甲醇合成的酒精溶剂的催化效应.doc

A New Low-Temperature Synthesis Route of Methanol: Catalytic Effect of the Alcoholic Solvent Introduction Gas-phase methanol is being produced industrially by 30-40 million ton per year around the world, from CO/ CO2/H2 at a temperature range of 523-573 K and a pressure range of 50-100 bar, using copper-zinc-based oxide catalyst. Under these extreme reaction conditions, the efficiency of methanol synthesis is severely limited by thermodynamics as methanol synthesis is an extremely exothermic reaction.1,2 For example, at 573 K and 50 bar, it is calculated by thermodynamics that theoretic maximum one-pass CO conversion is around 20% for flow-type reactor when H2/CO=2. Also it is reported that the one-pass CO conversion in the industrial ICI process is between 15 and 25%, even if H2-rich gas is used (H2/CO =5,523-573 K).3 Therefore, developing a low-temperature process for methanol synthesis, which will greatly reduce the production cost and utilize the thermodynamic advantage at low temperature, is challenging and important.3 If conversion is high enough in methanol synthesis, recycling of the unreacted syngas can be omitted and air can be used directly in the reformer, instead of pure oxygen. Generally, low-temperature methanol synthesis is conducted in the liquid phase. The BNL method first reported by Brookhaven National Laboratory (BNL), using a very strong base catalyst (mixture of NaH, acetate), realized this continuous liquid-phase synthesis in a semi-batch reactor at 373-403 K and 10-50 bar. However, a remarkable drawback of this process is that even a trace amount of carbon dioxide and water in the feed gas or reaction system will deactivate the strongly basic catalyst soon,4,5 resulting in high cost coming from the complete purification of the syngas from reformer, and reactivation of the deactivated catalyst. This is the main reason stopping the commercialization of this low-temperature methanol synthesis method. Liquid-phase methanol synthesis from pure CO