促进型甲酸甲酯氢解制甲醇铜基催化剂的研究

Study of Promoted Cu based Catalysts for Hydrogenolysis of Μethylformate to Μethanol

研制开发了一种耐ＣＯ低温高效四组分（Ｃｕ－Ｃｒ－Ｍｎ－Ｎｉ）改进铜铬催化剂，其原料合成气中ＣＯ允许含量可高达１３Ｖ％；在常压，４１３Ｋ，原料气Ｈ２／ＭＦ＝４／１（ｖ／ｖ），流速为１８００ｍＬ／ｈｇｃａｔａｌ．的反应条件下，ＭＦ转化率高达９９．８％，甲醇选择性为９９．９％（在相同反应条件下二组分的Ｃｕ－Ｃｒ催化剂上ＭＦ转化率仅为７３．１％，甲醇选择性为９８．０％），当向原料气中添加１３．１Ｖ％ＣＯ时，ＭＦ转化率仍可以稳定达到９５．９％，甲醇选择性为９６．３％．实验结果表明，ＣＯ导致催化剂失活的重要原因之一是ＣＯ导致Ｃｕ＋深度还原为Ｃｕ０。

A promoted Cu based catalyst composed of 4 components (Cu Cr Mn Ni) for Hydrogenolysis of Methyl Formate to Methanol has been studied and developed. Under reaction condition of 413 K, 0.1 MPa, H 2/MF=4/1 (mol/mol), and GHSV=1800 mL(STP)/h·g catal., the conversion of MF reached to 99.8% and selectivity to CH3OH up to 99.9% ; whereas under the same conditions, with the bi components Cu Cr catalyst, only 73.1% MF was converted. Furthermore, even in the case that CO content was increased to 13.1% in the feedstream, the MF conversion and CH 3OH selectivity still kept as high as 95.5% and 96.3%, respectively. The experimental results indicated that one of the important reasons for loss of the activity of catalyst caused by CO seemed that CO would lead to Cu + being deeply reduced to Cu 0, and as a consequence, the active sites on the surface of the functioning catalyst was going down.