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Direct Synthesis of Dimethylcarbonate from CO_2 and methanol with thermal driven loop reactor

热驱动环流反应器直接由CO_2和甲醇合成碳酸二甲酯

基本信息

批准号：
16360389
负责人：
INOMATA Hiroshi
金额：
$ 8.83万
依托单位：
Tohoku University
依托单位国家：
日本
项目类别：
Grant-in-Aid for Scientific Research (B)
财政年份：
2004
资助国家：
日本
起止时间：
2004 至 2005
项目状态：
已结题

来源：
https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-16360389/
关键词：
CO_2 DMC thermal driven loop reactor adsorption zirconia

项目摘要

Dimethyl carbonate (DMC) is a high-value added material because its application is quite wide such as an intermediate of polymer, fuel additive, and so on. A green synthesis of DMC is direct production from CO_2 and methanol. For the reaction, a catalyst is required to proceed effectively and ZrO_2 catalysts have been found to be suitable. The byproduct of the reaction is water and the water makes the DMC yield lower because of chemical equilibrium. In order to enhance the DMC yield, removal of water from the reaction, system is strongly demanded.In this study, we planed to develop a new synthesis process of DMC from CO_2 and methanol by a thermal driven loop reactor. The thermal driven loop reactor has a heating part for the reaction and a cooling pert for the elimination of water. The employed catalyst and the dehydration agent were ZrO_2 and molecular sieve 3 A, respectively. The optimization of the reaction condition was explored through the investigation of phase equilibria and th … More e reaction behavior. Especially, the effect of the amount of the dehydration agent was evaluated. Based on the experimental studies, the model development was performed and resulted in clarification of a controlling factor of the process.First of all, we evaluated the capability of dehydration agent in high pressure reaction media for methanol-water system. As a result, the dehydration agent worked well in the thermal driven loop reactor (temperature of the heating pert : 150-160 ℃, temperature of the cooling pert : 60 ℃). Next, the phase equilibria of CO_2-methanol-water-DMC system was calculated to explore the single phase region, by a model that was created from the basis of the literature. At the decided reaction condition from the calculation (the reactor : 170℃, the dehydration pert : 25℃, pressure : 15MPa), we performed the DMC synthesis by the thermal driven loop reactor. The DMC yield was finally attained 15 mol% (on the basis of the loaded amount of methanol), whereas the DMC yield in a batch reactor at the same reaction condition was merely 1 mol%. We developed a kinetic model for the DMC synthesis by the thermal driven loop reactor to know the controlling factor of the process. Then the model tells us that the flow rate of the reaction fluid in the loop reactor was controlling factor and that the modification of the dehydration pert must be needed to improve the performance of the loop reactor. Less

碳酸二甲酯(DMC)作为聚合物中间体、燃料添加剂等用途十分广泛，是一种高附加值材料。由二氧化碳和甲醇直接合成DMC是一种绿色合成方法。该反应需要一种催化剂才能有效地进行，而氧化锆催化剂是合适的催化剂。反应的副产物是水，由于化学平衡，水使DMC的产率较低。为了提高碳酸二甲酯的产率，脱除反应中的水分，对反应体系的要求很高。在本研究中，我们计划开发一种以二氧化碳和甲醇为原料，采用热驱动环流反应器合成碳酸二甲酯的新工艺。该热驱动环流反应器具有用于反应的加热部分和用于排出水的冷却温度。催化剂为氧化锆，脱水剂为3A分子筛。通过相平衡和…分析，探讨了反应条件的优化。更多的e反应行为。特别是对脱水剂用量的影响进行了评价。在实验研究的基础上，进行了模型开发，明确了该过程的控制因素。首先，对脱水剂在高压反应介质中对甲醇-水体系的性能进行了评价。结果表明，脱水剂在热驱动环流反应器中效果良好(加热温度150~160℃，冷却温度60℃)。其次，根据文献建立的模型，计算了CO_2-甲醇-水-二甲基甲酰胺体系的相平衡，探索了单相区。在计算确定的反应条件下(反应器：170℃，脱水温度：25℃，压力：15 Mpa)，利用热驱动环流反应器进行了碳酸二甲酯的合成。在相同的反应条件下，间歇反应器中DMC的产率仅为1mol%，最终DMC的产率可达15mol%(以甲醇负载量为基准)。为了了解反应过程的控制因素，我们建立了热驱动环流反应器合成DMC的动力学模型。模型表明，反应流体在环流反应器中的流量是控制因素，必须对脱水塔进行改造才能提高环流反应器的性能。较少