Knowledge Management System Of Institute of process engineering,CAS
甲基丙烯酸甲酯（MMA）作为重要的含氧化学品之一，其煤基合成路线被广泛关注。中国科学院过程工程研究所自2008年开始煤基MMA合成路线的研究，目前实验室研究已趋于完善。为了实现该技术的工业应用，必须进行工程设计方面的研发。本论文借助流程模拟软件，构建煤基MMA合成工艺反应及分离单元的计算模型，获得工业装置工艺流程、物料及能量平衡数据、单元操作参数等基础数据和最佳工艺操作条件，并进一步采用绿色度评价方法，量化分析了各反应单元对环境的影响，为推动该技术的工业化提供科学依据和技术支撑。本论文主要研究内容和相关结论如下：1）依据实验室研究结果、中间产物及产品的物性，构建了煤基MMA合成工艺的流程图，确定了UNIQUAC作为本体系热力学性质的计算方法，分别以RStioc、Radfrac、Heater、Flash、Extract等模块作为反应器、精馏塔、换热器、闪蒸罐、萃取塔等单元操作的模拟模型，在此基础上建立煤基MMA合成工艺的全流程计算模型；2）借助Aspen Plus模拟软件平台，采用灵敏度分析工具，以中间产物及目标产品的纯度、收率、能耗等为目标值，对关键设备的工艺参数及分离方案进行分析，获得优化的操作参数。分析发现，影响丙醛收率的因素为冷凝器的操作温度和闪蒸罐的操作压力，最佳条件为冷凝器的操作温度为20 ℃，闪蒸罐的操作压力为200 kPa；以甲基丙烯醛的纯度和反应体系内水含量为目标，发现先回收甲基丙烯醛的分离方案相比于先回收催化剂的方案能耗降低42.8%；通过对萃取剂正己烷和甲苯的萃取分离效果分析，发现适合甲基丙烯酸提纯的萃取工艺为甲苯萃取分离方案，甲苯萃取分离甲基丙烯酸的回收率相比于正己烷萃取工艺高6%；通过工艺指标和能耗数据的对比，发现双溶剂萃取分离方案是最优的提纯甲基丙烯酸甲酯的分离工艺，相比于水和正己烷的单溶剂萃取工艺，能耗分别降低15.1%和34.9%；3）采用绿色度评价方法，量化分析煤基MMA合成工艺对环境的影响。结合模拟计算结果及绿色度计算方法，分别获得了MMA合成工艺四个反应单元的绿色度，分别为-35.56 gd/h，879.05 gd/h，-20.14 gd/h，168.51 gd/h。分析发现氢甲酰化反应单元是绿色度最低的单元，开发低能耗丙醛分离工艺是提高本单元绿色度的主要途径。 ;The production of methyl methacrylate (MMA) attracted much attention in recent years since MMA is one of the important oxygen-containing chemicals. Various reaction routes have been developed, wherein the coal-based one has been extensively studied. In 2008, researchers at Institute of Process Engineering, Chinese Academy of Sciences joined in the coal-based project. To date, the laboratory scale of the reactions underwent quite well. In order to promote the industrial application of such a technology, it is necessary to provide comprehensive information of process and system optimization. To this end, simulation methods were firstly established for the coal-based production route for MMA synthesis. Consequently, all basic data of the process flow, material and energy balances, unit operating parameters and the optimum operating conditions were obtained. Finally, the impact of each reaction unit on the environment was quantitatively analyzed by the green degree evaluation method, which provides a theoretical basis for the industrialization of the technology.The main contents and conclusions of this thesis are as the following:1) The flow diagram of MMA synthesis process was designed based on the physical properties of the intermediates and final products, and the results of lab scale demonstration equipment, the calculation method of UNIQUAC was selected for the study of thermodynamic properties. Specifically, RStioc, Radfrac, Heater, Flash, Extract were employed for the simulation model of reactor, distillation column, heat exchanger, flash tank, extraction tower, respectively. Collectively, the calculation model of the whole process of coal-based MMA technology was obtained;2) The production process of MMA is simulated and analyzed by Aspen Plus simulation software. The operation parameters and separation schemes of the key equipment were analyzed and optimized towards the purity, yield and energy consumption of the intermediates and target product by using the sensitivity analysis tool. It was found that the operation temperature of the condenser and the operation pressure of the flash tank are the key factors of the yield of propionaldehyde. The optimal operation conditions are condensing at 20 oC and keeping the operation pressure of the flash tank at 200 kPa; Aiming at the purity of methacrylaldehyde and the content of water in the reaction system, the energy consumption of recovering MAL firstly process was reduced by 42.8% compared with the process of recovering the catalyst firstly; by analyzing of extraction and separation efficiency of n-hexane and toluene, it was found that the extraction process suitable for the purification of methacrylic acid is toluene extraction, and the recovery rate of methacrylic acid is 6% higher than that of n-hexane extraction; by comparing process specification and energy consumption, it was found that the bi-solvent extraction separation is the optimal separation process for purifying methyl methacrylate, and the energy consumption is reduced by 15.1% and 34.9% compared with the single solvent extraction process for water and n-hexane, respectively.3) The influence of coal-based MMA production process on the environment was analyzed quantitatively by using the green degree evaluation method. The green degree value of the four reaction units of MMA synthesis process were obtained on the simulation results, which were -35.56 gd/h, 879.05 gd/h, -20.14 gd/h, 168.51 gd/h, respectively. The analysis showed that the hydroformylation reaction unit was the least green unit. And the approach to improve the green degree of such a process is to develop a novel process of propionaldehyde separation with a lower energy consumption.
|张军平. 煤基甲基丙烯酸甲酯工艺过程模拟研究[D]. 中国科学院研究生院,2018.|
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