渣油的特征化参数

在对国外5种减压渣油进行超临界流体萃取分馏及其窄馏分性质分析的基础上，考察了已有的渣油特征化参数KH对国外减压渣油的适用性，研究结果表明，已有的渣油特征化参数KH和国外减压渣油的化学组成偏差较大，因此，笔者建立了一个新的渣油特征化参数KR，可以比较准确地关联国内外11种渣油馏分的性质和组成，并表征渣油馏分的催化裂化及热反应性能。     

哈国减压渣油的分离及性质研究

利用超临界流体萃取分馏技术，将哈国减压渣油分离成10-15个窄馏分，并对窄馏分的密度、平均分子量、元素硫、氮、Fe、Ni、V的含量和粘度进行分析，对窄馏分的平均沸点进行预测。通过对各窄馏分性质分析，提出对哈国减压渣油的加工方案。     

哈萨克斯坦减压渣油的评价

利用超临界流体萃取分馏技术，对哈萨克斯坦减压渣油进行评价。将哈萨克斯坦减压渣油分离成8个窄馏分，对各窄馏分的密度、残炭、粘度、折光率、H／C、平均相对分子质量等物理性质及元素（硫、氮）、铁、镍、钒含量进行分析并作图，呈现规律性变化；并对窄馏分的平均沸点进行预测，得出第八个馏分的沸点达到1066K。通过实验可知，窄馏分性质可以对中比收率进行拟合，进而进行化学转化性能的研究，为二次加工哈萨克斯坦减压渣油提供基础数据和信息。     

减压渣油结构参数及氢含量的预测

利用减压渣油及其超临界流体萃取分馏馏分的基本性质数据,由多元线性回归分析法得到了结构参数的关联式。并给出了在缺乏元素分析的条件下,渣油氢含量的预测式。模型简便可靠,有较大的实用价值。     

孤岛减压渣油窄馏分的热反应动力学：Ⅰ.微分法和积分法确定动力学参数

在超临界流体萃取精密分馏装置上，将孤岛减压渣油分离为１５个窄馏分。在升温速率为６℃／ｍｉｎ和Ｎ２气保护条件下，采用动态热重装置对各窄馏分进行热反应动力学研究，并运用总包反应微分法和积分法对各窄馏分的热重数据进行处理。     

加氢渣油超临界流体萃取分离及产物性质研究

利用超临界流体萃取分离技术对齐鲁渣油加氢装置的原料减压渣油（原料减渣）和加氢后减压渣油（加氢减渣）进行了分离,考察了相同分离条件下原料减渣和加氢减渣的萃取情况,对超临界流体萃取的窄馏分性质的变化规律及残渣性质进行了分析。结果表明：采用超临界流体萃取技术能够有效地分离加氢减渣;与原料减渣相比,超临界流体萃取技术对加氢减渣具有更好脱金属、脱硫和降残炭能力。可以利用溶剂脱沥青工艺对加氢减渣进行进一步分离,从而得到后续装置更易加工的脱沥青油。     

渣油中硫化物类型分布与化学转化性能

用X射线光电子能谱（XPS）定量研究了Athabasca渣油及其加氢裂化渣油，流化焦化渣油中的硫化物类型，用超临界流体萃取分馏将3种渣油分别分离成9－14个窄馏分及残渣，测定其中的硫醚，噻吩，亚砜和砜类硫原子的分布，讨论了加氢裂化和热裂化反应脱除硫化物的反应性能。     

孤岛减压渣油窄馏分的热反应动力学：Ⅱ.不同转化深度下动…

对于孤岛减压渣油超临界流体萃取精密分馏分所得的窄馏分，在５个不同的升温速率下进行了热重法研究。对所获实验数据运用Ｆｒｉｅｄ－ｍａｎ法进行处理，求出了各窄馏分在９个不同转化深度下的动力学参数值。结果表明，对于每一个窄馏分来说，随着转化深度的增大，活化能亦增加；而在同一转化深度下，随着各窄馏分分子量的增大及其结构中芳碳率和芳环数的提高，裂解活化能亦呈增大趋势。     

超临界流体萃取技术在哈国减压渣油中的应用研究

随着国家能源战略的调整，中哈石油管道的建成，对哈国减压渣油的深入研究和加工迫在眉睫。使用超临界萃取分馏仪对哈国减压渣油进行馏分切割，切割成8～9个窄馏分，切割深度达到减压渣油的81．08％。并测定各个窄馏分的性质，分析它们的变化规律，为我国的炼化企业加工哈国减压渣油提供基础的可行性数据。     

沸腾床加氢原料油超临界萃取分离与结构研究

采用超临界流体萃取分馏技术,将伊朗和沙轻减压渣油混合油分离成6个窄馏分和1个萃余残渣,对窄馏分的组成分布和结构进行了研究,为STRONG沸腾床加氢原料的结构提供重要基础数据。结果表明,随着窄馏分收率的增加,饱和分质量分数减小,胶质质量分数增大,芳香分质量分数逐渐增大,各窄馏分中基本不含沥青质,残炭值、硫和氮及金属元素含量逐渐增加,氮和金属在最后几个窄馏分和残渣中有富集现象。用改进的Brown-Ladner法计算了各个窄馏分和原料的结构参数,预测了窄馏分的二次加工性能,对特征化参数与窄馏分的性质进行了关联。建立了伊朗和沙轻减压渣油混合油窄馏分残炭值、芳碳率、与特征化参数之间的关联式。     

Preliminary Insights on the Crude Oil Maturation Effects on Asphaltene Stability and Processing

Abstract

Geochemical characterization of crude oils is one important classification and exploration tool within the oil business. One maturation parameter is the ratio of cyclic/open demetallized porphyrins (ratio DPEP types/Ethio types). Chromatographic properties of porphyrinic compounds are briefly reviewed. One high-performance liquid chromatography (HPLC) method was selected for measurement of the DPEP/Ethio parameter. This tool is suited for whole crude oils, vacuum residua, and nonvolatile fractions such as asphaltenes.

Exploratory data from heavy, medium, and light crude oils; their vacuum residua; and asphaltenes suggest a correlation between maturity [DPEP/(DPEP + Ethio) parameter] and aspects such as solid deposition and processability during upgrading operations.

Results with the studied set of samples will be discussed by considering “Earth” (time under reservoir conditions) as a reactor that steadily converts hydrocarbon mixtures, disproportioning them into two major types: I. light ends, II. molecules with a set of undesirable properties such as extended condensation, loss of alkyl appendages, higher density, higher intermolecular aggregation tendency, and high coking indexes. Examples with Venezuelan crude oils will illustrate these aspects.     

原油减压渣油馏分的油-水界面性质Ⅺ.伊朗轻质减压渣油和大庆减压渣油乳状液的粒度特征

采用动态光散射法研究了伊朗轻质减压渣油和大庆减压渣油模拟乳状液的粒度特征。研究表明，伊朗轻质减压渣油和大庆减压渣油模拟乳状液的初始粒径较小，粒度分布较窄；随着时间的延长，其粒径逐渐增大，粒度分布变宽；随着馏分增重或体相质量浓度的增加，模拟乳状液的初始粒径增大。随着油相中芳烃含量增加，伊朗轻质减压渣油和大庆减压渣油中重馏分模拟乳状液的初始粒径增大，而大庆减压渣油轻馏分模拟乳状液的初始粒径减小。随着水相中碱或盐的加入，伊朗轻质减压渣油和大庆减压渣油模拟乳状液的初始粒径均增大。     

METALLOPETROPORPHYRINS AS PROCESS INDICATORS: SEPARATION OF PETROPORPHYRINS IN GREEN RIVER OIL SHALE PYROLYSIS PRODUCTS

Product oils from the LLNL Hot-Recycled-Solids (HRS) retorting process were separated to isolate and concentrate the metallopetropor-phyrins. A modified column chromatography procedure developed previously for heavy crude oils and tar sand bitumens was used. The fractions were then examined by UV-vis spectroscopy to determine categories of porphyrins and other related metal-containing species.

No porphyrins were found in the hexane fraction (least polar fraction); Ni porphyrins were found in the methylene chloride fraction (moderate polar fraction); and a free-base porphyrin-like species was found in the methanol fraction (the most polar fraction) of some of the oils. The CH₂Cl₂ fractions were further examined to quantify the amount of porphyrins detected. In the whole oil samples examined, ∼ 40 wt % of the Ni was found as Ni petroporphyrins. The vacuum residua of two product oils had ∼ 20 wt % of the Ni bound as Ni por-phyrins indicating that the vacuum distillation process destroys porphyrins.     

一个反映重油平均分子结构的特征因数

构造了一个简单的粘重函数KL。考察了不同油品和纯烃的KL值，认为几值对于油品平均分子结构的反映是准确的，随重油的平均相对分子质量增大而降低。对于相对分子质量近似的烃，烷烃KL值＞环烷烃KL值＞芳烃KL值；重油的平均相对分子质量和环化程度越高，KL值越小；普通原油KL值＞重质原油KL值；对于同一种原油，常压馆分KL值＞减压憎分KL值＞原油KL＞常压渣油KL值＞减压渣油KL值；随拔出深度增大，渣油见值减小。     

TWO-DIMENSIONAL SOLUBILITY PARAMETER MAPPING OF HEAVY OILS

The solubility and insolubility of heavy oils and their fractions in dilute mixtures with various solvents were used to characterize heavy oil interactions. A two-dimensional solubility parameter, developed for the selection of solvents for organic polymers, was found to group all the solvents for each heavy oil fraction in polygon areas when the complexing solubility parameter component was plotted against the field force solubility parameter component. All fractions of Cold Lake vacuum residua, except for the saturate fraction, form concentric solubility areas. Therefore, in going in the direction of decreasing aromaticity from coke to asphaltenes to resins to aromatics, all solvents for the previous fraction in the series are also solvents for all subsequent fractions in the series. As a result, asphaltenes can be precipitated, but not extracted, from heavy oils. This is attributed to the interaction among polynuclear aromatics being the dominate interaction in petroleum that causes insolubility in hydrocarbon liquids. However, the paraffinic chains on the same petroleum molecules limit their solubility in highly complexing liquids. In contrast, even vacuum gas oils from the Exxon Donor Solvent coal liquefaction process are insoluble in aromatic liquids but soluble in moderately complexing liquids because of hydrogen bonding, resulting from oxygen functionality. Hydrotreating of these coal derived vacuum. gas oils reduces their oxygen functionality and increases their solubility areas so that they become compatible with petroleum liquids.     

TWO-DIMENSIONAL SOLUBILITY PARAMETER MAPPING OF HEAVY OILS

ABSTRACT

The solubility and insolubility of heavy oils and their fractions in dilute mixtures with various solvents were used to characterize heavy oil interactions. A two-dimensional solubility parameter, developed for the selection of solvents for organic polymers, was found to group all the solvents for each heavy oil fraction in polygon areas when the complexing solubility parameter component was plotted against the field force solubility parameter component. All fractions of Cold Lake vacuum residua, except for the saturate fraction, form concentric solubility areas. Therefore, in going in the direction of decreasing aromaticity from coke to asphaltenes to resins to aromatics, all solvents for the previous fraction in the series are also solvents for all subsequent fractions in the series. As a result, asphaltenes can be precipitated, but not extracted, from heavy oils. This is attributed to the interaction among polynuclear aromatics being the dominate interaction in petroleum that causes insolubility in hydrocarbon liquids. However, the paraffinic chains on the same petroleum molecules limit their solubility in highly complexing liquids. In contrast, even vacuum gas oils from the Exxon Donor Solvent coal liquefaction process are insoluble in aromatic liquids but soluble in moderately complexing liquids because of hydrogen bonding, resulting from oxygen functionality. Hydrotreating of these coal derived vacuum. gas oils reduces their oxygen functionality and increases their solubility areas so that they become compatible with petroleum liquids.     

KINEMATIC VISCOSITY-TEMPERATURE BEHAVIOR OF HEAVY TBP-FRACTIONS (455°C+) OF ARABIAN CRUDE OILS

A generalized kinematic viscosity-temperature correlation for undefined liquid heavy petroleum fractions has been developed to represent the data for a wide range of temperature from 100°C to 200°C. The correlation is based on the experimental kinematic viscosity data of true boiling point fractions of four Arabian crude oils. The characterization property required for estimation is 50% boiling point. The proposed correlation fits the experimental data with an overall absolute error of 6.1%. Experimental measurements of kinematic viscosity of heavy true boiling point fractions of Arabian crude oils were also obtained in order to develop the proposed correlation.     

原油减压渣油馏分的油-水界面性质Ⅱ.大庆减渣馏分与伊朗轻质减渣馏分油-水界面张力的比较

采用超临界萃取分离方法，将大庆减压渣油及伊朗轻质减压渣油按相对分子质量分割为两个系列共33个馏分。考察了它们的化学组成和界面张力，比较了两个系列减渣馏分在不同条件下油-水界面张力的变化规律。结果表明，大庆减渣馏分较伊朗轻质减渣馏分的芳香共轭结构和极性基团含量少，界面活性低。油相芳烃含量对两个系列油-水界面张力的影响不同，对大庆中间馏分的油-水界面张力影响大，而对伊朗轻质减渣中间馏分的影响小。水相因素对两个系列油-水界面张力的影响相似。水相中可溶性盐对油-水界面张力影响小，沉淀性盐对油-水界面张力影响大，对伊朗轻质减渣馏分的影响更明显。pH值对中间馏分油-水界面张力影响大，而对轻、重馏分影响小。     

KINEMATIC VISCOSITY-TEMPERATURE BEHAVIOR OF HEAVY TBP-FRACTIONS (455°C+) OF ARABIAN CRUDE OILS

ABSTRACT

A generalized kinematic viscosity-temperature correlation for undefined liquid heavy petroleum fractions has been developed to represent the data for a wide range of temperature from 100°C to 200°C. The correlation is based on the experimental kinematic viscosity data of true boiling point fractions of four Arabian crude oils. The characterization property required for estimation is 50% boiling point. The proposed correlation fits the experimental data with an overall absolute error of 6.1%. Experimental measurements of kinematic viscosity of heavy true boiling point fractions of Arabian crude oils were also obtained in order to develop the proposed correlation.     

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.