Synthesis of propylene carbonate from CO2 and 1,2-propylene glycol on fixed-bed reactor and its reaction mechanism catalyzed by Zn(OAc)2/AC

doi:10.11949/j.issn.0438-1157.20141163

CIESC Journal ›› 2015, Vol. 66 ›› Issue (2): 567-575.DOI: 10.11949/j.issn.0438-1157.20141163

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Synthesis of propylene carbonate from CO₂ and 1,2-propylene glycol on fixed-bed reactor and its reaction mechanism catalyzed by Zn(OAc)₂/AC

ZHANG Guangjie, GENG Yanlou, AN Hualiang, ZHAO Xinqiang, WANG Yanji

Hebei Provincial Key Laboratory of Green Chemical Technology and Efficient Energy Saving, Hebei University of Technology, Tianjin 300130, China

Received:2014-08-01 Revised:2014-11-20 Online:2015-02-05 Published:2015-02-05
Supported by:
supported by the National Natural Science Foundation of China (21076059, 21476058, 21236001), the Natural Science Foundation of Tianjin City (12JCYBJC12800) and the Key Basic Research Project of Applied Basic Research Plan of Hebei Province (12965642D).

Zn(OAc)₂/AC催化固定床上CO₂与1,2-丙二醇合成碳酸丙烯酯及其反应机理

张光洁, 耿艳楼, 安华良, 赵新强, 王延吉

河北工业大学化工学院, 绿色化工与高效节能河北省重点实验室, 天津 300130

通讯作者: 赵新强
基金资助:
国家自然科学基金项目(21076059,21476058,21236001);天津市自然科学基金项目(12JCYBJC12800);河北省应用基础研究计划重点基础研究项目(12965642D)。

Abstract

Abstract:

Propylene carbonate (PC) was synthesized on a fixed-bed reactor from CO₂ and propylene glycol (PG) catalyzed by supported Zn(OAc)₂ catalyst. Then the effect of the kind of carrier and its loading on the catalytic performance and the influence of reaction conditions on PC synthesis reaction were investigated. The results indicates that Zn(OAc)₂/AC with loading of 40% (mass) shows better catalytic performance. The suitable reaction conditions are obtained as follows: molar ratio of PG to acetonitrile(solvent) to CO₂ is 1:1.8:11, reaction temperature 160℃, CO₂ pressure 4.0 MPa and LHSV 0.9 h^-1. Under the above conditions, the yield and selectivity of PC were 6.3% and 49.0%, respectively. The interaction between Zn(OAc)₂and CO₂ or PG was investigated by in-situ IR technique combined with some designed experiments. It was found that the chemical adsorption of CO₂ on Zn(OAc)₂is weaker while it is much stronger between PG and Zn(OAc)₂. Chemical bond between PG and Zn(OAc)₂ is found, indicating that Zn(OAc)₂ can activate PG in this reaction. Accordingly, the role of Zn(OAc)₂ in the catalytic reaction of CO₂ and PG to PC is elucidated.

Key words: 1,2-propylene glycol, carbon dioxide, propylene carbonate, fixed-bed, catalyst, reaction mechanism

摘要：

以负载型乙酸锌为催化剂,在固定床上实现了CO₂和1,2-丙二醇(PG)合成碳酸丙烯酯(PC)反应。考察了不同载体和负载量对负载型乙酸锌催化性能的影响以及反应条件对PC合成反应的影响。结果表明:负载量为40% (质量分数)的Zn(OAc)₂/AC催化性能最好。CO₂与PG合成PC适宜的反应条件为:PG、乙腈和CO₂的摩尔比为1:1.8:11,CO₂ 压力 4.0 MPa,反应温度160 ℃和液空速0.9 h^-1。在此条件下,PC收率和选择性分别为6.3%和49.0%。采用原位红外结合设计实验研究了无水乙酸锌分别与CO₂和PG之间的相互作用,发现CO₂与乙酸锌之间的化学吸附比较弱,而PG与乙酸锌之间的化学吸附较强,能够活化PG。据此推测了乙酸锌催化CO₂与PG合成PC的反应机理。

关键词: 1,2-丙二醇, 二氧化碳, 碳酸丙烯酯, 固定床, 催化剂, 反应机理

CLC Number:

ZHANG Guangjie, GENG Yanlou, AN Hualiang, ZHAO Xinqiang, WANG Yanji. Synthesis of propylene carbonate from CO₂ and 1,2-propylene glycol on fixed-bed reactor and its reaction mechanism catalyzed by Zn(OAc)₂/AC[J]. CIESC Journal, 2015, 66(2): 567-575.

张光洁, 耿艳楼, 安华良, 赵新强, 王延吉. Zn(OAc)₂/AC催化固定床上CO₂与1,2-丙二醇合成碳酸丙烯酯及其反应机理[J]. 化工学报, 2015, 66(2): 567-575.

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Synthesis of propylene carbonate from CO₂ and 1,2-propylene glycol on fixed-bed reactor and its reaction mechanism catalyzed by Zn(OAc)₂/AC

Zn(OAc)₂/AC催化固定床上CO₂与1,2-丙二醇合成碳酸丙烯酯及其反应机理

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