Analysis of long term catalytic performance for isobutane alkylation catalyzed by NMA-AlCl3 based ionic liquid analog

doi:10.1016/j.cjche.2018.11.020

Chinese Journal of Chemical Engineering ›› 2019, Vol. 27 ›› Issue (8): 1857-1862.DOI: 10.1016/j.cjche.2018.11.020

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Analysis of long term catalytic performance for isobutane alkylation catalyzed by NMA-AlCl₃ based ionic liquid analog

Pengcheng Hu, Zhitao Wu, Junlin Wang, Yuqing Huang, Yang Deng, Shufeng Zhou

College of Chemical Engineering, Huaqiao University, Xiamen 361021, China

Received:2018-10-02 Revised:2018-11-17 Online:2019-11-16 Published:2019-08-28
Contact: Pengcheng Hu, Shufeng Zhou
Supported by:
Supported by the National Natural Science Foundation of China (No. 21802047), and the Scientific Research Funds of Huaqiao University (No. 600005-Z17Y0073).

Analysis of long term catalytic performance for isobutane alkylation catalyzed by NMA-AlCl₃ based ionic liquid analog

Pengcheng Hu, Zhitao Wu, Junlin Wang, Yuqing Huang, Yang Deng, Shufeng Zhou

College of Chemical Engineering, Huaqiao University, Xiamen 361021, China

通讯作者: Pengcheng Hu, Shufeng Zhou
基金资助:
Supported by the National Natural Science Foundation of China (No. 21802047), and the Scientific Research Funds of Huaqiao University (No. 600005-Z17Y0073).

Abstract

Abstract: Isobutane alkylation with 2-butene to produce high-quality gasoline was catalyzed by N-methylacetamide (NMA)-AlCl₃ based ionic liquid (IL) analog with a NMA/AlCl₃ molar ratio of 0.75 and CuCl modification, which was marked as CuCl-modified 0.75NMA-1.0AlCl₃. The long-term experiment was carried out in the autoclave operated in continuous mode to investigate the distribution of alkylate under different experimental nodes. The result indicated that the long-term alkylation was divided into three stages:rising, stable, and descending regions. C8 selectivity and molar ratio of trimethylpentanes (TMPs) to dimethylhexanes (DMHs) reached the highest level in the stable region, and research octane number (RON) of alkylate was as high as 97. Anionic Al species ([Al₂Cl₇]^-,[AlCuCl₅]^-) and cationic Al species ([AlCl₂L]⁺) from IL analog as two active Lewis acidic species played a catalytic role in the long-term alkylation, whereas the neutral Al species did not participate into the alkylation. Moreover, the structure of CuCl-modified 0.75NMA-1.0AlCl₃ was destroyed after the deactivation, and CuCl was enriched in the CD₂Cl₂-insoluble substance, resulting in a decreasing TMP/DMH ratio. The catalytic lifetime of IL analog was similar with CuCl-modified 0.55Et₃NHCl-1.0AlCl₃ IL, but IL analog had a lower cost.

Key words: Ionic liquid analog, Isobutane alkylation, Long-term experiment, Structural analysis

摘要： Isobutane alkylation with 2-butene to produce high-quality gasoline was catalyzed by N-methylacetamide (NMA)-AlCl₃ based ionic liquid (IL) analog with a NMA/AlCl₃ molar ratio of 0.75 and CuCl modification, which was marked as CuCl-modified 0.75NMA-1.0AlCl₃. The long-term experiment was carried out in the autoclave operated in continuous mode to investigate the distribution of alkylate under different experimental nodes. The result indicated that the long-term alkylation was divided into three stages:rising, stable, and descending regions. C8 selectivity and molar ratio of trimethylpentanes (TMPs) to dimethylhexanes (DMHs) reached the highest level in the stable region, and research octane number (RON) of alkylate was as high as 97. Anionic Al species ([Al₂Cl₇]^-,[AlCuCl₅]^-) and cationic Al species ([AlCl₂L]⁺) from IL analog as two active Lewis acidic species played a catalytic role in the long-term alkylation, whereas the neutral Al species did not participate into the alkylation. Moreover, the structure of CuCl-modified 0.75NMA-1.0AlCl₃ was destroyed after the deactivation, and CuCl was enriched in the CD₂Cl₂-insoluble substance, resulting in a decreasing TMP/DMH ratio. The catalytic lifetime of IL analog was similar with CuCl-modified 0.55Et₃NHCl-1.0AlCl₃ IL, but IL analog had a lower cost.

关键词: Ionic liquid analog, Isobutane alkylation, Long-term experiment, Structural analysis

Pengcheng Hu, Zhitao Wu, Junlin Wang, Yuqing Huang, Yang Deng, Shufeng Zhou. Analysis of long term catalytic performance for isobutane alkylation catalyzed by NMA-AlCl₃ based ionic liquid analog[J]. Chinese Journal of Chemical Engineering, 2019, 27(8): 1857-1862.

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Analysis of long term catalytic performance for isobutane alkylation catalyzed by NMA-AlCl₃ based ionic liquid analog

Analysis of long term catalytic performance for isobutane alkylation catalyzed by NMA-AlCl₃ based ionic liquid analog

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