石油学报(石油加工)2024,Vol.40Issue(3) :660-669.DOI:10.3969/j.issn.1001-8719.2024.03.010

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

高薇雅 胡志海 杨平 任亮 严张艳
石油学报(石油加工)2024,Vol.40Issue(3) :660-669.DOI:10.3969/j.issn.1001-8719.2024.03.010

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

高薇雅 1胡志海 1杨平 1任亮 1严张艳1
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作者信息

  • 1. 中石化石油化工科学研究院有限公司,北京 100083
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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/(Al2O3+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/(Al2O3+HY)、NiMo/(Al2O3+Beta)、NiMo/(Al2O3+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/(Al2O3+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/(Al2O3+MOR)催化剂上BTEX选择性较高.

Abstract

Four types of NiMo/(Al2O3+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/(Al2O3+HY),NiMo/(Al2O3+Beta)and NiMo/(Al2O3+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/(Al2O3+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/(Al2O3+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

Key words

n-butylbenzene/hydrocracking/HY zeolite/ZSM-5 zeolite/light aromatic/cyclization/dehydrogenation

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基金项目

国家重点研发计划(2021YFA1501204)

出版年

2024
石油学报(石油加工)
中国石油学会

石油学报(石油加工)

CSTPCD北大核心
影响因子:0.764
ISSN:1001-8719
参考文献量25
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