POLAROGRAPHIC CHARACTERIZATION OF AROMATIC STRUCTURES IN COAL LIQUID PRODUCTS

ABSTRACT

Reducible aromatic species in coal liquid products from five major processes (Synthoil, FMC COED, HRI H-Coal, PAMCO SRC, and Catalytic Inc. SRC) together with solvent elution chromatography fractions of a selected asphaltene has been evaluated. The half-wave potentials measurments are found to be consistant with other methods. The total polarographic reduction of measurement per average molecule for Synthoil solvent fractions, as measured by diffusion constant (i_d /C), increases in the following manner: gas oil → resin → asphaltene → carbene → carboid. The same trend was observed when color indices (I) and refractive indices (n ₂₅) were individually studied.     

CHARACTERIZATION OF HEAVY RESIDUA BY APPLICATION OF A MODIFIED D 2007 AND ASPHALTENE SEPARATION: EFFECT OF SOLVENTS ON PHYSICAL AND CHEMICAL PROPERTIES OF FRACTIONS DERIVED FROM HONDO 850°F RESIDOOM

Hondo 850 ^°F residuum was separated into saturate, aromatic, resin, and asphaltene fractions by a modified D 2007 and asphaltene separation. Two different asphaltene precipitation solvents were used — isooctane and heptane — and differences in selected physical and chemical properties of the derived fractions were compared.

The principal difference in the use of the two solvents was weight recovery after the separation. Isooctane yielded good recovery, while heptane exhibited poor recovery. Isooctane precipitated substantially more asphaltenes, as predicted from the solubility parameters of the two solvents.

The metals concentrations in the fractions were comparable for each solvent — no metals in the saturate and aromatic fractions, approximately 300 and 1500 ppm Ni + V in the resin and asphaltene fractions respectively. The relative distribution was also similar for both solvents, with the highest percentage coming from the asphaltenes.     

ASPHALTENE AND RESID PYROLYSIS: EFFECT OF REACTION ENVIRONMENT

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.     

Investigation of Molecular Weight and Aggregation of Asphaltenes in Organic Solvents Using Surface Tension Measurements

Abstract

The physico-chemical behavior of asphaltene is very useful to assist prediction and control the mechanisms of asphaltene deposition during the production of petroleum fluids. It has been realized that the first step in the formation of precipitated asphaltene particles is the self-aggregation mechanism to form colloidal particles or pseudo-micelles in several solvents. In this work, the critical micelle concentration (CMC) of two asphaltene fractions extracted from vacuum residues (VR) were obtained by surface tension measurements, using aromatic solvents. The molecular weight (1094-565 g/mol), calculated from average radii of the asphaltene molecules adsorbed at the air–solvent interface, are also in agreement with the values for small aggregates reported using small angle X-ray scattering.     

柱色谱分离法预测塔河常压渣油脱沥青油杂质含量的研究

塔河原油是一种沥青质含量高、残炭高、金属含量高、酸值高的重质原油,为避免传统加工过程中的高温腐蚀和塔河渣油进催化裂化装置的高残炭、高金属含量等问题,考虑将塔河原油经常压闪蒸后的渣油直接作为溶剂脱沥青的原料。采用挂片失重试验对塔河原油的腐蚀性进行了研究,同时对适宜闪蒸温度下的常压闪蒸渣油进行了六组分分离,并对各组分的化学性质和结构参数进行了分析。结果表明:53.89%的硫、86.97%的氮、98%以上的镍、钒金属存在于胶质和沥青质组分中;随着组分加重,芳碳率fA增加,H/C原子比、环烷碳分率fN和芳香环系缩合度参数HAU/CA减小;将塔河常压闪蒸渣油在不同柱色谱馏出油收率下的杂质脱除率曲线与溶剂脱沥青中试结果对比发现,两者有较好的相似度,表明采用柱色谱分离方法可以在一定程度上来预测溶剂脱沥青过程不同脱沥青油收率时的杂质含量,可指导塔河常压闪蒸渣油溶剂脱沥青过程的操作。     

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.     

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.     

Changes in the subfractional composition of heavy oil asphaltenes under aquathermolysis with oil-soluble CO-based catalyst

The asphaltenes extracted from the heavy oil sample and products of non-catalytic and catalytic aquathermolysis in the presence of cobalt-based catalyst precursors and hydrogen donor were investigated. Five fractions of asphaltenes and carbene-carboid were obtained by solvent extraction method. In the products of catalytic aquathermolysis processes, the content of resins and asphaltenes decreased, while the content of light hydrocarbon fractions (saturates and aromatics) slightly increased in contrast with non-catalytic processes. This result is due to intensification of destructive hydrogenation reactions, mostly on the weak –C–S–C– bonds of resins and asphaltenes. This study revealed redistribution phenomenon between the asphaltene fractions and decrease in average molecular mass of all asphaltene fractions under catalyst influence.     

渣油亚组分及其形成的胶粒颗粒尺寸的研究

 根据球形分子模型，采用特性粘度法和密度法计算了渣油亚组分(沥青质、胶质、芳香分)分子的颗粒直径；构筑了渣油中沥青质胶粒(胶团)模型，并据此计算了沥青质胶团尺寸。结果表明，采用特性粘度法，溶剂胶党性对测定沥青质大分子直径有影响，以甲基萘和苯为溶剂测定选择性粘度，关联出的沥青质分子直径分别为3.52~4.34nm和3.93~4.96nm。采用密度法计算得到的沥青质分子颗粒直径为2.39~2.79nm。大分子缔合作用对测定分子颗粒尺寸有影响。采用两种方法计算胶质、芳香分小分子颗粒直径均不受影响，分别约为1.60nm和1.25nm。渣油亚组分构成的胶团颗粒随着加氢处理深度的增加呈变小的趋势，73.3%质量分数的沥青质大分子转化成小分子。     

INTERFACIAL PROPERTIES OF THE PRODUCTS OF OZONOLYSIS OF HAMACA CRUDE OIL

A sample of extra-heavy Hamaca crude oil, dissolved in carbon tetrachloride, was oxidated with ozone for a few minutes. The reaction mixture was washed with a concentrated solution of HCl, neutralized with sodium carbonate, and the products were extracted from the aqueous phase. The products were characterized by using gel permeation chromatography (GPC), elemental analysis, ¹H nuclear magnetic resonance (NMR), and Fourier transformed infrared (FTIR) techniques. The results of the analyses show that the products have lower molecular weights, lower aromatic character, and higher oxygen content than the original sample. They also indicated that these products were mainly carboxylic acids, aldehydes, and/or ketones, with a higher affinity for water than for carbon tetrachloride, the organic solvent that was used. Interfacial tension γ measurements (water-toluene) performed with these products showed a linear dependence with concentration, where γ dropped from 32 to about 7.7 dinas/cm at the apparent critical Micelle concentration (cmc) (2 g/L). Larger quantities of a commercial sample of nonylphenol ethoxylated were needed for an equivalent γ drop. In another experiment the above oxidated product was mixed with Furrial asphaltene in toluene, and γ measurements were performed as above and compared with the values obtained for the same experiment using the ethoxylated surfactant. In this case, the γ values for the oxidated product were higher, suggesting a better adsorption on the asphaltene colloids. These preliminary results suggest that these oxidated products could be employed as general surfactants in the oil industry.     

EFFECTS OF ASPHALTENE PRECIPITATION AND REPRECIPTION ON THE METAL-CONTAINING COMPOUNDS IN HEAVY RESIDUA

Boscan vacuum residuum (VR) has been separated into isooctane insoluble asphaltenes and isooctane soluble maltenes. The asphaltenes were dissolved in a minimum of toluene and were further separated by two additional reprecipitations using isooctane as the precipitating solvent. We examined the fractions, including the recovered isooctane soluble material, by size exclusion chromatography (SEC) with inductively coupled plasma (ICP) emission spectroscopy to determine the effects, if any, the reprecipitations have on the size distribution of the metal-containing compounds.

The asphaltene fractions show little change in size upon reprecipitation, but removal of a small amount of the metal components does occur. The first reprecipitation produces isooctane soluble material which is very similar in size to the original maltene fraction. However, the second reprecipitation removes small amounts of material in the size range of the asphaltenes. When the amounts were weight balanced, the resulting separation did little to effect the overall maltene and asphaltene size profiles.     

SHALE OIL UPGRADING IN SUPERCRITICAL WATER SOLUTIONS

A supercritical water/HCl system was studied for upgrading Paraho shale oil (SO) at 400-425^°C. The key process parameters were water density (ρw) and HC1 loading. Increases in ρw increased the selectivity to distillate-range products at the expense of gas and coke products. Increases in ρw also enhanced the ability of HCl to catalyze N-removal. However, coke and gas make also increased with increases in HCl loading. Optimal or “best case” results and conditions were 897% N-removal and 75% distillate yield, at T = 425^°C, ρw = 0.2 g/cc, and HCl/SO = 0.05g/g. The underlying chemical mechanisms appeared to involve SCF solvent cage effects and hcterolytic N-removal brought about by dissociation of HCl.     

The Asphaltene and Wax Deposition Envelopes

Asphaltene and wax phase behavior is quite different than the conventional “PVT” phase behavior. Asphaltenes exhibit a behavior at some thermodynamic states called flocculation. That is, asphaltene particles or micelles aggregate or flocculate into larger aggregates or flocs. The locus of all thermodynamic points in a P-T-x phase diagram at which flocculation occurs is called the Asphaltene Deposition Envelope (ADE). Paraffin waxes, on the other hand, at some thermodynamic states, exhibit the phenomenon of crystallization. The locus of all thermodynamic points in a P-T-x phase diagram at which wax crystallization occurs is called the Wax Deposition Envelope (WDE). Asphaltene flocculation can be both reversible and irreversible (as expected from the asphaltene colloidal nature). Wax crystallization is generally a reversible process. However, paraffin waxes more than often precipitate together with resins and asphaltenes (which are said to be responsible for the observed irreversible thermodynamic phenomena). Hence, some wax precipitation is occasionally reported as irreversible. Measurement of the ADE and WDE boundaries, at in-situ conditions, is a challenging task. Measurement of asphaltene and wax solubility at in-situ conditions inside the ADE and WDE is even more challenging. The ADE and WDE data have practical significance and are very useful for modeling of reservoir fluid behavior. Asphaltene and wax data for a number of oils are presented and analyzed. This paper introduces and compares two powerful thermodynamic diagrams that summarize the phase behavior of asphaltenes and waxes, the ADE and WDE.     

反应时间对加氢残渣油四组分含量和结构的影响

以沙特轻质原油减压渣油（ALVR）为原料,采用高压釜考察了不同反应时间下加氢反应后残渣油的四组分含量及其结构组成变化。结果表明,与未加氢渣油相比,加氢残渣油中的饱和分含量大幅度增加,而芳香分、胶质和沥青质的含量均降低,四组分的H/C原子比和平均相对分子质量均降低,芳碳分率升高。加氢残渣油的四组分含量随反应时间的增加均呈规律性变化。随着加氢反应时间的增加,四组分的H/C原子比和平均相对分子质量降低,芳香分、胶质和沥青质的芳碳分率增加,胶质和沥青质的总环数和芳环数均降低。渣油加氢反应过程中,其四组分均发生了明显的氢解和脱烷基反应,胶质和沥青质结构单元间的各种桥键可发生明显的断裂,导致其结构单元数减少。不同来源和属性的渣油加氢反应后各组分的结构变化有一定区别。     

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.     

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.     

Development of an Artificial Neural Network Algorithm for the Prediction of Asphaltene Precipitation

Abstract

The precipitation and deposition of crude oil polar fractions such as asphaltenes in petroleum reservoirs considerably reduce rock permeability and oil recovery. Therefore, it is of great importance to determine how and how much the asphaltenes precipitate as a function of pressure, temperature, and liquid phase composition. The authors designed and applied an Artificial Neural Network (ANN) model to predict the amount of asphaltene precipitation at a given operating condition. Among this training, the back-propagation learning algorithm with different training methods was used. The most suitable algorithm with an appropriate number of neurons in the hidden layer, which provides the minimum error, was found to be the Levenberg-Marquardt (LM) algorithm. An extensive experimental data for the amount of asphaltene precipitation at various temperatures (293–343 K) was used to create the input and target data for generating the ANN model. The predicted results of asphaltene precipitation from the ANN model was also compared with the results of proposed scaling equations in the literature. The results revealed that scaling equations cannot predict the amount of asphaltene precipitation adequately. With an acceptable quantitative and qualitative agreement between experimental data and predicted amount of asphaltene precipitation for all ranges of dilution ratio, solvent molecular weight and temperature was obtained through using ANN model.     

沥青质在渣油加氢催化剂中的扩散受阻

以甲苯为溶剂,研究了沥青质在不同孔径的渣油加氢催化剂中的扩散受阻情况。结果表明：沥青质聚集体在渣油加氢催化剂中处于受阻扩散状态,不同孔径催化剂中的扩散受阻情况不同;扩散受阻因子F(λ)可以较好地表征沥青质在渣油加氢催化剂中的扩散受阻情况;扩散受阻因子随催化剂孔径的变化非常明显,催化剂孔径越小,沥青质聚集体扩散时受阻作用越严重,扩散受阻因子F(λ)值越小。此外,扩散受阻因子还与沥青质在溶液中的初始质量分数、催化剂的曲折因子等有关。     

EFFECTS OF ASPHALTENE PRECIPITATION AND REPRECIPTION ON THE METAL-CONTAINING COMPOUNDS IN HEAVY RESIDUA

ABSTRACT

Boscan vacuum residuum (VR) has been separated into isooctane insoluble asphaltenes and isooctane soluble maltenes. The asphaltenes were dissolved in a minimum of toluene and were further separated by two additional reprecipitations using isooctane as the precipitating solvent. We examined the fractions, including the recovered isooctane soluble material, by size exclusion chromatography (SEC) with inductively coupled plasma (ICP) emission spectroscopy to determine the effects, if any, the reprecipitations have on the size distribution of the metal-containing compounds.

The asphaltene fractions show little change in size upon reprecipitation, but removal of a small amount of the metal components does occur. The first reprecipitation produces isooctane soluble material which is very similar in size to the original maltene fraction. However, the second reprecipitation removes small amounts of material in the size range of the asphaltenes. When the amounts were weight balanced, the resulting separation did little to effect the overall maltene and asphaltene size profiles.     

CHARACTERIZATION OF HEAVY RESIDUA BY AAPPLICATION OF A MODIFIED D 2007 SEPARATION AND ELECTRON PARAMAGNETIC RESONANCE

Seven atmospheric residua (343^°C + [ 65O^°F + ]) were separated into saturate, aromatic, resin, and asphaltene fractions for detailled assessment of feed structure. The weight percent distribution of the fractions revealed two groupings of the residua. One grouping exhibited 20 wt % saturate composition, while the other only 10 wt %. The residua also exhibited high polar content (resin and asphaltene fractions) consisting of over 40% of the total residua. These results are related to the sulfur composition of the residua, and Indicate a fundamental relationship between the aromatic content and sulfur content. Discussion of the accuracy of the separation technique Is also Included.

The vanadium binding sites In the separated fractions were investigated by EPR spectroscopy. The resin and asphaltene fractions all appear to be dominated by 4N and N 0 2S coordination spheres. Discussion of this technique is also included.