Deasphalting of crude oils using supercritical fluids

A crude oil has four main SARA constituents: saturates, aromatics, resins, and asphaltenes. The asphaltenes in crude oil are the most complex and heavy organic compounds. The asphaltenes contain highly polar substituents and are insoluble in an excess of n-heptane (or n-pentane). The classic definition of asphaltenes is based on the solution properties of petroleum residuum in various solvents. Asphaltenes are a solubility range that is soluble in light aromatics such as benzene and toluene, but is insoluble in lighter paraffins. The particular paraffins, such as n-pentane and n-heptane, are used to precipitate asphaltenes from crude oil. The effects of four different solvents (water, carbon dioxide, propane, and ethanol) on the deasphalting process under the supercritical conditions were reviewed. Supercritical water is an excellent solvent for removing of high molecular weight organic compounds such as asphaltenes from crude oils under the supercritical conditions.     

Influence of resins and asphaltenes on thermal transformations of hydrocarbons of paraffin-base heavy crude oil

Thermal transformations of petroleum components of paraffin-base heavy crude oil and oils (hydrocarbon concentrate), a mixture of oils and resins (maltenes), and a mixture of oils with asphaltenes isolated from the crude have been studied in order to assess the effect of resins and asphaltenes on the hydrocarbon conversion direction. Thermolysis of samples has been conducted at 450°C for 2 h in the isothermal mode. Data on the material balance of the process have been obtained, and the composition of the gaseous and liquid products of thermolysis has been determined. The gaseous products of thermolysis consist of hydrogen, carbon dioxide, and C₁–C₅ hydrocarbons. It has been shown that the thermolysis of all the samples is accompanied by the appearance of newly formed resins and asphaltenes. Analysis of the dynamics of changes in the hydrocarbon composition of the liquid thermolysis products has shown that the resins, rather than asphaltenes affect to a greater extent the direction of hydrocarbon cracking reactions.     

Transformations of resins and asphaltenes in photoirradiation

The photooxidative transformations of resins and asphaltenes in petroleum residues were investigated by IR spectroscopy. In photooxidation, these substances undergo both degradation and condensation. Gaseous products are formed in degradation–hydrogen, low-molecular-weight alkanes, formaldehyde, carbon monoxide and dioxide, and in condensation, highly condensed aromatic structures and oxidation products insoluble in organic solvents are formed. __________ Translated from Khimiya i Tekhnologiya Topliv i Masel, No. 5, pp. 39–42, September–October, 2007.     

石油沥青质超分子聚集及解聚研究进展

石油沥青质组成复杂,氢/碳原子比低,硫、氮等杂原子含量高,给石油开采、运输和加工处理带来困难,究其原因是石油沥青质分子结构复杂,极易发生超分子聚集,形成聚集体。目前对沥青质超分子聚集的认识越来越广泛,并被石油化学工作者广泛接受。沥青质超分子聚集是通过电荷转移作用、偶极作用以及氢键作用形成沥青质分子之间的缔合,这些弱相互作用在石油体系的分子间普遍存在,实现沥青质聚集体的解聚是重质油高效轻质化的基础。研究表明,采用化学方法改变沥青质分子结构或采用物理方法改变沥青质物理状态,均能在一定程度上使得沥青质聚集体解聚。     

Structural Studies on Residual Fuel Oil Asphaltenes by RICO Method

Abstract

Structural characterization of asphaltenes isolated from Saudi Arabian heavy and medium crude oils was undertaken by using ruthenium ion catalyzed oxidation (RICO) method. The RICO method was capable to convert aromatic carbons selectively into carbon dioxide and carboxylic acids and esters group while leaving aliphatic and naphthenic structures of asphaltenes essentially unaffected. Detailed analyses of RICO products of both Arab heavy and Arab medium asphaltenes were conducted using FT-IR, ¹³C-NMR, IC, GPC, and GC-MS techniques. These analyses indicate that the aqueous phase fraction (water-soluble products) obtained from RICO reaction of asphaltenes consists of aliphatic dicarboxylic acids and aromatic poly carboxylic acids with longer alkyl chains. The ¹³C-NMR and GC-MS analyses of organic phase products of asphaltenes indicate that this fraction contains large amount of aliphatic carboxylic acids with longer alkyl groups. The oxidation products of both Arab heavy and Arab medium asphaltenes were found to be dominated by a homologous series of straight chain monocarboxylic acids suggesting that the normal alkyl chains are major and important constituents of the chemical structure of both asphaltenes.     

CHANGES IN THE COMPOSITION AND PROPERTIES OF THE VACUUM RESIDUES AS A RESULT OF VISBREAKING

ABSTRACT

Two vacuum residues of heavy petroleum blends and residues of the products of their visbreaking, on a commercial unit, were investigated by means of column chromatography, cryoscopic analysis, elemental analysis, NMR spectroscopy, etc. An increase in the contents of asphaltenes and saturated, increase in asphaltenes/polar components ratio, and decrease in the aromatics contents during visbreaking were observed for both kinds of feed. The N/C ratio increased, the S/C ratio did not change significantly. Most of the nickel and vanadium were concentrated in the asphaltenes and aromatics. The length of the paraffinic chains of the saturated decreases during visbreaking from about 50 to 30 carbon atoms. The number of carbon atoms per alkyl chain and the number of naphthenic rings in the average molecule of the aromatics decreased, whereas the number of aromatic rings increased. About 2/3 of the total aromatic carbon in the aromatics are non-bridged. The average asphaltenes molecule contains about 36-38 aromatic rings (mostly condensed), 5-7 naphthenic rings and 12-16 alkyl substituents having relatively short (n = 5-6) chains. Two contrary processes, relating asphaltenes, take place during visbreaking: 1) cracking of asphaltenes, which results in a decrease in their content and molecular weight, decrease in the number of the side chains and their length, and increase in asphaltenes aromaticity; 2) asphaltenes formation from the polar components of the feed. The resulting process may be expressed both in a decrease and in an increase in the asphaltenes content. Reactions of condensation of the asphaltenes precursors (resins, etc.) prevail for the light stocks. For heavier stocks, cracking of the asphaltenes plays a more significant role, and the increase in asphaltenes content takes place mainly due to concentrating them in the visbreaking residue as a result of the distillation of the visbroken product.     

PREDICTING THE TIMING AND CHARACTERISTICS OF PETROLEUM FORMATION USING TAR MATS AND PETROLEUM ASPHALTENES: A CASE STUDY FROM THE NORTHERN NORTH SEA

The Northern Viking Graben area in the Norwegian North Sea was studied in order to investigate the petroleum formation characteristics of the Upper Jurassic Draupne Formation. In this area, the organofacies of the Draupne Formation, and consequently its petroleum generation characteristics, show significant variations. These variations represent a major risk, particularly in the context of basin modelling studies. Therefore, tar‐mat asphaltenes, oil asphaltenes and source‐rock samples from this area were studied in order to evaluate the use of migrated asphaltenes from petroleum reservoirs and tar mats in basin modelling. The samples were studied using bulk kinetic analysis, open‐system pyrolysis‐gas chromatography and elemental analyses, and the results were integrated into a basin modelling study. The results from these different sample materials were compared both to each other and to natural petroleum, in order to assess their significance for future petroleum exploration activities. We show that in cumulative petroleum systems, the transformation characteristics of the asphaltenes incorporate those of the individual source rock intervals which have contributed to the relevant reservoir system. Thus, the petroleum formation window predicted by the use of asphaltene kinetics is broad, and covers the majority of the formation windows predicted from the individual source rock samples. In addition, the molecular characteristics of asphaltene‐derived hydrocarbons show that compositional characteristics, such as aromaticity, correspond more closely to natural oils than to the respective source‐rock products. Our results confirm that the heterogeneous nature of the Draupne Formation results in a significantly broader petroleum formation window than is conventionally assumed. We propose that oil and tar‐mat asphaltenes from related reservoirs represent macromolecules which account for this heterogeneity in the source rock, since they represent mixtures of charges from the different organofacies. One conclusion is that the use of oil and tar‐mat asphaltenes in kinetic studies and compositional predictions may significantly improve definitions of petroleum formation characteristics in basin modelling.     

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.     

STRUCTURAL TYPES IN PETROLEUM ASPHALTENES AS DEDUCED FROM PYROLYSIS/GAS CHROMATOGRAPHY/MASS SPECTROMETRY

An integrated technique has been developed for the study of the thermal chemistry of petroleum fractions—particularly the asphaltenes. The procedure involves the integrated use of a pyroprobe/gas chroma-tographic/mass spectrometric technique which offers information about the structuraI-types and distribution within the volatile products from the thermal decomposition of asphaltenes. The technique offers itself as an attractive on-line analytical method for the study of structural types that occur in asphaltenes as well as a technique for studying the parameters that can influence asphaltene decomposition. The concept of deducing “average” structures of asphaltenes is briefly discussed in terms of the observance of the lower molecular weight species in the volatile products of the thermal decomposition.     

CHANGES IN THE COMPOSITION AND PROPERTIES OF THE VACUUM RESIDUES AS A RESULT OF VISBREAKING

Two vacuum residues of heavy petroleum blends and residues of the products of their visbreaking, on a commercial unit, were investigated by means of column chromatography, cryoscopic analysis, elemental analysis, NMR spectroscopy, etc. An increase in the contents of asphaltenes and saturated, increase in asphaltenes/polar components ratio, and decrease in the aromatics contents during visbreaking were observed for both kinds of feed. The N/C ratio increased, the S/C ratio did not change significantly. Most of the nickel and vanadium were concentrated in the asphaltenes and aromatics. The length of the paraffinic chains of the saturated decreases during visbreaking from about 50 to 30 carbon atoms. The number of carbon atoms per alkyl chain and the number of naphthenic rings in the average molecule of the aromatics decreased, whereas the number of aromatic rings increased. About 2/3 of the total aromatic carbon in the aromatics are non-bridged. The average asphaltenes molecule contains about 36-38 aromatic rings (mostly condensed), 5-7 naphthenic rings and 12-16 alkyl substituents having relatively short (n = 5-6) chains. Two contrary processes, relating asphaltenes, take place during visbreaking: 1) cracking of asphaltenes, which results in a decrease in their content and molecular weight, decrease in the number of the side chains and their length, and increase in asphaltenes aromaticity; 2) asphaltenes formation from the polar components of the feed. The resulting process may be expressed both in a decrease and in an increase in the asphaltenes content. Reactions of condensation of the asphaltenes precursors (resins, etc.) prevail for the light stocks. For heavier stocks, cracking of the asphaltenes plays a more significant role, and the increase in asphaltenes content takes place mainly due to concentrating them in the visbreaking residue as a result of the distillation of the visbroken product.     

Structural Studies on Residual Fuel Oil Asphaltenes by RICO Method

Structural characterization of asphaltenes isolated from Saudi Arabian heavy and medium crude oils was undertaken by using ruthenium ion catalyzed oxidation (RICO) method. The RICO method was capable to convert aromatic carbons selectively into carbon dioxide and carboxylic acids and esters group while leaving aliphatic and naphthenic structures of asphaltenes essentially unaffected. Detailed analyses of RICO products of both Arab heavy and Arab medium asphaltenes were conducted using FT-IR, ¹³C-NMR, IC, GPC, and GC-MS techniques. These analyses indicate that the aqueous phase fraction (water-soluble products) obtained from RICO reaction of asphaltenes consists of aliphatic dicarboxylic acids and aromatic poly carboxylic acids with longer alkyl chains. The ¹³C-NMR and GC-MS analyses of organic phase products of asphaltenes indicate that this fraction contains large amount of aliphatic carboxylic acids with longer alkyl groups. The oxidation products of both Arab heavy and Arab medium asphaltenes were found to be dominated by a homologous series of straight chain monocarboxylic acids suggesting that the normal alkyl chains are major and important constituents of the chemical structure of both 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.     

沥青质中官能团结构和氢键的红外光谱表征

利用傅里叶红外光谱表征渣油沥青质和煤焦油沥青质分子的官能团结构,并通过软件Origin 2018对沥青质红外光谱的氢键区、脂肪族碳氢伸缩振动区和C—O区的吸收峰进行分峰拟合。结果表明：两种沥青质均主要以碳、氢元素为主,二者杂原子的含量存在明显差异,但杂原子官能团的类型基本相同;渣油沥青质中的氢键主要是由苯环O—H与芳香醚键中的O原子、O—H自缔合形成的氢键,而煤焦油沥青质中的氢键主要是苯环O―H与芳香醚键中的O原子形成的氢键;与渣油沥青质相比,煤焦油沥青质的烷基侧链更短。     

EVALUATION OF PARAFFINIC MATERIAL IN ASPHALTENES ISOLATED BY PRECIPITATION WITH LIGHT ALKANES

ABSTRACT

The precipitation of paraffins by the methods usually employed for isolation and quantification of asphaltenes was verified by a brief characterization of n-alkane insoluble material from a paraffinic petroleum. So, a technique was sought to allow ready detection of these paraffins in n-pentane and n-heptane asphaltenes of heavy petroleum fractions of interest, and that was achieved by the use of differential scanning calorimetry. Liquid chromatography, which might yield material for further characterization, was also studied, with high temperature elutions, but it could not resolve groups with asphaltenes as the initial sample.     

MOLECULAR SIZE AND STRUCTURE OF ASPHALTENES

Fluorescence depolarization measurements are used to determine the size of asphaltene molecules and of model compounds for comparison. Mean molecular weights of 750 amu have been found for petroleum asphaltenes. A strong correlation is established between the size of fused rings in asphaltene molecules and the overall size of these molecules, showing that asphaltenes have one or perhaps two fused ring systems per molecule. Coal asphaltene molecules are found to be much smaller than petroleum asphaltenes.     

STRUCTURAL TYPES IN PETROLEUM ASPHALTENES AS DEDUCED FROM PYROLYSIS/GAS CHROMATOGRAPHY/MASS SPECTROMETRY

ABSTRACT

An integrated technique has been developed for the study of the thermal chemistry of petroleum fractions—particularly the asphaltenes. The procedure involves the integrated use of a pyroprobe/gas chroma-tographic/mass spectrometric technique which offers information about the structuraI-types and distribution within the volatile products from the thermal decomposition of asphaltenes. The technique offers itself as an attractive on-line analytical method for the study of structural types that occur in asphaltenes as well as a technique for studying the parameters that can influence asphaltene decomposition. The concept of deducing “average” structures of asphaltenes is briefly discussed in terms of the observance of the lower molecular weight species in the volatile products of the thermal decomposition.     

MOLECULAR SIZE AND STRUCTURE OF ASPHALTENES

Fluorescence depolarization measurements are used to determine the size of asphaltene molecules and of model compounds for comparison. Mean molecular weights of 750 amu have been found for petroleum asphaltenes. A strong correlation is established between the size of fused rings in asphaltene molecules and the overall size of these molecules, showing that asphaltenes have one or perhaps two fused ring systems per molecule. Coal asphaltene molecules are found to be much smaller than petroleum asphaltenes.     

石油沥青质的化学和物理：Ⅱ沥青质的化学组成和结构

本文详细综述了有关于石油沥青质的化学组成和化学结构方面的研究。由于沥青质本身的复杂性和分析手段的有限性，至今在分子水平上对沥青质的化学组成和结构了解得不很多，而且相当一部分结论是推测性的。     

COMPARISON OF MOLECULAR WEIGHT DISTRIBUTIONS OF CORBETT ASPHALT FRACTIONS BY GEL PERMEATION CHROMATOGRAPHY

Accurate molecular weight distributions are essential to the determination of the molecular structures of asphalt. Due to molecular complexity and interaction among the molecules of asphalt, precise measurement for the molecular weights of asphalt can not be achieved. In order to minimize the interactions of asphaltic materials, a petroleum asphalt sample was separated into saturates, naphthalene aromatics, polar aromatics, and asphaltenes. These Corbett fractions were then analyzed by gel permeation chromatography against nondispersive polystyrene standards. The molecular weights and the molecular size profiles were obtained. Among these Corbett fractions, naphthalene aromatics have the lowest number average molecular weight; saturates have the lowest weight average molecular weight and dispersity; and asphaltenes have the highest number and weight average molecular weights and dispersity.     

The Solubility and Three-Dimensional Structure of Asphaltenes

The tendency of the asphaltenes to form aggregates in hydrocarbon solution is one of their most characteristic features and has tended to complicate the determination of the structure of petroleum In addition, if the composition and properties of the precipitated asphaltenes reflect those of the micelles in solution, the latter should be considered as mixed micelles. This is a reasonable assumption in view of the large quantities of soluble resins found in the precipitated solid

Empirical observations indicate that the resins play an important role in stabilizing asphaltenes in crude oil and under unfavorable solvent conditions the asphaltene species are prone to further aggregation into clusters that are unstable and precipitate from the crude oil. It is also suggested that the resins and the asphaltenes from a particular crude oil have points of structural similarity relative to the asphaltenes and resins from another crude oil. On a more localized scale, i.e. in one particular crude oil there are also structural differences within the constituents of asphaltenes and structural differences within the constituents of the resins are also anticipated

Therefore, the structure of the micelles within any one crude oil must be expected to be varied and non-homogenous. From the evidence cited herein, it follows that the potential for graphite-type stacking by the asphaltene molecules in the center of a micelle might not be as great as the potential for the micelles forming by asphaltene-resin interactions rather than by asphaltene-asphaltene interactions