醇原位催化转化制备芳烃及机理

doi:10.16085/j.issn.1000-6613.2016-1981

化工进展 ›› 2017, Vol. 36 ›› Issue (07): 2517-2524.DOI: 10.16085/j.issn.1000-6613.2016-1981

醇原位催化转化制备芳烃及机理

时旭^1,3, 周峰², 陈皓³, 傅杰³, 乔凯², 黄和^1,3

1 南京工业大学生物与制药工程学院, 材料化学工程国家重点实验室, 江苏南京 211816;
2 中国石油化工股份有限公司抚顺石油化工研究院, 辽宁抚顺 113001;
3 生物质化工教育部重点实验室, 浙江大学化学工程与生物工程学院, 浙江杭州 310027

收稿日期:2016-10-31 修回日期:2017-03-26 出版日期:2017-07-05 发布日期:2017-07-05
通讯作者: 黄和,教授,研究方向为生物质催化转化及微生物代谢工程。
作者简介:时旭(1992-),男,硕士研究生。
基金资助:
国家自然科学基金重点项目（21436007）及浙江省自然科学基金杰出青年项目（LR17B060002）。

Study on in-situ catalytic conversion of alcohols to aromatics and its mechanism

SHI Xu^1,3, ZHOU Feng², CHEN Hao³, FU Jie³, QIAO Kai², HUANG He^1,3

1 State Key Laboratory of Materials-Oriented Chemical Engineering, College of Biotechnology and Pharmaceutical Engineering, Nanjing Tech. University, Nanjing 211816, Jiangsu, China;
2 Fushun Research Institute of Petroleum and Petrochemicals, SINOPEC, Fushun 113001, Liaoning, China;
3 Key Laboratory of Biomass Chemical Engineering of Ministry of Education, College of Chemical and Biological Engineering, Zhejiang University, Hangzhou 310027, Zhejiang, China

Received:2016-10-31 Revised:2017-03-26 Online:2017-07-05 Published:2017-07-05

摘要/Abstract

摘要： 以不同的醇为原料，HZSM-5分子筛为催化剂，在微型固定床与气相色谱-质谱联用装置上进行了醇催化转化制备芳烃的研究，考察了醇的碳链长度以及反应温度的影响。结果表明，醇的碳链长度对产物的分布有明显的影响，400℃下芳烃产率随着醇的碳链增长先增加，在正丙醇处获得最大的芳烃产率39.6%，而后降低并趋于稳定。随着温度的升高，甲醇、乙醇和正丙醇3种醇的产物分布变化趋势相同，芳烃产率均先增加后减小，在500℃获得最大值，分别为26.0%、36.5%和42.5%；随着温度的升高，CO、CO₂ 和烯烃的产率逐渐升高，但烃类产物总收率逐渐下降。高温下大分子芳烃逐渐向小分子芳烃转化，使得苯和甲苯的选择性逐渐增大。最后，结合原位红外表征和实验结果探讨了醇芳构化的反应机理：短碳链醇通过脱水得到醚和低碳烯烃，低碳烯烃再经过聚合得到长链烯烃，长碳链醇则可直接脱水得到长链烯烃，长链烯烃再通过环化反应生成环烷烃，最后环烷烃经过脱氢芳构化或分子间氢转移得到芳烃。

关键词: 醇, 催化, HZSM-5, 芳烃, 微反应器

Abstract: The effects of carbon chain length of alcohol and reaction temperature on catalytic conversion of alcohols to produce aromatics over HZSM-5 were studied in a micro fixed-bed reactor coupled directly to GC/MS system.The results showed that the carbon chain length of alcohol had a significant effect on the product distribution.At 400℃,with the increase of carbon chain length of alcohol,the yield of aromatics increased firstly up to the maximum of 39.6%(1-propanol),then decreased and finally stabilized at a lower yield.As the temperature increased,the products distributions for methanol,ethanol,1-propanol showed the same tendency,and the yields of aromatics increased firstly,then decreased and the maximum values reached 26.0%,36.5% and 42.5% at 500℃ respectively.As the temperature increased,however,the yield of CO,CO₂ and olefins increased gradually while the total yield of hydrocarbons decreased.Higher temperature helped the conversion of larger aromatics to lighter aromatics,which contributed to the higher selectivity for benzene and toluene.Finally,the reaction mechanism of alcohol aromatization was discussed by the combination of in-situ FTIR and experimental results.It is supposed that the light olefins and ethers were produced by dehydration of short carbon chain alcohols,while long carbon chain olefins were produced by polymerization of the light olefins or direct dehydration of long carbon chain alcohols.The obtained long carbon chain olefins were then converted into cycloalkanes by cyclization.At last,aromatics were formed by dehydrogenation-aromatization or intermolecular hydrogen transfer of the cycloalkanes.

Key words: alcohol, catalysis, HZSM-5, aromatics, microreactor

中图分类号:

TQ032.4

时旭, 周峰, 陈皓, 傅杰, 乔凯, 黄和. 醇原位催化转化制备芳烃及机理[J]. 化工进展, 2017, 36(07): 2517-2524.

SHI Xu, ZHOU Feng, CHEN Hao, FU Jie, QIAO Kai, HUANG He. Study on in-situ catalytic conversion of alcohols to aromatics and its mechanism[J]. Chemical Industry and Engineering Progress, 2017, 36(07): 2517-2524.

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醇原位催化转化制备芳烃及机理

Study on in-situ catalytic conversion of alcohols to aromatics and its mechanism

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