Hydrotreating of Maya Crude Oil: I. Effect of Support Composition and Its Pore-diameter on Asphaltene Conversion

A systematic study for a concept governing support effect in heavy oil hydrotreating (HDT) catalysts is performed. Different Al₂O₃ and its mixed oxides supports were prepared and CoMo supported catalysts were tested for Maya heavy crude oil hydrotreating. Fresh and spent catalysts are characterized with N₂ adsorption-desorption, element analysis, and scanning electron microscopy-energy dispersion analysis by x-ray (SEM-EDAX), which confirms that coke and metals deposition on the surface of catalyst is most probably near the pore mouth. It is also demonstrated from these results that asphaltene conversion depends on the pore diameter of the catalyst, while other hydrotreating conversions (hydrodesulfurization (HDS), hydrodenitogenation (HDN), and in some extent hydrodemetallization (HDM)) are more likely affected by the nature of active metal distribution. The evaluation of alumina mixed oxide (TiO₂, ZrO₂, B₂O₃, and MgO) supported catalysts indicates that supports with basic nature have better stability than the acid ones.     

Hydrotreating of Maya Crude Oil: I. Effect of Support Composition and Its Pore-diameter on Asphaltene Conversion

Abstract

A systematic study for a concept governing support effect in heavy oil hydrotreating (HDT) catalysts is performed. Different Al₂O₃ and its mixed oxides supports were prepared and CoMo supported catalysts were tested for Maya heavy crude oil hydrotreating. Fresh and spent catalysts are characterized with N₂ adsorption-desorption, element analysis, and scanning electron microscopy-energy dispersion analysis by x-ray (SEM-EDAX), which confirms that coke and metals deposition on the surface of catalyst is most probably near the pore mouth. It is also demonstrated from these results that asphaltene conversion depends on the pore diameter of the catalyst, while other hydrotreating conversions (hydrodesulfurization (HDS), hydrodenitogenation (HDN), and in some extent hydrodemetallization (HDM)) are more likely affected by the nature of active metal distribution. The evaluation of alumina mixed oxide (TiO₂, ZrO₂, B₂O₃, and MgO) supported catalysts indicates that supports with basic nature have better stability than the acid ones.     

Prediction of Asphaltene Precipitation in Live and Tank Crude Oil Using Gaussian Process Regression

The study of asphaltene precipitation properties has been motivated by their propensity to aggregate, flocculate, precipitate, and adsorb onto interfaces. The tendency of asphaltenes to precipitation has posed great challenges for the petroleum industry. Since the nature of asphaltene solubility is yet unknown and several unmodeled dynamics are hidden in the original systems, the existing models may fail in prediction the asphaltene precipitation in crude oil systems. The authors developed some Gaussian process regression models to predict asphaltene precipitation in crude oil systems based on different subsets of properties and components of crude oil. Using feature selection techniques they found some subsets of properties of crude oil that are more predictive of asphaltene precipitation. Then they developed prediction models based on selected feature sets. Results of this research indicate that the proposed predictive models can successfully predict and model asphaltene precipitation in tank and live crude oils with good accuracy.     

胜利原油各组分对界面膜扩张流变性的影响

 采取经典的四组分分离方法(SARA)将胜利原油分离得到饱和分、芳香分、胶质和沥青质,利用醇碱萃取法得到酸性组分。通过滴外形分析方法系统研究了上述5类原油组分及稀释原油的界面扩张流变性质,考察了振荡频率和各组分质量分数的影响。结果表明,各类活性组分及稀释原油表现出与表面活性剂类似的界面扩张行为,扩张模量均随振荡频率增大而增大,随质量分数的增加先增大后减小;相角随振荡频率增大而降低,随质量分数增大而增加。各组分模拟油及稀释原油形成的界面膜均表现出较强的弹性行为,且按其界面行为可以分为3组：稀释原油和饱和分、酸性组分和胶质、芳香分和沥青质。模量最大值对应的质量分数高低顺序为稀释原油和饱和分、酸性组分和胶质、芳香分和沥青质。沥青质扩张模量的最大值在 25 mN/m 左右,略高于稀释原油和其它活性组分。     

原油泡沫稳定特性研究进展

在油气集输与处理,特别是油气分离过程中,易产生大量泡沫。泡沫的演化和衰变整体符合液膜排液、气体扩散进而破灭的过程,通常认为原油中胶质、沥青质及蜡等固体颗粒是影响泡沫稳定性的重要因素,但对其影响规律和机理的认识却不尽相同,甚至观点相反。究其原因是原油组分及其所处工况都比较复杂,而且不同学者所用研究手段也不相同,因此,建议根据实际工况研制针对性实验装置,并借助现代化精密仪器进行精细分析,将宏观原油泡沫现象与微观下胶质、沥青质、蜡等在原油泡沫中结构变化相结合,分析各物质作用机理,有助于增进对泡沫稳定性的定性和定量研究。     

用磺化稠油降低稠油粘度的初步研究

在低温下 (15～ 2 0℃ )用 5 0 %～ 6 0 %的硫酸将辽河稠油磺化 ,得到了一系列磺化稠油 ,在 5 0℃粘度为 115 3mPa·s的辽河稠油中按质量比 2 g/kg加入磺化稠油 ,使 5 0℃粘度降至 786～ 914mPa·s ,降粘率为 19.8%～31.8%。将磺化反应进行优化 ,得到磺化稠油的最好制备条件 :5 5 %硫酸 ,用量为稠油的 1.5 % ,在 15℃反应 2h。得到的磺化稠油在加剂量为 2 g/kg时使稠油 5 0℃粘度下降 30 .8%。稠油降粘率与加剂量的关系曲线很复杂 ,经过一个明显的极大值和一个极小值 ,极大值对应的加剂量为 2 g/kg ,即最佳加剂量。讨论了稠油降粘机理。图 1表 1参 2。     

Interfacial and Structural Properties of Different Natural Surfactants Extracted From Venezuelan Junin Extra Heavy Crude Oil

Abstract

In this work, acids, asphaltenes, maltenes, and acid-free asphaltenes were isolated from Venezuelan Junin extra heavy crude oil, and their interfacial properties studied using the pendant drop method. This study led to the conclusion that the acids present in the crude, which have molecular weights of about 400 Da and are present in higher concentrations in asphaltenes, account for the decrease in the interfacial tension. In other words, asphaltenes act as molecular traps for acids. Furthermore, it was possible to confirm with simpler methods that substances adsorbed at the water–crude oil interface have low molecular weights.     

Prediction of the Kinematic Viscosity of Crude Oil Fractions

Abstract

A generalized equation based on modified Eyring's theory for predicting kinematic viscosity of petroleum fractions is proposed in this work. The equation uses two reference fluids including a pair of (C6 and C10), (C10 and C14), or (C14 and C20) for petroleum fractions of molecular weight higher than 70 and lower than 300.

Validity and accuracy of this equation have been confirmed by comparing the obtained results of this equation with experimental data. In contrast to other correlations that require so many specific parameters for oil viscosity prediction, this type of equation requires only molecular weight and true boiling point. The results obtained in this work are in agreement with experimental data with an average absolute deviation (AAD) of less than 5%.     

胜利原油活性组分对原油-甜菜碱溶液体系油-水界面张力的影响

采用传统的柱色谱四组分分离方法（SARA）将胜利孤岛原油分离得到沥青质、饱和分、芳香分和胶质,采用碱醇液法萃取原油得到酸性组分。测定了正构烷烃、煤油以及原油活性组分模拟油与2种不同疏水结构的甜菜碱溶液组成的体系的油 水界面张力。结果表明,在原油活性组分模拟油 甜菜碱溶液体系中,直链甜菜碱由于疏水基团较小,与原油活性组分尤其是酸性组分和胶质发生正协同效应的混合吸附,使油 水界面上表面活性剂分子的含量增加,界面膜的排布更紧密,导致油 水界面张力降低;支链甜菜碱由于具有较大尺寸的疏水基团,煤油中少量的活性物质即可将油 水界面张力降至超低(<10-3 mN/m),而原油活性组分的加入,则使界面上表面活性剂分子的排布被破坏,削弱了界面膜原有的紧密性,导致油 水界面张力大幅度升高。     

稠油组分在水包油乳状液中作用机理的研究——Ⅰ．稠油组分分离及基本性质研究

本文主要研究了稠油的组分分离及其基本性质,为稠油组分在水包油乳状液中的作用机理研究提供基础数据.首次建立了将稠油分为酸性分、碱性分、两性分和中性分四组分的离子交换色谱分离技术.采用该分离技术对辽河杜-84稠油和胜利孤岛垦西稠油进行了组分分离,同时用极性分离法将稠油分为饱和分、芳香分、胶质和沥青质四组分.之后对这些纽分进行了元素、酸碱值、相对分子质量及红外光谱等组成结构测定.结果表明,杜-84稠油中酸性分、碱性分、两性分含量达36.92%;孤岛垦西稠油中酸性分、碱性分、两性分含量达20.65%.元素分析、酸碱值和红外光谱分析结果表明,分离效果较好,离子交换色谱分离法收率可达95%以上.极性四组分以沥青质相对分子质量最高(2000-3000),且辽河沥青质比孤岛沥青质要大许多,反映出辽河稠油的超稠油特性;相对分子质量大小顺序为沥青质＞胶质＞芳香分＞饱和分;官能团四组分中,碱性分相对分子质量最大(1150-1222),其它由大到小依次为两性分、酸性分、中性分.     

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.     

CO_2在原油中的扩散及引起的沥青质沉积

CO2在原油中扩散和溶解,使得原油体积膨胀和黏度降低的同时,原油组分也发生变化,可能引起沥青质等重有机质沉积,伤害储层,因此需全面评价CO2在原油中的扩散和影响因素以及可能引起的沥青质沉积程度。用压力降落法测定了压力和沥青质含量对CO2在原油中的扩散系数和溶解度的影响。结果表明,随着压力增加,CO2在原油中的扩散系数成线性增加,溶解度先增加后降低。随原油沥青质含量的增加,CO2扩散系数降低,溶解度增加。CO2扩散后的原油沥青质含量大幅降低,最高降幅达94.6%,表明CO2在扩散过程中引起了沥青质的沉积。     

The Structural Characterization of Saturate,Aromatic, Resin,and Asphaltene Fractions of Batiraman Crude Oil

Abstract

The structural characterization of fractions of Batiraman crude oil, which is the heavy crude oil from a field in the southeastern part of Turkey, was investigated. Batiraman crude oil and its saturate, aromatic, resin, and asphaltene (SARA) fractions were seperated. Treatment of crude oil with n-heptane provided the separation of asphaltene. Maltene was collected by evaporating the n-heptane from the filtrate. Then, maltene was separeted into saturates, aromatics, and resins by SARA technique. Maltene was separated into saturate, aromatic, and resin fractions using column chromatography. SARA fractions were quantified on a weight percent basis. Fractions of Batiraman crude oil were characterized by elemental analysis, proton nuclear magnetic resonance (¹H NMR) analysis, electrospray ionization mass spectrometry (ESI-MS), and Fourier transform infrared (FTIR) spectroscopy techniques.     

Hydrotreating of Gas Oil,Jatropha Oil,and Their Blends Using a Carbon Supported Cobalt-Molybdenum Catalyst

Hydrotreating of Jatropha oil and Jatropha oil blended gas oil feeds were studied under diesel hydrotreating conditions using Cobalt-Molybdenum catalyst on activated carbon. The experiments were carried out in pilot plant for more than 90 days first with gas oil, followed by 5%, 10%, and 20% Jatropha oil in gas oil and finally with Jatropha oil alone. Deactivation of the catalyst was not observed up to hydrotreating of 20 wt% Jatropha oil in gas oil, but, the reactor pressure shoots up after seven days of running neat Jatropha oil. The liquid products were characterized by GC-MS analysis, distillation, density, sulfur, nitrogen, and Cetane Index.     

Catalytic Neutralization Method for Naphthenic Acid Removal in Crude Oil by Alumina Supported Ca and Ba Catalysts

The presence of naphthenic acids in crude oils has caused a major corrosion problem to the production equipment, storage and transport facilities in the petroleum industry. To overcome this problem, catalytic neutralization method will be investigated on real petroleum crude oil sample with various parameters study such as the type of basic chemical used, dosing amount, type of catalyst, catalyst calcination temperature, and catalyst ratio of basic metal and dopant. Potential catalyst was characterized by XRD, NA, and TGA-DTA for its physical properties. Cu/Ca(10:90)/Al₂O₃ catalyst with calcination temperature of 1000°C was an effective catalyst for all three types of crude oil. In the presence of catalyst, all three types of crude oil samples showed enhancement in the removal of naphthenic acid.     

混炼原油的评定与研究

将大庆原油与俄罗斯原油按不同比例混合，并分析实沸点切割的宽馏分性质，结果表明：随着进口油比例的增加，混炼原油的粘度和凝点都随之降低，有利生产低凝的煤油，柴油。混合比为50：50时轻质油收率最大，60：40时总拔出率最高。     

稠油沥青质水热裂解供氢催化及地质协同作用研究

探讨了辽河稠油中沥青质在注蒸汽热采条件下供氢催化水热裂解反应行为,以及油藏矿物对沥青质水热裂解的强化作用,结果表明,油藏矿物与硫酸镍、甲酸供氢剂可协同催化沥青质水热裂解反应,最终可使沥青质降解率达到49.2%;供氢催化反应前后稠油中沥青质红外谱图说明稠油中沥青质在供氢催化改质降粘反应时所发生的化学结构的变化,反映了沥青质在反应过程中经历了侧链断裂、环烷脱氢芳构化以及芳香结构进一步缩合等反应;对沥青质水热裂解反应产物中轻组分进行气相色谱全烃分析,证实了在注蒸汽热采条件下沥青质可以实现部分催化降解。     

The Effect of Solvent Nature and Dispersant Performance on Asphaltene Precipitation from Diluted Solutions of Instable Crude Oil

Abstract

The asphaltene precipitation experiments were studied on El Furrial crude oil from western Venezuela, which is known to exhibit serious instability problems. A Turbiscan backscattering apparatus was used to evaluate the precipitation of asphaltenes with different solvents. The transmittance variation with time was studied as the crude was diluted with heptane, pentane, and cyclohexane. Linear alkanes-containing systems exhibit a two-stage behavior, whereas only one is found when diluting with cyclohexane. Dispersing agents were tested by using the precipitate height as a criterion of effectiveness. Results are reported for ethoxylated nonylphenols and a commercial dispersant.     

中原原油生产润滑油

本文对中原混合原油生产润滑油，从常减压蒸馏到溶剂脱蜡、酸碱精制及白土补充精制等生产过程进行了阐述，并与川中原油生产润滑油进行了比较。     

原油族组分的分离及检测方法

比较了SY/T5119—2008方法、原油族组分柱色谱分离常规方法和EPA3611方法等柱色谱法对原油族组分的分离效果;并在EPA3611方法的基础上,建立了一种新型原油族组分柱色谱分离方法(简称改良方法),改良方法以较少氧化铝为固定相,以正己烷、正己烷与二氯甲烷混合溶剂(体积比3∶1)、无水乙醇为洗脱液分别洗脱出原油中饱和烃、芳烃、胶质组分,达到较好分离原油族组分的目的。同时建立了TLC/FID评价原油族组分柱色谱分离效果的方法。用TLC/FID技术评价了4种柱色谱法分离原油族组分的效果。实验结果表明,较其他3种方法相比,改良方法的分离效果好、溶剂用量少、分析时间短、操作简便;同时,TLC/FID技术可一次性检测柱色谱分离的4种族组分,具有快速、微量等特点,可用于原油族组分柱色谱分离效果的监测。