ZrO2/SiO2催化乙醇乙醛制备1,3-丁二烯

doi:10.16085/j.issn.1000-6613.2015.09.019

化工进展 ›› 2015, Vol. 34 ›› Issue (09): 3331-3336.DOI: 10.16085/j.issn.1000-6613.2015.09.019

ZrO₂/SiO₂催化乙醇乙醛制备1,3-丁二烯

李翔^1,2, 刘宗章^1,2

1. 天津大学石油化工技术开发中心, 天津 300072;
2. 天津大学绿色合成与转化教育部重点实验室, 天津 300072

收稿日期:2014-11-21 修回日期:2015-01-23 出版日期:2015-09-05 发布日期:2015-09-05
通讯作者: 刘宗章。E-mail:zzliu@tju.edu.cn
作者简介:李翔(1989-),男,硕士研究生,研究方向为生物质能源及应用催化。

Study on the catalytic process of 1,3-butadiene from ethanol and acetaldehyde with ZrO₂/SiO₂ catalyst

LI Xiang^1,2, LIU Zongzhang^1,2

1. R&D Center for Petrochemical Technology, Tianjin University, Tianjin 300072, China;
2. Key Laboratory for Green Chemical Technology of Ministry of Education, Tianjin University, Tianjin 300072, China

Received:2014-11-21 Revised:2015-01-23 Online:2015-09-05 Published:2015-09-05

摘要/Abstract

摘要： 采用干混法、浸渍法、溶胶凝胶法3种制备方法制备ZrO₂/SiO₂,在固定床微型反应器中进行催化剂的活性评价。通过溶胶凝胶法制备的ZrO₂/SiO₂对丁二烯选择性最高,达到64.77%。采用氨气程序升温脱附(NH₃-TPD)、X射线衍射(XRD)、透射电镜(TEM)等手段对催化剂表面酸性以及表面结构进行了表征,结果表明锆在二氧化硅表面均匀分布有利于乙醇乙醛转化率以及对1,3-丁二烯选择性的提高,同时1,3-丁二烯的生成需要合适的酸性位。以溶胶凝胶法制备的ZrO₂/SiO₂为催化剂,对其制备条件进行了优化,得出最佳制备条件为焙烧温度650℃、硝酸浓度2mol/L、混合温度30℃。

关键词: 1, 3-丁二烯, ZrO₂/SiO₂, 醇, 乙醛, 催化剂, 反应

Abstract: Three preparation methods,dry-mixed,impregnation and sol-gel methods,of ZrO₂/SiO₂ were introduced to study the formation of 1,3-butadiene from bioethanol and acetaldehyde. Catalyst testing device was introduced and the best selectivity of 1,3-butadiene is 64.77% which is obtained by sol-gel method. To study the quantity and quality of acid sites and surface structure of catalysts,thermogravimetry,temperature programmed desorption,X-ray diffraction and transmission electron microscopy were conducted. Zr-Si shows a high selectivity for 1,3-butadiene and corresponding reason was illustrated. NH₃-TPD indicates the high intensity of strong acid sites and XRD indicates the high dispersed of ZrO₂,while both attributes to the good activity of ZrO₂-SiO₂. The effects of preparation parameters on sol-gel Zr-Si were also investigated. The result shows that the best roasting temperature,concentration of nitric acid and temperature of agitation are 650℃,2mol/L,30℃,respectively.

Key words: 1,3-butadiene, ZrO₂/SiO₂, alcohol, acetaldehyde, catalyst, reaction

中图分类号:

李翔, 刘宗章. ZrO₂/SiO₂催化乙醇乙醛制备1,3-丁二烯[J]. 化工进展, 2015, 34(09): 3331-3336.

LI Xiang, LIU Zongzhang. Study on the catalytic process of 1,3-butadiene from ethanol and acetaldehyde with ZrO₂/SiO₂ catalyst[J]. Chemical Industry and Engineering Progree, 2015, 34(09): 3331-3336.

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ZrO₂/SiO₂催化乙醇乙醛制备1,3-丁二烯

Study on the catalytic process of 1,3-butadiene from ethanol and acetaldehyde with ZrO₂/SiO₂ catalyst

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