基于不同孔径和酸性分子筛的催化剂异构反应差异性研究  

Study on Isomerization Differences of Catalysts Based onMolecular Sieves With Different Pore Sizes and Acidity

作　　者：黄若兰 杨清河 黄卫国 毕云飞 卢玉涛 HUANG Ruolan;YANG Qinghe;HUANG Weiguo;BI Yunfei;LU Yutao(SINOPEC Research Institute of Petroleum Processing Co.,Ltd.,Beijing 100083,China)

机构地区：[1]中石化石油化工科学研究院有限公司,北京100083

出　　处：《石油学报（石油加工）》2024年第2期382-391,共10页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：中国石油化工股份有限公司项目(119004)基金资助。

摘　　要：分别以2种不同孔径和酸性的一维十元环结构分子筛ZIP-1(小孔)和BCM-168(大孔)为酸性组分制备了2种贵金属临氢异构化催化剂A200和B350,采用微型反应装置考察其对正十六烷的异构化反应性能,并对其产物进行倾点与收率的计算以模拟实际油品的切割效果。结果表明,孔径较大且Bronsted酸强度较弱的BCM-168分子筛制备的B350催化剂对正十六烷的异构化选择性更好,且在高转化率下A200与B350的选择性差距增大。通过对正十六烷异构产物进行模拟切割,发现2种催化剂反应产物的组成结构不同,B350催化剂异构化产物支化度更高。在实际油品评价中,通过分析产物烃组成与碳数分布,发现B350催化剂使烷烃断键生成碳数较接近的产物;而由孔径较小且Br?nsted酸强度较高的ZIP-1分子筛制备的A200催化剂,易促进烷烃多次裂解生成碳数较少的短链烷烃。同时发现,催化剂的过度异构化会使产物裂解为沸点较低的组分,使得目的产物大分子异构烃类收率降低。Hydroisomerization catalysts A200 and B350 containing noble metal were prepared using the one-dimensional ten-membered ring zeolites ZIP-1(with smaller pore size)and BCM-168(with larger pore size)as acidic components,respectively;their isomerization reaction in n-hexadecane was investigated on a microreactor,and the actual oil distilling process was simulated by calculating the pour point and yield of the products.The results show that the catalyst B350(with larger pore size and weaker Br nsted acidity)containing BCM-168 has better selectivity for n-hexadecane isomerization,and as conversion rates rise,the selectivity gap between A200 and B350 is enlarged.It is found that the product structures of the two catalysts are different through simulated distilling,and the B350 catalyst containing BCM-168 zeolite has a higher branched degree of isomerization products.By analyzing the hydrocarbon composition and carbon number distribution,it is found in actual oil evaluation that B350 catalyst can make alkanes break bonds to produce products with close carbon numbers,while A200 catalyst(with smaller pore size and higher Br nsted acidity)containing ZIP-1 can easily promote the cracking of alkanes for multiple times to produce shorter alkanes with smaller carbon number.Meanwhile,it is found that over isomerization of the catalysts results in the decomposition of the product into lighter components,resulting in a lower yield of macromolecular isomerized hydrocarbons of the target product.

关 键 词：分子筛 异构化 孔径 酸性 倾点 收率 

分 类 号：TE624.9[石油与天然气工程—油气加工工程]