一氧化碳催化偶联合成草酸二甲酯

CATALYTIC SYNTHESIS OF OXALATE DIESTER BY CORBON MONOXIDE COUPLING

本文报告了pd/α·Al_2O_3催化剂添加助剂和改变温度。空速和Co/CH_3ONO比率等条件对常压CO催化偶联合成草酸二甲酯反应的影响结果。经适当改进制备方法和添加助剂制得的pd—2r/α·Al_2O_3。同传统的pd/α·Al_2O_3催化剂相比,在pd含量和反应条件相同的情况下,草酸二甲酯得率从645g提高至998g/l·h。TPR表明,H_2和CO还原气对pd/α·Al_2O_3的还原后果明显不同,前者在室温下pdo就较快速被还原,后者则缓和得多。

Oxalatae diester is prepared by the reaction of carbon monoxide with nitrite ester over Pdcatalysts.The influences of the promoters,temperature space velocity and the CO/CH_3ONO ratio on the reactions are examined.The results show that the Pd-Zr/α-Al_2O_3 catalyst gives de-Me oxalate with selectivity over 95% and space time yield 998g/l-h, while the space time yield for the traditional Pd/Al_2O_3 catalyst is only 645g/1-h under the same Pd loading and reaction conditions. In addition, TPR shows that the reduction of PdO/α-Al_2O_3 with H_2 is more rapid and severs than with CO.