甲醛乙炔化反应中CuO-Bi2O3/SiO2-MgO催化剂活化过程研究

甲醛与乙炔发生炔化反应合成1,4-丁炔二醇，选用铜铋作为催化剂。模拟最具代表性的工业炔化催化剂以研究甲醛乙炔化反应的活化过程，制备高性能CuO-Bi₂O₃/SiO₂-MgO催化剂，结合XRD、H₂-TPR、TG-DTA和N₂-TPD-MS等表征，研究炔化催化剂活化过程中铜物种的转变，获得最优催化剂活化方法。结果表明，CuO在甲醛溶液中无乙炔存在下可定向转化为Cu₂O，但经乙炔活化后活性较低，归因于还原过程中Cu物种的流失及晶粒长大。而在甲醛与乙炔协同作用下，CuO可快速转变为Cu的炔化物种，表现出较高的炔化活性。表明炔化催化剂的活化过程必须在甲醛与乙炔同时存在的条件下进行。

Researches on activation process of CuO-Bi2O3/SiO2-MgO catalyst in formaldehyde ethynylation reaction

Using copper and bismuth as the catalyst,1,4-butynediol was synthesized via formaldehyde ethynylation.By simulating the most representative industrial ethynylation catalyst,the activation process in formaldehyde ethynylation reaction was studied.CuO-Bi2O3/SiO2-MgO catalysts with high-performance were prepared.Combining XRD,H2-TPR,TG-DTA and N2-TPD-MS methods,the changing of the copper species during the activation process of ethynylation catalysts was investigated.The optimal activation method of the catalysts was obtained.The results showed that CuO in formaldehyde solution without acetylene could be directly converted into Cu2O,but after activation with acetylene its activity was lower,which was attributed to the loss and grain growth of Cu species in the reduction process.Under the synergistic action of formaldehyde and acetylene,CuO was quickly converted to ethynylation species of Cu,exhibiting higher ethynylation activity.Therefore,the activation process of the ethynylation catalyst must be carried out in the presence of formaldehyde and acetylene simultaneously.