Hβ分子筛的磷改性及其催化甲苯和叔丁醇烷基化反应性能  

Phosphprus modified Hβzeolites and the catalytic perpormance for alkylation of toluene with tert-butylalcohol

作　　者：王园园[1] 宋华[1] 孙兴龙 苑丹丹[1] 王雪芹[1] WANG Yuanyuan;SONG Hua;SUN Xinglong;YUAN Dandan;WANG Xueqin(School of Chemistry and Chemical Engineering,Northeast Petroleum University,Daqing,Heilongjiang 163318,China;Daqing Petrochemical Engineering Company Limited,Daqing,Heilongjiang 163714,China)

机构地区：[1]东北石油大学化学化工学院,黑龙江大庆163318 [2]大庆石化工程有限公司,黑龙江大庆163714

出　　处：《东北石油大学学报》2020年第4期85-90,I0007,共7页Journal of Northeast Petroleum University

基　　金：黑龙江省杰出青年基金项目(JC2018002);黑龙江省青年基金项目(QC2017005);东北石油大学青年基金项目(2018QNL-26);东北石油大学人才引进科研启动费资助项目(1305021821)。

摘　　要：分别以磷酸(PA)、磷酸氢二铵(DHP)、磷酸二氢铵(ADP)为磷源,对n(Si)/n(Al)为25的Hβ分子筛进行磷改性,采用SEM、XRD、FT-IR、BET和Py-IR等对催化剂样品进行表征,考察不同P_2O_5/Hβ催化剂对甲苯与叔丁醇烷基化反应性能的影响。结果表明:与未改性Hβ相比,不同磷源磷改性的P_2O_5/Hβ催化剂的催化活性和对位选择性明显增加,P_2O_5/Hβ(ADP)催化效果最好。随P_2O_5负载量的增加,P_2O_5/Hβ(ADP)晶体结构变化不大,比表面积、孔体积和孔径逐渐降低,B酸量增加,L酸量减少。当采用负载量为15%的P_2O_5/Hβ(ADP)为催化剂时,在适宜的反应条件下,甲苯转化率为73.7%,对叔丁基甲苯(PTBT)的选择性为81.1%。该结果为用于芳烃侧链烷基化反应的分子筛催化剂的设计及制备提供思路。Hβcatalysts,such as P 2O 5/Hβ(ADP),P 2O 5/Hβ(DHP)and P 2O 5/Hβ(PA),modified by several phosphate sources were successfully prepared and investigated in butylation of toluene.Scanning electron microscopy,X-ray diffraction,fourier-transform infrared spectroscopy,the brunauer emmett teller(BET)method and pyridine adsorption infrared spectroscopy were used to characterize the catalysts.The results showed that compared with parent Hβzeolite,both catalytic activity and para-selectivity of phosphate modified Hβcatalysts increased.The P 2O 5/Hβ(ADP)was found to be the most efficient catalyst for this particular alkylation process.With the increase of P 2O 5 contents in P 2O 5/Hβ(ADP),the crystal structure was retained,while the specific surface area,pore volume and pore size decreased,B acidity increased,L acidity decreased.The appropriate P 2O 5 loading was 15%and the toluene conversion of 73.7%with PTBT selectivity of 81.1%could be obtained.This method provide a new idea for the design and preparation of zeolite catalysts which used in alkylation of aromatic hydrocarbons.

关 键 词：HΒ分子筛 甲苯 叔丁醇 对叔丁基甲苯 烷基化 磷改性 

分 类 号：TQ241[化学工程—有机化工]