Characterization of Thermally Degraded Asphaltene Fractions Using Gel Permeation Chromatography

Petroleum asphaltene goes through three stages of mass reduction under thermogravimetric analysis from 25°C to 1,000°C at a heating rate of 1°C/min. The products from thermal degradation of asphaltene at three different temperature intervals are collected. Two residual fractions left in the sample cup are also obtained at two specific temperatures. The collected fractions and the residual fractions are characterized using gel permeation chromatography. The fraction collected between 25°C and 350°C demonstrates similar molecular weight distribution to that collected between 350°C and 450°C, with both fractions showing a typical molecular weight distribution for polymeric material. The fraction collected between 450°C and 650°C illustrates three different molecular weight distributions. The chromatogram of the residual fraction obtained at 350°C resembles that of the undegraded asphaltene. The residual fraction obtained at 450°C also demonstrates three different molecular weight distributions. The experimental data indicate that the mass reduction of asphaltene heated from 25°C to 350°C is mainly due to the evaporation of low boiling point and/or low molecular weight substances in asphaltene. Thermal decomposition and coke production occur significantly in the 350°C-450°C temperature interval. Thermal degradation continues to finish until 650°C.     

Thermal Degradation of Asphaltene and Infrared Characterization of Its Degraded Fractions

Abstract

Petroleum asphaltene and its thermally degraded fractions are characterized using thermal analysis and infrared spectrometry, respectively. Thermal analysis of asphaltene has demonstrated that heating rate is important in studying thermal degradation of asphaltene. Asphaltene goes through three stages of mass reduction under thermogravimetric analysis from 25 to 1,000°C at a heating rate of 1°C/min and below. The products from thermal degradation of asphaltene at three different temperature intervals are collected. The collected fractions are characterized using a Fourier transform infrared spectrometer. The fraction collected between 220 and 350°C demonstrates similar infrared spectrum to that of asphaltene, however, with less aromatic properties. The fraction collected between 350 and 450°C resembles the undegraded asphaltene most based on the infrared spectra obtained. The fraction collected between 450 and 650°C demonstrates a spectrum that is totally different from those of the undegraded asphaltene and the other two fractions. In addition, a high degree of oxidation is observed on all of the three degraded fractions of asphaltene.     

Thermal Degradation of Asphaltene and Infrared Characterization of Its Degraded Fractions

Petroleum asphaltene and its thermally degraded fractions are characterized using thermal analysis and infrared spectrometry, respectively. Thermal analysis of asphaltene has demonstrated that heating rate is important in studying thermal degradation of asphaltene. Asphaltene goes through three stages of mass reduction under thermogravimetric analysis from 25 to 1,000°C at a heating rate of 1°C/min and below. The products from thermal degradation of asphaltene at three different temperature intervals are collected. The collected fractions are characterized using a Fourier transform infrared spectrometer. The fraction collected between 220 and 350°C demonstrates similar infrared spectrum to that of asphaltene, however, with less aromatic properties. The fraction collected between 350 and 450°C resembles the undegraded asphaltene most based on the infrared spectra obtained. The fraction collected between 450 and 650°C demonstrates a spectrum that is totally different from those of the undegraded asphaltene and the other two fractions. In addition, a high degree of oxidation is observed on all of the three degraded fractions of asphaltene.     

VARIATION IN THE CHEMICAL NATURE OF ASPHALTENES WITH THE PROCESS,THE COAL AND THE REACTION CONDITIONS

ABSTRACT

Average structure data for twelve asphaltenes are reported, based on ¹³C- and H- n.m.r. spectroscopy combined with elemental, molecular weight and functional group analyses. The asphaltenes were from supercritical gas extraction, flash pyrolysis and hydrogenation of a brown and a bituminous coal. The effect of the reaction temperature and, for hydrogenation, the catalyst and solvent on the nature of the asphaltene produced was studied. The asphaltene obtained from supercritical gas extraction of the brown coal at 350°C was the least aromatic (f_a = 0.44) with the highest H/C atomic ratio (1.16) and probably consists mainly of single ring aromatlcs with about half of the aromatic sites substituted. A significant proportion of the carbon in this asphaltene is in long alkyl chains and the hydroxyl content is high. Whereas, the asphaltenes produced by hydrogenatlon of the bituminous coal at 450°C were far more aromatic with more highly condensed but less substituted aromatic ring systems and few, if any, long alkyl chains, together with a lower hydroxyl content. The asphaltenes obtained from the brown coal are less aromatic with less condensed aromatic ring systems but a higher degree of aromatic substitution than those produced from the bituminous coal under the same conditions. The asphaltenes formed at 450°C had lower H/C atomic ratios, molecular weights and degree of aromatic substitution, but higher aromaticities Ohan those produced at 35O°C or 400°C under like processing conditions. The asphaltene produced in the presence of both stannous chloride catalyst and tetralin was less aromatic than when either of these species was absent.     

The Impact of CO2 Injection and Pressure Changes on Asphaltene Molecular Weight Distribution in a Heavy Crude Oil: An Experimental Study

Abstract

This work concerns observing the pressure as well as CO₂ mole percentage effects on asphaltene molecular weight distributions at reservoir conditions. A high-pressure, high-temperature asphaltene measurement setup was applied, and the amount of precipitated asphaltene at different pressures as well as CO₂ mole percentage in an Iranian heavy crude oil was measured. Moreover, the asphaltene molecular weight distributions during titration of crude oil with different n-alkanes were investigated. The gel permeation chromatography (GPC) apparatus was used for characterization of asphaltene molecular weight under different conditions. It has been observed that some thermodynamic changes such as pressure depletion above the bubble point increase the average molecular weight of asphaltene and cause the asphaltene molecular weight distributions changes from a bimodal curve with two maxima to a single maxima curve. One the other hand, below the bubble point, pressure reduction causes a decrease in the average molecular weight of asphaltene and also causes the shape of asphaltene molecular weight distributions to restore, which might be due to dissolution of asphaltene aggregates. An interesting result is that asphaltene molecular weight distribution at the final step of pressure reduction tests, ambient condition, shows approximately the same trend as the distribution of asphaltene molecular weight obtained at reservoir condition. This behavior explains the reversibility of the asphaltene precipitation process under pressure depletion conditions. In the case of CO₂ injection, the graphs of asphaltene molecular weight distributions always show a single modal trend and shift toward larger molecular weight values when CO₂ mole percentage increases. The results of this work can be imported to thermodynamic models that use polydisperse data of heavy organic fractions to enhance their performance at reservoir conditions. The distributions obtained by this method are good indicators of asphaltene structures at reservoir conditions.     

STUDIES ON NIGERIAN CRUDES 3. ANALYSIS OF SULFURIZED ASPHALTS

ABSTRACT

The residual asphalts obtained from three Nigerian medium crudes were chemically treated with elemental sulfur at 210 to 250°C. The course of the reaction was followed by monitoring the growth of the asphaltene content of the products. The sulfurization reaction led to 5- to 10-fold increases in the asphaltene content of the products. The asphaltene content of one of the samples initially increased with temperature from 210 to 240°C and then dropped sharply. The results obtained revealed that the optimum temperature of the sulfurization reaction was 240°C. It was also observed that the lower the asphaltene content of the untreated asphalt, the higher the growth of the asphaltene content of the product at the same reaction temperature. The absolute viscosity of the sulfurized asphalts increased rapidly with increasing temperature of reaction.     

Changes in structural-group characteristics of resins and asphaltenes of heavy oils in the primary distillation process

Transformations of resins and asphaltenes of chemically different heavy oils during primary distillation have been studied using oils form the Usa (Komi Republic, Russia) and Zuunbayan (Mongolia) oil-fields as an example. The structural-group parameters of resins and asphaltene molecules of the crude oils and oil residues (fuel oils) obtained via atmospheric distillation involving the withdrawal of IBP–350°C fractions have been determined using elemental analysis, molecular weight, and NMR data. Changes in the average structures of molecules in the primary distillation process of crude oils have been revealed, and it has been found that these changes depend on the chemical composition of the original oils.     

Thermal transformations of high-molecular-mass-components of heavy petroleum residues

Transformations of high-molecular-mass heteroatomic compounds (resins, asphaltenes) present in atmospheric distillation residue of crude oil from the Usa field (Republic of Komi) by thermal cracking at temperatures of 350–450°C in the presence of fly ash ferrospheres as initiator additives have been studied. The structural group parameters of resin and asphaltene molecules existing in the feedstock and the thermolysis products have been determined using elemental analysis, molecular mass, and proton NMR data.     

The use of nonylphenol formaldehyde resins for preventing asphaltene precipitation in vacuum residues and hydroprocessed petroleum samples

This work focused on the synthesis and characterization of nonylphenol formaldehyde resins (NPFR) as examples of active molecules for preventing asphaltene precipitation in vacuum residue (VR) and hydroprocessed petroleum samples. The evaluation for the NPFR as asphaltene dispersants was carried out using the on-column filtration technique at room temperature and near process conditions (195°C). The results indicated that NPFR (molecular weight = 900–4800 Da) are active for the reduction of asphaltene content of gravimetrically separated asphaltene solutions and for VR and hydroprocessed samples at room temperature (35°C) and at 195°C. It was found that the activity of NPFR as asphaltene dispersants depends not only on the type of sample (asphaltenes, virgin or processed) but also on the temperature, molecular weight, and concentration.     

ASPHALTENE AND RESID PYROLYSIS: EFFECT OF REACTION ENVIRONMENT

ABSTRACT

Hondo and Maya vacuum resids and their isolated asphaltenes were pyrolyzed at 400, 425, and 450^°C (752, 797, 842^°F) for batch holding limes ranging from 20 to 180 minutes. Maltene, asphaltene, and coke product fractions were isolated by a solvent extraction sequence; gas yield was determined gravimetrically. Results were summarized in terms of a lumped reaction network. The variation of product yields, kinetics, and apparent activation energies with feedstock and asphaltene environment provided insight into asphaltene structure and thermal reaction pathways.     

Composition of products of analytical pyrolysis of resin and asphaltene fractions of Usa oil

Resin and asphaltene fractions of crude oil from the Usa field (Timan-Pechora oil-and-gas province, Russia) obtained by fractional precipitation of asphaltenes and chromatographic separation of resins have been analyzed using Rock-Eval pyrolysis and flash pyrolysis (650°C, 20 s) with on-line chromatographic/mass spectral detection of volatile products. It has been shown that the samples under study contain organic compounds with a relatively low molecular mass in an amount of 2.3 to 15.3 wt % as either impurities or moieties bound in resin and asphaltene molecules by labile chemical bonds. The products of flash pyrolysis of the samples under study differ in the relative amount of the “unresolvable complex mixture” of unidentified compounds; the chemical group and molecular composition; and the relative amount of identified types of compounds, such as normal and isoprenoid alkanes, α-olefins, cyclohexanes, cheilanthanes and hopanes, hopenes, pregnanes and steranes, alkylbenzenes, naphthalenes, phenanthrenes and anthracenes, and benzo- and dibenzothiophenes.     

PREPARATIVE SIZE-EXCLUSION CHROMATOGRAPHY SEPARATION OF SHRP ASPHALTS: CORRELATION WITH YISCOELASTIC PROPERTIES

ABSTRACT

Eight core asphalts and eleven other asphalts selected for study in the Strategic Highway Research Program have been separated into two or more fractions by means of preparative size-exclusion chromatography. The first fraction obtained by this technique is believed to consist of materials that form associations and correspond roughly to asphalt dispersed phases. This phase is polar, aromatic, and of high apparent molecular weight. Subsequent fractions obtained by size exclusion chromatography of the asphalts are of progressively lower molecular weight. When the asphalts were separated into nine fractions, the weights of each fraction were plotted versus elution volume to give distinctive bimodal chromatograms, with one exception.

The first eluted size exclusion fractions consist of the major viscosity-building components of the asphalts. When these fractions are removed from asphalts, the weight fractions of the residual materials correlate with tan δ (ratio of viscous to elastic moduli)s of the whole asphalts at 26° (77°F). Gel-type asphalts have low values of tan δ and large amounts of material in their initially eluted size-exclusion chromatography fractions. For sol-type asphalts, the reverse is true. For the nineteen asphalts studied size-exclusion chromatography fractionation patterns, which are a fundamental chemical property, correlate with the aforementioned fundamental physical property     

THE EFFECT OF ANTIOXIDANT ADDITIVE ON THE THERMOXIDATION STABILITY OF DISTILLATES FROM MEDIUM CRUDE OIL

ABSTRACT

Fractions 100-150, 150-200, 200-250°C were distilled from medium Iraqi crude oil. The thermo-oxidation stability experiments were carried out on original and inhibited (with Topanol 0) distillate fractions using the Alcor Jet Fuel Thermal Tester, over a temperature range 516-573 k. It was found that the antioxidant (Topanol 0) efficiency depends on the fractions composition and the oxidation temperature. Only 30 PPM of Topanol 0 stabilizes fraction 100-150°C to a considerable extent. Also, an inhibition effect is obtained in fraction 150-200°C but at a higher antioxidant concentration (90 PPM). Only, slight inhibition effect was observed in fraction 200-250°C at low oxidation temperature (below 551 K), while effect will be of no value at higher oxidation temperatures.     

DEVELOPMENT OF HIGH-PERFORMANCE HEAVY OIL HYDROCRACK1NG CATALYSTS: CHARACTERIZATION OF ATMOSPHERIC RESIDUE FEED

ABSTRACT

The characterization results of the atmospheric residue obtained from Saudi Arabian Light crude oil show the complex nature and composition of this material. The distillation results showed that about 50 percent of Arab Light crude is the atmospheric residue. The elemental analysis of the residue showed that high amount of carbon, sulfur and nitrogen is present along with heavy metals such as nickel and vanadium. The determination of hydrocarbon types by HPLC exhibited that 12% polars and 27% aromatics are present along with 6% asphaltenes. Nuclear magnetic resonance study conducted on the residue and its fraction provides a detailed composition in terms of aliphatic and aromatic nature of the residue and its fractions. The results showed that the residue contains 21% aromatic and 79% aliphatic carbon. The aliphatic carbon is present in saturates and as side chains of aromatic and polar molecules whereas the aromatic carbons are those in the ring structure. Asphaltenes separated from the residue were characterized for their different properties to understand its complexity. The use of electron spin resonance spectroscopy provides determination of the free radicals present in the residue. Asphaltenes were analyzed using the state-of-the-art high temperature high pressure electron spin resonance (ESR) technique in the temperature range 20 to 625 °C and at 30 and 50 bar hydrogen pressure. The ESR determination at 30 bar shows that me pressure was not enough to prevent the boiling of the asphaltene and thus a decrease in the spin concentration was observed beyond 350 °C temperature. The data at 50 bar pressure showed the adequacy of this pressure for ESR measurement. The PMRTA analysis of asphaltene showed a decrease in residual hydrogen with increasing temperature.     

VARIATION IN THE CHEMICAL NATURE OF ASPHALTENES WITH THE PROCESS, THE COAL AND THE REACTION CONDITIONS

Average structure data for twelve asphaltenes are reported, based on ¹³C- and H- n.m.r. spectroscopy combined with elemental, molecular weight and functional group analyses. The asphaltenes were from supercritical gas extraction, flash pyrolysis and hydrogenation of a brown and a bituminous coal. The effect of the reaction temperature and, for hydrogenation, the catalyst and solvent on the nature of the asphaltene produced was studied. The asphaltene obtained from supercritical gas extraction of the brown coal at 350°C was the least aromatic (f_a = 0.44) with the highest H/C atomic ratio (1.16) and probably consists mainly of single ring aromatlcs with about half of the aromatic sites substituted. A significant proportion of the carbon in this asphaltene is in long alkyl chains and the hydroxyl content is high. Whereas, the asphaltenes produced by hydrogenatlon of the bituminous coal at 450°C were far more aromatic with more highly condensed but less substituted aromatic ring systems and few, if any, long alkyl chains, together with a lower hydroxyl content. The asphaltenes obtained from the brown coal are less aromatic with less condensed aromatic ring systems but a higher degree of aromatic substitution than those produced from the bituminous coal under the same conditions. The asphaltenes formed at 450°C had lower H/C atomic ratios, molecular weights and degree of aromatic substitution, but higher aromaticities Ohan those produced at 35O°C or 400°C under like processing conditions. The asphaltene produced in the presence of both stannous chloride catalyst and tetralin was less aromatic than when either of these species was absent.     

Variation in Composition of Subfractions of Petroleum Asphaltenes

ABSTRACT

Boscan asphaltenes were precipitated from the crude oil using mixtures of toluene and heptane at temperatures of 24, 50, and 80°C. Another process of extracting solid n-heptane asphaltenes (24°C) using the same solvent systems and temperatures was also investigated. Asphaltene yield is different by the two processes at similar conditions although both increases in temperature or toluene content lead to lower solid yield. This way the asphaltene continuum was investigated from incipient flocculation to total n-heptane precipitated asphaltenes. The asphaltenes were analyzed using elemental analysis, fluorescence spectroscopy, vapor pressure osmometry, and HPLC size exclusion chromatography. The distribution of porphyrins was also measured using absor-bance spectroscopy. The asphaltenes were found to follow a regular trend in elemental ratios, H/C and N/C, indicating increased aromaticity and nitrogen content as the solid yield decreases. Also the molecular weight was seen to increase. Size exclusion chro-matograms and fluorescence spectra were found to be different comparing solids from the two separation processes. This indicates that the asphaltene fractions obtained by extraction of solid asphaltenes are altered relative to asphaltenes obtained by ordinary precipitation. The porphyrin concentration was found to diminish rapidly with solid yield decrease in both precipitation and extraction experiments, the latter fractions, however, containing significantly less asphaltenes indicating an adsorption step in the coprecipitation of porphyrins. Soluble fractions were found to exhibit relatively low molecular weights and an apparent lack of indications of association up to a point of solubles exceeding 50 % of the total asphaltenes. The-latter have implications for the further understanding and experimental investigation. of the associating nature of asphaltenes such as concentration effects during analytical characterization.     

Hydrotreating of Furrial Crude Oil Using NiMoS Supported on Alumina: Study of the Asphaltene and Their Fractions in Cyclohexane

Abstract

The Furrial crude oil originated in northern Monagas State. This shows problems such as the colloidal instability of the asphaltenes fraction present in them, causing its precipitation. This work is oriented to achieve an interpretation of the colloidal behavior of the asphaltenes through the study of the effect of the hydrotreating reactions (HDT) on the asphaltenes of the Furrial crude oil, using NiMoS/γ-Al₂O₃ as a catalyst. The results obtained after HDT reactions were analyzed to know the percentage of asphaltene and their fractions in cyclohexane, the measurement of flocculation thresholds and molecular weights by the VPO technique, and ¹³C NMR as well as the determination of the total sulfur content. Appreciable changes on the asphaltene of the Furrial crude oil and its fractions in cyclohexane after HDT, under conditions used, were observed. In general terms, the amount of asphaltene diminished and the percentage of distribution for insoluble fraction in cyclohexane (IFC) and for soluble fraction in cyclohexane (SFC) was affected causing an increase in the stability of the asphaltene. The asphaltene and IFC were observed to be a pronounced variation of the molecular weight average in number, in comparison with SFC. ¹³C NMR spectra indicate that the hydrotreated asphaltene shows structural change, and IFC presents a variation of the percentage of sulfur minor in comparison to SFC.     

Application of Coker Gas Oil Used as Industrial Hydrogen Donors in Visbreaking

Effectiveness of coker gas oil (CGO) used as industrial hydrogen donors in the visbreaking was revealed. Hydrogen-transferring abilities of different CGO narrow fractions were first analyzed. The fraction of 350–420°C (HDII) turned out to be the best selection as hydrogen donors and then we did visbreaking experimental tests. The results show that, in contrast with conventional visbreaking, the addition of HDII achieves higher conversion of residues to desirable liquid product and effectively suppresses coke formation: the coke induction period is prolonged from 17 to 27 min and the liquid-coke particle size decreases from 0.307 to 0.186 μm. The hydrogen shuttle between asphaltene and hydrogen donors is of great significance during this thermal processing.     

AGGREGATION OF ASPHALTENES OBTAINED FROM A BRAZILIAN CRUDE OIL IN AROMATIC SOLVENTS

Abstract

Surface and interfacial tensions in model systems formed by a Brazilian crude oil n-pentane insolubles (C5I) and n-heptane insolubles (C7I) in three different aromatic solvents: toluene, pyridine and nitrobenzene, were measured at room temperature, employing an automatic tensiometer and using the ring method. The results obtained indicated possible asphaltene aggregation and allowed the determination of critical micelle concentrations (c.m.c) for both C5I and C7I fractions in each of the three solvents considered. In toluene and pyridine solutions, the C5I fraction consistently presented higher c.m.c. values indicating a lower tendency of association for the organic fraction contained in the C5I, and absent in the C7I. In nitrobenzene solutions, this extra organic fraction appears to facilitate asphaltene association, possibly due to the formation of mixed aggregates. Average molecular areas for asphaltenes adsorbed at different interfaces were estimated using measured tensions and found to be in agreement with literature values and suggest a the flatwise surface adsorption of asphaltene molecules. This is consistent with the currently accepted stacking aggregation mechanism of asphaltenes.     

Rheology of Middle Distillate. I. Role of Composition

Abstract

The rheological behavior of middle distillate (250–375°C) fraction, obtained from the waxy Bombay-High Off-shore crude oil, and its five narrow sub-fractions of 25°C interval each, i.e., Fr 1 (250–275°C), Fr 2 (275–300°C), Fr 3 (300–325°C), Fr 4 (325–350°C), and Fr 5 (350–375°C), have been studied below their ASTM pour point temperatures. The rheograms (the shear stress vs. rate of shear) of the fraction and sub-fractions, at various temperatures below their pour points, are recorded on a Haake RV-12 Co-axial Rota Viscometer fitted with a NV sensor and a temperature programmer (PG-20) and attached with a programmed heating/cooling system. From these rheograms the flow parameters like plastic viscosity, apparent viscosity, and yield stress are obtained and their variations with temperature and shear rate have been studied in terms of compositions of the fraction/sub-fractions. These results might be useful in devising methodology for overcoming the wax separation phenomenon from middle distillates at low temperatures.