磷改性SPP沸石催化甲醇制丙烯反应  

Phosphorus-Modified SPP Zeolite Catalysts for Methanol to Propylene Reaction

作　　者：邢亚茹 刘民[1] 郭新闻[1] XING Yaru;LIU Min;GUO Xinwen(State Key Laboratory of Fine Chemicals,Frontier Science Center for Smart Materials,School of Chemical Engineering,Dalian University of Technology,Dalian 116024,China)

机构地区：[1]大连理工大学化工学院,精细化工国家重点实验室,智能材料化工前沿科学中心,辽宁大连116024

出　　处：《化学反应工程与工艺》2024年第5期385-393,共9页Chemical Reaction Engineering and Technology

基　　金：国家自然科学基金项目资助(21972013);辽宁省“兴辽英才计划”项目资助(XLYC2008032)。

摘　　要：为开发甲醇制丙烯(MTP)反应的高性能催化剂,制备了不同硅铝比的SPP沸石,再进行磷改性处理。采用X射线衍射(XRD)、扫描电镜(SEM)、电感耦合等离子发射光谱(ICP)、氮气物理吸附、NH_(3)程序升温脱附(NH_(3)-TPD)和热重分析等手段表征了样品的孔结构和酸性质等,并比较了各催化剂在甲醇制丙烯(MTP)反应中的催化性能。结果表明:相比于普通ZSM-5沸石,SPP沸石具有更大的比表面积和孔容,可以显著提高分子的扩散速率和活性位点的可接触性,提高了反应性能。得益于弱碱性磷酸铵的孔道清洁作用,磷改性后的SPP沸石的总孔容均增加。同时,随着磷改性浓度的增加,SPP沸石的强酸量逐渐降低。磷改性得到的SPP沸石(磷的质量分数为0.2%)催化MTP反应时,丙烯选择性达到50.4%,C_(2)^(=)-C_(4)^(=)选择性达到72.1%,积炭量为1.4%。In order to develop high-performance catalysts for methanol to propylene(MTP)reaction,SPP zeolites with different silica-alumina ratios were prepared,and then treated with phosphorus modification.The pore structure and acid properties of the samples were characterized by X-ray diffraction(XRD),scanning electron microscopy(SEM),inductively coupled plasma(ICP),nitrogen physical adsorption,NH_(3) temperature-programmed desorption(NH_(3)-TPD)and thermogravimetric analysis(TG).The catalytic performance of each sample was compared in the MTP reaction.The results showed that SPP zeolites had larger specific surface area and pore volume than ordinary ZSM-5 zeolites,which could significantly improve the molecular diffusion rate and the accessibility of active sites,and improve the reaction performance.Due to the pore cleaning effect of weakly alkaline ammonium phosphate,the total pore volume of all samples modified by P increased,and the strong acid content decreased with the increase of the modified P concentration.The MTP reaction catalyzed by SPP zeolite modified with a phosphorus mass fraction of 0.2%,the selectivity of propylene was 50.4%,the selectivity of C_(2)^(=)-C_(4)^(=)was 72.1%,and the coke deposition was 1.4%.

关 键 词：SPP沸石 磷改性 甲醇制丙烯 

分 类 号：O643.38[理学—物理化学]