内蒙古油砂油减压渣油制备特种沥青的研究

以内蒙古油砂油减压渣油为原料，分别与克拉玛依减压渣油、孤岛减压渣油、辽河减压渣油和胜利减压渣油以不同比例调合，考察制备抛光沥青、油漆石油沥青等特种沥青的可行性。结果表明，油砂油减压渣油与克拉玛依减压渣油以25：75的质量比调合后，可作60号抛光沥青，以30：70质量比调合后，可作3号油漆石油沥青；油砂油减压渣油与孤岛减压渣油以 40 ： 60的质量比调合后，可做60号抛光沥青；油砂油减压渣油与辽河减压渣油、胜利减压渣油调合后，调合沥青不宜作特种沥青。     

沙特阿拉伯减压渣油超临界抽出油催化裂化反应性能

利用超临界溶剂萃取技术将沙特阿拉伯减压渣油进行不同抽出率的切割分离，并对抽出油及阿拉伯减压渣油进行了全面的性质分析，提出了表征减压渣油及其各抽出油的特性因数KH。在固定流化床反应装置上对上述各种原料进行了催化裂化反应，得到了反应产品分布与原料性质及KH之间的关系，从而可为沙特阿拉伯减压渣油的合理加工提供基础数据和指导。     

接触剂性质和油膜厚度对减压渣油接触裂化反应性能的影响

为考察接触剂对减压渣油接触裂化反应的影响，以石家庄减压渣油为原料，采用热解色谱(Py GC)和热重质谱(TG MS)分别评价无孔无酸接触剂(A)、有孔无酸接触剂(B)和有孔有酸接触剂(C)的孔结构、酸性，以及接触剂上油膜厚度对减压渣油裂化反应条件和反应产物的影响。结果表明，与无孔接触剂相比，接触剂上孔道的引入，使减压渣油分子能进入到孔径大于10 nm的孔道进行初步裂化，初步裂化产物能够进入孔径小于10 nm的孔道内进行二次裂化，生成更小分子。在A剂上减压渣油的油膜厚度对其热裂化反应产物的分布和生焦率没有明显影响；在B剂上减压渣油热裂化反应强度增强，生焦率增大至12%~13%；在C剂上，随着减压渣油油膜厚度的减小，其裂化产物中C12-和C12~C20馏分相对质量分数增大，C20+馏分相对质量分数减小，生焦率增大。TG MS结果表明，接触剂上酸中心的引入大大降低了减压渣油的起始裂化温度。     

吉林减压渣油催化裂化工艺技术浅析

减压渣油催化裂化在我国尚属首次，本文通过扼要介绍吉林减压渣油全馏分在前郭炼油厂重油催化裂化装置连续运行２７４天的生产实践，分析了减压渣油催化裂化的几项关键工艺技术，认为吉林减压渣油催化裂化在技术上是可行的，经济效益也很好。     

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。     

阿曼渣油溶剂脱沥青研究

对阿曼渣油丁烷溶剂脱沥青进行了研究，结果表明：阿曼渣油丁烷溶剂脱沥青，在适宜的脱沥青油收率下，脱油沥青可以满足ＡＨ—９０高等级道路沥青的要求；将阿曼减压渣油与阿曼减压渣油或鲁宁管输油减压渣油丁烷溶剂脱沥青的高软化点脱油沥青调合也可以获得ＡＨ—７０、ＡＨ—９０高等级道路沥青，溶剂脱沥青技术是有效加工阿曼减压渣油的加工技术之一。     

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。     

我厂减压渣油溶剂抽提路线的探讨

利用实验室眼临驻体抽提装置，选用两种溶剂对我厂减压渣油进行分离。在考察各窄馏分性质的基础上，结合我厂实际情况，着重探讨我厂减压渣油的利用途径。     

基于分子组成的减压渣油聚类分析

基于减压渣油的结焦性能受化合物的类型分布的影响,将高分辨质谱分析得到的数据按照芳烃（HC）、含1个硫原子的硫化物(S1)、含2个硫原子的硫化物(S2)、含1个氮原子的氮化物(N1),按碳数的分布分成10类,并从分子组成上对71种减压渣油进行了聚类分析。结果表明：聚类分析将71种减压渣油按分子组成特点分为Ⅰ类、Ⅱ类和Ⅲ类减压渣油;为验证聚类的准确性,以减压渣油的残炭值作为聚类分析结果合理性判断的依据,发现Ⅰ类减压渣油残炭值最低,属于不易结焦的减压渣油;Ⅲ类减压渣油残炭值最大,属于最易结焦的减压渣油;Ⅱ类减压渣油残炭值高于Ⅰ类减压渣油,低于Ⅲ类减压渣油,结焦倾向居中。本研究利用聚类分析对多个减压渣油样本按分子组成进行分类,实现了FT-ICR MS数据的有效管理,为减压渣油的加工提供指导。     

减压渣油加氢处理装置原料优化的研究

在中型固定床渣油加氢处理试验装置上研究了减压渣油加氢处理过程中，几种稀释油对减压渣油加氧效果的影响。对比研究表明，润滑油糠醛精制装置抽出油、丙烷脱沥青装置脱沥青油、减压渣油加氢生成油350℃以上馏分均可作为减压渣油加氢处理过程中所需稀释油的替代品种，尤其是后两种油品作稀释油对生产用户更具实际意义。     

CHARACTERIZATION OF VACUUM RESIDS, HYDROCRACKED PRODUCTS AND ASPHALTENES BY PYROLYSIS-GAS CHROMATOGRAPHY (FID-FPD)

This paper describes an exploratory study on the characterization of oil heavy-end fractions through pyrolysis coupled with gas chromatography. A pulse heating pyrolyzer with a platinum-strip sample holder, directly coupled with a capillary column gas chromatograph and equipped with a universal detector (FID) and a sulfur-selective detector (FPD), was used for that purpose.

An analysis of vacuum residua, asphaltenes and resins from different crudes was made, as well as analogous fractions from the hydrocracking products of these vacuum residua. Hydrocarbon qualitative profiles (pyrograms) were very much alike for all fractions studied. However, some differences were observed in pyrogram intensity. In general, fractions from untreated samples showed more intense signals than those from the hydrotreated ones. Besides, each of the fractions from vacuum residua generated more intense pyrograms than the combination thereof (entire residue). It was possible to correlate the process-ability of a vacuum residue during hydrocracking and its hydrocarbon yield in analytical pyrolysis.     

CHARACTERIZATION OF VACUUM RESIDS,HYDROCRACKED PRODUCTS AND ASPHALTENES BY PYROLYSIS-GAS CHROMATOGRAPHY (FID-FPD)

ABSTRACT

This paper describes an exploratory study on the characterization of oil heavy-end fractions through pyrolysis coupled with gas chromatography. A pulse heating pyrolyzer with a platinum-strip sample holder, directly coupled with a capillary column gas chromatograph and equipped with a universal detector (FID) and a sulfur-selective detector (FPD), was used for that purpose.

An analysis of vacuum residua, asphaltenes and resins from different crudes was made, as well as analogous fractions from the hydrocracking products of these vacuum residua. Hydrocarbon qualitative profiles (pyrograms) were very much alike for all fractions studied. However, some differences were observed in pyrogram intensity. In general, fractions from untreated samples showed more intense signals than those from the hydrotreated ones. Besides, each of the fractions from vacuum residua generated more intense pyrograms than the combination thereof (entire residue). It was possible to correlate the process-ability of a vacuum residue during hydrocracking and its hydrocarbon yield in analytical pyrolysis.     

实时监控渣油热反应过程的光学显微镜法

在胜利减压渣油热反应体系中，随着热处理时间的延长，依次出现了3个可为光学显微镜所检测和辨识的特征状态点。分析结果表明：第一个特征状态点与渣油胶体体系丧失动力学稳定性后原生沥青质的聚集和分相有关，它决定着体系的生焦诱导期；第三个特征状态点与体系中次生沥青质的浓度高达相分离的临界状态相对应，它决定着开始大量生焦的时刻。据此认为，光学显微镜法在实验室条件下预报渣油热反应体系物理化学状态的突变特性是可行的，且有可能在工业上应用。     

LABORATORY STUDY OF REAL-TIME OPTICAL MICROSCOPE TRACKING OF THERMAL REACTION PROGRESS OF VACUUM RESIDUA II: CHEMICAL RELEVANCE OF PHYSICAL PROCESSES IN THERMAL REACTION SYSTEMS OF VACUUM RESIDUA

It has been indicated from analyses of the vicissitude of chemical states and their comparisons with the occurring physical processes in the thermal reaction systems of vacuum residua that the first characteristic state point coincides with the induction period of coke formation, and the third characteristic state point, immediately after which a large amount of coke is yielded, manifests the critical point at which concentration of the neo-asphaltenes generated in-situ by the fast-reaction resins is high enough to approach its phase separation. The industrial implication of the second characteristic state point is not clear enough. It is accordingly pointed out, in combination with the conclusions drawn in the first part of the serial, that the real-time optical microscope tracking of the thermal reaction progress of vacuum residua based on the first and third characteristic state points is feasible on the laboratory scale for forecasting the sudden changes of the physical and/or chemical states of the thermal reaction systems of vacuum residua, and is expected to find applications in the industrial visbreaking process.     

减压渣油特征化参数的研究

在对多种渣油进行超临界流体萃取分馏及窄馏分性质分析的基础上，计算了三种减压渣油超临界流体萃取分馏窄馏分的Ｗａｔｓｏｎ Ｋ值，发现适用于原油及其轻馏分的ａｔｓｏｎＫ值不能表达渣油及其馏分的特性和分类。首次提出了以Ｈ／Ｃ原子比、分子量及密度三因素来表征减压渣油的特征参数ＫＨ。利用文献数据，以ＫＨ为依据对渣油的物性、热裂化、催化裂化及高温热解的结果进行了分析研究，表明ＫＨ值可以较好地体现渣油或其馏分的整     

渣油热反应体系中第二液相形成与液相掺兑物的关系

向渣油体系中掺兑具有不同芳香度和芳香性分布的液相掺兑物，能够不同程度地改变渣油热反应体系中第二液相的相分离特性，从而改变渣油热反应体系的生焦特性。液相掺兑物的芳香度越高，芳香性分布范围越宽，其抑制第二液相形成和推迟相分离点出现时间的作用越显著。     

Incipient Phase Separation Behavior and Colloidal Stability in Liquid-Phase Carbonization of Residua

A thermal-stage polarized light microscopy was used to study the phase separation behaviors of three typical Chinese petroleum vacuum residua (Daqing, Shengli, and Gudao) during liquid-phase carbonization process. The resulting observations show that during thermal reaction, phase change occurs in two stages: physical and chemical. The effects of temperature during heat treatment and colloidal stability of vacuum residua on phase separation were investigated.     

PHASE SEPARATION BEHAVIORS AND THEIR RELATIONS WITH COKE FORMATION IN THERMAL REACTION SYSTEMS OF VACUUM RESIDUA

A real-time optical microscope monitoring of the physical process of coke formation in the batch-type thermal reaction systems of three typical Chinese vacuum residua has evidenced that, as the residence time extends, there appear successively three kinds of neophases identified themselves by their morphology, onset point and bulk effect. The solubility test has demonstrated that all the three categories of neophases are of the same solubility class. Additional proofs from the comprehensive time-sequential approach to the thermal reaction process of vacuum residua and the morphological relations disclosed by SEM between the neophases and coke have justified the heavy dependence of coke formation upon the neophases and their phase separation behaviors.     

COMPARATIVE STUDY OF THE COMPOSITIONAL CHARACTERISTICS OF LIQUIDS DERIVED BY HYDROTREATING OF NIGERIAN TAR SAND BITUMEN. I. SIMULATED DISTILLATION

Nigerian tar sand bitumen was hydrotreated at relatively low temperatures and initial hydrogen pressures. The liquid products derived from the hydrotreating process were characterized by the means of instrumental analysis of simulated distillation on gas chromatography. Results show that the liquid products are amenable to the characterization procedure and provided basic data that should be useful in formulating refining processes for Nigerian tar sand bitumen and the liquids derived from its hydrotreating operations. The liquids show differences in products distribution for different temperature but have almost identical structures for same temperatures and different pressures. Generally, increase in temperature caused an increase in conversion of bitumen to distillable products. The characterization data of the derived liquid products will serve as a basis for the identification of processes for upgrading bitumen and such other fossil fuels like coal liquids or heavy vacuum residua.