CO与亚硝酸甲酯氧化偶联制草酸二甲酯及其副反应的研究  

Study on oxidative coupling of CO with methyl nitrite to dimethyl oxalate and its side reactions

作　　者：李卓 迟子怡 李学刚[1] 薛敏钊[1] 肖文德[1] LI Zhuo;CHI Zi-yi;LI Xue-gang;XUE Min-zhao;XIA O Wen-de(School of Chemistry and Chemical Engineering,Shanghai Jiao Tong University,Shanghai 200240,China)

机构地区：[1]上海交通大学化学化工学院,上海200240

出　　处：《天然气化工—C1化学与化工》2021年第4期46-51,共6页Natural Gas Chemical Industry

摘　　要：合成气制乙二醇路线的重要步骤为CO与亚硝酸甲酯(MN)偶联生成草酸二甲酯(DMO)中间体,同时副产碳酸二甲酯(DMC)和甲酸甲酯(MF)。在管式固定床反应器中采用商用Pd/α-Al_(2)O_(3)催化剂,考察了原料气体积分数、配比、温度、空速(SV)和NO体积分数对主、副反应的影响。结果表明,在130℃、10000~20000 mL/(h·g)条件下,MN转化率85%~90%,DMO选择性大于95%;高温、低空速、低反应物体积分数和低V(CO)/V(MN)比有利于DMC的生成,当CO与MN进料体积分数均为2.5%,空速20000 m L/(h·g)时,DMC选择性可达8.6%。进一步根据实验数据提出了反应动力学模型,模型表明CO、MN和NO具有较明显的阻尼吸附作用,与实验结果相符。An important step in the synthesis of ethylene glycol from syngas is the coupling reaction of CO with methyl nitrite(MN)to dimethyl oxalate(DMO)intermediate,with dimethyl carbonate(DMC)and methyl formate(MF)as the main by-products.The effects of feed gas concentration,ratio,reacting temperature,space velocity(SV)and NO content on the main and side reactions were investigated in a tubular fixed bed reactor packed with commercial Pd/α-Al_(2)O_(3) catalyst.The results show that the conversion of MN achieves 85%-90%with the DMO selectivity above 95%at 130℃and within space velocity range of 10000-20000 mL/(h·g).High reacting temperature,low space velocity,low reactant concentration and V(CO)/V(MN)are favorable to the formation of DMC.When the feed concentration of CO and MN is 2.5%and the space velocity is 20000 mL/(h·g),the selectivity of DMC can reach up to8.6%.According to the experimental data,a kinetic model was further proposed.And the kinetic model showes that CO,Mn and NO has obvious negative adsorption effect,which is consistent with the experimental results.

关 键 词：CO偶联反应 亚硝酸甲酯 草酸二甲酯 工艺条件 副反应 动力学 

分 类 号：TQ223[化学工程—有机化工] O624[理学—有机化学]