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.     

渣油的催化裂化反应特性

介绍了一种渣油分离方法－超临界液体萃取分离技术，并对ＳＣＥＦ窄馏分及其按四组分分离得到的饱和分、芳香分、胶质的催化裂化反应性能进行了考察，结果表明，采用ＳＣＥＦ按需分配译渣油进行分离，并研究其化学组成和性质，是一个有效的方法；ＳＣＥＦ窄馏分及其亚组分的裂化性能与各组分的组成和性质密切相关。     

反应温度及掺渣比对渣油催化裂化生焦率的影响

用扶余减压馏分油和减压渣油研究掺渣油催化裂化过程的生焦率受反应温度及掺渣比的影响。结果表明，反应温度升高，生焦率下降，且随掺渣比的升高，下降幅度越大。减压馏分油和减压渣油之间存在相互作用，生焦率并不是减压渣油和减压馏分油生焦率的简单加和，由于减压馏分油的存在对渣油的胶体体系有破坏和稀释作用，降低了渣油固有的生焦率，所以掺渣油催化裂化反应过程应采用较高的反应温度，且注意原料中各组分的配伍问题     

正己烷热裂解链式反应机理和选择性分析

 采用柱塞流连续流动管式反应器考察了正己烷在923 K下的热裂解反应。结果表明,主要产物包括C2~C4烷烃、C2~C5烯烃、 异己烷、焦炭和H2。根据产物种类和选择性分布,建立了正己烷热裂解的自由基链式反应机理模型,并对所含各基元反应的选择性进行了定量分析。     

渣油加氢裂化反应机理的研究

在高压釜内，在不同的气体气氛下（如Ｎ２、ＮＨ４、ＳＯ２、ＣＯ、ＮＨ３以及Ｈ２）对渣油裂化反应进行了考察。并对有无催化存在下的产品分布及性质进行了。，地大分子渣油的加氢反庆，催化剂的作用并不象想象的那第显著，相反，加氢热裂化的液体收率反比催化加氢要高，并且总的焦炭产率低。从加氢反应机理并结合大渣油分子在加氢催化剂孔内的扩散问题进行了分析和讨论。     

双亲分子稳定辽河沥青质的作用及其机理

 为认识双亲分子化合物对沥青质的稳定作用及稳定机理,采用X射线光电子能谱（XPS）分析了辽河沥青质颗粒表面杂原子官能团的类型和含量;采用紫外－可见光谱(UV-Vis)测定添加双亲分子前后沥青质甲苯－正庚溶液中沥青质浓度的变化,进而分析了不同双亲分子化合物对辽河沥青质的分散稳定作用;采用红外光谱(FT-IR)分析初步探讨了十二烷基苯磺酸（DBSA）对沥青质分散稳定作用的机理。结果表明,沥青质颗粒表面含氮官能团主要为碱性的吡啶氮官能团和弱碱性的吡咯氮官能团,含氧官能团主要为碳氧单键和碳氧双键结构,表面杂原子官能团的数量虽然较少,但为沥青质与双亲分子作用的关键因素;双亲分子头部官能团和沥青质颗粒表面杂原子之间的酸碱作用越强,其分散稳定沥青质的能力越强;DBSA通过其磺酸基官能团与沥青质颗粒表面的羟基和氨基形成分子间氢键而吸附在沥青质上。     

稀乙烯在ZSM－5沸石上叠合与芳构化反应环境因素的影响

对利用催化裂化干气中的稀乙烯生产汽油馏分的环境因素进行了考察，尤其是催化裂化于气中存在的氢和水的加入对乙烯叠合与芳构化反应的影响在实验室进行了研究。试验结果表明，氢的存在使ＺＳＭ－５沸石上乙烯叠合与芳构化反应中芳烃产物的选择性提高，但同时使乙烷的产率增加，汽油产率下降。水的加入可抑制氢的不利影响，同时可提高乙烯的转化率并进一步降低催化剂上积炭的速度。     

胶质、沥青质对水-苯乳状液稳定性的影响

为深入研究胶质、沥青质对原油乳状液稳定性的影响,从孤岛渣油中分离出胶质和沥青质,用滴体积法、Ｌａｎｇｍｕｉｒ膜天平、单滴寿命法、瓶试法等研究了它们的水－苯界面活性、Ｌａｎｇｍｕｉｒ膜压,阻止水－苯界面上的水滴向水相融并的能力及稳定水－苯乳状液的能力。结果表明,胶质比沥青质具有更强的水－苯界面活性;沥青质比胶质具有更大的Ｌａｎｇｍｕｉｒ膜压;沥青质阻止水－苯界面上的水滴向水相融并的能力远大于胶质;沥     

EFFECT OF ASPHALTENE AND RESINS ON THE STABILITY OF WATER-IN-WAXY OIL EMULSIONS

Asphaltene, resins and paraffin waxes, their mutual interactions and their influence on the stability of water-in-oil emulsions have been studied. 20 wt % paraffin wax dissolved in decalin was used to model the waxy crude oil. Asphaltene and resins separated from a crude oil were used to stabilize the water-in-oil emulsions. Synthetic formation water was utilized as the aqueous phase of the emulsion. The emulsion stability increased with increasing the concentration of asphaltene with a subsequent decrease in the average particle size distribution of the emulsion. Resins alone are not capable of stabilizing the emulsion, however, in the presence of asphaltene they form very stable emulsions. Dynamic viscosity and pour point measurements provided evidence for resins-paraffin waxes interactions. Asphaltene in the form of solid aggregates form suitable nuclei for the wax crystallites to build over with a mechanism similar to that of paraffin wax crystal-modifiers. As asphaltene are polar in nature they are derived at the oil/water interface which was proved by the ability of asphaltene to reduce oil/water interfacial tension. Consequently, nucleation of the wax crystallites by asphaltene and resins at the interface will add to the thickness of the oil-water interfacial film and hence increase the stability of the emulsion.     

EFFECT OF ASPHALTENE AND RESINS ON THE STABILITY OF WATER-IN-WAXY OIL EMULSIONS

ABSTRACT

Asphaltene, resins and paraffin waxes, their mutual interactions and their influence on the stability of water-in-oil emulsions have been studied. 20 wt % paraffin wax dissolved in decalin was used to model the waxy crude oil. Asphaltene and resins separated from a crude oil were used to stabilize the water-in-oil emulsions. Synthetic formation water was utilized as the aqueous phase of the emulsion. The emulsion stability increased with increasing the concentration of asphaltene with a subsequent decrease in the average particle size distribution of the emulsion. Resins alone are not capable of stabilizing the emulsion, however, in the presence of asphaltene they form very stable emulsions. Dynamic viscosity and pour point measurements provided evidence for resins-paraffin waxes interactions. Asphaltene in the form of solid aggregates form suitable nuclei for the wax crystallites to build over with a mechanism similar to that of paraffin wax crystal-modifiers. As asphaltene are polar in nature they are derived at the oil/water interface which was proved by the ability of asphaltene to reduce oil/water interfacial tension. Consequently, nucleation of the wax crystallites by asphaltene and resins at the interface will add to the thickness of the oil-water interfacial film and hence increase the stability of the emulsion.     

十氢萘分散作用对沥青质加氢反应的影响

以十氢萘为溶剂,通过增加升温过程中的低温搅拌,强化十氢萘对沥青质的解聚和分散作用,提高沥青质加氢过程中在催化剂微孔中的扩散性能。研究表明：在373 K时恒温搅拌1 h,可以使沥青质加氢反应的转化率提高14.97百分点,焦炭产率降低2.68百分点;残渣油收率降低3.01百分点,四组分组成发生明显变化,饱和分、芳香分和胶质的含量均增加;硫、氮脱除率也有不同程度的提高。低温搅拌过程改变了沥青质的存在状态,有利于沥青质的加氢转化反应。     

重油催化裂化钒污染催化剂对生产的影响与对策

洛阳石油化工总厂加工塔里木原油，催化裂化原料中钒含量上升，催化剂钒污染加重。该厂采取调和原油的掺炼比例、优化操作参数、加大催化剂的置换速率、试用复合抗钒钝化剂、使用抗钒催化剂等措施，得到了好的效果。当催化剂上钒含量达９～１０ｍｇ／ｇ时，生产仍能保持正常运行。     

胶质对沥青质稳定性的影响

为了进一步研究胶质与沥青质之间的相互作用对沥青质稳定性的影响,在分析表征沥青质和胶质的平均结构单元并计算溶解度参数的基础上,向沥青质模型油（沉积物计为AS沉积物）中分别加入胶质NBR和胶质VRR得到AS+NBR沉积物和AS+VRR沉积物,通过分析沉积物颗粒粒径分布,考察胶质对沥青质稳定性的影响程度。结果表明：沥青质的芳香性最强、溶解度参数最大（20.61 MPa1/2）,胶质VRR的芳香性和溶解度参数（17.80 MPa1/2）高于胶质NBR;在沥青质模型油中,随着胶质VRR浓度的增加,沉积物颗粒粒径减小,而胶质NBR的加入并不能使沉积物颗粒粒径变小,当其质量浓度达到1 000 mg/L时,沉积物颗粒粒径反而增加。3种沉积物的热重、凝胶渗透色谱（GPC）和X射线衍射（XRD）分析结果表明：胶质与沥青质之间存在缔合作用,使沉积物芳香片层厚度和直径减小、层间距增大,芳香片层数减小;3种沉积物的相对分子质量从大到小的顺序为AS沉积物＞AS+NBR沉积物＞AS+VRR沉积物。因此芳香性强、溶解度参数接近沥青质的胶质VRR能更好地分散稳定沥青质,使得沉积物颗粒粒径变小、石墨化程度减弱,从而不易沉积和结焦。     

ADSORPTION OF ASPHALTENE FUNTIONALITIES AND ASPHALTENE ON GOETHTTE

ABSTRACT

Solid-stabilized water-in-oil emulsions cause many problems such as oil loss, fouling of a processing unit, and environmental hazard in the petroleum production and refining. The ability of finely divided solids to stabilize these emulsions is due to the adsorption of asphaltenes and other heavy constituents. This study presents the individual and competitive adsorption of asphaltene functionalities in cyclohexane solution and asphaltene in heptol solution onto goethite (FeOOH) particle surfaces at 25 °C to quantitatively understand the FeOOH particle-fluid interactions. The functionalities used were carboxylic acid (represented by benzoic acid), sulfoxide (by diphenylsulfoxide), and pyrrolic (by indole). The single component adsorption of these functionalities was well represented by both the Langmuir and Freundlich models, showing that adsorptive affinity for FeOOH increased in the order of indole < diphenylsulfoxide < benzoic acid. This observation was supported by the results of bi-component competitive adsorption of three functionality pairs on FeOOH, which were interpreted by the Fritz model. The adsorption of asphaltene was performed using dry and moist FeOOH surfaces and well represented by both the Langmuir and Freundlich models. The moist FeOOH yielded a decrease in the adsorption of asphaltene compared to adsorption on dry FeOOH.     

ZSM—5分子筛中引入过渡金属对催化热裂解反应的影响

应用含有不同过渡金属的ZSM－5分子筛及催化剂对轻柴油进行催化热裂解反应,研究了在分子筛及催化剂中引入过渡金属对于催伦热裂解反应机理及乙烯、丙烯产率的影响。结果表明,ZSM－5分子筛或催化剂中引入过渡金属后,反应产物分布发生了变化,催化热裂解反应的机理有了一定程度的改变,尤其是银的引入提高了乙烯的产率,而且并未降低丙烯产率,说明银在催化热裂解反应中既可以促进正碳离子的生成,又有可能通过氧化－还原作用部分改变反应机理,促进自由基的生成。     

沥青质对稠油黏度的影响

选用新疆地区的6种高黏稠油为主要研究对象,测定各稠油的性质并配制不同沥青质含量的同源调合稠油、异源调合稠油,利用黏度法考察沥青质含量对稠油黏度的影响。结果表明：无论是同源调合稠油还是异源调合稠油,随着沥青质添加量的增加,稠油黏度均呈增大的趋势,且在沥青质添加量达到一定值时黏度出现突变;相同温度、相同沥青质含量下,四氢呋喃处理过的稠油黏度比甲苯处理过的稠油黏度要大,且增加幅度较甲苯处理过的要大。     

渣油胶质和沥青质在分散型催化剂作用下的临氢热反应行为

采用四组分法从辽河减压渣油中分离出胶质、沥青质，分别考察了它们在分散型催化剂作用下的临氢热反应行为。结果表明，胶质、沥青质一方面要裂化生成较轻的产物；另一方面也要发生缩合反应生成较重的反应产物以及甲苯不溶物。渣油在临氢热反应过程中，沥青质是生焦的主要来源，其次才是胶质。比较了热反应生成的沥青质与原生沥青质之间以及热反应生成的胶质与原生胶质之间化学组成的区别，结果表明，反应生成的沥青质和胶质较原生的沥青质和胶质分子结构缩合程度高，并且反应苛刻度越高，缩合程度也越高。     

加氢体系构成对沥青质加氢效果的影响

将从玉门原油常压渣油和委内瑞拉原油常压渣油中抽提得到的沥青质,分别在渣油体系和十氢萘体系中进行加氢反应,从加氢产物分布、杂原子脱除率、加氢后沥青质缩合程度3个方面综合考察两种沥青质在不同体系中的加氢效果。结果表明：在十氢萘体系中,沥青质加氢的轻质产物收率更高,焦炭收率更低,但杂原子脱除效果较差;在渣油体系中,沥青质加氢的焦炭收率更高,杂原子脱除效果更好,沥青质的缩合程度更高。主要原因是十氢萘对沥青质具有溶解、分散作用,且对加氢过程具有供氢作用,可以改善沥青质加氢产物的分布,并减缓沥青质的缩合趋势,减少焦炭生成;而渣油体系中重组分大分子易缩合生成焦炭,有助于硫、氮杂原子通过生成焦炭的形式脱除。     

沥青质和环烷酸含量对原油乳状液稳定性影响

以大庆油田原油为研究对象,与环烷酸、室内模拟污水配制成不同的原油乳状液.通过对各体系的析水率、界面张力和稳定性指数(TSI)的测试,考察了沥青质和环烷酸共同作用对乳状液稳定性的影响.结果表明,随着沥青质和环烷酸质量分数增大,乳状液的析水率从56.0％增加至93.8％;界面张力从0.984 mN/m增加至9.702 mN...