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

doi:10.16085/j.issn.1000-6613.2015.09.019

Abstract

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

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

CLC Number:

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.

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.

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

ZrO₂/SiO₂催化乙醇乙醛制备1,3-丁二烯

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