Pt/ZSM-35催化长链正构生物烷烃加氢裂化/异构化制航空煤油

doi:10.16085/j.issn.1000-6613.2020-0274

摘要/Abstract

摘要：

以生物质油加氢脱氧得到的长链正构生物烷烃为原料，考察了H-MCM-49、H-ZSM-5、H-ZSM-22和 H-ZSM-35这4种不同分子筛催化剂的物化性质及其加氢裂化/异构化制生物航空煤油的性能。在此基础上，以H-ZSM-35分子筛为载体，制备并表征了一系列低负载量（0.1%、0.2%和0.3%）的Pt/ZSM-35双功能催化剂，以长链正构生物烷烃转化率、C₉~C₁₆产物选择性、生物航空煤油收率和异正比为指标，对其加氢裂化/异构化制生物航空煤油反应性能进行了评价，并对反应工艺条件进行优化。结果表明：H-ZSM-35的强酸中心强度高、酸量大，其结构中较小的孔口和较大的球型笼使其具有一定的容烃量和较好的择形性能，0.1%~0.3% Pt负载后， Pt/ZSM-35双功能催化剂表现出很好的加氢裂化/异构化活性和选择性。采用0.1% Pt/ZSM-35双功能催化剂在反应条件为320℃、1MPa、0.7h^-1、氢油比840∶1时，长链正构生物烷烃的转化率为84.3%，生物航空煤油收率达41.1%，产物异正比为1.34。81h长运转测试结果表明，该催化剂具有很好的稳定性。

关键词: 生物航空煤油, 双功能催化剂, 长链正构生物烷烃, 加氢裂化/异构化, 收率, 选择性

Abstract:

Four catalysts prepared from H-MCM-49, H-ZSM-5, H-ZSM-22 and H-ZSM-35 molecular sieves were used for the hydrocracking and hydroisomerization of the long-chain normal bio-paraffins obtained by hydrodeoxygenation of biomass oil to bio-jet fuel. Their physicochemical properties and catalytic performance were investigated. On this basis, a series of Pt/ZSM-35 bifunctional catalysts with low Pt loadings (0.1%, 0.2%, 0.3%) were prepared by using H-ZSM-35 as the carrier. The performance of the Pt/ZSM-35 catalysts in the hydrocracking and hydroisomerization of long-chain normal bio-paraffins to bio-jet fuel was evaluated by the conversion of the bio-paraffins, the selectivity of C₉—C₁₆ products, and the yield and the iso/n-paraffin ratio of bio-jet fuel. Then the reaction conditions were optimized. The results showed that the strength and the amount of the strong acid center of H-ZSM-35 were the highest. Meanwhile, due to the small pore and large spherical cage, H-ZSM-35 possessed a certain amount of hydrocarbon capacity and good shape-selectivity. The Pt/ZSM-35 catalysts with Pt loading of 0.1%—0.3% exhibited high activity and high selectivity to bio-jet fuel. The optimized reaction conditions were obtained as 320℃, 1MPa, 0.7h^-1 and H₂/n-paraffin volume ratio of 840∶1. The conversion of long-chain normal bio-paraffins over the 0.1%Pt/ZSM-35 bifunctional catalyst reached 84.3%, and the yield of bio-jet fuel was as high as 41.1% with an iso/n-paraffin ratio of 1.34. In the long-term operation test for 81h, the 0.1% Pt/ZSM-35 catalyst showed good stability.

Key words: bio-jet fuel, bifunctional catalyst, long-chain normal bio-paraffins, hydrocracking and hydroisomerization, yield, selectivity

中图分类号:

S216

刘宇, 谭涓, 刘靖, 王慧风. Pt/ZSM-35催化长链正构生物烷烃加氢裂化/异构化制航空煤油[J]. 化工进展, 2020, 39(12): 5086-5094.

Yu LIU, Juan TAN, Jing LIU, Huifeng WANG. Production of bio-jet fuel by hydrocracking and hydroisomerization of long-chain normal bio-paraffins over Pt/ZSM-35 catalysts[J]. Chemical Industry and Engineering Progress, 2020, 39(12): 5086-5094.

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