C4/C5烯烃骨架异构化催化剂的制备及工业应用  

Preparation and industrial application of skeleton isomerization catalyst for C4/C5 olefin

作　　者：徐亚荣 陈蓝天 龚涛 樊金龙 XU Ya-rong;CHEN Lan-tian;GONG Tao;FAN Jin-long(Research Institute of Urumqi Petrochemical Company,PetroChina,Urumqi 830019,China)

机构地区：[1]中国石油乌鲁木齐石化公司研究院,新疆乌鲁木齐830019

出　　处：《石化技术与应用》2020年第2期76-79,96,共5页Petrochemical Technology & Application

基　　金：中国石油天然气集团有限公司科技开发资助项目(项目编号:2018B-1907)。

摘　　要：采用水热晶化法合成了FER-S(加结构导向剂)和FER-01(不加结构导向剂)2种FER型ZSM-35分子筛,制备出C4/C5烯烃骨架异构化催化剂,利用X射线衍射法、氨气-程序升温脱附法等测试方法表征了分子筛结构,在固定床反应器装置上评价了催化剂异构化反应性能,并在中国石油乌鲁木齐石化公司40万t/a轻汽油醚化装置上考察了FER-S的工业应用情况。结果表明:FER-S,FER-01的结晶度分别为98%,83%,前者的强酸中心少于后者,且前者含有更多的微孔,催化剂性能更佳;FER-S在催化C4和C5烯烃异构化的反应中,正构烯烃转化率分别大于35%,45%,异构化选择性均高于90%;工业用FER-S在工业装置运行第1周期(769 h)内的72 h标定期间,C5正构烯烃转化率达到62.4%~76.8%,异构化选择性高于90%,催化剂经过再生后,第2周期(1 053 h)的运行时间比第1周期至少延长37%。Two FER type ZSM-35 zeolites FER-S(with structure-directing agent) and FER-01(free structure-directing agent) were synthesized by hydrothermal crystallization and two C4/C5 olefin skeleton isomerization catalysts were prepared accordingly.The two molecular sieves′ structures were characterized and analyzed by X-ray diffraction and ammonia temperature programmed desorption.The relevant catalysts′ light olefin(C4/C5) isomerization performances were evaluated in fixed-bed reactor. In addition, the industry application of FER-S catalyst was investigated in 400 kt/a light gasoline etherification unit of Urumqi Petrochemical Company of PetroChina. The results showed that the crystallinities of FER-S and FER-01 were 98% and 83%, respectively. The former had less strong acid center than the latter,more microspores and better catalyst performance.When FER-S catalyst was applied in C4/C5 olefin isomerization, the conversion of normal olefin was more than 35% and 45% respectively, and the isomerization selectivity was more than 90%.During the 72 h calibration of industrial FER-S catalyst′s first commercial application period(769 h), the conversion of normal olefin had reached 62.4%-76.8% respectively and the isomerization selectivity was more than 90%.After catalyst regeneration, the running time(1 053 h) of the second period had extended at least 37% comparing to the first period.

关 键 词：C4/C5烯烃 骨架异构化 ZSM-35分子筛 催化剂 水热合成法 异丁烯 异戊烯 

分 类 号：TE624.47[石油与天然气工程—油气加工工程]