Characterization of Asphaltenes and Resins Separated from Water-in-Oil Emulsions

Knowledge of the properties and behavior of asphaltenes and resins is indispensable for the design of preventive and curative measure for emulsion problems created by the presence of asphaltene, resins, and other organic and inorganic solids. In order to understand the phenomena of water-oil emulsions formed in Kuwaiti oil fields and determine the factors involved in the stabilization of these emulsions, the role of asphaltenes, resins and wax separated from various samples of oil field emulsions formed in Burgan oil field have been evaluated. Physicochemical properties of asphaltenes, resins, wax, and de-asphalted de-resined (DADR) oil samples have been studied via FT-IR, ¹H, and ¹³C NMR, elemental analysis, and differential scanning calorimetry (DSC). These emulsion samples contain different amounts of water ranges from 24 to 35%, asphaltene content ranges from 0.9 to 1.7%, and resin content from 3.7 to 4.6%. IR-FT spectra were performed to identify the various functional groups which have an effect on the stability of water-oil emulsions. The freezing behavior of an emulsion was characterized by differential scanning calorimetry to determine whether the water in the emulsion is free water or emulsified water.     

Stability of Water-in-Crude Oil Emulsions: Effect of Oil Aromaticity,Resins to Asphaltene Ratio,and pH of Water

Abstract

The formation of tight water-in-oil emulsions during production and transport of crude oils is a great problem challenging the petroleum industry. Tremendous research works are directed to understanding the mechanism of formation, stabilization, and controlling of oil field emulsions. This article presents experimental results of some of the factors controlling the formation and stabilization of water-in-crude oil emulsions. In this study, asphaltenes and resins separated from emulsion samples collected from Burgan oil field in Kuwait have been used to study emulsion stability. Model oils of resin to asphaltene ratio of 5:1 and toluene-heptane mixtures have been used to study the effect of oil aromaticity on emulsion stability. Results indicate that at low toluene content (below 20%) or high content (above 40%) less stable emulsions are formed. At a threshold value of 30% toluene, a very tight model oil emulsion is formed. The effect of resins to asphaltene (R/A) ratio on stability of model oil has also been investigated. Results reported in this paper show that as the R/A increases the emulsions become less stable. The effect of pH on stability of model oil emulsion made of 50/50 heptane-toluene mixture having R/A ratio of 5:1 have been studied. Experimental results revealed that as the pH of the aqueous phase of model oil increased from 2 to 10, the emulsion became less stable. At high pH, the asphaltene particles are subjected to complete ionization leading to destruction of the water-oil interface and eventually breakdown of the emulsion.     

Relationship of Light Absorption and Vanadium Content in Asphaltenes and Resins of Heavy Oils

Abstract

The relationship of the light absorption of asphaltenes and resins with vanadium content has been investigated on the example of heavy oils of various deposits. In the oils of various deposits in Permian and Carboniferous producing complexes of Volga–Ural oil-and-gas bearing basin, the asphaltene content varies from 5.3 to 21.2?wt %, while the vanadium content is from 0.009 to 0.165?wt %. It has been shown that there is a direct correlation of the light absorption of asphaltenes and vanadium content with the correlation coefficient of higher than 0.96 in the case of each producing complex. There is also a direct relationship between the light absorption of resins and vanadium content in the HOs under study with the correlation coefficient of higher than 0.92 in the case of each producing complex.     

Interfacial and Thermal Characterization of Asphaltenes Separated from Crude Oils Having Different Geological Origins

Abstract

Three crude oils having different geological origins, namely, DK from Eocene (Sylhet limestone and Langpar), SL from Barail (Oligocene), and JN from Tipam (lower Miocene), were selected. Asphaltenes were separated and characterized. Fourier transform infrared (FTIR) spectroscopy showed the presence of polar groups. Interfacial tension studies of the asphaltenes between benzene–water, toluene–water, and xylene–water showed the lowest interfacial tension with SL asphaltenes in a toluene–water system. Thermogravimetric analysis of asphaltenes indicates greater thermal degradation for DK asphaltenes. Asphaltenes were pyrolyzed and the pyrolyzed products were analyzed by gas chromatography/mass spectrometry (GC/MS). Based on the distribution pattern of n-alkanes in pyrolyzed product of asphaltenes, crude oils, and kerogens, it was concluded that crude oil and asphaltenes originate from the same source and asphaltenes are the unconverted parts of kerogens.     

The Preparation of a Polyether Demulsifier Modified by Nano-SiO2 and the Effect on Asphaltenes and Resins

Abstract

In order to enlarge the range of applications of nanomaterials and improve the performance of macromolecular polymer demulsifier, nano-SiO₂ was integrated with polyether demulsifier TA1031 to form nanomodified demulsifier using an in situ synthesis method. Analysis of the polyether demulsifier modified by nano-SiO₂ was performed using transmission electron microscopy (TEM) and Fourier transform infrared (FTIR) spectroscopy. The result showed that applying nanomaterials to crude oil demulsifier greatly improves the performance of the original demulsifier. When the ratio of nano-SiO₂ and TA1031 is 1:10, the performance of the nanomodified demulsifier was best, and the ratio of demulsification was improved by about 20%. The time of demulification and dewatering was also greatly shortened by about 30 min. The influence of nanomodified demulsifier on the asphaltenes and resins was studied by FTIR.     

Correlation Between Properties of Asphaltenes and Precipitation Conditions

Abstract

Asphaltenes from three crude oils were precipitated by using a pressurized system. Different conditions during the precipitation of asphaltenes were studied: pressure was varied between 15 and 45 kg/cm² and temperature between 40°C and 100°C. The effect of contact time and solvent-to-oil ratio was also studied in the range of 0.5–6 hr and 2:1 to 5:1 mL/g, respectively. Asphaltenes properties were analyzed as a function of pressure and temperature. It was found that in a deeper way temperature influences the asphaltenes properties than pressure in the range studied in this work. Asphaltenes properties were highly dependent on the nature of crude oil. Various correlations were developed and experimental and calculated asphaltenes contents and properties were in good agreement with absolute error less than 0.2%.     

Correlation Between Properties of Asphaltenes and Precipitation Conditions

Asphaltenes from three crude oils were precipitated by using a pressurized system. Different conditions during the precipitation of asphaltenes were studied: pressure was varied between 15 and 45 kg/cm² and temperature between 40°C and 100°C. The effect of contact time and solvent-to-oil ratio was also studied in the range of 0.5-6 hr and 2:1 to 5:1 mL/g, respectively. Asphaltenes properties were analyzed as a function of pressure and temperature. It was found that in a deeper way temperature influences the asphaltenes properties than pressure in the range studied in this work. Asphaltenes properties were highly dependent on the nature of crude oil. Various correlations were developed and experimental and calculated asphaltenes contents and properties were in good agreement with absolute error less than 0.2%.     

Maltenes and Asphaltenes of Petroleum Vacuum Residues: Physico-Chemical Characterization

Abstract

Solvent separation is frequently applied to petroleum vacuum residues to reduce the coke-forming tendencies of these materials. This process is capable of removing all or a substantial amount of asphaltenes from feedstocks that are destined for further processing and thus applied as the first step of refining. Maltenes and asphaltenes obtained from vacuum residues of Heera (HVR) and Jodhpur (JVR) Indian crude oils using n-hexane, n-heptane, and soluble and insoluble fractions obtained using ethyl acetate, were characterized for elemental analysis, molecular weight, conradson carbon residue (CCR), specific gravity, and pour points. The resulting degree of removal of asphaltenes ranged from 10–28 wt% of the HVR and 25–50 wt% of the JVR. The increasing trend of the American Petroleum Institute (API) gravity and the decreasing trend of CCR and pour point are observed with the increase in removal of asphaltenes.     

Maltenes and Asphaltenes of Petroleum Vacuum Residues: Physico-Chemical Characterization

Solvent separation is frequently applied to petroleum vacuum residues to reduce the coke-forming tendencies of these materials. This process is capable of removing all or a substantial amount of asphaltenes from feedstocks that are destined for further processing and thus applied as the first step of refining. Maltenes and asphaltenes obtained from vacuum residues of Heera (HVR) and Jodhpur (JVR) Indian crude oils using n-hexane, n-heptane, and soluble and insoluble fractions obtained using ethyl acetate, were characterized for elemental analysis, molecular weight, conradson carbon residue (CCR), specific gravity, and pour points. The resulting degree of removal of asphaltenes ranged from 10-28 wt% of the HVR and 25-50 wt% of the JVR. The increasing trend of the American Petroleum Institute (API) gravity and the decreasing trend of CCR and pour point are observed with the increase in removal of asphaltenes.     

The Application of a New Association Equation of State (AEOS) for Prediction of Asphaltenes and Resins Deposition During CO2 Gas Injection

Abstract

Asphaltene deposition is a serious problem that can cause fouling in the reservoir, well, pipeline, and the oil production and processing facilities. An association equation of state (AEOS) is one of the most useful models used to predict asphaltene phase behavior and asphaltene deposition conditions. For an AEOS, it is assumed that the total compressibility factor consists of physical and chemical parts. The authors apply the conventional form of compressibility factor developed by G. Soave (1972) Soave, G. 1972. Equilibrium constants from a modified Redlich-Kwong equation of state. Chem. Eng. Sci., 27: 1197–1203. [Crossref], [Web of Science ®] , [Google Scholar] to the physical compressibility factor. However, for the chemical compressibility factor a new form is proposed. The total compressibility factor obtained is then used to calculate the asphaltene and resin deposits. The amounts of deposited asphaltenes calculated through the proposed model along with the experimental results are used to calculate resin deposit. A comparison with the experimental results shows that the new proposed model can be used to predict the amounts of deposited resins and asphaltenes within an acceptable range of accuracy.     

原油泡沫稳定特性研究进展

在油气集输与处理,特别是油气分离过程中,易产生大量泡沫。泡沫的演化和衰变整体符合液膜排液、气体扩散进而破灭的过程,通常认为原油中胶质、沥青质及蜡等固体颗粒是影响泡沫稳定性的重要因素,但对其影响规律和机理的认识却不尽相同,甚至观点相反。究其原因是原油组分及其所处工况都比较复杂,而且不同学者所用研究手段也不相同,因此,建议根据实际工况研制针对性实验装置,并借助现代化精密仪器进行精细分析,将宏观原油泡沫现象与微观下胶质、沥青质、蜡等在原油泡沫中结构变化相结合,分析各物质作用机理,有助于增进对泡沫稳定性的定性和定量研究。     

Microbial and Enzymatic Biotransformations of Asphaltenes

Asphaltenes are considered the most recalcitrant fraction of oils. Nevertheless, there are reports with rigorous experimental procedures that clearly demonstrate the capacity of enzymes and few microorganisms to transform asphaltenes. These microorganisms, fungi and bacteria, may contain a unique or very versatile enzymatic system that allows the transformation and mineralization of the highly complex asphaltene molecules. For enzymatic reactions, the biotransformation may occur only when the asphaltenes and the enzyme are in the same phase, reducing the mass transfer limitations. In this work, literature on the biotransformations of asphaltene fraction is critically reviewed.     

Characterization of Petroleum Asphaltenes by Size Exclusion Chromatography, UV-fluorescence and Mass Spectrometry

The molecular weight of petroleum asphaltenes remains the subject of debate. Our previous work using size exclusion chromatography with 1-methyl-2-pyrrolidinone (NMP) as eluent, combined with mass spectrometry and fluorescence spectroscopy has indicated molecular masses up to 40,000 u. The present work investigates the asphaltene fraction of Kuwaiti crude oil. The asphaltene was separated into several NMP-soluble fractions and an insoluble residue. The evidence from size exclusion chromatography (SEC) and UV-fluorescence spectroscopy (UV-F) shows that the molecular size range and the size of the aromatic chromophores increased with increasing insolubility in NMP. A steady increase in the sizes of the range of chromophores was shown by UV-fluorescence in going from the maltene fraction, via the asphaltene sample to the NMP-insoluble residue, using chloroform as solvent. Laser-desorption mass spectra showed very wide mass ranges for the whole asphaltene and the NMP-insoluble residue of asphaltenes, with a signal up to m/z 200,000 and slightly more ion intensity at high masses for the residue compared to that from the asphaltene.     

Structural Characterization of Asphaltenes and Ethyl Acetate Insoluble Fractions of Petroleum Vacuum Residues

Asphaltenes and insoluble fractions of vacuum residues (VRs) of two Indian crude oils (viz. Heera and Jodhpur) of different specific gravity were obtained by precipitation of VRs in n-hexane, n-heptane, and ethyl acetate, and also by subsequent reprecipitation of n-heptane and ethyl acetate soluble fractions by n-pentane. The effect of various solvents on average molecular structure of asphaltenes and insolubles was studied using nuclear magnetic resonance spectroscopy (NMR), Fourier transform infrared spectroscopy (FTIR), and size exclusion chromatography (SEC). The asphaltenes and insolubles of Jodhpur VR have higher amounts of high molecular weight species with a high concentration of condensed and substituted aromatic rings, branched and/or short alkyl side chains, oxygen and nitrogen functionalities, compared to that of Heera VR. Ethyl acetate insolubles comprise a higher number of substituted aromatic structures, branched aliphatic structures, complex average unit structures, nitrogen and oxygen functionalities, and high molecular weight (MW) species as compared to hexane and heptane asphaltenes. Heptane insolubles consist of more naphthenic rings condensed with aromatic rings than C6A and EAI.     

Structural Characterization of Asphaltenes from Raw and Desulfurized Vacuum Residue and Correlation Between Asphaltene Content and the Tendency of Sediment Formation in H-oil Heavy Products

Asphaltenes obtained from raw vacuum residue from Russian (Ural) petroleum have been characterized by means of elemental analysis and ¹H proton nuclear magnetic resonance (NMR) and compared with asphaltenes separated from the residue desulfurized in the H-oil process. The latter have much lower molecular weight and more aromatic character. In high-temperature conditions of fractionation of the whole H-oil product and in the presence of catalyst dust carried away from reactors, asphaltenes tend to condense, dehydrogenate, and separate from the desulfurized oil as a coke-like sediment. Some correlations have been found between the asphaltene contents of raw and desulfurized residue and the tendency of sediment formation in desulfurized residual oil that causes serious operating problems in H-oil units.     

Behavior and Role of Asphaltenes in a Two-stage Fixed Bed Hydrotreating Process

Residue upgrading processes are very important for the production of distillates and low sulfur fuel oils. Among those, fixed bed technologies are very efficient for deep desulfurization of petroleum residue heavy oils, even for highly asphaltenic feeds. This work analyzes the effects of the operating conditions on the evolution of asphaltenes and on their inhibition effect during the hydrodesulfurization reactions. Residue hydrotreating experiments were performed on a pilot plant and asphaltene fractions were investigated using size exclusion chromatography (SEC), ¹³C nuclear magnetic resonance (NMR), liquid chromatography, and elemental analyses. Besides the overall decrease in asphaltenes yield, significant changes in the average structure of the asphaltenes were also observed.     

Behavior and Role of Asphaltenes in a Two-stage Fixed Bed Hydrotreating Process

Abstract

Residue upgrading processes are very important for the production of distillates and low sulfur fuel oils. Among those, fixed bed technologies are very efficient for deep desulfurization of petroleum residue heavy oils, even for highly asphaltenic feeds. This work analyzes the effects of the operating conditions on the evolution of asphaltenes and on their inhibition effect during the hydrodesulfurization reactions. Residue hydrotreating experiments were performed on a pilot plant and asphaltene fractions were investigated using size exclusion chromatography (SEC), ¹³C nuclear magnetic resonance (NMR), liquid chromatography, and elemental analyses. Besides the overall decrease in asphaltenes yield, significant changes in the average structure of the asphaltenes were also observed.     

Synthesis and Characterization of Cured Allyl/Propargyl Ether Novolac Resins

A new kind of modified thermoset resins were synthesized by phase-transfer Williamson reaction from novolac resin and mixtures of allyl- and propargyl-chlorides. The compositions of the resins were defined by 1H NMR （nuclear magnetic resonanse） spectroscopy and the dependence of the cured materials properties on the composition was established. Increase of a propargyl content resulted in char yield raise and the maximum value had been found for propargylated resin--58%. DSC （differential scanning calorimetry）-analysis of the resins has demonstrated that exothermic enthalpy of the curing process could be adjusted by varying the content of propargyl and allyl groups in the resin.     

An Active Carbon Catalyst Prevents Coke Formation from Asphaltenes during the Hydrocracking of Vacuum Residue

Active carbons were prepared by the steam activation of a brown coal char. The active carbon with mesopores showed greater adsorption selectivity for asphaltenes. The active carbon was effective at suppressing coke formation, even with the high hydrocracking conversion of vacuum residue. The analysis of the change in the composition of saturates, aromatics, resins, and asphaltenes in the cracked residue with conversion demonstrated the ability of active carbon to restrict the transformation of asphaltenes to coke. The active carbon that was richer in mesopores was presumably more effective at providing adsorption sites for the hydrocarbon free-radicals generated initially during thermal cracking to prevent them from coupling and polycondensing.     

An Active Carbon Catalyst Prevents Coke Formation from Asphaltenes during the Hydrocracking of Vacuum Residue

Abstract

Active carbons were prepared by the steam activation of a brown coal char. The active carbon with mesopores showed greater adsorption selectivity for asphaltenes. The active carbon was effective at suppressing coke formation, even with the high hydrocracking conversion of vacuum residue. The analysis of the change in the composition of saturates, aromatics, resins, and asphaltenes in the cracked residue with conversion demonstrated the ability of active carbon to restrict the transformation of asphaltenes to coke. The active carbon that was richer in mesopores was presumably more effective at providing adsorption sites for the hydrocarbon free-radicals generated initially during thermal cracking to prevent them from coupling and polycondensing.