工业失效的甲醇制烯烃催化剂微球原位晶化研究  

Research on in-situ crystallization of industrial failed catalyst microspheres for methanol to olefins

作　　者：丁佳佳 申学峰 叶迎春 刘红星 DING Jiajia;SHEN Xuefeng;YE Yingchun;LIU Hongxing(State Key Laboratory of Green Chemical Engineering and Industrial Catalysis,SINOPEC Shanghai Research Institute of Petrochemical Technology Co.,Ltd.,Shanghai 201208,China)

机构地区：[1]中石化(上海)石油化工研究院有限公司,绿色化工与工业催化全国重点实验室,上海201208

出　　处：《低碳化学与化工》2024年第6期1-8,共8页Low-Carbon Chemistry and Chemical Engineering

基　　金：国家重点研发计划(2023YFA1507704);上海市青年科技英才扬帆计划(21YF1459600)。

摘　　要：为了解决工业失效的甲醇制烯烃(MTO)催化剂的资源化利用问题,实现MTO催化剂的循环利用,通过原位晶化的方法,以工业失效的MTO催化剂微球为原料,在水热合成体系中成功制备了以SAPO-34分子筛为活性组分的MTO催化剂。利用XRD、SEM、N_(2)吸/脱附、XRF、NH_(3)-TPD和氘代乙腈(CD_(3)CN)红外等表征手段分析了原位晶化前后催化剂的晶体结构、形貌特征、孔道结构、元素组成及酸性等,并采用固定流化床反应器考察了原位晶化前后催化剂在MTO反应中的催化性能(催化剂40.0 g、反应温度480℃、常压、甲醇质量空速4 h^(-1)、原料为纯甲醇)。结果表明,与原位晶化前催化剂相比,原位晶化后催化剂的相对结晶度提高了76%,比表面积增加了1.4倍,B酸活性中心数量增加了1.1倍;在MTO反应中,双烯(乙烯和丙烯)选择性最高达到89.64%,与原位晶化前催化剂相比,双烯选择性提升了3.3%,二甲醚以及C_(4)和C_(5+)等重烃含量(质量分数)明显降低,且原位晶化后催化剂具有优异的稳定性。In order to solve the problem of resource utilization of industrially failed catalyst for methanol to olefins(MTO)and achieve the recycle of MTO catalysts,MTO catalysts with SAPO-34 molecular sieves as the active component were successfully prepared in a hydrothermal synthesis system using industrial failed MTO catalyst microspheres as raw materials through in-situ crystallization.XRD,SEM,N_(2) adsorption/desorption,XRF,NH_(3)-TPD and infrared spectra of deuterated acetonitrile(CD_(3)CN)were used to analyze the crystal structures,morphology characterizations,pore structures,elemental compositions and acidities of catalysts before and after in-situ crystallization.The catalytic performances of catalysts before and after in-situ crystallization in MTO reaction were evaluated in a fixed fluidized bed reactor.The research conditions were reaction temperature of 480℃,atmospheric pressure and methanol mass space velocity of 4 h^(-1),and raw material was pure methanol.The results show that compared with the catalyst before in-situ crystallization,the relative crystallinity of the catalyst after in-situ crystallization increases by 76%.And the specific surface area and content of B acid increase separately by 1.4 times and 1.1 times.In MTO reaction,the selectivity of dienes(ethylene and propylene)reaches the highest of 89.64%.Compared with the catalyst before in-situ crystallization,the selectivity of dienes increases by 3.3%.The contents(mass fraction)of dimethyl ether and heavy hydrocarbons such as C_(4) and C_(5+)are significantly reduced,and the catalyst after in-situ crystallization has excellent stability.

关 键 词：失效催化剂 甲醇制烯烃 微球 原位晶化 

分 类 号：TQ426.6[化学工程]