Characterization of Thermally Degraded Asphaltene Fractions Using Gel Permeation Chromatography

Abstract

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.     

Changes in Asphaltenes Properties Modified with Fe in Hydrotreating Reactions

Abstract

The properties of the Hamaca of asphaltenes extra-heavy crude oil (AsfH) of Petroliferous Orinoco Belt can be modified for evaluating the changes produced with hydrotreating (HDT). One characterized the solid modified by means of UV-visible spectroscopy and nuclear magnetic proton resonance (NMR ¹H). The samples were put under hydrotreating to 200°C to avoid thermal cracking, atmospheric pressure, and a flow of feeding of 10.5 mL/hr in a fixed-bed reactor in the presence of H₂S generated in situ. The reactivity was followed by gas chromatography (GC). All the samples were evaluated before and after being hydrotreated by ¹H NMR, total sulfur analysis, and determination of molecular weight average by vapor pressure osmometry (VPO). The obtained results suggest the iron possibly is inserted in the structure of the asphaltene forming a new active phase catalytically, presumably a mixed sulfide (pyrrotite type) of iron-metal of transition (V and Ni) present in the asphaltene.     

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.     

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.     

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.     

Experimental investigation of dodecylbenzene sulfonic acid and toluene dispersants on asphaltene precipitation of dead and live oil

Asphaltene is the heaviest fraction of oil, and if the thermodynamic conditions of oil change, it can be separated from oil precipitate. Of common methods for preventing asphaltene precipitation, using predictive methods, biological methods and injection of dispersants can be mentioned. In this study, the effect of two dispersants of toluene and dodecylbenzene sulfonic acid on asphaltene precipitation of a dead and a live oil sample has been investigated. According to the results, these dispersants in dead oil create an optimum point for asphaltene precipitation. In live oil, these dispersants reduce asphaltene precipitation down to 70%. In addition, it was observed that as an effect of injecting these dispersants, the average sizes of asphaltene flocculation have reduced.     

Soil Microbial Degradation of Vacuum Residue

Abstract

The effect of microbial consortia on the alteration of petroleum residual structure and portions was studied, which can propose an alternative or complementary method for stringent upgrading heavy crude oil methods, which consist of heavy and complex hydrocarbons. Biological processing of petroleum heavy fractions and residua may provide an alternative or complementary process in refining heavy crudes—the dominant refinery feed in the future—with less severe process conditions and higher selectivity to upgrade heavy fractions of crude oil. The primary objective was to observe the ability of an indigenous bacterial consortium taken from a soil bellow the vacuum column contaminated with vacuum residue (VR) for several decades from the Tehran refinery distillation unit, in degradation of residua components. Enrichment with VR, as sole source of carbon and energy, is the selected biosurfactant-producing microbial consortium. The biodegradation of net VR using indigenous consortia from this specific ecosystem was studied. The considered period of biodegradation of these heavy hydrocarbons was remarkably shorter than usual studies. Bacterial growth and VR biodegradation ability of this consortium analyzed with SARA test in 20 days. Studying the inoculum size and aeration effect revealed the significance of oxygen for this consortia activity and the similarity of 7% and 5% inoculation on alteration percentage of alkane, aromatic, and asphaltene and resin in VR. Results study revealed a 30.4%, 6.9%, and 9.4% decrease in the asphaltene, aromatics, and saturated aliphatic contents of VR, respectively, in only 20 days in 30°C at 150 rpm.     

Experimental and modeling analysis of asphaltene precipitation in the near wellbore region of oil wells

In this work, effect of reservoir temperature (in a range of 50–100°С) on the amount of asphaltene precipitation was determined. Rate of asphaltene precipitation was increased by increasing temperature. Damaged permeability of carbonate core samples was investigated at different asphaltene contents conducting core flood tests. The results showed the experimental and predicted data of damaged permeability ratio due to asphaltene precipitation matched. Moreover, the optimum mass concentration of components of the developed asphaltene inhibitor was determined by measuring interfacial tension on the boundary of oil and inhibitor solution. In addition, the change in the concentration of asphaltene inhibitor was simulated depending on the radial distance to well, production time and type of isotherm.     

Study of asphaltene deposition from Tahe crude oil

Borehole blockage caused by asphaltene deposition is a problem in crude oil production in the Tahe Oilfield, Xinjiang, China. This study has investigated the influences of crude oil compositions, temperature and pressure on asphaltene deposition. The asphaltene deposition trend of crude oil was studied by saturates, aromatics, resins and asphaltenes (SARA) method, and the turbidity method was applied for the first time to determine the onset of asphaltene flocculation. The results showed that the asphaltene deposition trend of crude oil by the turbidity method was in accordance with that by the SARA method. The asphaltene solubility in crude oil decreased with decreasing temperature and the amount of asphaltene deposits of T739 crude oil (from well T739, Tahe Oilfield) had a maximum value at 60 o C. From the PVT results, the bubble point pressure of TH10403CX crude oil (from well TH10403CX, Tahe Oilfield) at different temperatures can be obtained and the depth at which the maximum asphaltene flocculation would occur in boreholes can be calculated. The crude oil PVT results showed that at 50 , 90 and 130 o C, the bubble point pressure of TH10403CX crude oil was 25.2, 26.4 and 27.0 MPa, respectively. The depth of injecting asphaltene deposition inhibitors for TH10403CX was determined to be 2,700 m.     

Effect of pressure,temperature, and mass fraction of CO2 on the stability of the asphaltene constituents in crude oil

This paper focus on the main influence factors (temperature, pressure, and mass fraction of CO₂) on the state of asphaltene in the crude oil during CO₂ flooding by using high temperature and high pressure microanalysis system of solid precipitation. For the simulated oil sample – CO₂ system, the state of asphaltene is not affected by temperature within this range of 50°C to 100°C, the particle size of the asphaltene has an increase with the increase of the pressure from 8MPa to 40 MPa. When the mass fraction of CO₂ is less than 35%, the state of the asphaltene has not changed and the asphaltene particles are in a suspension state. When the mass fraction of CO₂ increases to 40%, the aggregation of the asphaltenes occurs and then form precipitation. With the further increase of the mass fraction of CO₂, the particle of the asphaltene aggregates has a significant increase. For the field development project design of CO₂ flooding, the influence of the temperature can be ignored, the appropriate mass fraction of CO₂ is below 35% and the gas injection pressure should maintain a relatively low value. The results can provide a theoretical basis to avoid the asphaltene precipitation during CO₂ flooding.     

水力空化改质对减压渣油性质的影响

利用水力空化过程产生局部的高温、高压、高射流以及强大的剪切力等极端化学物理条件改质处理减压渣油,改质处理后减压渣油的密度、黏度、残炭等理化性能均得到改善.通过APPI FT-IR、沥青质粒径分布技术和多重光散射技术进一步研究了减压渣油水力空化改质机理.结果表明:水力空化改质后减压渣油相对分子质量分布、芳烃类化合物缔合作...     

Changes in Asphaltenes Properties Modified with Fe in Hydrotreating Reactions

The properties of the Hamaca of asphaltenes extra-heavy crude oil (AsfH) of Petroliferous Orinoco Belt can be modified for evaluating the changes produced with hydrotreating (HDT). One characterized the solid modified by means of UV-visible spectroscopy and nuclear magnetic proton resonance (NMR ¹H). The samples were put under hydrotreating to 200°C to avoid thermal cracking, atmospheric pressure, and a flow of feeding of 10.5 mL/hr in a fixed-bed reactor in the presence of H₂S generated in situ. The reactivity was followed by gas chromatography (GC). All the samples were evaluated before and after being hydrotreated by ¹H NMR, total sulfur analysis, and determination of molecular weight average by vapor pressure osmometry (VPO). The obtained results suggest the iron possibly is inserted in the structure of the asphaltene forming a new active phase catalytically, presumably a mixed sulfide (pyrrotite type) of iron-metal of transition (V and Ni) present in the asphaltene.     

新型油溶性沥青质分散剂抑制重质原油沥青质沉积的研究

针对新疆重质原油沥青质沉积严重的问题,以聚异丁烯丁二酸酐、苯胺和对氨基苯酚为原料合成了尾部基团为高度枝链化的聚异丁烯基,头部基团分别为苯基及酚羟基的新型油溶性沥青质分散剂PA1和PA2。采用分光光度法与显微镜法评价了所合成分散剂对沥青质沉积的抑制效果。实验结果表明,分散剂PA2抑制沥青质沉积作用效果优于PA1。通过对分散剂PA2抑制沥青质沉积作用效果的评价,确定了最佳合成条件：对氨基苯酚与聚异丁烯丁二酸酐摩尔比为1.2,反应温度为120 ℃,反应时间为6 h。在分散剂PA2加入量为200 mg/L的条件下可以将新疆重质原油的初始絮凝点由-19.87提高到8.63,显著改善了新疆重质原油稳定性。     

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.     

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.     

Thermal stability and sorption properties of asphaltene sulfocathionites

Abstract

Using simultaneous thermogravimetry and differential scanning calorimetry, thermal stability and possible phase transitions of asphaltene sulfocationites and native asphaltenes have been evaluated; the kinetic characteristics of heating have been determined, namely, onset temperature of decomposition, stages of decomposition, and temperature ranges of stability. It has been determined that asphaltene sulfocationites retain structural-group features (IR spectroscopy method) and sorption characteristics while heating up to 350?°C.     

The Effect of Temperature and Pressure on the Reversibility of Asphaltene Precipitation

A lot of hindrances are seen in petroleum operation, production, and transportation as a results of factors that related to asphaltene precipitation. It has great importance to investigate the reversibility of asphaltene precipitation under changes of effective factors on thermodynamic conditions such as pressure, temperature, and composition. In the present work the reversibility of asphaltene precipitation under changes of pressure and temperature was investigated for two kind of Iranian heavy oil. The stability test shows these samples are located at unstable region in aspect of asphaltene precipitation. The experimental procedure includes two parts, (a) decreasing pressure from initial reservoir pressure to near saturation pressure and surveying asphaltene content hysteresis with redissolution process at reservoir temperature, and (b) investigation of precipitated asphaltene in both precipitation and redissolution processes at different temperature and reservoir pressure. At each step IP143 standard test was used to measure precipitated asphaltene. It was concluded that above bubble point pressure, asphaltene precipitation is nearly reversible with respect to pressure for both samples and it was partially reversible with respect to the temperature for sample A, and accordingly pressurizing is acceptable method for solving the problem in both heavy asphaltenic crude oil samples and increasing temperature is acceptable method for solving asphaltene problem in crude oil sample A. Also density measurement of flashed oil confirmed that there is a little hysteresis in asphaltene content during redissolution and precipitation processes.     

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.     

加氢反应温度对塔河沥青质结构组成的影响

以塔河常压渣油的正庚烷沥青质为原料,在高压釜内考察了加氢反应温度对沥青质结构组成的影响。结果表明,与原生沥青质相比,加氢后次生沥青质的H/C原子比、平均相对分子质量、单元薄片数目和芳香环系缩合度参数HAU/CA均减小,芳碳率fA增大;加氢后沥青质单元薄片的平均相对分子质量增大,Hα、Hβ和Hγ减小,HA增加,总环数RT和芳香环数RA也都明显增加,质子芳碳比例增加,取代芳碳比例减小,表明沥青质在加氢过程中发生了明显的烷基侧链和单元薄片的脱除反应及少量的脱氢缩合反应。随加氢反应温度升高,沥青质结构参数的变化更明显,且在653～673 K范围时各结构参数的变化幅度最大。     

An Experimental Investigation of Asphaltene Precipitation During Natural Production of Heavy and Light Oil Reservoirs: The Role of Pressure and Temperature

Abstract

Many oil reservoirs encounter asphaltene precipitation as a major problem during natural production. In spite of numerous experimental studies, the effect of temperature on asphaltene precipitation during pressure depletion at reservoir conditions is still obscure in the literature. To study their asphaltene precipitation behavior at different temperatures, two Iranian light and heavy live oil samples were selected. First, different screening criteria were applied to evaluate asphaltene instability of the selected reservoirs using pressure, volume, and temperature data. Then, a high pressure, high temperature filtration (HPHT) setup was designed to investigate the asphaltene precipitation behavior of the crude samples throughout the pressure depletion process. The performed HPHT tests at different temperature levels provided valuable data and illuminated the role of temperature on precipitation. In the final stage, the obtained data were fed into a commercial simulator for modeling and predicting purposes of asphaltene precipitation at different conditions. The results of the instability analysis illustrated precipitation possibilities for both reservoirs which are in agreement with the oil field observations. It is observed from experimental results that by increasing the temperature, the amount of precipitated asphaltene in light oil will increase, although it decreases precipitation for the heavy crude. The role of temperature is shown to be more significant for the light crude and more illuminated at lower pressures for both crude oils. The results of thermodynamic modeling proved reliable applicability of the software for predicting asphaltene precipitation under pressure depletion conditions. This study attempts to reveal the complicated role of temperature changes on asphaltene precipitation behavior for different reservoir crudes during natural production.