CAJ | 학술논문

围绕碳酸二甲酯的高效、绿色、安全、节能合成目标，构建了联合生产碳酸二甲酯、甲缩醛和二甲醚反应体系及节能工艺。借助Aspen Plus软件对独立反应及复杂体系进行了热力学分析。由结果可知，升高反应压力或降低温度可明显提高碳酸二甲酯的平衡组成；与甲缩醛和二甲醚合成工艺相耦合后，可大幅提升甲醇平衡转化率，由0.5%～5.9%提高到91.7%～96.3%。根据热力学计算结果和动力学因素，提出顺序生产碳酸二甲酯、甲缩醛和二甲醚的串联催化反应器工艺。甲缩醛和二甲醚的分离采用简单精馏方式，碳酸二甲酯和水共沸物的分离采用变压精馏，3种产品的质量浓度均可达到99%以上。可有效解决单独生产碳酸二甲酯和甲缩醛生产中原料循环量大、能耗高和易爆炸等缺陷。
위요탄산이갑지적고효、록색、안전、절능합성목표，구건료연합생산탄산이갑지、갑축철화이갑미반응체계급절능공예。차조Aspen Plus연건대독립반응급복잡체계진행료열역학분석。유결과가지，승고반응압력혹강저온도가명현제고탄산이갑지적평형조성；여갑축철화이갑미합성공예상우합후，가대폭제승갑순평형전화솔，유0.5%～5.9%제고도91.7%～96.3%。근거열역학계산결과화동역학인소，제출순서생산탄산이갑지、갑축철화이갑미적천련최화반응기공예。갑축철화이갑미적분리채용간단정류방식，탄산이갑지화수공비물적분리채용변압정류，3충산품적질량농도균가체도99%이상。가유효해결단독생산탄산이갑지화갑축철생산중원료순배량대、능모고화역폭작등결함。
To achieve the target of the efficient, green, safe and energy saving synthesis of dimethyl carbonate, a combined reaction system with energy saving is proposed for synthesis of dimethyl carbonate, methylal and dimethyl ether from methanol. Thermodynamics of single reaction and the complex system is analyzed by Aspen Plus software. The results show that there is thermodynamic equilibrium limit for the synthesis of dimethyl carbonate from methanol in gas phase, to improve significantly equilibrium concentration of dimethyl carbonate higher reaction pressure and lower reaction temperature is necessary, even so, large amount of unreacted methanol must be recycled which consume a lot of energy. When synthesis of dimethyl carbonate is combined with methylal and dimethyl ether synthesis, the equilibrium conversion of methanol can be improved observably from 0.5%—5.9%to 91.7%—96.3%. Based on the thermodynamic calculations and kinetics of these reactions, a series process of three catalytic reactors are proposed for synthesis of dimethyl carbonate, methylal and dimethyl ether in order, and the system including reaction and separation processes is simulated. The results show that the mixture of methylal and dimethyl carbonate can be separated by simple distillation and the separation of dimethyl carbonate-H2O azeotrpoe need to employ pressure swing distillation. Mass concentration of three products can be reached above 99%. The process proposed could effectively solve the problems as follows: recycle of large amount un-reacted materials, high energy consumption, easy explosion and so on, which exist in the process for detached production of dimethyl carbonate and methylal.