SiO_2负载磷钼酸铵液相催化氧化二苯并噻吩  

Liquid Phase Catalytic Oxidation of Dibenzothiophene over Silica Supported Ammonium Molybdophosphate Catalyst

作　　者：贾连洋[1] 耿辉[1] 于丽敏[1] 龚树文[1] 申文忠[2] 尹汉东[1] 

机构地区：[1]山东省化学储能与新型电池技术重点实验室聊城大学化学化工学院,山东聊城252059 [2]中国科学院山西煤炭化学研究所,山西太原030001

出　　处：《石油化工》2011年第11期1184-1189,共6页Petrochemical Technology

基　　金：国家重点基础研究发展规划项目前期研究专项基金资助项目(2010CB234601)

摘　　要：以正硅酸乙酯为硅源,采用溶胶-凝胶法制备了不同负载量的SiO2负载磷钼酸铵(AMPA)催化剂(AMPA/SiO2);利用XRD,FTIR,SEM等手段对AMPA/SiO2催化剂进行了表征;并以二苯并噻吩等含硫化合物为底物、以30%(w)H2O2为氧化剂,初步评价了AMPA/SiO2催化剂催化氧化噻吩类化合物的性能。实验结果表明,溶胶-凝胶法制备的AMPA/SiO2催化剂保持了磷钼酸铵的Keggin结构;含有AMPA/SiO2催化剂、30%H2O2(w)的正己烷/乙酸的双液相氧化体系可高效地将噻吩类化合物氧化为相应的砜,噻吩类化合物氧化反应活性的高低顺序为:4,6-二甲基二苯并噻吩>二苯并噻吩>苯并噻吩>噻吩;在MoO3质量分数为10%的AMPA/SiO2催化剂用量0.20 g、H2O2与二苯并噻吩摩尔比2∶1、反应温度50℃、反应时间30 min的优化条件下,二苯并噻吩砜的收率达94%,AMPA/SiO2催化剂可多次重复使用。A series of silica supported ammonium molybdophosphate（AMPA/SiO2） catalysts withdifferent loadings were prepared by a sol-gel method and characterized by means of XRD,FTIR and SEM.The activities of the catalysts in the oxidation reactions of dibenzothiophene and the other sulfocompoundswith 30%（w） H2O2 as oxidant were evaluated.The experimental results indicated that the Keggin structurewas retained after ammonium molybdophosphate was supported on silica,and that dibenzothiophene and theother sulfocompounds were oxidized with H2O2 on the catalysts in the n-hexane/acetic acid binary system tothe corresponding sulfones.The oxidative reactivities of the sulfocompounds decreased in the order of 4,6-dimethyl dibenzothiophene dibenzothiophene benzothiophene thiophene.Under the optimalconditions for the oxidative desulfurization： AMPA /SiO2 catalyst（MoO3 mass fraction 10%） dosage0.20 g,n（H2O2） ∶ n（DBT） 2 ∶ 1,reaction temperature 50 ℃ and reaction time 30 min,the yield ofdibenzothiophene sulfone reached 94%.The optimum catalyst could be reused for many times.

关 键 词：过氧化氢 磷钼酸铵/二氧化硅催化剂 催化氧化 脱硫 二苯并噻吩 

分 类 号：TQ032.4[化学工程]