重油加工產(chǎn)品加氫改質(zhì)催化劑及反應(yīng)工程基礎(chǔ)研究

劉晨光 柳云騏 柴永明 殷長龍 鮑曉軍

摘 要：該報告借助高分辨透射電鏡、擴展X射線吸收精細(xì)結(jié)構(gòu)（EXAFS）、X射線光電子能譜（XPS）和激光拉曼光譜等先進表征手段，深入研究汽柴油加氫改質(zhì)催化劑活性相組成、結(jié)構(gòu)、形貌與其加氫性能的關(guān)系，闡明載體性質(zhì)、制備方法和活化過程對催化劑中活性相形成的影響規(guī)律，發(fā)展降低雜原子脫除苛刻度的新型催化材料和制備方法，研制系列汽、柴油加氫改質(zhì)催化劑。以大幅增加汽油產(chǎn)品中的異構(gòu)烷烴含量（提高汽油辛烷值）和適度增加芳烴含量（提高汽油辛烷值）、降低柴油產(chǎn)品中的芳烴含量（提高十六烷值）和增加異構(gòu)烷烴含量（降低柴油凝點）為目標(biāo)，研制了將汽油中的烯烴和柴油中的直鏈烷烴定向轉(zhuǎn)化為異構(gòu)烷烴、飽和柴油中芳烴的催化材料，發(fā)展其改性方法，開發(fā)出具有超深度脫硫、脫氮和芳烴加氫選擇性開環(huán)和實現(xiàn)石油烴類定向轉(zhuǎn)化的系列催化劑。研究了汽柴油中含硫、含氮化合物與烯烴、芳烴在催化劑活性位上的競爭吸附-反應(yīng)機理，輔之以加氫改質(zhì)反應(yīng)的熱力學(xué)研究，建立了汽柴油加氫改質(zhì)過程中雜原子化合物和烴類化合物的化學(xué)反應(yīng)網(wǎng)絡(luò)和動力學(xué)模型，并借以分析反應(yīng)工藝配置、催化劑級配方式以及操作條件對汽、柴油加氫改質(zhì)過程的影響，確定適合加氫改質(zhì)目標(biāo)的工藝流程配置和催化劑級配方式。采用冷模試驗與熱模實驗相結(jié)合的方式，系統(tǒng)考察催化劑尺寸、幾何構(gòu)型、裝填方式和反應(yīng)器構(gòu)型、級聯(lián)方式對汽柴油加氫改質(zhì)過程操作性能的影響，建立加氫改質(zhì)工藝和反應(yīng)器的設(shè)計放大方法。

關(guān)鍵詞：加氫改質(zhì) 催化劑 汽油 柴油 反應(yīng)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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