SCI和EI收录∣中国化工学会会刊

Chinese Journal of Chemical Engineering ›› 2020, Vol. 28 ›› Issue (1): 143-151.DOI: 10.1016/j.cjche.2019.04.010

• Catalysis, Kinetics and Reaction Engineering • Previous Articles     Next Articles

Light olefin production by catalytic co-cracking of Fischer-Tropsch distillate with methanol and the reaction kinetics investigation

Hui Zou1,2, Teng Pan1, Yanwen Shi1, Youwei Cheng1,2, Lijun Wang1,2, Yu Zhang3, Xi Li1   

  1. 1 Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China;
    2 Institute of Zhejiang University, Jiuhua Boulevard North, Qzhou 324000, China;
    3 Ningxia Shenyao Technology Co., Ltd., China Energy Investment Co., West Desheng Road 1, Yinchuan 750200, China
  • Received:2019-02-17 Revised:2019-03-28 Online:2020-03-31 Published:2020-01-28
  • Contact: Youwei Cheng

Light olefin production by catalytic co-cracking of Fischer-Tropsch distillate with methanol and the reaction kinetics investigation

Hui Zou1,2, Teng Pan1, Yanwen Shi1, Youwei Cheng1,2, Lijun Wang1,2, Yu Zhang3, Xi Li1   

  1. 1 Zhejiang Provincial Key Laboratory of Advanced Chemical Engineering Manufacture Technology, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, China;
    2 Institute of Zhejiang University, Jiuhua Boulevard North, Qzhou 324000, China;
    3 Ningxia Shenyao Technology Co., Ltd., China Energy Investment Co., West Desheng Road 1, Yinchuan 750200, China
  • 通讯作者: Youwei Cheng

Abstract: Catalytic co-cracking of Fischer-Tropsch (FT) light distillate and methanol combines highly endothermic olefin cracking reaction with exothermic methanol conversion over ZSM-5 catalyst to produce light olefins through a nearly thermoneutral process. The kinetic behavior of co-cracking reactions was investigated by different feed conditions:methanol feed only, olefin feed only and co-feed of methanol with olefins or F-T distillate. The results showed that methanol converted to C2-C6 olefins in first-order parallel reaction at low space time, methylation and oligomerization-cracking prevailed for the co-feed of methanol and C2-C5 olefins, while for C6-C8 olefins, monomolecular cracking was the dominant reaction whether fed alone or co-fed with methanol. For FT distillate and methanol co-feed, alkanes were almost un-reactive, C3-C5 olefins were obtained as main products, accounting for 71 wt% for all products. A comprehensive co-cracking reaction scheme was proposed and the model parameters were estimated by the nonlinear least square method. It was verified by experimental data that the kinetic model was reliable to predict major product distribution for co-cracking of FT distillate with methanol and could be used for further reactor development and process design.

Key words: Fischer-Tropsch distillate, Catalytic co-cracking, Light olefins, Methanol, Reaction kinetics

摘要: Catalytic co-cracking of Fischer-Tropsch (FT) light distillate and methanol combines highly endothermic olefin cracking reaction with exothermic methanol conversion over ZSM-5 catalyst to produce light olefins through a nearly thermoneutral process. The kinetic behavior of co-cracking reactions was investigated by different feed conditions:methanol feed only, olefin feed only and co-feed of methanol with olefins or F-T distillate. The results showed that methanol converted to C2-C6 olefins in first-order parallel reaction at low space time, methylation and oligomerization-cracking prevailed for the co-feed of methanol and C2-C5 olefins, while for C6-C8 olefins, monomolecular cracking was the dominant reaction whether fed alone or co-fed with methanol. For FT distillate and methanol co-feed, alkanes were almost un-reactive, C3-C5 olefins were obtained as main products, accounting for 71 wt% for all products. A comprehensive co-cracking reaction scheme was proposed and the model parameters were estimated by the nonlinear least square method. It was verified by experimental data that the kinetic model was reliable to predict major product distribution for co-cracking of FT distillate with methanol and could be used for further reactor development and process design.

关键词: Fischer-Tropsch distillate, Catalytic co-cracking, Light olefins, Methanol, Reaction kinetics