摘要
针对甲基丙烯酸甲酯-甲醇-水共沸体系,分别选择水、正己烷和水-正己烷双溶剂为萃取剂建立分离流程进行模拟,建立单溶剂、双溶剂萃取工艺过程进行全流程模拟,采用灵敏度分析优化工艺过程的溶剂比和操作温度.结果表明,双溶剂萃取工艺比水、正己烷单溶剂萃取工艺能耗分别降低15.1%和34.9%.采用绿色度评价方法量化3种分离工艺对环境的影响,水、正己烷、水-正己烷双溶剂萃取工艺的绿色度分别为–7.25,–21.3和–6.75 gd.
As one of the important oxygen-containing chemicals, methyl methacrylate(MMA) is widely used in producing organic glass(PMMA), coatings, ACR/MBS and so on. The triple azeotropic systems of MMA-methanol-water are formed in the production process, which resulting in difficulty in product purification. In order to solve the problem on separation of MAA-methanol-water azeotropic system, the separation processes of using a single solvent(water or n-hexane) and bi-solvent(a combination of water and n-hexane) as the extractants were established in this study. The models of extraction processes for single solvent and bi-solvent system were simulated. The ratio of solvent and operating temperature were analyzed and systematically optimized using sensitivity analysis method. It demonstrated that the extraction process using bi-solvent had relatively lower energy consumption compared to those of the single ones, and the energy consumption was reduced by 15.0%(vs. n-hexane) and 34.9%(vs. water), respectively. Meanwhile, the influence of three extraction processes on the environmental impact assessment was quantitatively analyzed using green degree analysis method. The results suggested that bi-solvent process was much more environmental friendly. The green degree of separation process using water, n-hexane and bi-solvent as extractant was-7.25,-21.3 and-6.75 gd, respectively.
引文
[1]李涛.MMA生产工艺技术的比较及投资分析[J].石油化工技术与经济,2008,24(5):17-22.Li T.Process comparison and investment analysis of MMA[J].Technology&Economics in Petrochemicals,2008,24(5):17-22.
[2]Nagai K.New developments in the production of methyl methacrylate[J].Appl.Catal.,A,2001,221(1):367-377.
[3]李铭岫,高元哲,王继业,等.异丁烯两段法制甲基丙烯酸甲酯[J].精细化工,2002,19(12):727-728.Li M X,Gao Y Z,Wang J Y,et al.Preparation of methyl methacrylate bytwo-stage reaction of isobutene[J].Fine Chemicals,2002,19(12):727-728.
[4]左杰,田绍友.甲基丙烯酸甲酯工业化合成路线及发展现状[J].天津化工,2017,31(3):13-16.Zuo J,Tian S Y.The industrialization synthetic process of MMAand the Current development situation[J].Tianjin Chemical Industry,2017,31(3):13-16.
[5]Zhao Y,Ma K,Bai W,et al.Energy-saving thermally coupled ternary extractive distillation process by combining with mixed entrainer for separating ternary mixture containing bioethanol[J].Energy,2018,148:296-308.
[6]Liang K,Li W,Luo H,et al.Energy-efficient extractive distillation process by combining preconcentration column and entrainer recovery column[J].Ind.Eng.Chem.Res.,2014,53(17):7121-7131.
[7]Tripodi A,Compagnoni M,Ramis G,et al.Pressure-swing or extraction-distillation for the recovery of pure acetonitrile from ethanol ammoxidation process:a comparison of efficiency and cost[J].Chem.Eng.Res.Des.,2017,127:92-102.
[8]高晓新,朱碧云,顾强,等.双溶剂协同萃取精馏分离乙酸甲酯-甲醇-水工艺模拟[J].过程工程学报,2017,17(2):254-258.Gao X X,Zhu B Y,Gu Q,et al.Process simulation for separation of methylacetate-methanol-water by double solvent synergistic extractive distillation[J].Chin.J.Process Eng.,2017,17(2):254-258.
[9]Xu H,He C.Extraction of Isoflavones from stem of pueraria lobata(willd.)ohwi using n-butanol/water two-phase solvent system and separation of daidzein[J].Sep.Purif.Technol.,2007,56(1):85-89.
[10]郭伟,闫瑞一,周清,等.甲基丙烯酸甲酯-甲醇体系的双溶剂萃取[J].化工学报,2014,65(7):2717-2723.Guo W,Yan R Y,Zhou Q,et al.Liquid-liquid equilibrium for double solvent extraction of methyl methacrylate from methanol[J].CIESC Journal,2014,65(7):2717-2723.
[11]傅金彦,王琨,胡英.甲醇-甲基丙烯酸甲酯-水三元系汽液平衡和液液汽平衡的研究(I)三对二元系[J].化工学报,1988,39(1):64-76.Fu J Y,Wang K,Hu Y.Studies on the vapor-liquid equilibrium and vapor-liquid-liquid equilibrium for a methanol-methyl methacrylate-water ternary system(I)three different binary systems[J].CIESC Journal,1988,39(1):64-76.
[12]傅金彦,王琨,胡英.甲醇-甲基丙烯酸甲酯-水三元系汽液平衡和液液汽平衡的研究(II)三元系部分[J].化工学报,1988,39(1):77-88.Fu J Y,Wang K,Hu Y.Studies on the vapor-liquid equilibrium and vapor-liquid-liquid equilibrium for a methanol-methyl methacrylate-water ternary system(II)ternary system[J].CIESCJournal,1988,39(1):77-88.
[13]Wu Y C,Hsu C S,Huang H-P,et al.Design and control of a methyl methacrylate separation process with a middle decanter[J].Ind.Eng.Chem.Res.,2011,50(8):4595-4607.
[14]耿兴山,王井志,田桂兰,等.粗甲基丙烯酸甲酯中甲醇萃取分离的研究[J].化学工程师,1994,1(5):15-16.Geng X S,Wang J Z,Tian G L,et al.Study of the extraction separation of methanol in crude MMA[J].Chemical Engineer,1994,1(5):15-16.
[15]Yan R,Li Z,Diao Y,et al.Green process for methacrolein separation with ionic liquids in the production of methyl methacrylate[J].AIChE J.,2011,57(9):2388-2396.
[16]Abrams D S,Prausnitz J M.Statistical thermodynamics of liquid mixtures:a new expression for the excess gibbs energy of partly or completely miscible systems[J].AIChE J.,1975,21(1):116-128.
[17]Smith J M,Ness H C V,Abbott M M.Introduction to chemical engineering thermodynamics[M].New York:McGraw Hill Higher Education,2005:545-590.
[18]程能林.溶剂手册,第5版[M].北京:化学工业出版社,2015:103-105.Cheng N L.Solvent handbook 5th ed.[M].Beijing:Chemical Industry Press,2015:103-105.
[19]Zhang X,Li C,Fu C,et al.Environmental impact assessment of chemical process using the green degree method[J].Ind.Eng.Chem.Res.,2008,47(4):1085-1094.
[20]Li C,Zhang X,Zhang S,et al.Environmentally conscious design of chemical processes and products:multi-optimization method[J].Chem.Eng.Res.Des.,2009,87(2):233-243.
[21]付超,张香平,闫瑞一,等.绿色度方法中环境影响因子权值的确定[J].计算机与应用化学,2008,25(9):1068-1074.Fu C,Zhang X P,Yan R Y,et al.Weighting Factors of environmental impact categories in green degree method[J].Computers and Applied Chemistry,2008,25(9):1068-1074.
[22]李茜,王二强,项曙光,等.丙烯酸甲酯-甲醇-水体系精制过程的模拟与优化[J].计算机与应用化学,2014,31(5):536-540.Li Q,Wang E Q,Xiang S G,et al.Simulation and optimization of purification process for methyl acrylate-methanol-water system[J].Computers and Applied Chemistry,2014,31(5):536-540.