CO低压气相催化偶联合成草酸二乙酯的宏观动力学研究
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摘要
CO气相催化偶联合成草酸二乙酯(DEO)是C1化学研究开发的重要课题,对于改变草酸酯、草酸、乙二醇、草酰胺和某些医药、染料中间体的传统工艺技术路线,具有重要的理论意义和应用价值。
本文采用负载型钯系双金属催化剂,在固定床反应器中对CO低压气相偶联合成草酸二乙酯进行考察,分别考察了温度、停留时间、压力及原料气组成对催化反应性能的影响。结果表明,在温度90℃~ 130℃、停留时间1.5s~3s、压力0.1MPa~0.3MPa、亚硝酸乙酯的摩尔浓度在10%~20%范围内、CO的摩尔浓度为20%~30%的条件下,催化剂的活性及稳定性均达到工业应用水平。在反应温度为130℃,反应压力为0.3MPa,停留时间为1.5s,原料气中亚硝酸乙酯与CO的摩尔浓度均为20%时,草酸二乙酯的时空收率最佳,为578g/(L·h)。
较详细的研究了CO低压气相催化偶联合成草酸二乙酯及生成碳酸二乙酯(DEC)这一副反应的宏观动力学特征。采用一维拟均相模型建立微分方程,对合成草酸二乙酯的主、副反应采用幂函数型动力学模型,通过对不同反应条件下的实验数据进行优化计算,确定了宏观动力学参数,得出了相应的宏观动力学方程式:
The coupling reaction of carbon monoxide to produce diethyl oxalate (DEO) in gaseous phase is an important subject of C1 chemical technology. It’s very significant in the process substutided for conventional production of oxalate ester, oxalate acid, ethylene glycol and intermediates for pharmaceuticals and dyestuffs.
The synthesis of diethyl oxalate from carbon monoxide and ethyl nitrite which was carried out on the supported palladium bimetal catalyst was studied in a continuous flow fixed-bed reactor at low-pressure. The effect of temperature, residence time, the mole concentration of ethyl nitrite (EN) and CO and the pressure on the reaction were studied. The results showed that the activity and stability of the catalyst had reached the level of industrial application in the condition of the temperature 90℃~ 130℃, the residence time 1.5 s~3 s, the pressure 0.1 MPa~0.3 MPa, EN molar concentration 10%~20%, CO molar concentration 20%~30%. The STY of DEO was 578 g/(L·h) at 130℃and 0.3 MPa with residence time 1.5 s and molar concentration of EN and CO 20%.
This work aimed mainly at the micro-kinetics study of the coupling reaction of the synthesis of diethyl oxalate and it’s side reaction, the formation of diethyl carbonate (DEC), in vapor phase at low-pressure from CO. The reaction model of power function type was established both for the formation of DEO and DEC by the one dimensional pseudo homogenous reactor model. By optimization of the results in different reaction conditions, the parameters of the macro-kinetics were determined. The equations of the kinetics were as follows:
本文采用负载型钯系双金属催化剂,在固定床反应器中对CO低压气相偶联合成草酸二乙酯进行考察,分别考察了温度、停留时间、压力及原料气组成对催化反应性能的影响。结果表明,在温度90℃~ 130℃、停留时间1.5s~3s、压力0.1MPa~0.3MPa、亚硝酸乙酯的摩尔浓度在10%~20%范围内、CO的摩尔浓度为20%~30%的条件下,催化剂的活性及稳定性均达到工业应用水平。在反应温度为130℃,反应压力为0.3MPa,停留时间为1.5s,原料气中亚硝酸乙酯与CO的摩尔浓度均为20%时,草酸二乙酯的时空收率最佳,为578g/(L·h)。
较详细的研究了CO低压气相催化偶联合成草酸二乙酯及生成碳酸二乙酯(DEC)这一副反应的宏观动力学特征。采用一维拟均相模型建立微分方程,对合成草酸二乙酯的主、副反应采用幂函数型动力学模型,通过对不同反应条件下的实验数据进行优化计算,确定了宏观动力学参数,得出了相应的宏观动力学方程式:
The coupling reaction of carbon monoxide to produce diethyl oxalate (DEO) in gaseous phase is an important subject of C1 chemical technology. It’s very significant in the process substutided for conventional production of oxalate ester, oxalate acid, ethylene glycol and intermediates for pharmaceuticals and dyestuffs.
The synthesis of diethyl oxalate from carbon monoxide and ethyl nitrite which was carried out on the supported palladium bimetal catalyst was studied in a continuous flow fixed-bed reactor at low-pressure. The effect of temperature, residence time, the mole concentration of ethyl nitrite (EN) and CO and the pressure on the reaction were studied. The results showed that the activity and stability of the catalyst had reached the level of industrial application in the condition of the temperature 90℃~ 130℃, the residence time 1.5 s~3 s, the pressure 0.1 MPa~0.3 MPa, EN molar concentration 10%~20%, CO molar concentration 20%~30%. The STY of DEO was 578 g/(L·h) at 130℃and 0.3 MPa with residence time 1.5 s and molar concentration of EN and CO 20%.
This work aimed mainly at the micro-kinetics study of the coupling reaction of the synthesis of diethyl oxalate and it’s side reaction, the formation of diethyl carbonate (DEC), in vapor phase at low-pressure from CO. The reaction model of power function type was established both for the formation of DEO and DEC by the one dimensional pseudo homogenous reactor model. By optimization of the results in different reaction conditions, the parameters of the macro-kinetics were determined. The equations of the kinetics were as follows:
引文
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