化工学报2017，Vol.68Issue(10)：3739-3746,8.DOI:10.11949/j.issn.0438-1157.20170327
磺酸树脂催化甲缩醛一步羰化制高附加值甲氧基乙酸甲酯
Efficient sulfonic acid resin catalysts for carbonylation of dimethoxymethane to value-added methyl methoxyacetate
摘要
Abstract
Methyl methoxyacetate (MMAc), an important fine chemical, is an intermediate product producing ethylene glycol from syngas. Literature reports showed that high molar ratio of CO to DMM (>100) and low CO conversions (<0.5%) were obviously beneficial for vapor-phase carbonylation of dimethoxymethane (DMM) to MMAc. Using a slurry phase reactor, this work systematically studied the effects of different solvents, sulfonic acid resin catalysts, reaction temperature, pressure, reaction time and drying temperature on DMM conversion and MMAc selectivity. The solubility of CO in liquid phase was significantly increased by sulfolane solvent , thus obviously promoting the carbonylation reaction and suppressing the hydration as well as disproportionation reactions of DMM. Comparing with H-Y, the carbonylation activity of sulfonic acid resin catalyst was higher. The high rate of DMM disproportionation for H-Y was attributed to the micropores of zeolite, which facilitated a critical initial step in the formation of DME and MF. With the increased reaction temperature, pressure or reaction time, the conversion of DMM increases, whereas the selectivity of MMAc first increased and then decreased. With increasing the drying temperature, the moisture content left in the resin gradually decreased. But higher drying temperature resulted in the collapse of pores and surface sintering. For the liquid phase carbonylation process, many complicated and unreported side reactions were accompanied. The DMM conversion can reach to about 100% with 74.32% MMAc selectivity using sulfolane as solvent and D-009B as the catalyst at 110℃ and 5 MPa for 6 h. It was anticipated that this direct carbonylation of DMM to produce MMAc process was promising for industrial manufacture.关键词
甲缩醛/甲氧基乙酸甲酯/羰基化反应/磺酸树脂/环丁砜/催化Key words
dimethoxymethane/methyl methoxyacetate/carbonylation/sulfonic acid resion/sulfolane/catalysis分类
化学化工引用本文复制引用
石磊,姚杰,朱文良,刘中民..磺酸树脂催化甲缩醛一步羰化制高附加值甲氧基乙酸甲酯[J].化工学报,2017,68(10):3739-3746,8.基金项目
国家自然科学基金项目(21303106) （21303106）
辽宁省自然科学基金项目(2015020243) （2015020243）
一等博后基金项目(2014M560224) （2014M560224）
第八批特别资助博后基金项目(2015T80275). Foundation item:supported by the National Natural Science Foundation of China (21303106), theNatural Science Foundation of Liaoning Province (2015020243), the First Class General Financial Grant from the China Postdoctoral Science Foundation(2014M560224) and the Special Financial Grant from the China Postdoctoral Science Foundation(2015T80275). （2015T80275）
