悬浮物制备介微孔分子筛复合材料及其催化性能  

Preparation of mesoporous molecular sieve composites by suspended sludge and their catalytic performance

作　　者：刘超伟 张莉 张吉华 胡清勋 柳黄飞 方华 王久江 刘宏海 曹庚振 LIU Chao-wei;ZHANG Li;ZHANG Ji-hua;HU Qing-xun;LIU Huang-fei;FANG Hua;WANG Jiu-jiang;LIU Hong-hai;CAO Geng-zhen(Petrochemical Research Institute,PetroChina,Beijing 102200,China;Lanzhou Petrochemical Research Center,Petrochemical Research Institute,PetroChina,Lanzhou 730060,China;Catalyst Division of Lanzhou Petrochemical Company,PetroChina,Lanzhou 730060,China)

机构地区：[1]中国石油石油化工研究院,北京102200 [2]中国石油石油化工研究院兰州化工研究中心,甘肃兰州730060 [3]中国石油兰州石化公司催化剂事业部,甘肃兰州730060

出　　处：《石化技术与应用》2024年第6期401-407,共7页Petrochemical Technology & Application

基　　金：中国石油重大科技专项计划资助项目(项目编号:2016 E-0701)。

摘　　要：借助X射线衍射仪、扫描电子显微镜、X射线荧光光谱仪、红外光谱仪等表征手段,对原位晶化型催化裂化催化剂晶化工序中产生的悬浮物进行了表征,并评价了其复配量(质量分数,下同)为10%~30%时的相应介微孔分子筛复合材料及其催化剂的催化反应性能。结果表明:该悬浮物为Y型分子筛、钠菱沸石及无定型硅铝物质的混合物,约含质量分数为40%的Y型分子筛,硅铝(SiO_(2)与Al_(2)O_(3))摩尔比为4.81~5.42,比表面积、孔容分别达496 m^(2)/g和0.40 cm^(3)/g,可作为催化裂化用介微孔分子筛复合材料。悬浮物的引入改变了Y型分子筛孔结构,使介孔孔容占比增大,结晶度保留率从66.3%提高至77.8%,结构稳定性优异。当悬浮物复配量为30%时,介微孔分子筛复合材料的相对结晶度降低4个百分点,同时总B酸量降幅明显,其相应催化剂17 h微反活性达65%。随悬浮物复配量从10%增至30%时,液化气、汽油、柴油收率呈现波动趋势,原料油转化率从84.58%降低至83.69%,同时重油收率从5.29%提高至5.87%,综合考虑,推荐的悬浮物复配量在20%以内较佳。The suspended sludge generated during the crystallization process of in-situ crystallized catalytic cracking catalysts were characterized by using the characterization methods such as X-ray diffraction,scanning electron microscopy,X-ray fluorescence spectrometer and infrared spectrometer.Then the catalitic reaction performance of the corresponding mesoporous molecular sieve composites and their catalysts were evaluated when the compounding amount(mass fraction,the same below)of suspended sludge solids mass fraction at 10%-30%.The results showed that such above suspended sludge solids was the mixture of Y zeolite,sodium rhombohedral zeolite,and amorphous silicon aluminum material.It contained about 40%Y zeolite,with the molar ratio of SiO_(2)to Al_(2)O_(3)at 4.81-5.42,and the specific surface area and pore volume at 496 m^(2)/g and 0.40 cm^(3)/g,respectively.It could be used as a mesoporous molecular sieve composite material for catalytic cracking.The introduction of suspended sludge solids changed the pore structure of the Y zeolite by increasing the proportion of mesoporous volume and improving the crystallinity retention rate from 66.3%to 77.8%,and the corresponding mesoporous molecular sieve composites demonstrated the excellent structural stability.When the compounding amount of suspended sludge solids was 30%,the relative crystallinity of the mesoporous molecular sieve composites decreased by 4 percentage points and the total amount of B acid decreased significantly,and the corresponding catalyst′s 17 h micro-reaction reactivity reached 65%.As the amount of suspended sludge solids increased from 10%to 30%,the yields of liquefied gas,gasoline,and diesel showed a fluctuating trend,meanwhile,the conversion rate of raw oil decreased from 84.58%to 83.69%,the yield of heavy oil increased from 5.29%to 5.87%.All things considered,the recommended compounding amount of suspended sludge solids was better within 20%.

关 键 词：催化裂化 悬浮物 介微孔分子筛复合材料 催化性能 

分 类 号：TE624.41[石油与天然气工程—油气加工工程]