用于合成气制高值产物的InZrO_(x)制备及性能  

Preparation and performance of InZrO_(x)on conversion of syngas to high-value products

作　　者：郭玉静 郑和平 肖大强 任宇 冉龙腾 唐建华[1] GUO Yujing;ZHENG Heping;XIAO Daqiang;REN Yu;RAN Longteng;TANG Jianhua(College of Chemical Engineering,Sichuan University,Chengdu 610065,Sichuan,China;Sichuan Coal Industry Group Limited Liability Company,Chengdu 610091,Sichuan,China;Panzhihua Coal United Coking Limited Liability Company,Panzhihua 617000,Sichuan,China)

机构地区：[1]四川大学化学工程学院,四川成都610065 [2]四川煤炭产业集团有限责任公司,四川成都610091 [3]攀煤联合焦化有限责任公司,四川攀枝花617000

出　　处：《精细化工》2023年第9期2003-2012,2019,共11页Fine Chemicals

基　　金：国家自然科学基金(22178236,21878194);横向项目二氧化碳耦合瓦斯气催化制乙烯技术开发(22H0551)。

摘　　要：以四水合硝酸铟和五水合硝酸锆为原料,通过共沉淀法和水热法制备了InZrO_(x),并在最佳制备方法下探究煅烧温度对合成InZrO_(x)晶体结构和催化效果的影响。与SAPO-34分子筛结合为双功能催化剂用于合成气催化转化制高值产物。采用XRD、SEM-EDS、HRTEM、XPS和BET对InZrO_(x)的织构性质、晶体结构、形貌特征及表面元素进行了表征与测试,并在固定床反应器中研究了空速、原料气H_(2)/CO物质的量比(简称氢碳比)、InZrO_(x)与分子筛质量比、反应温度及反应压力对催化效果的影响规律。结果表明,共沉淀法得到的In ZrO_(x)在各方面表现均优于水热法,最佳煅烧温度为550℃。在空速为2000 mL/(g_(cat)·h)、原料气氢碳比为3:1、m(InZrO_(x))∶m(SAPO-34)=1:1、400℃、3 MPa的反应条件下,得到了较高的CO转化率(67.58%)、高值产物选择性[低碳烯烃(C_(2~4))选择性为37.74%、液体燃料(C_(5+))烃类选择性为33.07%]和C_(2~4)收率(23.98%),副产物CO_(2)选择性仅为5.99%。InZrO_(x)was prepared from co-precipitation and hydrothermal reaction of indium nitrate tetrahydrate and zirconium nitrate pentahydrate respectively,and the effect of calcination temperature on the crystal structure and catalytic performance of the synthesized InZrO_(x)was investigated under the optimal preparation method.The InZrO_(x)obtained was then combined with SAPO-34 molecular sieve to form a bifunctional catalyst,which was applied in the catalytic conversion of syngas to high-value products.The texture properties,crystal structure,morphology features,and surface elements of the InZrO_(x)were characterized by XRD,SEM-EDS,HRTEM,XPS and BET.And the catalytic performance influencing factors,including space velocity,mole ratio of H_(2) to CO in feed gas(hydrogen carbon ratio),mass ratio of InZrO_(x)to molecular sieve,reaction temperature,and reaction pressure,were analyzed in a fixed bed reactor.The results showed that the InZrO_(x)obtained by co-precipitation method exhibited better performance in all aspects in comparison to that from hydrothermal reaction,with the optimum calcination temperature of 550℃.Under the conditions of space velocity 2000 mL/(gcat·h),hydrogen carbon ratio 3∶1,m(InZrO_(x))∶m(SAPO-34)=1∶1,400℃,and 3 MPa,the catalytic reaction displayed high CO conversion rate(67.58%),high-value product selectivity[(The selectivity of light olefins(C_(2~4))and liquid fuels(C_(5+))were 37.74%and 33.07%)]and C_(2~4)yield(23.98%),and by-product CO_(2)selectivity of 5.99%.

关 键 词：合成气 轻烯烃 双功能催化剂 水热法 共沉淀法 催化技术 

分 类 号：O643.36[理学—物理化学] TQ133.53[理学—化学]