化工学报2015，Vol.66Issue(9)：3333-3340,8.DOI:10.11949/j.issn.0438-1157.20150834
低温甲醇合成研究进展
Research developments of low-temperature methanol synthesis
摘要
Abstract
Conventional production of methanol is very inefficient since only 10%—15% one-pass conversion is achieved typically at 5.0—10.0 MPa and 523—573 K due to the severe thermodynamic limitations of its exothermal reaction (CO + 2H2 = CH3OH). A novel route of low-temperature methanol synthesis developed by Tsubaki et al from CO2-containing syngas only by adding alcohols including methanol itself is reviewed. These alcohols act as the homogeneous co-catalysts and solvent, realizing 70%—100% one-pass conversion at only 5.0 MPa and 443 K. The key step is the reaction of the adsorbed formate species with alcohols to yield ester species at low temperatures, followed by the hydrogenation of ester by hydrogen atoms on metallic Cu. This changes the normal reaction path of conventional, high-temperature methanol synthesis from formate via methoxy to methanol. A series of new methods, such as sol-gel auto-combustion, solid-state combustion and formic acid assisted combustion methods, to prepare highly active metallic Cu/ZnO catalysts without further reduction are also reviewed. During the decomposition of metal-contained precursors in an argon atmosphere, H2 and CO are liberated and act in situ as the reducing agents to obtain pure metals and metallic catalysts. The X-ray diffraction, X-ray photoelectron spectroscopy, energy dispersive spectroscopy, and temperature-programmed reduction analysis reveal that the as-prepared catalyst without further reduction is converted into metallic Cu0 and ZnO species.关键词
催化剂/酯化/加氢/反应动力学/低温甲醇合成/Cu/ZnO/原位红外/免还原Key words
catalyst/esterification/hydrogenation/reaction kinetics/low-temperature methanol synthesis/Cu/ZnO/in-situ FT-IR/reduction-free分类
化学化工引用本文复制引用
石磊,张婉莹,王玉鑫,TsubakiNoritatsu..低温甲醇合成研究进展[J].化工学报,2015,66(9):3333-3340,8.基金项目
国家自然科学基金项目(21303106) （21303106）
辽宁省教育厅优秀人才项目(LJQ2013045).supported by the National Natural Science Foundation of China (21303106) and Program for Liaoning Excellent Talents in University(LJQ2013045). （LJQ2013045）
