2010-08-012024-05-17https://scholars.lib.ntu.edu.tw/handle/123456789/679830摘要：反應蒸餾系統在工業界日漸應用，此種程序強化之製程將反應器及蒸餾分離合併於一裝置，能夠大幅度的節省投資成本、改良反應的轉化率、減少副產物與廢棄物的產生量、並且能夠節省操作能源，增加經濟效益。但是其設計、操作、及控制因為包括反應、萃取、汽提、精餾等數項功能於一個單元操作設備，故頗為複雜。本研究計畫預期以三年時間徹底探討碳酸二甲酯、碳酸二乙酯、及碳酸二苯酯整廠製程採用反應蒸餾方式之程序設計，並會與傳統將反應段與分離段分開的製程相比較，以確切瞭解採用反應蒸餾方式的優勢。每年度計畫的後期亦會探討各反應蒸餾整廠製程之動態操作與控制，務期使提出的整廠控制策略能夠在有進料組成干擾或產量增減的情況下，均能保持產物的純度與反應的高轉化率及選擇率。 本研究計畫的第一年為以碳酸乙烯酯與甲醇進行酯類置換反應，產製生物可分解之綠色化學品碳酸二甲酯及另一有用的乙二醇化學品為研究的重點。碳酸二甲酯可以取代硫酸二甲酯用做使化學物接上甲基之化學劑，亦可取代光氣用做使化學物接上 C=O官能基進而製造聚碳酸酯之化學劑。而硫酸二甲酯及光氣均為危險性之化學品，故將其取代而使用無毒性之碳酸二甲酯，可稱為是一綠色製程。碳酸二甲酯亦可用做塗料之溶劑及汽油添加劑等多種用途。另外值得一提的是此酯類置換反應的反應物(碳酸乙烯酯)可由二氧化碳及環氧乙烯(Ethylene Epoxide)反應而得，故此一系列的反應可以消耗二氧化碳之溫室效應氣體，而生成無毒性之碳酸二甲酯，達到減少二氧化碳總量的綠色目標。 本研究計畫的第二年及第三年將分別探討利用酯類置換反應進一步由碳酸二甲酯產製碳酸二乙酯或碳酸二苯酯。碳酸二乙酯是一個重要的溶劑及中間體以產製一種抗生素(norfloxacin)，以往產製此抗生素的溶劑及中間體為使用具劇毒性的光氣。碳酸二苯酯是一個利用無光氣途徑來產製聚碳酸酸的重要單體，故以上製程亦可稱為綠色製程。此兩年度所探討的製程其反應均為串級反應包含一不欲生成的中間副產物，此為以往反應蒸餾文獻鮮少探討，故最適化設計及控制研究結果亦極富學術價值。 文獻中有關本系統碳酸二甲酯、碳酸二乙酯、及碳酸二苯酯之最適化設計、動態操作、及整廠控制策略的探討幾乎未見，故本計畫除了工業上的極佳應用價值外，亦甚富有學術上之研究價值。 <br> Abstract: Reactive distillation, combines reactive section and separation section into one unit operation, has started to show wider industrial applications in recent years. This process intensification design has demonstrated its potential for capital productivity improvements, selectivity and conversion improvements, reduced energy use, and the reduction or elimination of solvents in the process. However, this kind of design combines tasks including reaction, rectification, stripping, and even extraction into a single unit operation, thus the design, operation, and control of reactive distillation is more complex and needed careful investigation. In this three-year research proposal, thorough study of the processes to produce dimethyl carbonate (DMC), diethyl carbonate (DEC), and diphenyl carbonate (DPC) will be made using reactive distillation technology. The economical benefit of such reactive distillation process will be compared to conventional process flowsheet which starts with the reactive section and then the separation section. In the latter part of each year’s research, the overall control strategy of the DMC, DEC, and DPC processes will be studied. The goal is to maintain the product at high purity and also maintain reaction high selectivity and conversion despite feed composition disturbances and throughput changes. In the first year of this research project, the trans-esterification reaction of producing DMC and ethylene glycol from ethylene carbonate and methanol will be studied. DMC, an environmentally benign and biodegradable chemical, can be used as a methylation agent replacing dimethyl sulfate, a carbonylation agent replacing phosgene, a solvent for coating, and a gasoline additive for anti-breaking and oxygen-content improvement. Since the reactant (ethylene carbonate) can be produced from CO2 and ethylene epoxide, therefore this series of reactions is such an excellent green chemical process that it turns the waste greenhouse gas CO2 into the valuable chemicals with a zero-discharge and a 100% atom economy. In the second and third year of this research project, reactive distillation processes of producing diethyl carbonates and diphenyl carbonate will be studied. Diethyl carbonate is an important solvent and an intermediate to produce an antibiotic (norfloxacin) from non-phosgene route. Diphenyl carbonate is an essential monomer in the non-phosgene route for producing polycarbonates. Thus, both processes can be considered as green processes as well. There are two cascade reversible reactions presented in the above two processes with an undesirable intermediate. This was seldom discussed in the reactive distillation literature. The discussion of process design and control of the above three products (DMC, DEC, and DPC) is relatively scarce in the previous literature. Thus, this three-year research project, not only has high industrial application potential, but also is valuable to other researchers.反應蒸餾碳酸二甲酯碳酸二乙酯碳酸二苯酯製程設計控制策略Reactive DistillationDimethyl CarbonateDiethyl CarbonateDiphenyl CarbonateProcess DesignControl Strategy