TiO_2/SiO_2催化剂的1-己烯异构化性能研究  

1-Hexene Isomerization on TiO_2/SiO_2 Composite Oxides

作　　者：张胜振[1] 董鹏[1] 张毓莹[1] 杜维君[1] 陈胜利[1] 

机构地区：[1]石油大学重质油国家重点实验室

出　　处：《石油与天然气化工》2005年第1期3-7,共5页Chemical engineering of oil & gas

基　　金：国家自然科学基金项目(批准号 20276040)。

摘　　要：以商业粗孔硅胶为载体、钛酸四丁酯为原料制备了负载型TiO2 /SiO2 复合氧化物,分别采用H2SO4 和USY、PREHY、Hβ、SAPO-11等分子筛对其进行改性,并以1-己烯的异构化反应为探针反应,在加氢微反装置上考察了复合氧化物及改性复合氧化物对1 -己烯的异构化性能。结果表明,TiO2 /SiO2 具有比商业Al2O3 更大的酸量和更高的1-己烯骨架异构化选择性;TiO2 /SiO2 经硫酸改性后表面酸量和酸强度有所提高, 1-己烯的骨架异构化性能得到改善;在所用分子筛中,SAPO-11改性的TiO2 /SiO2 具有最高的1-己烯骨架异构化选择性;但同时具有较高的1-己烯缩合-裂解反应选择性。TiO_2/SiO_2 composite oxides were prepared by impregnating tetrabutyl titanate on commercial SiO_2 microsphere as support. The composite oxides themselves, and further modified by H 2SO 4 and different molecular sieves such as USY, PREHY, Hβ and SAPO-11 were used as the catalysts for the isomerization of 1-hexene and their catalytic performance were examined in a microreactor. The results indicated that the TiO 2/SiO 2 composite oxides had higher acidity and better isomerization activity for 1-hexene than commercial γ-Al 2O 3. The number of the total acidic sites and the strength of acidity on the TiO 2/SiO 2 composite oxides could be enhanced by modification with H 2SO 4, resulted in improved performance for the skeletal isomerization of 1-hexene. The skeletal isomerization selectivity of 1-hexene on SAPO-11 modified TiO 2/SiO 2 reached as high as 64.8%, only 9.2% lower than the equilibrium value (74%) at the same temperature. The SAPO-11 modified TiO 2/SiO 2 showed much better performance than those modified by other molecular sieves and by H 2SO 4. The present investigation showed that the TiO 2/SiO 2 composite oxides played an important role in optimizing the product distribution, especially in increasing the yield of dimethyl isomers. It was noted that further researches should be addressed to lessen their high selectivity to polymerization and cracking.

关 键 词：TIO2/SIO2 1-己烯 性能研究 催化剂 复合氧化物 骨架异构化 SAPO-11 钛酸四丁酯 H2SO4 异构化反应 Al2O3 反应选择性 原料制备 探针反应 1-已烯 表面酸量 分子筛 负载型 USY 酸强度 酸改性 商业 硅胶 裂解 缩合 硫 

分 类 号：O643.32[理学—物理化学]