CAJ | 학술논문

以生物柴油副产物甘油为原料合成碳酸二甲酯新工艺既能减少对石油的依赖，又能充分利用生物质资源。本研究首先对环氧氯丙烷和环氧丙烷分别为原料合成碳酸二甲酯反应体系进行了热力学分析和对比，计算了不同反应温度和压力下的碳酸二甲酯平衡收率。环氧氯丙烷作为原料较环氧丙烷在热力学上具有明显优势，在3.0 MPa、460 K时，其平衡收率分别为90.4%和18.2%。在此基础上，考察了碱金属化合物、负载型碱金属催化剂、季铵盐及其复合催化剂等对环氧氯丙烷与甲醇和二氧化碳直接合成碳酸二甲酯的催化反应性能。实验结果表明，钠金属化合物为催化剂时的碳酸二甲酯收率高于钾金属化合物。负载型催化剂Na 2 CO 3(NaHCO 3)/γ-Al 2 O 3的催化活性较均相催化剂明显提高，碳酸二甲酯的收率达到21.0%左右。发现四丁基溴化铵与碳酸氢钠混合物作为催化剂可显著提高碳酸二甲酯收率，达到25.2%。
이생물시유부산물감유위원료합성탄산이갑지신공예기능감소대석유적의뢰，우능충분이용생물질자원。본연구수선대배양록병완화배양병완분별위원료합성탄산이갑지반응체계진행료열역학분석화대비，계산료불동반응온도화압력하적탄산이갑지평형수솔。배양록병완작위원료교배양병완재열역학상구유명현우세，재3.0 MPa、460 K시，기평형수솔분별위90.4%화18.2%。재차기출상，고찰료감금속화합물、부재형감금속최화제、계안염급기복합최화제등대배양록병완여갑순화이양화탄직접합성탄산이갑지적최화반응성능。실험결과표명，납금속화합물위최화제시적탄산이갑지수솔고우갑금속화합물。부재형최화제Na 2 CO 3(NaHCO 3)/γ-Al 2 O 3적최화활성교균상최화제명현제고，탄산이갑지적수솔체도21.0%좌우。발현사정기추화안여탄산경납혼합물작위최화제가현저제고탄산이갑지수솔，체도25.2%。
Dimethyl carbonate was synthesized from glycerol, a by-product in the production of biodiesel, as a raw material in this paper. The novel synthetic process may not only reduce dependence on fossil oil, but also fully utilize biomass resources. Using epichlorohydrin and propylene epoxide as the raw material, the thermodynamic analysis for reactions of dimethyl carbonate synthesis was conducted respectively. It was found that the reaction of using epichlorohydrin as raw material is much more thermodynamically favorable than that of using propylene epoxide, and under 3 MPa and 460 K, the equilibrium yields of dimethyl carbonate are 90.4% and 18.2%, respectively. Based on above results, the influences of various catalysts, including alkali-metal compounds, supported alkali-metal compounds and the mixtures ofn-Bu4NBr and alkali-metal compounds catalyst on the synthesis of dimethy carbonate from epichlorohydrin, methanol and carbon dioxide were studied. The results show that the yield of dimethyl carbonate by sodium compounds is higher than that by potassium compounds. A mixture ofn-Bu4NBr and NaHCO3 was used as a catalyst, critical to improve the yield of dimethyl carbonate (25.2%).