重油加工产品加氢改质催化剂及反应工程基础研究

刘晨光 柳云骐 柴永明 殷长龙 鲍晓军

摘 要：该报告借助高分辨透射电镜、扩展X射线吸收精细结构（EXAFS）、X射线光电子能谱（XPS）和激光拉曼光谱等先进表征手段，深入研究汽柴油加氢改质催化剂活性相组成、结构、形貌与其加氢性能的关系，阐明载体性质、制备方法和活化过程对催化剂中活性相形成的影响规律，发展降低杂原子脱除苛刻度的新型催化材料和制备方法，研制系列汽、柴油加氢改质催化剂。以大幅增加汽油产品中的异构烷烃含量（提高汽油辛烷值）和适度增加芳烃含量（提高汽油辛烷值）、降低柴油产品中的芳烃含量（提高十六烷值）和增加异构烷烃含量（降低柴油凝点）为目标，研制了将汽油中的烯烃和柴油中的直链烷烃定向转化为异构烷烃、饱和柴油中芳烃的催化材料，发展其改性方法，开发出具有超深度脱硫、脱氮和芳烃加氢选择性开环和实现石油烃类定向转化的系列催化剂。研究了汽柴油中含硫、含氮化合物与烯烃、芳烃在催化剂活性位上的竞争吸附-反应机理，辅之以加氢改质反应的热力学研究，建立了汽柴油加氢改质过程中杂原子化合物和烃类化合物的化学反应网络和动力学模型，并借以分析反应工艺配置、催化剂级配方式以及操作条件对汽、柴油加氢改质过程的影响，确定适合加氢改质目标的工艺流程配置和催化剂级配方式。采用冷模试验与热模实验相结合的方式，系统考察催化剂尺寸、几何构型、装填方式和反应器构型、级联方式对汽柴油加氢改质过程操作性能的影响，建立加氢改质工艺和反应器的设计放大方法。

关键词：加氢改质 催化剂 汽油 柴油 反应工程

The Report of Hydro-upgrading Catalysts and Reaction Engineering for Heavy oil Processing Products

Liu Chenguang1 Liu Yunqi1 Chai Yongming1 Yin Changlong1 Bao Xiaojun2

（1.China University of Petroleum-East China；2.China University of Petroleum-Beijing）

Abstract：With the help of high-resolution transmission electron microscopy，Extended X-ray absorption fine structure（EXAFS）， X-ray photoelectron spectroscopy and Laser Raman Spectroscopy and other advanced characterization methods， the relationship between activity phase composition， structure， morphology and hydrogenation ability of gasoline and diesel hydro-upgrading catalyst is studied. The influence of support， preparation process and activation on activity phase formation is clarified. The novel catalytic materials and preparation methods as well as series of gasoline and diesel hydro-upgrading catalysts are developed. The aim is to increase the content of isomerization alkanes significantly and aromatics modestly （improve octane number） in gasoline， reduce the content of aromatics （increase cetane number） and increase the content of isomerization alkanes （reduce the solidifying point） in diesel. Catalytic materials which can transform the olefins in gasoline and straight-chain alkanes in diesel into isomerization alkane were developed. We also developed methods to modify the catalytic materials. A series of catalysts with ultra deep desulfurization， denitrogenation and selectively ring-opening of aromatics were developed These catalysts realized directional transformation of petroleum hydrocarbons The article studied the competitive adsorption mechanism in the catalytic active sites of S- and N- compounds with olefins and aromatics in gasoline and diesel. With the thermodynamics study of hydro-upgrading， we established the chemical reaction networks and kinetic modes of heteroatomic compounds and hydrocarbons in hydro-upgrading process of gasoline and diesel， then analyzed the impact of reaction process， catalyst composition and operation conditions on the gasoline and diesel hydro-upgrading process to find the optimum operation conditions and catalyst composition. By combination of cold model test and hot model test， we studied systematically the influences of catalyst size， geometry， packing， reactor and cascade method on the performance of hydro-upgrading of gasoline and diesel， and then established the optimum hydro-upgrading process and the expansion method of the reactor design.

Key Words：Hydro-upgrading；Catalyst；Gasoline；Diesel；Reaction Engineering

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