电化学还原合成N-甲基羟胺研究-高校化学工程学报.PDF

20 3 No.3 Vol.20 2006 6 Journal of Chemical Engineering of Chinese Universities June 2006 1003-9015(2006)03-0437-06 N- , , , ( , 310032) N- N- −0.65 ~ −0.75 V (vs. SCE)N- 90% 86% 1200~2500A⋅m−2 80% N- N- N- TQ226.51 O646.541 A Synthesis of N-methylhydroxylamine by Electrochemical Reduction Method GAN Yong-ping, ZHANG Wen-kui, HUANG Hui, XIA Xin-hui (College of Chemical Engineering and Materials Science, Zhejiang University of Technology, Hangzhou 310032, China) Abstract: N-methylhydroxylamine and its HCl salts have been extensively used in the synthesis of pharmaceutical and pesticide intermediate, and the reprocessing of nuclear waste etc. In this paper, the electrochemical reduction characterizations of nitromethane to form N-methylhydroxylamine on Cu, amalgamation Cu(Cu-Hg), nickel and graphite electrodes in HCl solutions were investigated respectively. The excellent electroreduction activity of nitromethane were observed on Cu, Cu/Hg and nickel electrodes except graphite electrode, and the order of activity is CuCu-HgNiC(graphite). The reduction of nitromethane on Cu electrode is in the potential range of −0.65~ −0.75V (vs.SCE). The results of the eletrosynthesis experiments show that using Cu and Cu-Hg as the cathode, the electrolysis efficiency is 90% and the product yield is 86%, whereas when using nickel or graphite as the cathode, the current efficiency and product yields are relatively low. The highest current efficiency may be obtained when the electrolysis time is about 80% of the theoretical time and the current density is in the range of 1200~