

  18. 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

  19. 反应温度对加氢残渣油四组分含量和结构的影响%Influence of reaction temperature on the content and structure of four fractions in residue hydrotreating

    Institute of Scientific and Technical Information of China (English)

    孙昱东; 杨朝合; 谷志杰; 韩忠祥

    2013-01-01

    以沙轻减渣为原料,在高压釜内研究了不同反应温度下加氢反应前后渣油的四组分含量及其结构组成变化.结果表明,加氢残渣油中的饱和分含量明显增加,而芳香分和胶质的含量均降低,四组分含量随反应温度的升高均呈现规律性变化.加氢后四组分的H/C摩尔比和平均相对分子质量均降低,芳碳分率增加.随反应温度升高,四组分的H/C摩尔比和平均相对分子质量降低,烷基碳分率降低;芳香分、胶质和沥青质的芳碳分率增加;胶质和沥青质的总环数和芳环数均降低.渣油加氢过程中四组分都发生了明显的氢解和脱烷基反应.加氢反应中,胶质和沥青质结构单元间的各种桥键可发生明显地断裂,导致其结构单元数减少,且结构单元数随反应温度的升高而减少.%The changes of the content and structure of four fractions in the vacuum residue of Saudi Arabia light crude oil ( ALVR) pre- and post hydrotreating were investigated in an autoclave at different reaction temperatures. The results showed that after the hydrotreating, the saturate content is increased greatly, while the aromatic and resin contents are decreased in the hydrotreated residue; the contents of four fractions changes regularly with the increase of the reaction temperature. The H/C mol ratio and molecular weight of four fractions in the hydrotreated residue are decreased while the fraction of aromatic carbons (fa) is increased after the hydrotreating. With the increase of reaction temperature, the H/C mol ratio, molecular weight and the fraction of paraffin carbons (fp) of four fractions are decreased, while fa and the content of resin and asphaltene are increased in the hydrotreated residue; meanwhile, the total rings and aromatic rings of resin and asphaltene are decreased. The four fractions in the residue have undergone hydrogenolysis and hydrodealkylation during the hydrotreating. Bridge bonds between the units of

  20. 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.

  1. Application of Heavy Solvent Deasphalting in Sour Resid Processing

    Institute of Scientific and Technical Information of China (English)

    Long Jun; Wang Zijun; Huang Weiqi; Zu Deguang

    2003-01-01

    Complete conversion of resid into light oil needs to consume large amount of hydrogen, because the light oil has higher hydrogen content. The conversion of whole resid into light oil is not economic at the normal price gap between the light and heavy oils. Hence a combination of hydrogenation process with carbon removal process is generally adopted.The heavy solvent deasphalting can selectively remove the asphaltenes and metals contained in resid while providing a large amount of easily convertible deasphalted oil for the down-stream processes.This article refers to the characteristics of heavy solvent deasphalting and its application in sour resid processing, along with various routes for utilization of deoiled asphalt.

  2. 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......In order to facilitate the study of the influence of reservoir process characteristics in In-Situ combustion modeling and advance the work of Kristensen et al. in this domain; a fully compositional In-situ combustion (ISC) model of Virtual Kinetic Cell (VKC; single-cell model) for laboratory scale...... 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...

  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. High temperature ceramic membrane reactors for coal liquid upgrading

    Energy Technology Data Exchange (ETDEWEB)

    Tsotsis, T.T. (University of Southern California, Los Angeles, CA (United States). Dept. of Chemical Engineering); Liu, P.K.T. (Aluminum Co. of America, Pittsburgh, PA (United States)); Webster, I.A. (Unocal Corp., Los Angeles, CA (United States))

    1992-01-01

    Membrane reactors are today finding extensive applications for gas and vapor phase catalytic reactions (see discussion in the introduction and recent reviews by Armor [92], Hsieh [93] and Tsotsis et al. [941]). There have not been any published reports, however, of their use in high pressure and temperature liquid-phase applications. The idea to apply membrane reactor technology to coal liquid upgrading has resulted from a series of experimental investigations by our group of petroleum and coal asphaltene transport through model membranes. Coal liquids contain polycyclic aromatic compounds, which not only present potential difficulties in upgrading, storage and coprocessing, but are also bioactive. Direct coal liquefaction is perceived today as a two-stage process, which involves a first stage of thermal (or catalytic) dissolution of coal, followed by a second stage, in which the resulting products of the first stage are catalytically upgraded. Even in the presence of hydrogen, the oil products of the second stage are thought to equilibrate with the heavier (asphaltenic and preasphaltenic) components found in the feedstream. The possibility exists for this smaller molecular fraction to recondense with the unreacted heavy components and form even heavier undesirable components like char and coke. One way to diminish these regressive reactions is to selectively remove these smaller molecular weight fractions once they are formed and prior to recondensation. This can, at least in principle, be accomplished through the use of high temperature membrane reactors, using ceramic membranes which are permselective for the desired products of the coal liquid upgrading process. An additional incentive to do so is in order to eliminate the further hydrogenation and hydrocracking of liquid products to undesirable light gases.

  6. High temperature ceramic membrane reactors for coal liquid upgrading. Final report, September 21, 1989--November 20, 1992

    Energy Technology Data Exchange (ETDEWEB)

    Tsotsis, T.T. [University of Southern California, Los Angeles, CA (United States). Dept. of Chemical Engineering; Liu, P.K.T. [Aluminum Co. of America, Pittsburgh, PA (United States); Webster, I.A. [Unocal Corp., Los Angeles, CA (United States)

    1992-12-31

    Membrane reactors are today finding extensive applications for gas and vapor phase catalytic reactions (see discussion in the introduction and recent reviews by Armor [92], Hsieh [93] and Tsotsis et al. [941]). There have not been any published reports, however, of their use in high pressure and temperature liquid-phase applications. The idea to apply membrane reactor technology to coal liquid upgrading has resulted from a series of experimental investigations by our group of petroleum and coal asphaltene transport through model membranes. Coal liquids contain polycyclic aromatic compounds, which not only present potential difficulties in upgrading, storage and coprocessing, but are also bioactive. Direct coal liquefaction is perceived today as a two-stage process, which involves a first stage of thermal (or catalytic) dissolution of coal, followed by a second stage, in which the resulting products of the first stage are catalytically upgraded. Even in the presence of hydrogen, the oil products of the second stage are thought to equilibrate with the heavier (asphaltenic and preasphaltenic) components found in the feedstream. The possibility exists for this smaller molecular fraction to recondense with the unreacted heavy components and form even heavier undesirable components like char and coke. One way to diminish these regressive reactions is to selectively remove these smaller molecular weight fractions once they are formed and prior to recondensation. This can, at least in principle, be accomplished through the use of high temperature membrane reactors, using ceramic membranes which are permselective for the desired products of the coal liquid upgrading process. An additional incentive to do so is in order to eliminate the further hydrogenation and hydrocracking of liquid products to undesirable light gases.

  7. WETTABILITY AND PREDICTION OF OIL RECOVERY FROM RESERVOIRS DEVELOPED WITH MODERN DRILLING AND COMPLETION FLUIDS

    Energy Technology Data Exchange (ETDEWEB)

    Jill S. Buckley; Norman R. Morrow

    2005-04-01

    Exposure to crude oil in the presence of an initial brine saturation can render rocks mixed-wet. Subsequent exposure to components of synthetic oil-based drilling fluids can alter the wetting toward less water-wet or more oil-wet conditions. Mixing of the non-aromatic base oils used in synthetic oil-based muds (SBM) with an asphaltic crude oil can destabilize asphaltenes and make cores less water-wet. Wetting changes can also occur due to contact with the surfactants used in SBM formulations to emulsify water and make the rock cuttings oil-wet. Reservoir cores drilled with SBMs, therefore, show wetting properties much different from the reservoir wetting conditions, invalidating laboratory core analysis using SBM contaminated cores. Core cleaning is required in order to remove all the drilling mud contaminants. In theory, core wettability can then be restored to reservoir wetting conditions by exposure to brine and crude oil. The efficiency of core cleaning of SBM contaminated cores has been explored in this study. A new core cleaning procedure was developed aimed to remove the adsorbed asphaltenes and emulsifiers from the contaminated Berea sandstone cores. Sodium hydroxide was introduced into the cleaning process in order to create a strongly alkaline condition. The high pH environment in the pore spaces changed the electrical charges of both basic and acidic functional groups, reducing the attractive interactions between adsorbing materials and the rock surface. In cores, flow-through and extraction methods were investigated. The effectiveness of the cleaning procedure was assessed by spontaneous imbibition tests and Amott wettability measurements. Test results indicating that introduction of sodium hydroxide played a key role in removing adsorbed materials were confirmed by contact angle measurements on similarly treated mica surfaces. Cleaning of the contaminated cores reversed their wettability from oil-wet to strongly water-wet as demonstrated by spontaneous

  8. 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.

  9. Meeting the flow assurance challenges of deep water developments - from CAPEX development to field start up

    Energy Technology Data Exchange (ETDEWEB)

    Jordan, M.M.; Feasey, N.D. [National Aluminium Company Ltd. (Nalco), Cheshire (United Kingdom); Afonso, M.; Silva, D. [NALCO Brasil Ltda., Sao Paulo, SP (Brazil)

    2008-07-01

    As oil accumulations in easily accessible locations around the world become less available developments in deeper water become a more common target for field development. Deep water projects, particularly sub sea development, present a host of challenges in terms of flow assurance and integrity. In this paper the focus will be on the chemical control of flow assurance challenges in hydrate control, scale control and wax/asphaltene control within deep water (>750 meter) developments. The opportunities for kinetic hydrate control vs. conventional thermodynamic hydrate control will be outlined with examples of where these technologies have been applied and the limitations that still exist. The development of scale control chemical formulations specifically for sub sea application and the challenges of monitoring such control programs will be highlighted with developments in real time and near real time monitoring. Organic deposit control (wax/asphaltene) will focus on the development of new chemicals that have higher activity but lower viscosity than currently used chemicals hence allowing deployment at colder temperatures and over longer distances. The factors that need to be taken into account when selecting chemicals for deep water application will be highlighted. Fluid viscosity, impact of hydrostatic head on injectivity, product stability at low temperature and interaction with other production chemicals will be reviewed as they pertain to effective flow assurance. This paper brings learning from other deep water basins with examples from the Gulf of Mexico, West Africa and Brazil, which will be used to highlight these challenges and some of the solutions currently available along with the technology gaps that exist. (author)

  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. 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.

  12. Sequential Isolation of Saturated, Aromatic, Resinic and Asphaltic Fractions Degrading Bacteria from Oil Contaminated Soil in South Sumatera

    Directory of Open Access Journals (Sweden)

    Pingkan Aditiawati

    2012-04-01

    Full Text Available Sequential isolation has been conducted to obtain isolates of saturated, aromatic, resin, and asphaltene fractions degrading bacteria from oil contaminated sites. Five soil samples were collected from South Sumatera. These were analyzed using soil extract medium enriched with oil recovery or Remaining-Oil recovery Degradated (ROD as sole carbon and energy sources according to the isolation stage. ROD at the end of every isolation stage analyzed oil fractions by use of the SARA analysis method. Six isolates of bacteria have been selected, one isolate was fraction saturates degrading bacteria that are Mycobacterium sp. T1H2D4-7 at degradation rate 0.0199 mgs/h with density 8.4x106 cfu/g from stage I. The isolate T2H1D2-4, identified as Pseudomonas sp. was fraction aromatics degrading bacteria at accelerate 0.0141 mgs/h with density 5.1x106 cfu/g are obtained at stage II. Two isolates namely Micrococcus sp. T3H2D4-2 and Pseudomonas sp. T1H1D5-5 were fraction resins degrading bacteria by accelerate 0.0088 mgs/h at density 5.6x106 cfu/g and 0.0089 mgs/h at density 5.7x106 cfu/g are obtained at stage III. Isolation of stage IV has been obtained two isolates Pseudomonas sp. T4H1D3-1and Pseudomonas sp. T4H3D5-4 were fraction asphaltenes degrading bacteria by accelerate 0.0057 mgs/h at density 5.6x106 cfu/g and accelerate 0.0058 mgs/h at density 5.7x106 cfu/g.

  13. 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)

  14. Toxicity assessment of unrefined crude oil fractions in soil ecosystems

    Energy Technology Data Exchange (ETDEWEB)

    Goudey, J.S.; Wilson, J.J. [HydroQual Lab. Ltd., Calgary, AB (Canada); Chu, A. [Calgary Univ., AB (Canada)

    2001-07-01

    The chemical and physical differences amongst crude oils and bioavailability (toxicity) of crude oil constituents are not addressed with existing numerical criteria for remediation of hydrocarbon contaminated soils. The constituents of crude oil include short chain hydrocarbons, such as light ends or gasoline, and long chain hydrocarbons (saturates), aromatic and polar compounds and heavier asphaltenes. Natural weathering and biodegradation take care of the lighter compounds. Less biodegradable are the heavier compounds which tend to be immobile. A range of questions concerning these immobile substances need to be answered to determine their effect on the bioavailability, hence toxicity, when solutes become solvents, etc. In this study, different crude oils and crude oil fractions were assessed as to their effect on the bioavailability (as toxicity) to microbes, plants and invertebrates. Five fractions with boiling point distillation were obtained from the separation of each of three base crude oils for a total of fifteen fractions. This practical approach to fractionating hydrocarbon represents the standard method for crude characterization. Ecological relevance, volume requirements, and availability of standard methods formed the basis for the selection of the tests and test species. The relative amounts of the different compounds (aromatics, saturates, polars, and asphaltenes) were different for each crude. Worm survival and lettuce seeding emergence tests were conducted on the spiked soils, and the extracts were tested with bacterial luminescence and lettuce root elongation. The results obtained for the three crude oils were similar. It was found that the heavier fractions were not toxic. Aging decreased the toxicity of aqueous extracts of spiked soils. Methanol extracts showed no loss of toxicity. The toxicity of whole crude was compared to the toxicity recovered in the fractions. The aqueous extracts of the naphthenic crude and the methanol extract of the

  15. 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

  16. 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

  17. 地层原油黏温曲线的分形特征%Fractal Feature of Viscosity-Temperature Curves to In-Place Oil

    Institute of Scientific and Technical Information of China (English)

    唐红瑛

    2011-01-01

    The comprehensive analysis of in-place oil viscosity-temperature curves and oil analysis data aims at deepening the understanding of crude physical property.The study shows that the crude oil viscosity-temperature curves from different oil fields,different horizons and different well depths have good fractal feature.Under the fractal conditions that we regard viscosity as scale and temperature as object,the fractal dimension D is decimal,and the numerical value ranges from 0.1 to 0.3.With increase of the fractal dimension,the effect of temperature on viscosity becomes smaller.The fractal dimension and the parameters such as density,viscosity and initial boiling point of crude oil have good correlativity.So the fractal dimension D can be taken as a new characteristic parameter reflecting crude oil physical properties.It is only related with asphaltene content,rather than wax content and gel content,showing that the asphaltene and its content is the main factor influencing fractal dimension value of crude property and viscosity-temperature curve.This conclusion is accordant with the viewpoint that asphaltene fraction takes principal part in changing wettability of rocks,compared with other fractions.%为了加深对原油物性的认识,对地层原油黏温曲线与油分析资料进行了综合分析。研究表明:不同油田、不同层位、不同井深的地层原油黏温曲线均具有良好的分形特征。在以黏度为测量标尺,以温度为测量对象的定义分形条件下,其分形维数为0.1~0.3.随着分形维数的增加,温度对黏度的影响变小。分形维数与原油物性中的参数如密度、黏度、初馏点等相关性良好,因此,可以将分形维数作为一个新的反映原油物性的特征参数。分形维数与原油中的含蜡量、含胶量不相关,唯独与沥青质含量基本相关,说明沥青质及其含量是影响原油性质、原油黏温曲线分形维数的主要因素,这和"沥青质馏分与

  18. 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.

  19. ASE3OO与快速索氏抽提仪处理沉积岩样品的地化参数对比%The Comparison of Geochemical Parameters of Sedimentary Rock Samples Extracted by ASE300 and Fast Soxhlet Apparatus

    Institute of Scientific and Technical Information of China (English)

    魏彩云; 王汇彤; 赵丽娜; 张水昌; 程磊

    2012-01-01

    本文对加速溶剂萃取仪(ASE300)和快速索氏抽提仪提取的氯仿沥青“A”及由其分离出的饱和烃、芳烃、胶质和沥青质组分做了详细对比.结果表明:多数情况下ASE300抽提出的氯仿沥青“A”的量比快速索氏抽提仪抽提出的量略多,主要是胶质和沥青质量的增加;不同抽提装置得到的饱和烃和芳烃组分的色谱-质谱谱图高度一致,定量结果的相对偏差在5%以内.各组分的稳定碳同位素分析精度±0.5‰.所有的地化参数表明ASE300完全可以替代快速索氏抽提仪,从而降低消耗、提高分析效率.%Two groups of chloroform bitumen "A" samples were separated from some selected sedimentary rock samples using an accelerated solvent extraction apparatus (ASE300) and a fast Soxhlet extraction apparatus, respectively. The geochemical parameters of saturated hydrocarbons, aromatics, resin and asphaltene from the different chloroform bitumen "A" sample groups were systematically studied and compared. The experiment results showed that the obtained amounts of chloroform bitumen "A" are slightly higher using the ASE300 than using the fast Soxhlet in most cases, and that the main increments of using ASE300 are resin and asphaltene. GC-MS study indicated that saturated and aromatic hydrocarbons extracted from two groups of chloroform bitumen "A" samples are highly consistent, the deviations of the quantitative results are less than 5 % , the differences of measured carbon stable isotope compositions for any identical component obtained respectively from two extraction methods fall into the range of ± 0. 5‰. These results indicated that ASE300 and fast Soxhlet extracted instruments are comparative. Therefore, the ASE300, the relatively consumption saving and analytically efficient method, can replace the fast Soxhlet extraction apparatus in geochemical pretreatment experiments.

  20. 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

  1. 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

  2. Solids precipitation in crude oils, gas-to-liquids and their blends

    Science.gov (United States)

    Ramanathan, Karthik

    Gas-to-liquids (GTL) liquids are obtained from syngas by the Fischer-Tropsch synthesis. The blending of GTL liquids produced from natural gas/coal reserves and crude oils is a possibility in the near future for multiple reasons. Solids precipitation is a major problem in pipelines and refineries leading to significant additional operating costs. The effect of the addition of a paraffinic GTL liquid to crude oils on solids precipitation was investigated in this study. A Fourier transform infrared (FT-IR) spectroscopic technique was used to obtain solid-liquid equilibria (SLE) data for the various samples. The SLE of multiple systems of model oils composed of n-alkanes was investigated preliminarily. Blends of a model oil simulating a GTL liquid composition and a crude oil showed that the wax precipitation temperature (WPT) decreased upon blending. Three crude oils from different geographic regions (Alaskan North Slope, Colorado and Venezuela) and a laboratory-produced GTL liquid were used in the preparation of blends with five different concentrations of the GTL liquid. The wax precipitation temperatures of the blends were found to decrease with the increasing addition of the GTL liquid for all the oils. This effect was attributed to the solvent effect of the low molecular weight-paraffinic GTL liquid on the crude oils. The weight percent solid precipitated that was estimated as a function of temperature did not show a uniform trend for the set of crude oils. The asphaltene onset studies done on the blends with near-infrared spectroscopy indicated that the addition of GTL liquid could have a stabilizing effect on the asphaltenes in some oils. Analytical techniques such as distillation, solvent separation, HPLC, GC, and GPC were used to obtain detailed composition data on the samples. Two sets of compositional data with 49 and 86 pseudo-components were used to describe the three crude oils used in the blending work. The wax precipitation was calculated using a

  3. Research on the Pipeline Technology of Heavy Crude Oil%稠油管道输送技术研究

    Institute of Scientific and Technical Information of China (English)

    邹帅; 吴明; 刘佳春

    2014-01-01

    高粘的稠油使得输送成为管道从业者的一个难题,尤其是发生凝管事故后的再启动问题。对稠油高粘的实质迚行研究发现,决定稠油粘度的实质为原油体系中沥青质分子和非沥青质分子相互作用所形成的大分子胶束聚集体所致。国内外稠油输送方法有加热法、裂解降粘法、掺稀输送法、添加改性剂法、低粘液环输送法、微生物法、超声波法和超临界CO2输送法。各方法各具优缺点,没有一种方法适用于所有稠油,另外还需要考虑经济性问题。目前国内最常用的输送方法为加热法和掺稀法。在实际中,针对不同稠油要迚行一定的技术分析和研究才能决定选择何种输送技术。%The pipeline transportation of heavy crude oil with high viscosity has become a difficult problem to operators of pipelines, especially restarting of the pipeline transportation after the pipeline congelation accident. Through research on properties of heavy crude, it’s concluded that the high viscosity of heavy crude depends on macromolecule micelles aggregates formed by interaction between asphaltene molecules and non-asphaltene molecules in the system of crude oil. There are some pipeline processes at home and abroad, such as heating, pyrolytic decomposition, blending method, adding modifiers, ultrasonic method, microbiological process and supercritical CO2 transport method. Every method has its advantages and disadvantages, and none can fit all kinds of heavy crude oil. At present, heating and blending methods are the most common at home and abroad. In the practical condition, the most suitable process should be chosen based on analysis and research on the heavy crude oil.

  4. 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

  5. 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.

  6. Effects of weathering on the dispersion of crude oil through oil-mineral aggregation.

    Science.gov (United States)

    Gustitus, Sarah A; John, Gerald F; Clement, T Prabhakar

    2017-02-08

    Crude oil that is inadvertently spilled in the marine environment can interact with suspended sediment to form oil-mineral aggregates (OMA). Researchers have identified OMA formation as a natural method of oil dispersion, and have sought ways to enhance this process for oil spill remediation. Currently there is a lack of understanding of how the weathering of oil will affect the formation of OMA due to a lack of published data on this relationship. Based on literature, we identified two conflicting hypotheses: OMA formation 1) increases with weathering as a result of increased asphaltene and polar compound content; or 2) decreases with weathering as a result of increased viscosity. While it is indeed true that the viscosity and the relative amount of polar compounds will increase with weathering, their net effects on OMA formation is unclear. Controlled laboratory experiments were carried out to systematically test these two conflicting hypotheses. Experimental results using light, intermediate, and heavy crude oils, each at five weathering stages, show a decrease in OMA formation as oil weathers.

  7. 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)

  8. Kinetics and mechanisms of hydroliquefaction and hydrogasification of lignite. [Cellulose, wood, manure, municipal waste, coal of various ranks, fuel oil and natural gas

    Energy Technology Data Exchange (ETDEWEB)

    Weiss, A.H.; Kranich, W.L.; Geureuz, K.

    1981-01-01

    A high pressure, continuous, stirred-tank reactor system has been constructed for the study of the catalytic liquefaction of North Dakota lignite slurried in anthracene oil. The conversion of lignite using a cobalt-molybdenum on alumina catalyst and the distribution of products as preasphaltenes, asphaltenes, oils and gases has been studied at the following conditions: temperature, 375 to 440/sup 0/C; pressure, 1000 to 1600 psig; agitator speed, 800 to 1500 rpm; catalyst concentration, 0 to 10% (based on lignite); initial lignite concentration, 5 to 30%; and space time, 16 to 52 minutes. At reactor pressures above 1500 psig and agitator speeds above 1000 rpm, reaction rate was essentially independent of pressure. At catalyst concentrations above 1% (based on lignite), the conversion of lignite was essentially independent of catalyst concentration. Experiments were conducted above these limits to find the effect on lignite conversion rate, of initial lignite concentration, and space time, or degree of conversion. The results at constant temperature were correlated by an equation which is given in the report. The relationship between the rate constant, K, and temperature, and between the maximum conversion and temperature was established. The effect of reaction conditions on the distribution of products was studied. In the presence of catalyst, the oil yield was increased, even under conditions where the catalyst did not affect overall lignite conversion. Under the most favorable conditions the oil yield was a little better than that obtained by Cronauer in the uncatalyzed hydroliquefaction of subbituminous coal at similar temperature and pressure.

  9. Minimising hydrogen sulphide generation during steam assisted production of heavy oil

    Science.gov (United States)

    Montgomery, Wren; Sephton, Mark A.; Watson, Jonathan S.; Zeng, Huang; Rees, Andrew C.

    2015-02-01

    The majority of global petroleum is in the form of highly viscous heavy oil. Traditionally heavy oil in sands at shallow depths is accessed by large scale mining activities. Recently steam has been used to allow heavy oil extraction with greatly reduced surface disturbance. However, in situ thermal recovery processes can generate hydrogen sulphide, high levels of which are toxic to humans and corrosive to equipment. Avoiding hydrogen sulphide production is the best possible mitigation strategy. Here we use laboratory aquathermolysis to reproduce conditions that may be experienced during thermal extraction. The results indicate that hydrogen sulphide generation occurs within a specific temperature and pressure window and corresponds to chemical and physical changes in the oil. Asphaltenes are identified as the major source of sulphur. Our findings reveal that for high sulphur heavy oils, the generation of hydrogen sulphide during steam assisted thermal recovery is minimal if temperature and pressure are maintained within specific criteria. This strict pressure and temperature dependence of hydrogen sulphide release can allow access to the world's most voluminous oil deposits without generating excessive amounts of this unwanted gas product.

  10. 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.

  11. Probing the molecular weight distributions of non-boiling petroleum fractions by Ag+ electrospray ionization mass spectrometry.

    Science.gov (United States)

    Roussis, Stilianos G; Proulx, Richard

    2004-01-01

    This work explores the possibility of Ag+ electrospray ionization mass spectrometry (ESI-MS) to determine the molecular weight distributions of non-boiling petroleum fractions. Information about the molecular weight distributions is needed for fundamental studies on the nature of heavy crude oils and bitumens and for the development of novel recovery and processing methods. The method does not depend on thermal processes for the introduction of the fractions into the gas phase of the mass spectrometer, which is a considerable advantage over most other ionization methods. The Ag+ electrospray mass spectra of the fractions analyzed by using a toluene/methanol/cyclohexane (60:28:12%) solvent system display bimodal distributions in the ranges m/z approximately 300 to approximately 3000 and m/z 3000 to approximately 20,000. The abundances of the high molecular weight peak distributions can be reduced by in-source collisional activation experiments. Comparisons with the results obtained for model heteroatom-containing compounds (molecular weight method in this study for the saturate, aromatic, and polar fractions in a bitumen are in qualitative agreement with published molecular weight average results obtained for Cold Lake bitumen fractions analyzed by conventional gel permeation chromatography and field desorption mass spectrometry. Further work is needed to study the nature of the bonds and the interactions of the molecules in the asphaltene fractions by Ag+ ESI-MS.

  12. Bitumen modification with a low-molecular-weight reactive isocyanate-terminated polymer

    Energy Technology Data Exchange (ETDEWEB)

    F.J. Navarro; P. Partal; M. Garcia-Morales; F.J. Martinez-Boza; C. Gallegos [Universidad de Huelva, Huelva (Spain). Departamento de Ingenieria Quimica, Facultad de Ciencias Experimentales

    2007-10-15

    A low-molecular-weight polyethyleneglycol functionalized with a polymeric MDI (4,4'-diphenylmethane diisocynate) was used as a modifying agent for a 60/70 penetration grade bitumen. The rheological properties of the resulting modified binder, at both low and intermediate temperatures, before and after curing at room temperature were studied and compared with those corresponding to a SBS modified bitumen. The analysis showed that the addition of a small quantity of this reactive polymer leads to enhanced rheological properties mainly at high in-service temperature (50{sup o}C). However, modification was found to be rather slow during binder curing at room temperature. Moreover, storage stability analysis showed that phase separation did not take place after bitumen storage at 163{sup o}C, though storage at high temperature affects the modification capability of the reactive polymer. Atomic force microscopy measurements showed that the reactive polymer addition leads to asphaltene-rich regions with lower thermal susceptibility, which are present even at high temperature, yielding an improved bitumen viscosity in this range of in-service temperatures. 38 refs., 7 figs., 2 tabs.

  13. Effectiveness of bioremediation for the Prestige fuel spill : a summary of case studies

    Energy Technology Data Exchange (ETDEWEB)

    Gallego, J.R. [Oviedo Univ., Asturias (Spain); Gonzalez-Rojas, E.; Pelaez, A.I.; Sanchez, J [Oviedo Univ., Asturias (Spain). Inst. de Biotecnologia de Asturias; Garcia-Martinez, M.J.; Llamas, J.F. [Univ. Polictenica de Madrid, Madrid (Spain). Laboratorio de Estratigrafia Biomolecular

    2006-07-01

    This paper described novel bioremediation strategies used to remediate coastal areas in Spain impacted by the Prestige fuel oil spill in 2002. The bioremediation techniques were applied after hot pressurized water washing was used to remove hydrocarbons adhering to shorelines and rocks. Bioremediation strategies included monitored natural attenuation as well as accelerating biodegradation by stimulating indigenous populations through the addition of exogenous microbial populations. The sites selected for bioremediation were rocky shorelines of heterogenous granitic sediments with grain sizes ranging from sands to huge boulders; limestone-sandstone pebbles and cobbles; and fuel-coated limestone cliffs. Total surface area covered by the fuel was determined through the use of image analysis calculations. A statistical measurement of the fuel layer thickness was calculated by averaging the weights of multiple-fuel sampling increments. Bioremediation products included the use of oleophilic fertilizers; a biodegradable surfactant; and a microbial seeding agent. Determinations of saturate, aromatic, resins, and asphaltene (SARA) were performed using maltenes extraction and liquid chromatography. Microbial plating and selective enrichment with fuel as the sole carbon source were used to monitor the evolution of microbial populations in a variety of experiments. It was concluded that the biostimulation technique enhanced the efficiency of the in situ oleophilic fertilizers. 17 refs., 2 tabs., 6 figs.

  14. 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)

  15. 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.

  16. Sulfur speciation in heavy petroleums: Information from X-ray absorption near-edge structure

    Science.gov (United States)

    Waldo, Geoffrey S.; Carlson, Robert M. K.; Moldowan, J. Michael; Peters, Kenneth E.; Penner-hahn, James E.

    1991-03-01

    The chemical speciation of sulfur in heavy petroleums, petroleum source rock extracts, and source rock pyrolysis products was studied using X-ray absorption near-edge structure (XANES) spectroscopy. The good energy resolution (ca. 0.5 eV) at the sulfur K edge and the strong dependence of XANES on the sulfur environment combine to give excellent sensitivity to changes in the electronic and structural environment of the sulfur. This has permitted identification and approximate quantitation of different classes of sulfur-containing compounds (e.g., sulfur, sulfides (including disulfides and polysulfides as a group), thiophenes, sulfoxides, sulfones, sulfinic acids, sulfonic acids, and sulfate) in a series of petroleums and petroleum source rocks. Our results indicate that the sulfur speciation of geological samples can be correlated with differences in source depositional environment, thermal maturity, and aromaticity. We report organosulfur compositions for the asphaltene, maltene, and liquid Chromatographie fractions of two sulfur-rich oils. In addition, we find that the organosulfur species in some, but not all, oils are subject to oxidation upon storage and thus may also be susceptible to oxidation in shallow reservoirs exposed to oxic waters. This work illustrates the utility of XANES as a direct spectroscopic probe for the quantitative determination of sulfur species in geological samples.

  17. 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.

  18. 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.

  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. Hydrocarbon charge history of the Paleogene reservoir in the northern Dongpu Depression, Bohai Bay Basin, China

    Directory of Open Access Journals (Sweden)

    You-Lu Jiang

    2016-11-01

    Full Text Available Abstract The hydrocarbon charge history of the Paleogene in the northern Dongpu Depression was analyzed in detail based on a comprehensive analysis of the generation and expulsion history of the major hydrocarbon source rocks, fluorescence microscopic features and fluid inclusion petrography. There were two main stages of hydrocarbon generation and expulsion of oil from the major hydrocarbon source rocks. The first stage was the main hydrocarbon expulsion stage. The fluorescence microscopic features also indicated two stages of hydrocarbon accumulation. Carbonaceous bitumen, asphaltene bitumen and colloidal bitumen reflected an early hydrocarbon charge, whereas the oil bitumen reflected a second hydrocarbon charge. Hydrocarbon inclusions also indicate two distinct charges according to the diagenetic evolution sequence, inclusion petrography features combined with the homogenization temperature and reservoir burial history analysis. According to these comprehensive analysis results, the hydrocarbon charge history of the Paleogene reservoir in the northern Dongpu Depression was divided into two phases. The first phase was from the late Dongying depositional period of the Oligocene to the early uplift stages of the late Paleogene. The second phase was from the late Minghuazhen period of the Pliocene to the Quaternary. Reservoirs formed during the first period were widely distributed covering the entire area. In contrast, reservoirs formed during the second period were mainly distributed near the hydrocarbon generation sags. Vertically, it was characterized by a single phase in the upper layers and two phases in the lower layers of the Paleogene.

  1. Neutron scattering applications in hydrocarbon materials

    Energy Technology Data Exchange (ETDEWEB)

    Lin, Min Y.; Peiffer, Dennis G. [ExxonMobil Research and Engineering Company, Annandale, NJ (United States); Zhang, Yimin; Rafailovich, Miriam [Dept. of Materials Sci. and Eng., State University of New York, NY (United States)

    2001-03-01

    Neutron scattering methods are a powerful probe to complex fluids, soft matters as well as solid materials of nano- and micro-structures and their related dynamic properties. They complement other microstructural probing tools, such as microscopes, x-ray and light scattering techniques. Because neutron does not carry charges, it interacts only with nuclei of the matter, therefore not only can it penetrate a longer length into matters, it can also see' many features other methods can't due to their lack of proper contrast or heavy absorption. One of the largest contrasts in neutron methods is from hydrogen/deuterium (H/D) difference. Therefore, hydrocarbons can be easily studied by neutrons when H/D isotope substitution is applied. Here at National Institute of Standards and Technology's Center for Neutron Research (NCNR) in Gaithersburg, Maryland, one of the USA's premier neutron scattering facilities, we have been using neutron scattering techniques to study microstructures of asphaltenes, waxes, gas hydrates, porous media, surfactant solutions, engine oils, polymers, nanocomposites, fuel cell element and other hydrocarbon materials. With the completion of a new Neutron Spin Echo instrument, we can also look at the dynamics of the above mentioned systems. (author)

  2. Wettability evaluation of a carbonate reservoir rock from core to pore level

    Energy Technology Data Exchange (ETDEWEB)

    Al-Yousef, H.Y.; Lichaa, P.M.; Al-Kaabi, A.U.; Alpustun, H.

    1995-10-01

    Wettability evaluation was performed during stags of as received, cleaned, and restored states on core samples form a Saudi Arabian carbonate reservoir. The wettability behavior from the chemistry of brine-oil-carbonate rock interaction was found to be neutral to slightly oil-wet. The pore-size distribution obtained from mercury injection data indicated that about 15--20 percent of the pore volume is not accessible to asphaltene particles in the crude oil. Therefore a mixed-wettability state can exist. These results were confirmed by the evaluation of the wettability of the cores using USBM and Amott techniques. The wettability at the pore level was studied using Cryo-Scanning Electron Microscopy. Rock samples were examined at irreducible water and residual oil saturations during cleaned and restored states. At irreducible water saturation, both oil and brine were present in the intergranular macroporosity and intragranular macropores and micropores. At residual oil saturation,oil was found in the form of isolated globules in the cleaned case. After aging, the oil is more loosely distributed in the porosity and generally contacts the pore walls. This indicates an evolution toward oil wetness with aging. These results are in agreement with the changes of wettability indices obtained using USBM technique.

  3. 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.

  4. Identification of compounds in heavy fuel oil that are chronically toxic to rainbow trout embryos by effects-driven chemical fractionation.

    Science.gov (United States)

    Adams, Julie; Bornstein, Jason M; Munno, Keenan; Hollebone, Bruce; King, Thomas; Brown, R Stephen; Hodson, Peter V

    2014-04-01

    The present study isolated and identified compounds in heavy fuel oil 7102 (HFO 7102) that are bioavailable and chronically toxic to rainbow trout embryos (Oncorhynchus mykiss). An effects-driven chemical fractionation combined the chemical separation of oil with toxicity testing and chemical analyses of each fraction to identify the major classes of compounds associated with embryo toxicity. Toxicity was assessed with 2 exposure methods, a high-energy chemical dispersion of oil in water, which included oil droplets in test solutions, and water accommodated fractions which were produced by oiled gravel desorption columns, and which did not contain visible oil droplets. Fractions of HFO with high concentrations of naphthalenes, alkanes, asphaltenes, and resins were nontoxic to embryos over the range of concentrations tested. In contrast, fractions enriched with 3- to 4-ringed alkyl polycyclic aromatic hydrocarbons (PAHs) were embryotoxic, consistent with published studies of crude oils and individual alkyl PAHs. The rank order of fraction toxicity did not vary between the exposure methods and was consistent with their PAH content; fractions with higher-molecular weight alkyl PAHs were the most toxic. Exposure of juvenile trout to most fractions of HFO induced higher activities of cytochrome P450 enzymes, with a rank order of potency that varied with exposure method and differed somewhat from that of embryotoxicity. Induction reflected the bioavailability of PAHs but did not accurately predict embryotoxicity.

  5. Study on Producing Heavy Paving Asphalt

    Institute of Scientific and Technical Information of China (English)

    Liu Daosheng; Gao Zhirong; Huo Kaifu; Liao Kejian

    2002-01-01

    The highly viscous crude oil from Shuguang No. 1 zone of Liaohe oilfield features high density,high viscosity and low wax content. It contains no gasoline fraction and its diesel oil fraction yield is only 7.19%, which belongs to the low sulfur naphthenic stocks crude oil. Its heavy fraction is not suited for producing lubricating oil. Its heavy oil, which contains more resins and asphaltenes and less wax, is not an ideal feedstock for catalytic cracking, but is the ideal raw material for producing high-grade paving asphalt.Now this highly viscous crude oil is used as fuel oil after being emulsified in Liaohe oilfield, but its viscosity is so high that it cannot be atomized uniformly and burned completely, resulting not only in waste of oil resource but also in reduction of economical benefit. To make full use of this oil resource and alleviate the shortfall of high grade paving asphalt in China, various brands of asphalt meeting Q/SHR003-1998and ESSO specifications were developed by blending vacuum residue of the said oil and a blending component which are rich in aromatics and deficient in wax. The impact of blending component on properties of blended asphalt has been investigated and road performances of these blended asphalts were studied. The laboratory test results show that the blended asphalts have good road performance and antiaging property.

  6. ASSESSING THE CHEMICAL PROPERTIES OF DAMMAR ASPHALT USING FOURIER TRANSFORM INFRARED SPECTROSCOPY

    Directory of Open Access Journals (Sweden)

    Ary Setyawan

    2016-03-01

    Full Text Available Dammar Asphalt (Daspal is expected to be used as a bio-asphalt renewable binder for road construction. It is made with a modification of the "Jabung", which is the dammar gum based material mixed with grounded red brick debris and low quality cooking oil at a certain ratio. Dammar gum is obtained from the Dipterocarpaceae family of trees in India and East Asia, most are produced by tapping trees. The gum varies in color from clear to pale yellow. Dammar gum is a triterpenoid resin, containing a large number of triterpenes and their oxidation products. Many of them are low molecular weight compounds. The objective of this research is to analyze the chemical properties of Daspal uses a Resonance Fourier Transform Infrared Spectroscopy (FTIR method to compare with conventional asphalt. The investigation using spectral data showed that all types of Daspal have similar functional groups of Saturate, Aromatic, Resins, and Asphalten as the 60/70 penetration conventional bitumen, so that based on its chemical properties Daspal can be considered as bioaspal.

  7. Viscosity, relaxation time, and dynamics within a model asphalt of larger molecules

    Science.gov (United States)

    Li, Derek D.; Greenfield, Michael L.

    2014-01-01

    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.

  8. 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.

  9. Geological and Geochemical Studies of Heavy Oil Reservoirs in China

    Institute of Scientific and Technical Information of China (English)

    胡见义; 徐树宝; 等

    1989-01-01

    Thickened heavy oils in China are genetically characteristic of continenta .As to their physico-chemical properties,these oils are very high in viscosity and low in sulphur and trace element con-tents.In the group constituents,the concentrations of non-hydrocarbons and asphaltene are very high but those of saturated hydrocarbons and aromatics are very low.The gas chromatograms of alkanes show that these heavy oils have high abundances of iso-alkanes and cyclic hydrocarbons.In all the steroids and terpenoids ,bicyclic sesquiterpenoids,tricyclic diterpenoids,re-arranged steranes and gammacerane are strongly bildegradation-resistent.The formation of heavy oil reservoirs is controlled mainly by late basin ascendance,biodegradation,flushing by meteoric water and oxidation in the oil-bearing formations.Ac-cording to their formation mechanisms,heavy oil reservoirs can be classified as four categories:weathering and denudation,marginal oxidation,secondary migration and thickening of bottom water .Spacially,heavy thick oil reservoirs are distributed regularly:they usually show some paragenetic relationships with normal oil reservoirs.Heavy oil reservoirs often occur in structural highs or in overlying younger strata.Their burial depth is about 200m.Horizontally,most of them are distributed on the margins of basins or depressions.

  10. 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.

  11. Removal Capacities of Polycyclic Aromatic Hydrocarbons (PAHs) by a Newly Isolated Strain from Oilfield Produced Water

    Science.gov (United States)

    Qi, Yi-Bin; Wang, Chen-Yu; Lv, Cheng-Yuan; Lun, Zeng-Min; Zheng, Cheng-Gang

    2017-01-01

    The polycyclic aromatic hydrocarbon (PAH)-degrading strain Q8 was isolated from oilfield produced water. According to the analysis of a biochemical test, 16S rRNA gene, house-keeping genes and DNA–DNA hybridization, strain Q8 was assigned to a novel species of the genus Gordonia. The strain could not only grow in mineral salt medium (MM) and utilize naphthalene and pyrene as its sole carbon source, but also degraded mixed naphthalene, phenanthrene, anthracene and pyrene. The degradation ratio of these four PAHs reached 100%, 95.4%, 73.8% and 53.4% respectively after being degraded by Q8 for seven days. A comparative experiment found that the PAHs degradation efficiency of Q8 is higher than that of Gordonia alkaliphila and Gordonia paraffinivorans, which have the capacities to remove PAHs. Fourier transform infrared spectra, saturate, aromatic, resin and asphaltene (SARA) and gas chromatography–mass spectrometry (GC–MS) analysis of crude oil degraded by Q8 were also studied. The results showed that Q8 could utilize n-alkanes and PAHs in crude oil. The relative proportions of the naphthalene series, phenanthrene series, thiophene series, fluorene series, chrysene series, C21-triaromatic steroid, pyrene, and benz(a)pyrene were reduced after being degraded by Q8. Gordonia sp. nov. Q8 had the capacity to remediate water and soil environments contaminated by PAHs or crude oil, and provided a feasible way for the bioremediation of PAHs and oil pollution. PMID:28241412

  12. An investigation of problematic solids in oil sands processing : separation and characterization of organic matter strongly bound to oil sands solids

    Energy Technology Data Exchange (ETDEWEB)

    McCracken, T.; Woods, J.R.; Kung, J.; Fu, D.; Kingston, D.; Kotlyar, L.S. [National Research Council of Canada, Ottawa, ON (Canada). Inst. for Chemical Process and Environmental Technology; Sparks, B.D. [V. Bede Technical Associates, Ottawa, ON (Canada)

    2009-07-01

    Some of the solid fractions in Athabasca oilsands are associated with strongly bound organic matter that is insoluble in toluene, a solvent commonly used to extract bitumen. The presence of toluene insoluble organic matter (TIOM) increases oil wettability of solids which may adversely affect the release of bitumen from the oilsands. Some of the solid material from the coking operation may be carried over to downstream operations where it can cause fouling. This study used supercritical fluid extraction with methanol to remove TIOM from oilsands after extraction of bitumen by toluene. The methanol extract (ME) is soluble in toluene and was analyzed. Results were compared with corresponding bitumen fractions prepared using a modified HPLC SARA separation technique. Number average molecular weights for the ME were similar to those for resins separated from bitumen. The study also showed that the number of alkyl substituents on aromatic ring systems and the lengths of paraffinic straight chains for resins and ME samples were similar, with only minor differences in terms of H/C atomic ratios and aromaticities. The ME was more polar than the resin and asphaltene fractions, which may explain the selective adsorption of this fraction. tabs., figs.

  13. 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)

  14. Effect of Alkali on Daqing Crude Oil/Water Interfacial Properties

    Institute of Scientific and Technical Information of China (English)

    Guo Jixiang; Li Mingyuan; Lin Meiqin; Wu Zhaoliang

    2007-01-01

    Alkaline-surfactant-polymer (ASP) flooding using sodium hydroxide as the alkali component to enhance oil recovery in Daqing Oilfield,northeast China has been successful,but there are new problems in the treatment of produced crude. The alkali added forms stable water-in-crude oil emulsion,hence de-emulsification process is necessary to separate oil and water. The problems in enhanced oil recovery with ASP flooding were investigated in laboratory by using fractions of Daqing crude oil. The oil was separated into aliphatics,aromatics,resin and asphaltene fractions. These fractions were then mixed with an additive-free jet fuel to form model oils. The interfacial properties,such as interfacial tension and interfacial pressure of the systems were also measured,which together with the molecular parameters of the fractions were all used to investigate the problems in the enhanced oil recovery. In our work,it was found that sodium hydroxide solution reacts with the acidic hydrogen in the fractions of crude oil and forms soap-like interfacially active components,which accumulate at the crude oil-water interface.

  15. Lignin Peroxidase Oxidation of Aromatic Compounds in Systems Containing Organic Solvents

    Science.gov (United States)

    Vazquez-Duhalt, Rafael; Westlake, Donald W. S.; Fedorak, Phillip M.

    1994-01-01

    Lignin peroxidase from Phanerochaete chrysosporium was used to study the oxidation of aromatic compounds, including polycyclic aromatic hydrocarbons and heterocyclic compounds, that are models of moieties of asphaltene molecules. The oxidations were done in systems containing water-miscible organic solvents, including methanol, isopropanol, N, N-dimethylformamide, acetonitrile, and tetrahydrofuran. Of the 20 aromatic compounds tested, 9 were oxidized by lignin peroxidase in the presence of hydrogen peroxide. These included anthracene, 1-, 2-, and 9-methylanthracenes, acenaphthene, fluoranthene, pyrene, carbazole, and dibenzothiophene. Of the compounds studied, lignin peroxidase was able to oxidize those with ionization potentials of <8 eV (measured by electron impact). The reaction products contain hydroxyl and keto groups. In one case, carbon-carbon bond cleavage, yielding anthraquinone from 9-methylanthracene, was detected. Kinetic constants and stability characteristics of lignin peroxidase were determined by using pyrene as the substrate in systems containing different amounts of organic solvent. Benzyl alkylation of lignin peroxidase improved its activity in a system containing water-miscible organic solvent but did not increase its resistance to inactivation at high solvent concentrations. PMID:16349176

  16. 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)

  17. Geochemical characteristics of light hydrocarbons in cracking gases from chloroform bitumen A,crude oil and its fractions

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    The composition characteristics of light hydrocarbons from crude oil,chloroform bitumen A,saturated hydrocarbon fraction,aromatic hydrocarbon fraction,and asphaltene fraction during cracking have been studied systematically. The results revealed that the content of n-alkanes,branched alkanes and cycloalkanes in light hydrocarbons from the samples gradually decreased as the simulation temperature increased,and finally almost depleted completely,while the abundance of methane,benzene and its homologues increased obviously and became the main products. The ratios of benzene/n-hexane and toluene/n-heptane can be used as measures for oil cracking levels. Variation characteristics of maturity parameters of light hydrocarbons,for example,iC4/nC4,iC5/nC5,isoheptane value,2,2-DMC4/nC6,and 2-MC6+3-MC6/nC7 for different samples with increasing pyrolysis temperature,are consistent with those in petroleum reservoirs,indicating that these parameters may be efficient maturity index.

  18. 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.

  19. 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.

  20. 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.

  1. 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.

  2. 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.)

  3. Petroleomics: chemistry of the underworld.

    Science.gov (United States)

    Marshall, Alan G; Rodgers, Ryan P

    2008-11-25

    Each different molecular elemental composition-e.g., C(c)H(h)N(n)O(o)S(s)-has a different exact mass. With sufficiently high mass resolving power (m/Deltam(50%) approximately 400,000, in which m is molecular mass and Deltam(50%) is the mass spectral peak width at half-maximum peak height) and mass accuracy (/=9.4 T) Fourier transform ion cyclotron resonance mass spectrometry, it is possible to resolve and identify uniquely and simultaneously each of the thousands of elemental compositions from the most complex natural organic mixtures, including petroleum crude oil. It is thus possible to separate and sort petroleum components according to their heteroatom class (N(n)O(o)S(s)), double bond equivalents (DBE = number of rings plus double bonds involving carbon, because each ring or double bond results in a loss of two hydrogen atoms), and carbon number. "Petroleomics" is the characterization of petroleum at the molecular level. From sufficiently complete characterization of the organic composition of petroleum and its products, it should be possible to correlate (and ultimately predict) their properties and behavior. Examples include molecular mass distribution, distillation profile, characterization of specific fractions without prior extraction or wet chemical separation from the original bulk material, biodegradation, maturity, water solubility (and oil:water emulsion behavior), deposits in oil wells and refineries, efficiency and specificity of catalytic hydroprocessing, "heavy ends" (asphaltenes) analysis, corrosion, etc.

  4. A liquid chromatography-atmospheric pressure photoionization tandem mass spectrometric method for the determination of organosulfur compounds in petroleum asphalt cements.

    Science.gov (United States)

    da Silveira, Géssica Domingos; Faccin, Henrique; Claussen, Luis; Goularte, Rayane Bueno; Do Nascimento, Paulo C; Bohrer, Denise; Cravo, Margareth; Leite, Leni F M; de Carvalho, Leandro Machado

    2016-07-29

    We present a sensitive liquid chromatography-atmospheric pressure photoionization tandem mass spectrometric (UHPLC-APPI-MS/MS) method for the determination of selected organosulfur compounds in Brazilian asphalt cements. It was possible to detect 14 organosulfur compounds of different classes where sulfoxides and sulfones presented higher sensibility in ionization than thiophenes and aromatic sulfides. A dopant-assisted APPI method was also tested, however, when chromatographic flow rate was optimized a decrease in signal was observed for all compounds. PAHs were tested and ruled out as possible interfering compounds and the matrix effect of asphalt cements was within an acceptable range for the quantification of organosulfur compounds. The proposed method was found to have satisfactory linearity and accuracy with recoveries between 83.85 and 110.28% for thianaphthene and 3-methylbenzothiophene, respectively. Therefore, the method allowed the characterization of organosulfur compounds in Brazilian asphalt cements and demonstrated changes in the amount quantified in asphaltenic and maltenic fractions after the RTFOT+SUNTEST aging process.

  5. 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)

  6. Metal coordination chemistry: removal and recovery of metal compounds from heavy crude and shale oils with multidentate ligands. Annual report, October 1981-October 1982

    Energy Technology Data Exchange (ETDEWEB)

    Fish, R.H.

    1982-01-01

    The separation and identification by HPLC-GFAA analysis of organic and organoarsenic compounds occurring in oil shale retort and process waters, shale oils and Green River Formation oil shale are described in this report. The molecular characterization of these compounds has given new insight into developing innovative methods for their removal from oil shale retorting products. Catechol (1,2-dihydrocylbenzene) derivatives of both inorganic and organoarsenic compounds may in fact provide the means by which these compounds can be successfully removed from the above mentioned retort products. In addition to model compounds experiments with catechols and characterized inorganic arsenic and organoarsenic compounds, we have also synthesized a polymer that was modified with catechol and are in the process of determining its reactivity with the characterized arsenic compounds. Progress in preparing these catechol-bonded polymers is discussed. In a complimentary study, we have performed molecular characterizations and profile identifications of vanadyl porphyrin and non-porphyrin complexes in various heavy crude petroleums and their asphaltenes by HPLC-GFAA analysis. Results are discussed. (DMC)

  7. Change of isoprenoids, steranes and terpanes during ex situ bioremediation of mazut on industrial level

    Directory of Open Access Journals (Sweden)

    Beškoski Vladimir P.

    2010-01-01

    Full Text Available The paper presents results of the ex situ bioremediation of soil contaminated by mazut (heavy residual fuel oil in the field scale (600 m3. A treatment-bed (thickness 0.4 m consisted of mechanically mixed mazut-contaminated soil, softwood sawdust as the additional carbon source and crude river sand, as bulking and porosity increasing material. The inoculation/reinoculation was conducted periodically using a biomass of a consortium of zymogenous microorganisms isolated from the bioremediation substrate. The biostimulation was performed through addition of nutritious substances (N, P and K. The aeration was improved by systematic mixing of the bioremediation system. After 50 days, the number of hydrocarbon degraders increased 100 times. Based on the changes in the group composition, the average biodegradation rate during bioremediation was 24 mg/kg/day for the aliphatic fraction, 6 mg/kg/day for the aromatic fraction, and 3 mg/kg/day for the nitrogen-sulphuroxygen compounds (NSO-asphaltene fraction. In the saturated hydrocarbon fraction, gas chromatography-mass spectrometry (GC-MS in the single ion-monitoring mode (SIM was applied to analyse isoprenoids pristane and phytane and polycyclic molecules of sterane and triterpane type. Biodegradation occurred during the bioremediation process, as well as reduction of relative quantities of isoprenoids, steranes, tri- and tetracyclic terpanes and pentacyclic terpanes of hopane type.

  8. Bio-electrochemical remediation of real field petroleum sludge as an electron donor with simultaneous power generation facilitates biotransformation of PAH: effect of substrate concentration.

    Science.gov (United States)

    Chandrasekhar, K; Venkata Mohan, S

    2012-04-01

    Remediation of real-field petroleum sludge was studied under self-induced electrogenic microenvironment with the function of variable organic loads (OLs) in bio-electrochemical treatment (BET) systems. Operation under various OLs documented marked influence on both electrogenic activity and remediation efficiency. Both total petroleum hydrocarbons (TPH) and its aromatic fraction documented higher removal with OL4 operation followed by OL3, OL2, OL1 and control. Self-induced biopotential and associated multiple bio-electrocatalytic reactions during BET operation facilitated biotransformation of higher ring aromatics (5-6) to lower ring aromatic (2-3) compounds. Asphaltenes and NSO fractions showed negligible removal during BET operation. Higher electrogenic activity was recorded at OL1 (343mV; 53.11mW/m(2), 100Ω) compared to other three OLs operation. Bioaugmentation to anodic microflora with anaerobic culture documented enhanced electrogenic activity at OL4 operation. Voltammetric profiles, Tafel analysis and VFA generation were in agreement with the observed power generation and degradation efficiency.

  9. Self-induced bio-potential and graphite electron accepting conditions enhances petroleum sludge degradation in bio-electrochemical system with simultaneous power generation.

    Science.gov (United States)

    Mohan, S Venkata; Chandrasekhar, K

    2011-10-01

    Bio-electrochemical treatment (BET) documented effective degradation of real field petroleum sludge over the conventional anaerobic treatment (AnT). BET (41.08%) operation showed enhanced total petroleum hydrocarbons (TPH) removal over AnT (20.72%). Aromatic fraction visualized higher removal (75.54%) compared to other TPH fractions viz., aliphatics, asphaltenes and NSO (nitrogen, sulfur and oxygen) during BET operation. Higher ring aromatics (5-6) documented easy degradation in BET, while AnT was limited to lower ring (2-3) compounds. Voltammetric analysis evidenced simultaneous redox behavior during BET operation due to presence of graphite electrode as electron acceptor, while AnT showed extended reduction behavior only. Self-induced primary and secondary oxidation reactions and capacitive-deionization might have enhanced the degradation capability of BET. BET documented higher charge/capacitance (2810 mJ/1120 mF) than AnT (450 mJ/180 mF). Power output corroborated well with observed results supporting BET performance as fuel cell. Electrodes offer a potential alternative electron acceptor for promoting the degradation of organic contaminants.

  10. 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.

  11. 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.

  12. 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.

  13. Mechanisms and kinetics of coal hydrogenation

    Energy Technology Data Exchange (ETDEWEB)

    Baldwin, R M; Furlong, M W

    1981-05-01

    Colorado School of Mines is engaged in an experimental program to develop comprehensive models for the effects of coal composition upon the kinetics and mechanisms of coal hydrogenation, for the effects of mineral matter additives (disposable catalysts) upon kinetics and mechanisms of coal hydrogenation, and for the kinetics and mechanisms of the hydrogenation of coal derived products such as preasphaltenes, and asphaltenes. Experimental work was completed on a suite of bituminous coals, thus completing the initial phase of the coal reactivity study. Eleven of the 14 coals of the suite were successfully run in duplicate. Conversion to THF solubles was correlated well by pseudo-second order kinetics. The resulting kinetic rate constants correlated with H/C ratio, mean-max vitrinite reflectance, and a specially-defined fraction of reactive macerals. The data did not correlate well with O/C ratios of the parent coals. Computer-derived statistical fits of various kinetic models were limited in their effectiveness at fitting the experimental data. Experimental work on the first phase of the disposal catalyst studies was completed. Statistical significance testing of the experimental data showed: fractional conversion and yield of light hydrocarbon products increased with time; and mineral properties of the additives were more significant in increasing overall conversion than the additive surface areas. The relative effects of the additives are given.

  14. 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.

  15. PRODUCTION IMPROVEMENT FROM INCREASED PERMEABILITY USING ENGINEERED BIOCHEMICAL SECONDARY RECOVERY METHODOLOGY IN MARGINAL WELLS OF THE EAST TEXAS FIELD

    Energy Technology Data Exchange (ETDEWEB)

    R.L. Bassett; William S. Botto

    2004-07-14

    A regenerating biochemical mixture and organic surfactant has been applied to wells in the East Texas Field with the goal of restoring permeability, reversing formation damage, mobilizing hydrocarbons, and ultimately increasing production. Initial work in task 1 was designed to open the perforations and remove blockages of scale, asphaltene, and other corrosion debris. This was accomplished on three wells that produce from the Woodbine, and was necessary to prepare the wells for more substantial future treatments. Secondly, in task 2, two wells were treated with much larger quantities of the biochemical mixture, e.g. 25 gallons, followed by approximately 140 barrels of a 2% KCl solution that carried the active biochemical solution into the near wellbore area and into the producing reservoir. After a 7 to 10 day acclamation and reaction period, the wells were put back into production. The biochemical solution successfully broke down the scale, paraffin and other binders blocking permeability and released significant debris which was immediately produced into the flowlines and separators. Oil production was clearly improved and the removed debris was a maintenance issue until the surface equipment could be modified. Next steps include larger treatments and tracer tests to better understand the fluid flow dynamics.

  16. Biodegradation of heavy oils by halophilic bacterium

    Institute of Scientific and Technical Information of China (English)

    Ruixia Hao; Anhuai Lu

    2009-01-01

    A halophilic bacterial strain TM-1 was isolated from the reservoir of the Shengli oil field in East China. Strain TM-1, which was found to be able to degrade crude oils, is a gram-positive non-motile bacterium with a coccus shape that can grow at temperatures of up to 58 ℃ and in 18% NaCl solution. Depending on the culture conditions, the organism may occur in tetrads. In addition, strain TM-1 pro-duced acid from glucose without gas formation and was catalase-negative. Furthermore, strain TM-I was found to be a facultative aer-obe capable of growth under anaerobic conditions. Moreover, it produced butylated hydroxytoluene, 1,2-benzenedicarboxylic acid-bis ester and dibutyl phthalate and could use different organic substrates. Laboratory studies indicated that strain TM-1 affected different heavy oils by degrading various components and by changing the chemical properties of the oils. In addition, growth of the bacterium in heavy oils resulted in the loss of aromatic hydrocarbons, resins and asphaltenes, and enrichment with light hydrocarbons and an overall redistribution of these hydrocarbons.

  17. 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.

  18. Gravimetric analysis of the solubility of methane in high boiling hydrocarbons and petroleum products; Gravimetrische Bestimmung der Loeslichkeit von Methan in hoeher siedenden Kohlenwasserstoffen und Erdoelprodukten

    Energy Technology Data Exchange (ETDEWEB)

    Laux, H.; Rahimian, I. [Institut fuer Erdoel- und Erdgasforschung, Clausthal-Zellerfeld (Germany)

    2001-05-01

    The solubility of methane has a great influence on the colloid stability of crude oils at the conditions of production. Adequate data are needed for the modelling of the beginning of asphaltene precipitation as the result of the destabilization. Because such data are limited in the literature a magnetic suspension balance was used. By means of the magnetic suspension balance the solubility of gases in high boiling products can be determined by the weight difference resulting from the steped pressure reduction. The solubility of methane was investigated in different n-alkanes and squalane as well as a wax, a slack wax, a extract from the solvent raffination and a atmospheric crude oil residue. The aim was to investigate the influence of the molare weight, the structure and the composition of mixture on the solubility of methane. The pressure was varied in the region to 120 bar, the temperature was predominantly 75 C. The influence of the temperature on the solubility of methane was studied in the slack wax and the atmospheric residue. The results and the advantage as well as the disadvantage of the using of the magnetic suspension balance will be discussed. (orig.)

  19. Organosulphur compounds in coals as determined by reaction with Raney nickel and microscale pyrolysis techniques. Fifth quarterly report, October 1, 1995--December 31, 1995

    Energy Technology Data Exchange (ETDEWEB)

    Philp, R.P.

    1996-01-31

    This project is designed to study the nature of sulphur-containing organic compounds and their respective linkages in coals and related materials using a variety of microscale pyrolysis techniques combined with gas chromatography--mass spectrometry. The majority of the work will be undertaken using a PYRAN pyrolysis system purchased with funds from the DOE University Instrumentation Program. Since the last report, we have reached the point in the project that we are satisfied with the nickel boride chemical degradation method, and are now working our way through the large amounts of data collected by gas chromatography-mass spectrometry analysis. While we have tentatively identified a variety of compounds produced by the chemical degradation method with spectra from the literature, we have yet to confirm many of these identifications with pure standards or specialized oil samples. As a result we will present in this report chromatograms of one of the coals (Illinois No. 6) and compare the free aliphatic hydrocarbons with those compounds cleaved from the polar extract, asphaltenes and pre-extracted coal matrix.

  20. Hindered diffusion of coal liquids. Quarterly report No. 5, September 18, 1993--December 17, 1993

    Energy Technology Data Exchange (ETDEWEB)

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

    1994-05-01

    The design of industrial catalysts requires that the diffusivity of the reacting species within the catalyst be accurately known. Nowhere is this more important than in the area of coal liquefaction and upgrading of coal liquids. In this area one is faced with the task of processing a number of heavy oils, containing metals and other contaminants, in a variety of process dependent solvents. It is important, therefore, on the basis of predicting catalyst activity, selectivity, and optimizing reactor performance, that the diffusivities of these oil species be accurately known. In this report, the authors report the publication of model studies of the diffusivity of Lennard-Jones particles in porous systems with dimensionality between two and three. Such a modeled system includes pillared clays. They also published a paper which addresses the sorption and aggregation of asphaltene particles with porous media such as catalysts. The paper presents new experimental data for the amount of asphalt precipitation formed with various solvents. The experimental results are compared to model calculations.

  1. 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.

  2. A river runs through it: Athabasca River ecosystem challenged by oilsands mega-projects

    Energy Technology Data Exchange (ETDEWEB)

    Collision, M.

    2004-06-01

    The environmental consequences of oilsands development on the Athabasca region are discussed, with emphasis on the measures put in place primarily by Suncor and Syncrude, as well as the other oilsands companies to mitigate the environmental impacts of their operations, and to design innovative extraction methods that will leave coke and asphaltenes and sulphur in the ground, while cutting back on the amount of water they use, as well as on the high quality fuels and solvents they use to extract the resource. The work of the Cumulative Environmental Management Association (CEMA), and the Regional Sustainable Development Strategy (RSDS), composed of representatives of every First Nations group, NGOs such as the Pembina Institute and ToxicWatch, industry, Alberta Environment and the Alberta Energy and Utilities Board, is also reviewed. Details of their mandate, which is to develop recommendations on how best to address concerns about wildlife, soil and plant species, air emissions, heavy metals deposition, fish habitats and populations, tailings ponds, surface and groundwater quality and quantity, and land reclamation, are also provided. Avoiding social disruption as far as possible, primarily of First Nations groups, and minimizing changes to the landscape are the group's highest priorities. Unattainable as it may seem, the hope and objective is that 100 years after oilsands extraction and land reclamation have been completed the observable ecological difference between 'before and after' would be negligible.

  3. Influence of Polyphosphoric Acid on the Consistency and Composition of Formulated Bitumen: Standard Characterization and NMR Insights

    Science.gov (United States)

    Varanda, Catarina; Ribeiro, Jorge

    2016-01-01

    Over the recent years, bitumen modification with polymers, acids, or mineral fillers has gained relevance to adjust its performance properties. This work reports the use of polyphosphoric acid (PPA) for the modification of formulated bitumen. With this objective, an in-depth literature review on PPA modification was firstly performed. Subsequently, five individual refinery components were selected for the preparation of bitumen blends, namely, asphaltic residue, vacuum residue, and three lube oils extracts. Seven binary/ternary bitumen blends were prepared and then treated with PPA. Afterwards, the five components and the unmodified and PPA-modified bitumen were characterized by standard methods (penetration, softening point, and penetration index), SARA analysis, elemental analysis, and 31P and 1H nuclear magnetic resonance (NMR) spectroscopy. The results evidenced higher asphaltenes and lower saturates/resins contents in PPA-modified bitumen. The NMR data suggest that the paraffinic chains became longer, the content of condensed aromatics increased, more substituted aromatic structures appeared, and α-hydrogen in aromatic structures diminished. These findings disclosed the improved consistency and oxidation stability of PPA-modified bitumen blends. PMID:27579214

  4. Hydrodemetallization of petroleum residue (Part 2). Influence of feedstock properties on demetallization reactivity

    Energy Technology Data Exchange (ETDEWEB)

    Koinuma, Yutaka; Kushiyama, Satoshi; Kobayashi, Satoru; Aizawa, Reiji; Inoue, Keiichi; Shimizu, Yoshikazu (National Research Inst. for Pollution and Resources, Tsukuba (Japan))

    1989-03-30

    In the heavy oil hydrodemetallization, factors which have and influence on the reactivity were studied. Four different heavy oils, Khafji and Gach Saran atmospheric residues, and Morichal and Tia Juana crudes, were subjected to an experiment. Fixed-bed hydrotreatments were conducted under an identical reaction condition, hydrogen pressure 100 kg/cm{sup 2}, LHSV 1.0 h{sup {minus}1}, reaction temperature 380-420{degree}C. Such parameters as V, Ni, asphaltenes (APs) and sulfur contents were not related to the reactivity toward hydrodemetallization of each feedstock. Instead, the molecular size distribution of APs determined by GPC and NMR structural parameters of APs such as the degree of condensation of aromatic rings, the number of aromatic rings per molecule and the molecular weight of structural unit were seemed to correlate well with the reactivity. Hydrodemetallization proceeded more easily for the feedstocks whose APs are smaller in molecular size and lower both in the unit sheet weight and the degree of aromatic ring condensation. The reaction of metals removal is strongly influenced by the intraparticle diffusion of Ap molecules. Ni was more difficult to be removed than V. The main reason for this was considered to be that the reaction of Ni removal depends much on the degree of AP cracking. 13 refs., 8 figs., 5 tabs.

  5. Characterization of Venezuelan heavy oil vacuum residua

    Energy Technology Data Exchange (ETDEWEB)

    Izquierdo, A.; Carbognani, L.; Leon, V.; Parisi, A. (Dept. of Analysis and Evaluation, Intevep, S.A. P.O. Box 76343, Caracas 1070A (VE))

    1988-06-01

    Characterization of abundant ''heavy'' feedstocks such as tar sands, heavy oils and vacuum residua will play a fundamental role in the use of these energy sources. Their physical and chemical properties vary from one feed to another, and this can have some consequences in their necessary upgrading processes. In this paper results on the characterization of 510/sup 0/C-vacuum residua (VR) obtained from Venezuelan Heavy and Medium Oils are presented. These are Morichal (Mo), Merey (Me), Guafita (Gu) and Barinas (Ba). The VR have all an API gravity between 3 and 6, more than 15% asphaltenes, metals above 200 ppm, as well as high contents of nitrogen, more than 6000 ppm, and sulphur, over 1%. It has been found that when these feeds are hydrotreated under similar conditions the processability improves in the order Ba

  6. Catalytic activity of oil soluble molybdenum compounds for heavy oil hydrotreatment

    Energy Technology Data Exchange (ETDEWEB)

    Kushiyama, Satoshi; Aizawa, Reiji; Kobayashi, Satoru; Koinuma, Yutaka; Uemasu, Isamu; Shimizu, Yoshikazu (National Research Institute for Pollution and Resources, Tsukuba (Japan))

    1989-04-20

    Catalytic activity of oil-soluble molybdenum compounds in the hydrotreatment of heavy oil, with high content of the catalyst-poison compounds such as vanadium compounds and asphaltene, was studied. Reactions were performed using Venezuela Morichal crude and catalysts: molybdenum-dithiophoshpates, -dithiocarbamates and -naphthenates; and cobalt-cotylates, -dioctylphosphates. Catalyst systems containing Mo, Co, P and S (or mixtures of compounds containing each element) were found to show high activity for sulfur and vanadium removal. It was revealed that the addition of P compounds is essential for vanadium removal and the effect of Co compounds on the activity enhancement is shown in the only case of coexistence of P and S. No Mo, Co, P were found in the oil products. Recycle use of the Mo-Co-P-S catalyst resulted in a gradual decline of activity. However, the activity seems to be constant after three to four recycle uses, its activity was still higher than the initial activity of conventional Co-Mo-Al{sub 2}O{sub 3} catalyst. 13 refs., 5 tabs.

  7. Hydrodemetallization of residue (Part 3). Influence of catalyst pore size

    Energy Technology Data Exchange (ETDEWEB)

    Hinuma, Yutaka; Kushiyama, Akira; Kobayashi, Satoru; Aizawa, Reiji; Inoue, Keiichi; Shimizu, Yoshikazu (National Research Inst. for Pollution and Resources, Tsukuba (Japan))

    1989-03-25

    Influence of catalyst pore size on hydrodemetallization of residues was studied, Starting oils were Khafji atmospheric residue and Morichal crude and two catalysts of alumina which have 93A and 160A mean pore diameters respectively and Mo was supported, were used. The rate at which asphaltene(A) was decomposed to maltene(M), related large to the demetallization of whole heavy oil and larger the pore diameter of catalyst, higher the demetallizing activity. But in the demetallization from A and M, the influence of pore size was different and vanadium(V) removal from A was preferable for larger pore size but was reverse from M. These were caused by the difference of diffusion in their pores. Ni was more difficult to remove than V. Catalyst of small pore size was preferable for simultaneous desulfurization, because sulfur compounds were composed of smaller molecular weight distribution. The decomposition of A started preferentially from part having large number of peripheral carbon in condensed aromatic ring or f{sub a} (aromaticity) and the catalyst of large pore size affected large on the structural change of A. 12 ref., 7 figs., 5 tabs.

  8. Influence of Polyphosphoric Acid on the Consistency and Composition of Formulated Bitumen: Standard Characterization and NMR Insights.

    Science.gov (United States)

    Varanda, Catarina; Portugal, Inês; Ribeiro, Jorge; Silva, Artur M S; Silva, Carlos M

    2016-01-01

    Over the recent years, bitumen modification with polymers, acids, or mineral fillers has gained relevance to adjust its performance properties. This work reports the use of polyphosphoric acid (PPA) for the modification of formulated bitumen. With this objective, an in-depth literature review on PPA modification was firstly performed. Subsequently, five individual refinery components were selected for the preparation of bitumen blends, namely, asphaltic residue, vacuum residue, and three lube oils extracts. Seven binary/ternary bitumen blends were prepared and then treated with PPA. Afterwards, the five components and the unmodified and PPA-modified bitumen were characterized by standard methods (penetration, softening point, and penetration index), SARA analysis, elemental analysis, and (31)P and (1)H nuclear magnetic resonance (NMR) spectroscopy. The results evidenced higher asphaltenes and lower saturates/resins contents in PPA-modified bitumen. The NMR data suggest that the paraffinic chains became longer, the content of condensed aromatics increased, more substituted aromatic structures appeared, and α-hydrogen in aromatic structures diminished. These findings disclosed the improved consistency and oxidation stability of PPA-modified bitumen blends.

  9. Geochemical study on oil-cracked gases and kerogencracked gases (I)——Experimental simulation and products analysis

    Institute of Scientific and Technical Information of China (English)

    2009-01-01

    Eight types of samples:crude oil,chloroform bitumen A,oil fractions(saturated hydrocarbon,aromatic hydrocarbon,resin and asphaltene) ,source rock and kerogen,have been pyrolyzed in laboratory. The products have also been systematically analyzed. The results indicate that gaseous hydrocarbons yields for different types of samples at various temperatures are different,especially for different fractions of crude oil. There is difference for molecular compositions. The C2/C3 ratios of cracking gases in different types of samples have positive relationships with C2/iC4 as well as pyrolysis temperatures. Moreover,the ratios of C2/C3 and C2/iC4 are about 2 and 10,respectively,at the temperature of 500℃― 550℃. However,when the temperature is higher than 500℃,the ratios of C1/C2,C1/C3 and dryness index for gases cracking from source rock and kerogen are higher than those from oil and bitumen,indicating an important different feature between oil-cracked gases and kerogen-cracked gases at the high or over-mature stage. The ratios of C1/C2,C1/C3 vary more than 10% at 500℃―800℃. In this paper,experimental results can provide important academic foundation and useful geochemical parameters for distinguishing of oil-cracked gases and kerogen-cracked gases.

  10. 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.

  11. Preparation of bitumen from charkchemical tar by catalytic oxidation and study of its structure and properties

    Directory of Open Access Journals (Sweden)

    Zhaksyntay Kairbekov

    2012-12-01

    Full Text Available Optimal conditions (temperature, time are determined for processes of oxidation of chark-chemical tar in the presence of FеСl3·6H2O catalyst. In the course of oxidation during increase of quantity of catalyst from 0.4 mass. % to 1.0 mass. % in the composition of initial tar the amount of tar decreased from 42,75 mass.% to 28,56 mass.%, the amount of hydrocarbons from 30,18 mass.% to  28,92 mass.%, and the quantity of asphaltene increased from 15,84 mass.% to   38 mass.%. The  values of physical-mechanical indicators of obtained products in the presence of 0,8 mass.% to 1,0 mass.% catalyst corresponds to the requirements of the standard, hence they may be quantitatively attributed to viscous construction oil bitumen of mark BH 70/30, BN 90/10. Chemical transformation in the composition of obtained products during catalytic oxidation is proved by the results of IR-spectroscopic analysis.

  12. [Determination of the four generic fractions of aged bitumen by thin-layer chromatography with flame ionization detection].

    Science.gov (United States)

    Feng, Zhengang; Zhang, Jianbin; Li, Xinjun; Yu, Jianying

    2015-02-01

    The aging process of bitumen has been paid more and more attention by the researchers. The four generic fractions (saturates, aromatics, resins and asphaltenes) of bitumen change significantly during the aging process. The analysis of the changes of the four generic fractions of bitumen is very helpful to reveal the bitumen aging mechanisms and guide its engineering applications. In this study, the bitumen was aged by thin film oven test (TFOT) , pressurized aging vessel (PAV) test and ultraviolet (UV) aging test, respectively. Then the four generic fractions of bitumen before and after aging were analyzed by thin-layer chromatography with flame ionization detection (TLC-FID) , which was further compared with the solubility procedures and chromatographic technique ( named as Corbett method). The compositions of the expanded solvents were also investigated. Finally, the correlation between the TLC-FID and Corbett method was further studied, which revealed a proper TLC-FID meth- od for detection of aged bitumen. The bitumen solution dissolved by dichloromethane was successively expanded by n-heptane, toluene/n-heptane (80 :20, v/v) and toluene/ethanol (55: 45, v/v) , followed by TLC-FID. This method is of great significance for the analysis of the four generic fractions of bitumen and for the exploration of bitumen aging mechanisms.

  13. Heavy Oil and Natural Bitumen Resources in Geological Basins of the World

    Science.gov (United States)

    Meyer, Richard F.; Attanasi, E.D.; Freeman, P.A.

    2007-01-01

    Heavy oil and natural bitumen are oils set apart by their high viscosity (resistance to flow) and high density (low API gravity). These attributes reflect the invariable presence of up to 50 weight percent asphaltenes, very high molecular weight hydrocarbon molecules incorporating many heteroatoms in their lattices. Almost all heavy oil and natural bitumen are alteration products of conventional oil. Total resources of heavy oil in known accumulations are 3,396 billion barrels of original oil in place, of which 30 billion barrels are included as prospective additional oil. The total natural bitumen resource in known accumulations amounts to 5,505 billion barrels of oil originally in place, which includes 993 billion barrels as prospective additional oil. This resource is distributed in 192 basins containing heavy oil and 89 basins with natural bitumen. Of the nine basic Klemme basin types, some with subdivisions, the most prolific by far for known heavy oil and natural bitumen volumes are continental multicyclic basins, either basins on the craton margin or closed basins along convergent plate margins. The former includes 47 percent of the natural bitumen, the latter 47 percent of the heavy oil and 46 percent of the natural bitumen. Little if any heavy oil occurs in fore-arc basins, and natural bitumen does not occur in either fore-arc or delta basins.

  14. 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.

  15. Study of Effect of Heavy Oil Properties on Oil Gathering Technology%稠油原油物性对集输工艺影响规律研究

    Institute of Scientific and Technical Information of China (English)

    王忠民; 胡炎兴

    2011-01-01

    由于稠油中沥青质和胶质含量高,密度和粘度较大,其集输与处理难度较大.以研究稠油区块油品物性为切入点,分析了化学组分对原油粘度影响,并对不同含水率下稠油乳状液进行了粘温关系测试以及对乳化稠油粘温性质及流变性进行分析,找出稠油原油物性对集输工艺影响规律,为稠油集输上艺奠定理论基础.%Because content of asphaltene and colloid in heavy oil is high and its density and viscosity is bigger,gathering and treatment of the heavy oil are very difficult. In this paper, taking study of oil properties in heavy oil blocks as the breakthrough point, effect of chemical composition on oil viscosity was analysed, and the viscosity-temperature relation of heavy oil emulsion liquid with different moisture contents was tested,and viscosity-temperature properties and rheological properties of emulsified heavy oil were analyzed, effect law of heavy oil property on oil gathering was found out, which can settle theoretical foundation for heavy oil gathering technology.

  16. 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)

  17. 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.

  18. Study of the processes of radionuclides transfer, heavy metals and aero-particles among the solid, dissolved phase and the air; Estudio de los procesos de transferencia de radionuclidos, metales pesados y aeroparticulas entre la fase solida, disuelta y el aire

    Energy Technology Data Exchange (ETDEWEB)

    Romero G, E. T.; Ordonez R, E. [ININ, Departamento de Quimica, Carretera Mexico-Toluca s/n, 52750 Ocoyoacac, Estado de Mexico (Mexico); Reyes G, L. R. [Instituto Potosino de Investigacion Cientifica y Tecnologica, Division de Geociencias Aplicadas, Camino a la Presa San Jose 2055, Col. Lomas 4 seccion, 78216 San Luis Potosi (Mexico); Jose Y, M., E-mail: elizabeth.romero@inin.gob.m [University of Texas at San Antonio, Department of Physics and Astronomy, One UTSA Circle, San Antonio TX 78249 (United States)

    2010-07-01

    In this chapter the investigations developed in the Instituto Nacional de Investigaciones Nucleares (ININ) are presented, in collaboration with specialists in diverse fields of the science. In the first place, is presented the objective and an introduction of each one of the following projects: Study of the uranium migration through the not saturated area, and Synthesis and characterization of phosphate materials by conventional techniques, projects developed under the direction and collaboration of the Ph D. Eduardo Ordonez Regil. Identification of the chemical-morphologic composition of painting mural pigments: the blue Mayan, indigo blue, the secret of the color, and investigation of the physiochemical components of the asphaltenes and malthenes of heavy crudes and vacuum residual, with the supervision of the Ph D. Miguel Jose Yacaman. Evaluation of the water quality and type of sediments of the lake-crater The Pool: one of the seven stars of Santiago Valley, Guanajuato; Study of the sorption kinetics of Cr(Vi) in floor of a container of chromium residuals in Buenavista, Guanajuato, Mexico; Investigation of the underground water hydrochemistry of the basin of the Avenues River in Pachuca de Soto, Hidalgo, and Characterization of the particle material and modeled of the dispersion and pollutants transport in the air of the Metropolitan Area of the Toluca Valley, projects carried out under the direction and collaboration of the Ph D. Lazaro Raymundo Reyes Gutierrez. Finally, is presented the most representative of the obtained results, as well as a discussion of the same ones. (Author)

  19. Rapid Quantitative Analysis of Hydrocarbon Composition of Furfural Extract Oils Using Attenuated Total Reflection Infrared Spectroscopy%衰减全反射红外光谱法快速测定糠醛抽出油烃族组成含量方法研究

    Institute of Scientific and Technical Information of China (English)

    李娜; 徐晓轩; 袁洪福; 胡爱琴; 刘伟; 宋春风; 李效玉; 宋以常; 何启军; 刘莎

    2014-01-01

    A set of rapid analysis system for hydrocarbon composition of heavy oils was designed using attenuated total reflection FTIR spectrometer and chemometrics to determine the hydrocarbon composition of furfural extract oils .Sixty two extract oil samples were collected and their saturates and aromatics content data were determined according to the standard NB /SH/T0509-2010 ,then the total contents of resins plus asphaltenes were calculated by the subtraction method in the percentage of weight . Based on the partial least squares(PLS) ,calibration models for saturates ,aromatics ,and resin+asphaltene contents were estab-lished using attenuated total reflection FTIR spectroscopy ,with their SEC ,1.43% ,0.91% and 1.61% ,SEP ,1.56% ,1.24%and 1.81% ,respectively ,meeting the accuracy and repeatability required for the standard .Compared to the present standard method ,the efficiency of hydrocarbon composition analysis for furfural extract oils is significantly improved by the new method which is rapid and simple .The system could also be used for other heavy oil analysis ,with excellent extension and application foreground .%提出了一种衰减全反射红外光谱法快速测定糠醛抽出油烃族组成含量的方法,设计了一套重油烃族组成快速分析系统。实验收集了62个减压蜡油经糠醛精制后的抽出油样品,采用NB/SH/T0509-2010方法测定其饱和烃、芳烃含量,由差减法求得胶质和沥青质总含量。采用偏最小二乘法(PLS )分别建立了糠醛抽出油饱和烃、芳烃和胶质+沥青质含量的定量校正模型,其SEC分别为1.43%,0.91%和1.61%,SEP分别为1.56%,1.24%和1.81%,均小于NB/SH/T0509-2010方法规定的再现性误差,模型预测精密度小于标准方法的重复性误差要求。与现行标准方法相比,该方法速度快,操作简单,可显著提高糠醛抽出油烃族组成分析效率。该分析系统也可用于其他重油分析

  20. Diagenetic bitumen in Ordovician carbonate reservoirs of the northern Tarim Basin%塔北地区奥陶系碳酸盐岩中的储层沥青

    Institute of Scientific and Technical Information of China (English)

    张鼐; 王招明; 鞠凤萍; 肖中尧; 房启飞; 张宝收; 卢玉红; 余小庆

    2013-01-01

    According to the relationship between the relative intensity of D-peak, G-peak and G-D peak spacing of bitumens and the maturity of bitumen evolution, we deduced that the Dh/Gh ratio and G-D peak spacing are positively proportional to bitumen maturity. Bitumens in Ordovician reservoir in the northern Tarim Basin are thought to have evolved in three stages and the Dh/Gh ratio and G-D peak spacing of Raman measurements on these bitumens indicated that the first-stage bitumen is highly-mature carbonaceous reservoir bitumen, the second-stage one is mature asphaltene reservoir bitumen, and the third-stage one is a combination of overmature oily reservoir bitumen and asphaltene reservoir bitumen. The formation of the first- and second-stage bitumens is attributed to thermal metamorphism, while the co-existence of two different bitumens for the third-stage bitumen is mainly due to selective adsorption of rocks. The distribution and property of these three-stages bitumens in Ordovician reservoirs of the northern Tarim Basin may determine the nature of Ordovician reservoirs, which is characterized by the southern condensate oil later than the northern heavy oil. The observation of oily reservoir bitumen in the northern Halahatang-Yingmaili region can provide evidence and targets for exploring Himalayan condensate oil reservoirs in this area.%利用沥青质拉曼D峰相对强度、G峰相对强度、两峰间距宽窄与沥青演化成熟度关系,推出Dh/Gh和G-D与沥青成熟度成正比关系图.塔北奥陶系储层中发育3期储层沥青,通过3期储层沥青拉曼Dh/Gh和G-D认为:第Ⅰ期为高热成熟炭质储层沥青,第Ⅱ期为成熟沥青质储层沥青,第Ⅲ期为过成熟油质储层沥青和沥青质储层沥青共存.前两期储层沥青是由于热变质而成,第Ⅲ期两种储层沥青共存主要是岩石选择性吸附导致.3期储层沥青的分布及性质决定塔北奥陶系成藏北部老、南部新,北部重质油、南部凝析油的

  1. Carbonate reservoir features and karst mode in the Yingmai-2 well field of Tabei uplift%塔北隆起英买2井区碳酸盐岩储层特征及岩溶模式

    Institute of Scientific and Technical Information of China (English)

    姜华; 张艳秋; 潘文庆; 王瑞菊; 客伟利

    2013-01-01

    According to the relationship between the relative intensity of D-peak, G-peak and G-D peak spacing of bitumens and the maturity of bitumen evolution, we deduced that the Dh/Gh ratio and G-D peak spacing are positively proportional to bitumen maturity. Bitumens in Ordovician reservoir in the northern Tarim Basin are thought to have evolved in three stages and the Dh/Gh ratio and G-D peak spacing of Raman measurements on these bitumens indicated that the first-stage bitumen is highly-mature carbonaceous reservoir bitumen, the second-stage one is mature asphaltene reservoir bitumen, and the third-stage one is a combination of overmature oily reservoir bitumen and asphaltene reservoir bitumen. The formation of the first- and second-stage bitumens is attributed to thermal metamorphism, while the co-existence of two different bitumens for the third-stage bitumen is mainly due to selective adsorption of rocks. The distribution and property of these three-stages bitumens in Ordovician reservoirs of the northern Tarim Basin may determine the nature of Ordovician reservoirs, which is characterized by the southern condensate oil later than the northern heavy oil. The observation of oily reservoir bitumen in the northern Halahatang-Yingmaili region can provide evidence and targets for exploring Himalayan condensate oil reservoirs in this area.%中国海相碳酸盐岩储层具有鲜明的非均质性特征及复杂的形成机理.应用三维地震、岩心、成像测井、薄片等资料对英买2井区储层特征进行了研究,认为该区域储层并非典型的风化壳型岩溶储层,而属于断裂岩溶或断控岩溶储层,储集空间以方解石半充填或未充填的裂缝、小型溶蚀孔洞-裂缝为主,且分布受到断裂系统的强烈控制.结合构造活动背景以及包裹体盐度综合分析,认为该区断裂岩溶先后经历了地表水沿断裂向下溶蚀和深部热液沿断裂向上溶蚀2个阶段.前者以建设性作用为主,后者以

  2. 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

  3. PRODUCTION IMPROVEMENT FROM INCREASED PERMEABILITY USING ENGINEERED BIOCHEMICAL SECONDARY RECOVERY METHODOLOGY IN MARGINAL WELLS OF THE EAST TEXAS FIELD

    Energy Technology Data Exchange (ETDEWEB)

    R.L. Bassett; William S. Botto

    2005-04-29

    A combination of a regenerating biochemical mixture and an organic surfactant has been applied to wells in the East Texas Field with the goal of restoring permeability, reversing formation damage, mobilizing hydrocarbons, and ultimately increasing production. Initial work in task 1 was designed to open the perforations and remove blockages of scale, asphaltene, and other corrosion debris. This was accomplished on three wells that produce from the Woodbine, and was necessary to prepare the wells for more substantial future treatments. Secondly, in task 2, two wells were treated with much larger quantities of the biochemical mixture, e.g. 25 gallons, with a 2% KCl carrier solution that carried the active biochemical solution into the near wellbore area adjacent to producing reservoir. After a 7 to 10 day acclamation and reaction period, the wells were put back into production. The biochemical solution successfully broke down the scale, paraffin and other binders blocking permeability and released significant debris, which was immediately produced into the flow lines and separators. Oil production was clearly improved and the removed debris was a maintenance issue until the surface equipment could be modified. In task 3 the permeability restrictions in a cylindrical area of 10 to 20 feet from the wellbore within the reservoir were treated with the biochemical solution. Fluid was forced into the producing horizon using the hydraulic head of the well filled with 2 % KCl solution, allowed to acclimate, and then withdrawn by pumping. The chloride content of the produce water was measured and production of oil and water monitored. The most significant effect in improving permeability and removing scale and high molecular weight hydrocarbons was accomplished in the wellbore perforations and near wellbore treatments of tasks 1 and 2. The effect the deeper insertion of solution in task 3 had minimal impact on production.

  4. 兖州煤与石家庄减压渣油共处理的研究Ⅱ ——甲苯可溶重质产物组成性质的变化规律%Coprocessing of Yanzhou coal with Shijiazhuang vacuum resid Ⅱ ——characteristics of heavy toluene soluble fractions

    Institute of Scientific and Technical Information of China (English)

    阎瑞萍; 朱继升; 王志杰; 杨建丽; 刘振宇

    2001-01-01

    The characteristics of heavy toluene soluble fractions (HTSF) from coprocessing of Yanzhou coal with Shijiazhuang vacuum resid (SVR) was studied using thin layer chromatography (TLC), nuclear magnetic resonance (NMR) and gel permeation chromatography (GPC). The results showed that strong interaction between the coal and the resid took place in coprocessing. With increasing the reaction severity, the yield of asphaltenes increased, while the yield of saturates and resins decreased. The aromaticity of the HTSF increased and the average molecular weight decreased with increasing the temperature.%借助棒状薄层色谱/氢火焰(TLC/FID)、核磁共振(1H-NMR)以及凝胶渗透色谱(GPC), 对兖州煤与石家庄减压渣油单独处理及其共处理所得的甲苯可溶重质产物的组成、结构和分子量进行了研究, 得到了重质产物的组成性质随反应条件的变化规律. 结果表明, 共处理重质产物的组成性质并非煤与渣油各自加氢处理所得重质产物的简单物理混合, 而是在二者之间发生了化学反应, 说明通过共处理反应可从分子水平调配重质产物的组成性质, 为重质产物的优化利用提供了理论基础.

  5. Simple, Expendable, 3D-Printed Microfluidic Systems for Sample Preparation of Petroleum.

    Science.gov (United States)

    Kataoka, Érica M; Murer, Rui C; Santos, Jandyson M; Carvalho, Rogério M; Eberlin, Marcos N; Augusto, Fabio; Poppi, Ronei J; Gobbi, Angelo L; Hantao, Leandro W

    2017-03-08

    In this study, we introduce a simple protocol to manufacture disposable, 3D-printed microfluidic systems for sample preparation of petroleum. This platform is produced with a consumer-grade 3D-printer, using fused deposition modeling. Successful incorporation of solid-phase extraction (SPE) to microchip was ensured by facile 3D element integration using proposed approach. This 3D-printed μSPE device was applied to challenging matrices in oil and gas industry, such as crude oil and oil-brine emulsions. Case studies investigated important limitations of nonsilicon and nonglass microchips, namely, resistance to nonpolar solvents and conservation of sample integrity. Microfluidic features remained fully functional even after prolonged exposure to nonpolar solvents (20 min). Also, 3D-printed μSPE devices enabled fast emulsion breaking and solvent deasphalting of petroleum, yielding high recovery values (98%) without compromising maltene integrity. Such finding was ascertained by high-resolution molecular analyses using comprehensive two-dimensional gas chromatography and gas chromatography/mass spectrometry by monitoring important biomarker classes, such as C10 demethylated terpanes, ααα-steranes, and monoaromatic steroids. 3D-Printed chips enabled faster and reliable preparation of maltenes by exhibiting a 10-fold reduction in sample processing time, compared to the reference method. Furthermore, polar (oxygen-, nitrogen-, and sulfur-containing) analytes found in low-concentrations were analyzed by Fourier transform ion cyclotron resonance mass spectrometry. Analysis results demonstrated that accurate characterization may be accomplished for most classes of polar compounds, except for asphaltenes, which exhibited lower recoveries (82%) due to irreversible adsorption to sorbent phase. Therefore, 3D-printing is a compelling alternative to existing microfabrication solutions, as robust devices were easy to prepare and operate.

  6. Effect of modifying host oil on coprocessing

    Energy Technology Data Exchange (ETDEWEB)

    Hajdu, P.E.; Tierney, J.W.; Wender, I.

    1995-05-01

    The world`s supply of petroleum crudes is becoming heavier in nature so that the amount of vacuum bottoms has been steadily increasing. Coprocessing of coal with these resids (1,000 F+) is an attractive way of obtaining useful distillates from these readily available cheap materials. The objective of this work is to pretreat the host oil in ways that would improve its performance in coprocessing with coal. The following are examples of some ways in which heavy oil could be made into a better host oil: converting aromatic structures to hydroaromatics capable of donating hydrogen to coal, cracking the heavy oil to lower molecular weight material that would be a better solvent, and removing metals, sulfur, and nitrogen. The work reported here used a Venezuelan oil obtained from the Corpus Christi refinery of Citgo. Two coals, Illinois No. 6 and Wyodak subbituminous, were coprocessed with host oils. The authors have found that mild pretreatment of a Citgo resid (1,000 F) using either Mo naphthenate or Mo/Fe{sub 2}O{sub 3}/SO{sub 4}, as well as a pretreatment using the homogeneous catalyst Co{sub 2}(CO){sub 8} under synthesis gas can increase the available (donatable) hydrogen content of the resid. When these pretreated oils were thermally (no added catalyst) coprocessed with an Illinois No. 6 coal, about 90 wt% of the coal (maf) was converted to soluble products. This high coal conversion was realized even at a high coal loading of 50 wt%. The products from coprocessing coal and oil were equally split between high boiling material, mostly asphaltenes, and distillate. Distillate yields appeared to be affected by the concentration of coal in the feed, with maximum yields at coal loadings below 50 wt%.

  7. Oil-source correlation for the paleo-reservoir in the Majiang area and remnant reservoir in the Kaili area, South China

    Science.gov (United States)

    Fang, Yunxin; Liao, Yuhong; Wu, Liangliang; Geng, Ansong

    2011-05-01

    There are different viewpoints on the oil-source correlation of the Majiang paleo-reservoir and the neighbouring Kaili remnant reservoir in the Southern Guizhou Depression of China. Three potential source rocks in this depression could be inferred: the Lower-Cambrian marine mudstone, Lower-Silurian shale and Lower-Permian mudstone. Most of the potential source rocks are of high maturity. The solid bitumens and oil seepages in the Southern Guizhou Depression suffered severe secondary alterations, such as thermal degradation and biodegradation. The solid bitumens of the Majiang paleo-reservoir are also of high maturity. The oil seepages and soft bitumen of the Kaili remnant reservoir were severely biodegraded. All these secondary alterations may obscure oil-source correlations by routine biomarkers. Thus, it is very important to select appropriate biomarker parameters for the oil-source correlation. In this work, biomarkers resistant to thermal degradation and biodegradation and the data of organic carbon isotopic compositions were used for the correlation. The δ 13C values of n-alkanes in asphaltene pyrolysates were also used to make oil-oil and oil-source correlations between severely biodegraded oils. The results indicate that the Lower-Cambrian marine mudstones are the main source for the Ordovician-Silurian (O-S) solid bitumens of the Majiang area and the Ordovician-Silurian oil seepages and soft bitumens of the Kaili area. Remnant reservoir in the eastern Kaili area might have been charged at least twice by the oil generated from the Lower-Cambrian marine source rocks.

  8. 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.

  9. 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

  10. 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.

  11. Determination of oxygen and nitrogen derivatives of polycyclic aromatic hydrocarbons in fractions of asphalt mixtures using liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization.

    Science.gov (United States)

    Nascimento, Paulo Cicero; Gobo, Luciana Assis; Bohrer, Denise; Carvalho, Leandro Machado; Cravo, Margareth Coutinho; Leite, Leni Figueiredo Mathias

    2015-12-01

    Liquid chromatography coupled to mass spectrometry with atmospheric pressure chemical ionization was used for the determination of polycyclic aromatic hydrocarbon derivatives, the oxygenated polycyclic aromatic hydrocarbons and nitrated polycyclic aromatic hydrocarbons, formed in asphalt fractions. Two different methods have been developed for the determination of five oxygenated and seven nitrated polycyclic aromatic hydrocarbons that are characterized by having two or more condensed aromatic rings and present mutagenic and carcinogenic properties. The parameters of the atmospheric pressure chemical ionization interface were optimized to obtain the highest possible sensitivity for all compounds. The detection limits of the methods ranged from 0.1 to 57.3 μg/L for nitrated and from 0.1 to 6.6 μg/L for oxygenated derivatives. The limits of quantification were in the range of 4.6-191 μg/L for nitrated and 0.3-8.9 μg/L for oxygenated derivatives. The methods were validated against a diesel particulate extract standard reference material (National Institute of Standards and Technology SRM 1975), and the obtained concentrations (two nitrated derivatives) agreed with the certified values. The methods were applied in the analysis of asphalt samples after their fractionation into asphaltenes and maltenes, according to American Society for Testing and Material D4124, where the maltenic fraction was further separated into its basic, acidic, and neutral parts following the method of Green. Only two nitrated derivatives were found in the asphalt sample, quinoline and 2-nitrofluorene, with concentrations of 9.26 and 2146 mg/kg, respectively, whereas no oxygenated derivatives were detected.

  12. 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.

  13. Mechanism of conversion of cellulosic wastes to liquid fuels in alkaline solution

    Energy Technology Data Exchange (ETDEWEB)

    Molton, P.M.; Demmitt, T.F.; Donovan, J.M.; Miller, R.K.

    1978-01-01

    Conversion of cellulosic wastes into liquid oils is being practiced on a pilot plant scale at Albany, OR, but the fundamental chemistry of the process is poorly understood. We report our findings on the aqueous alkaline digestion of pure cellulose, on a laboratory scale, in a closely related system. Our intent is to elucidate the reaction mechanisms involved in oil and tar formation, and to identify products of potential value. A 30 wt % aqueous slurry of pure cellulose in up to 1.2 N alkali (sodium hydroxide or carbonate), heated to 350/sup 0/C over a 3.5 hour period showed a sharp discontinuity in heating rate at 265 to 270/sup 0/C, indicating the onset of a discrete liquefaction reaction not hitherto observed. A series of 129 autoclave experiments analyzed by statistical methods indicated that carbon monoxide, while it promotes the attainment of high yields as claimed by the Bureau of Mines, is not necessary for the reaction to proceed. Analysis of the products by /sup 13/C-NMR, GC/MS, and gel permeation chromatography indicated that the nonvolatile fraction of the oil consists of 44% aromatic carbon and 7% aromatic hydrogen, corresponding to a benzenoid polyaromatic with a substitution ratio of 5:1. However, oxygen content of the nonvolatile fraction and distillable oil is approximately the same. Since the oil contains a series of polyalkylated furans, this suggests that the char is a poly-furan rather than a conventional asphaltene derivative. Volatile products from the oil fraction consist of furans, cyclic ketones, linear and branched alkenes, and phenolics. The high proportion of phenolics relative to normal crude oil could explain the observed highly corrosive nature of the biomass-derived oils.

  14. 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)

  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. 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.

  17. 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.

  18. Ex situ bioremediation of a soil contaminated by mazut (heavy residual fuel oil)--a field experiment.

    Science.gov (United States)

    Beškoski, Vladimir P; Gojgić-Cvijović, Gordana; Milić, Jelena; Ilić, Mila; Miletić, Srdjan; Solević, Tatjana; Vrvić, Miroslav M

    2011-03-01

    Mazut (heavy residual fuel oil)-polluted soil was exposed to bioremediation in an ex situ field-scale (600 m(3)) study. Re-inoculation was performed periodically with biomasses of microbial consortia isolated from the mazut-contaminated soil. Biostimulation was conducted by adding nutritional elements (N, P and K). The biopile (depth 0.4m) was comprised of mechanically mixed polluted soil with softwood sawdust and crude river sand. Aeration was improved by systematic mixing. The biopile was protected from direct external influences by a polyethylene cover. Part (10 m(3)) of the material prepared for bioremediation was set aside uninoculated, and maintained as an untreated control pile (CP). Biostimulation and re-inoculation with zymogenous microorganisms increased the number of hydrocarbon degraders after 50 d by more than 20 times in the treated soil. During the 5 months, the total petroleum hydrocarbon (TPH) content of the contaminated soil was reduced to 6% of the initial value, from 5.2 to 0.3 g kg(-1) dry matter, while TPH reduced to only 90% of the initial value in the CP. After 150 d there were 96%, 97% and 83% reductions for the aliphatic, aromatic, and nitrogen-sulphur-oxygen and asphaltene fractions, respectively. The isoprenoids, pristane and phytane, were more than 55% biodegraded, which indicated that they are not suitable biomarkers for following bioremediation. According to the available data, this is the first field-scale study of the bioremediation of mazut and mazut sediment-polluted soil, and the efficiency achieved was far above that described in the literature to date for heavy fuel oil.

  19. 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)

  20. 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.

  1. Analysis of Adhesive Characteristics of Asphalt Based on Atomic Force Microscopy and Molecular Dynamics Simulation.

    Science.gov (United States)

    Xu, Meng; Yi, Junyan; Feng, Decheng; Huang, Yudong; Wang, Dongsheng

    2016-05-18

    Asphalt binder is a very important building material in infrastructure construction; it is commonly mixed with mineral aggregate and used to produce asphalt concrete. Owing to the large differences in physical and chemical properties between asphalt and aggregate, adhesive bonds play an important role in determining the performance of asphalt concrete. Although many types of adhesive bonding mechanisms have been proposed to explain the interaction forces between asphalt binder and mineral aggregate, few have been confirmed and characterized. In comparison with chemical interactions, physical adsorption has been considered to play a more important role in adhesive bonding between asphalt and mineral aggregate. In this study, the silicon tip of an atomic force microscope was used to represent silicate minerals in aggregate, and a nanoscale analysis of the characteristics of adhesive bonding between asphalt binder and the silicon tip was conducted via an atomic force microscopy (AFM) test and molecular dynamics (MD) simulations. The results of the measurements and simulations could help in better understanding of the bonding and debonding procedures in asphalt-aggregate mixtures during hot mixing and under traffic loading. MD simulations on a single molecule of a component of asphalt and monocrystalline silicon demonstrate that molecules with a higher atomic density and planar structure, such as three types of asphaltene molecules, can provide greater adhesive strength. However, regarding the real components of asphalt binder, both the MD simulations and AFM test indicate that the colloidal structural behavior of asphalt also has a large influence on the adhesion behavior between asphalt and silicon. A schematic model of the interaction between asphalt and silicon is presented, which can explain the effect of aging on the adhesion behavior of asphalt.

  2. Phytoremediation potential and ecological and phenological changes of native pioneer plants from weathered oil spill-impacted sites at tropical wetlands.

    Science.gov (United States)

    Palma-Cruz, Felipe de J; Pérez-Vargas, Josefina; Rivera Casado, Noemí Araceli; Gómez Guzmán, Octavio; Calva-Calva, Graciano

    2016-08-01

    Pioneer native plant species from weathered oil spill-affected sites were selected to study their potential for phytoremediation on the basis of their ecological and phenological changes during the phytoremediation process. Experiments were conducted in field and in greenhouse. In field, native plants from aged oil spill-impacted sites with up 400 g of weathered petroleum hydrocarbons per kilogram soil were selected. In the impacted sites, the principal dominant plant species with potential for hydrocarbons removal were Cyperus laxus, Cyperus esculentus, and Ludwigia peploides. In greenhouse, the phenology of the selected plant species was drastically affected by the hydrocarbons level above 325 g total petroleum hydrocarbons (TPH) per kilogram soil after 2 years of phytoremediation of soils from the aged oil spill-impacted sites. From the phytoremediation treatments, a mix-culture of C. laxus, C. esculentus, and L. peploides in soil containing 325 g TPH/kg soil, from which 20.3 % were polyaromatic hydrocarbons (PAH) and 34.2 % were asphaltenes (ASF), was able to remove up 93 % of the TPH, while in unvegetated soil the TPH removal was 12.6 %. Furthermore, evaluation of the biodiversity and life forms of plant species in the impacted sites showed that phytoremediation with C. esculentus, alone or in a mix-culture with C. laxus and L. peploides, reduces the TPH to such extent that the native plant community was progressively reestablished by replacing the cultivated species resulting in the ecological recovery of the affected soil. These results demonstrate that native Cyperus species from weathered oil spill-affected sites, specifically C. esculentus and C. laxus, alone or in a mix-culture, have particular potential for phytoremediation of soils from tropical wetlands contaminated with weathered oil hydrocarbons.

  3. The comparison of naturally weathered oil and artificially photo-degraded oil at the molecular level by a combination of SARA fractionation and FT-ICR MS

    Energy Technology Data Exchange (ETDEWEB)

    Islam, Ananna; Cho, Yunju [Kyungpook National University, Department of Chemistry, Daegu 702-701 (Korea, Republic of); Yim, Un Hyuk; Shim, Won Joon [Oil and POPs Research Group, Korea Institute of Ocean Science and Technology, Geoje 656-834 (Korea, Republic of); Kim, Young Hwan [Division of Mass Spectrometry Research and Center for Analytical Research in Disease Sciences, Korea Basic Science Institute, Ochang 863-883 (Korea, Republic of); Graduate School of Analytical Science and Technology, Chungnam National University, Daejeon 305-764 (Korea, Republic of); Kim, Sunghwan, E-mail: sunghwank@knu.ac.kr [Kyungpook National University, Department of Chemistry, Daegu 702-701 (Korea, Republic of); Division of Mass Spectrometry Research and Center for Analytical Research in Disease Sciences, Korea Basic Science Institute, Ochang 863-883 (Korea, Republic of)

    2013-12-15

    Highlights: • Weathered oils from the Hebei Spirit oil spill and photo degraded oils are compared. • We investigate changes of polar species at the molecular level by 15T FT-ICR MS. • Significant reduction of sulfur class compounds in saturates fraction is observed. • The relative abundance of protonated compounds (presumably basic nitrogen compounds) increase after degradation. • Changes of polar compounds occurred by natural and photo degradation are similar. -- Abstract: Two sets of oil samples, one obtained from different weathering stages of the M/V Hebei Spirit oil spill site and the other prepared by an in vitro photo-degradation experiment, were analyzed and compared at the molecular level by atmospheric pressure photo-ionization coupled with Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS). For a more detailed comparison at the molecular level, the oil samples were separated into saturate, aromatic, resin, and asphaltene (SARA) fractions before MS analysis. Gravimetric analysis of the SARA fractions revealed a decreased weight percentage of the aromatic fraction and an increased resin fraction in both sets of samples. Molecular-level investigations of the SARA fractions showed a significant reduction in the S{sub 1} class in the saturate fraction and increase of S{sub 1}O{sub 1} class compounds with high DBE values in resin fraction. Levels of N{sub 1} and N{sub 1}O{sub 1} class compounds resulting in protonated ions (presumably basic nitrogen compounds) increased after degradation compared to compounds generating molecular ions (presumably non-basic nitrogen compounds). This study revealed changes occurring in heteroatom polar species of crude oils such as sulfur and nitrogen containing compounds th