分子筛类型对丁基苯加氢裂化反应的影响  

Effect of Zeolite Types on the Hydrocracking Reaction of n-Butylbenzene

作　　者：高薇雅 胡志海 杨平 任亮 严张艳 GAO Weiya;HU Zhihai;YANG Ping;REN Liang;YAN Zhangyan(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3期660-669,共10页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家重点研发计划项目(2021YFA1501204)基金资助。

摘　　要：以丁基苯为模型化合物,分别采用HY、Beta、ZSM-5、MOR分子筛为酸性组分制备4种NiMo/(Al_(2)O_(3)+分子筛)催化剂,采用高压加氢微型反应装置进行加氢裂化反应实验,系统考察分子筛类型对丁基苯转化率及脱烷基/断侧链、环化、脱氢等产物分布的影响。结果表明:在温度340~400℃、压力4.0 MPa、氢气/丁基苯体积比500、反应时间2 h的条件下,丁基苯主要发生脱烷基/断侧链反应和环化反应;4种催化剂上,提高反应温度均有利于丁基苯的转化和脱烷基/断侧链反应的发生,同时抑制了环化与环化脱氢反应。当丁基苯转化率相近(约46%)时,分子筛类型对产物尤其是苯、甲苯、乙苯、二甲苯等轻质芳烃混合物(BTEX)的收率与分布影响显著,具有十二元环结构的分子筛催化剂NiMo/(Al_(2)O_(3)+HY)、NiMo/(Al_(2)O_(3)+Beta)、NiMo/(Al_(2)O_(3)+MOR)上BTEX选择性较高,分别为40.41%、37.04%、43.65%;而十元环结构分子筛催化剂NiMo/(Al_(2)O_(3)+ZSM-5)上BTEX选择性仅有19.30%。分子筛上总酸量也是影响BTEX选择性的重要因素,总酸量最低的NiMo/(Al_(2)O_(3)+MOR)催化剂上BTEX选择性较高。Four types of NiMo/(Al_(2)O_(3)+molecular sieve)catalysts were prepared using HY,Beta,ZSM-5 and MOR zeolites as acidic components and n-butylbenzene as the model compound.Then the hydrocracking reaction of n-butylbenzene was investigated on a high pressure fixed-bed micro-reactor.On this basis,the effects of zeolite types on the conversion rate of n-butylbenzene and the distribution of dealkylation/broken side-chain reaction,cyclization and dehydrogenation are systematically investigated.The results show that at the temperature of 340—400℃,pressure of 4.0 MPa,volume ratio of hydrogen to n-butylbenzene of 500 and reaction time of 2 h,n-butylbenzene mainly underwent dealkylation/broken side-chain reaction and cyclization reaction;over the four catalysts,the increase of temperature is beneficial to the transformation of n-butylbenzene and the dealkylation/broken side-chain reaction,and able to inhibit the cyclization and dehydrogenation reactions.When the conversion of n-butylbenzene is similar(about 46%),the type of zeolite can significantly affect the yield and distribution of the products,especially the light aromatic mixture(BTEX)of benzene,toluene,ethylbenzene and xylene.The BTEX selectivity of NiMo/(Al_(2)O_(3)+HY),NiMo/(Al_(2)O_(3)+Beta)and NiMo/(Al_(2)O_(3)+MOR)catalysts with 12-MR structure are high and up to 40.41%,37.04%and 43.65%,respectively.By contrast,the selectivity of BTEX over NiMo/(Al_(2)O_(3)+ZSM-5)catalyst with 10-MR structure is only 19.30%.The total acid amount of the zeolites is also an important factor affecting the BTEX selectivity,and the selectivity of BTEX is higher over the NiMo/(Al_(2)O_(3)+MOR)catalyst with the lowest total acid amount.

关 键 词：丁基苯 加氢裂化 HY分子筛 ZSM-5分子筛 轻质芳烃 环化 脱氢 

分 类 号：TE6[石油与天然气工程—油气加工工程]