合成碳酸二甲酯宏观动力学及反应器数值模拟  

Macrokinetics and Numerical Simulation of the Dimethyl Carbonate Synthesis in the Fixed-Bed Reactor

作　　者：闫亚辉 丁晓墅[1] 王淑芳[1] 王延吉[1] 

机构地区：[1]河北工业大学绿色化工与高效节能河北省重点实验室,天津300130

出　　处：《化学反应工程与工艺》2016年第3期252-260,共9页Chemical Reaction Engineering and Technology

基　　金：国家自然科学基金(21236001);高等学校博士学科点专项科研基金(20121317110009);河北省重大技术创新项目(12275603Z);河北省高等学校科学技术研究项目(QN2015163);河北省青年科学基金项目(B2016202256)

摘　　要：在固定床反应器中研究了PdCl_2-CuCl_2-KOAc/AC催化剂上甲醇气相氧化羰基化合成碳酸二甲酯(DMC)反应的宏观动力学,建立了以CO、O_2、甲醇分压表示的幂函数动力学模型,统计检验表明所得模型具有较高的可信度。依据动力学模型,建立了用于该反应过程的固定床反应器二维拟均相模型,借助Matlab软件,模拟分析了空速、原料组成、进口温度、操作压力和管外介质温度等因素对反应过程的影响。模拟计算结果显示,操作压力和空速对反应器的热点温度影响显著,而甲醇的转化率及DMC对CO的选择性受原料组成影响较大。优化确定了在PdCl_2-CuCl_2-KOAc/AC催化剂上甲醇气相氧化羰基化合成碳酸二甲酯适宜的条件为进料组成CH_3OH/CO/O_2的体积比为0.20:0.27:0.53,空速7 500 h^(-1),进口温度160℃,操作压力0.30 MPa。在该条件下,床层的热点温度为214.96℃,甲醇的转化率为51.69%,DMC对CO的选择性为65.92%。The macrokinetics of dimethyl carbonate（DMC） synthesized by the gas-phase oxidative carbonylation of methanol over PdCl_2-CuCl_2-KOAc/AC was investigated in the fixed-bed reactor.The kinetic model of power functions presented by the form of partial pressures of carbon monoxide,oxygen and methanol was established.The statistic test showed that the model had high credibility.Based on the macrokinetics model,a two-dimensional pseudo-homogeneous fixed-bed reactor model of this process was established.The effects of space velocity,feed composition,inlet temperature and operating pressure on the process were simulated and analyzed by Matlab,respectively.The results showed that the hot-spot in the reactor was greatly influenced by the operating pressure and the space velocity,while the conversion of methanol and the selectivity of DMC to CO were largely influenced by the feed composition.The optimum operating conditions of dimethyl carbonate synthesis by the gas-phase oxidative carbonylation of methanol over PdCl2-CuCl_2-KOAc/AC was determined as follows：the volume ratio of CH_3OH/CO/O_2 was0.20：0.27：0.53,the space velocity was 7 500 h^（-1）,the inlet temperature was 160 ℃ and the operating pressure was 0.30 MPa.The hot-spot temperature was found to be 214.96 ℃,the methanol conversion was51.69%and the selectivity of DMC to CO was 65.92%under this condition.

关 键 词：碳酸二甲酯 宏观动力学 参数估计 二维拟均相模型 

分 类 号：TQ223.2[化学工程—有机化工] O643.11[理学—物理化学]