化工学报2019，Vol.70Issue(1)：116-127,12.DOI:10.11949/j.issn.0438⁃1157.20180925
环丁砜处理磺酸树脂高效催化聚甲氧基二甲醚合成
High-efficiency catalytic synthesis of polyoxymethoxy dimethylether from sulfolane-treated sulfonic acid resin
摘要
Abstract
Polymethoxy dimethylether (DMM3—7) as a diesel additive can improve diesel cetane number and fuel utilization rate, and has broad application prospects. For the synthesis of DMM3—7 from dimethoxymethane (DMM) and trioxymethylene(TOX), this work systematically studied the effects of different conditional parameters on the conversions and products selectivity with the sulfolane-treated sulfonic acid as the catalyst and the reaction routes were proposed according to the results of products analysis by GC-MS. It was observed that trace amounts (mg/kg level) of H2O left in the reaction system significantly influenced the reactants conversions and products selectivity. With raising H2O content, more white precipitation paraformaldehyde (PF) was gradually produced, while methanol was substantially generated to lower the selectivity of DMM3—7. The sulfolane-treated method was first proposed and sulfolane solvent was acted as dehydration and pore-forming reagent, that resulted in the absorbed H2O in the surface/pores of NKC-9sulfolane obvious decrease from 2154 mg/kg to 198 mg/kg. Meanwhile, 13X molecular sieve was applied to significantly reduce H2O content of DMM from 710 mg/kg to 54 mg/kg. When the reaction temperature is 313 K (40℃), the reaction is 2 h, the pressure is 1.0 MPa, and the mass ratio of DMM to TOX is 2/1, the DMM and TOX conversion rates and the DMM3-7 mass selectivity increase from 48.27%, 88.41% and 45.27% to 52.91%, 93.34% and 61.58%, respectively. Comparing to literatures reports, the mass selectivity to DMM3-7 was higher than 60% that makes it promising for industrial applications.关键词
聚甲氧基二甲醚/甲缩醛/三聚甲醛/磺酸树脂/环丁砜处理Key words
polymethoxy dimethyl ether (DMMn)/dimethoxymethane (DMM)/trioxane (TOX)/sulfonic acid resin/treated by sulfolane分类
化学化工引用本文复制引用
王岩,石磊,范家麒,陈飞,姚杰,许光文..环丁砜处理磺酸树脂高效催化聚甲氧基二甲醚合成[J].化工学报,2019,70(1):116-127,12.基金项目
国家重点研发计划项目(2018YFB0604500) （2018YFB0604500）
国家自然科学基金项目(21303106) （21303106）
辽宁省高等学校创新人才项目(LR2016015) （LR2016015）
辽宁省自然科学基金项目(2015020243) （2015020243）
沈阳市科技计划项目(17-231-1-68) （17-231-1-68）
