金属改性Ti-HMS的制备表征及催化氧化脱硫性能  

Preparation and Characterization of Metal Modified Ti-HMS and its Catalytic Performance on Oxidative Desulfurization Reaction

作　　者：王广建[1] 王冠庆[1] 牛鑫善 陈晓婷[1] 王芳[1,2] WANG Guang-jian;WANG Guan-qing;NIU Xin-shan;CHEN Xiao-ting;WANG Fang(College of Chemical Engineering, Qingdao University of Science and Technology, Qingdao 266042, China;State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Engineering,Beijing 100029, China)

机构地区：[1]青岛科技大学化工学院,山东青岛266042 [2]北京化工大学化工资源有效利用国家重点实验室,北京100029

出　　处：《高校化学工程学报》2017年第1期97-103,共7页Journal of Chemical Engineering of Chinese Universities

基　　金：国家自然科学基金(21276130;21506107);山东省自然科学基金(ZR2014BP009);北京化工大学化工资源有效利用国家重点实验室开放课题项目(CRE-2015-C-303)

摘　　要：通过超声浸渍的方式对原位合成的Ti-HMS分子筛进行负载金属改性,制备Fe/Ti-HMS、Cu/Ti-HMS和Zn/Ti-HMS催化剂,并采用XRD、SEM、TEM、FTIR、BET等手段对催化剂的结构和形貌进行表征,以模型油中噻吩的氧化脱除为探针反应对各催化剂的催化氧化脱硫性能进行研究,并考察了反应时间、n(H_2O_2)/n(S)、Zn/Ti-HMS催化剂用量和反应温度对脱硫率的影响。实验结果表明,原位合成的Ti-HMS分子筛具有典型的介孔孔道结构,金属组分以氧化物的形式分散在分子筛的表面,金属组分的存在可以有效地提高催化剂的催化活性,负载金属组分的催化剂催化活性由大到小依次为Zn/Ti-HMS>Cu/Ti-HMS>Fe/Ti-HMS。在反应温度为70℃、n(H_2O_2)/n(S)=6、Zn/Ti-HMS催化剂用量0.2 g×(10 m L)^(-1)、反应时间60 min时,噻吩的脱除率达到94.03%。催化剂再生后催化氧化脱硫性能有所下降,表面金属活性组分的消耗和分子筛部分孔道被堵塞是导致催化剂催化活性下降的原因。Fe/Ti-HMS, Cu/Ti-HMS and Zn/Ti-HMS catalysts were successfully prepared by ultrasonic impregnation and characterized by XRD, SEM, TEM, FTIR, BET. The catalytic performance of these catalysts was tested through oxidative desulfurization (ODS) of thiophene (Th) in model oil. The effects of reaction time,H2O2/S molar ratio, Zn/Ti-HMS catalyst dosage, and reaction temperature on desulfurization rate were also investigated. The results show that the obtained Ti-HMS molecular sieves have typical mesoporous structure,and the metal species dispersed on the surface of Ti-HMS carriers are in the form of metallic oxides. The experimental results indicate that metal species can effectively improve catalytic performance, which decreases in the order of Zn/Ti-HMS > Cu/Ti-HMS > Fe/Ti-HMS. Under the optimal conditions (reaction temperature,70℃; H2O2/S molar ratio, 6; catalyst dosage, 0.2 g?(10 mL)?1; reaction time, 60 min), the desulfurization rate ofZn/Ti-HMS can reach up to 94.03%. The desulfurization performance of the catalysts decreases obviously after regeneration, which is caused by metal leaching and molecular sieve pore blockage.

关 键 词：TI-HMS 合成 金属改性 表征 氧化脱硫 

分 类 号：O643[理学—物理化学]