環氧氯丙烷是化學工業中重要的產品之一，由於具有反應性的環氧基團及可移動之氯原子，使其可和化合物的許多基團做反應。其用途除了在生產環氧樹脂外，各種清漆、油漆、膠水、合成纖維、離子交換樹脂以及高耐油、耐熱、防止氣體穿透的橡膠也是從環氧氯丙烷生產出來的產品。氯醇法是現今合成環氧氯丙烷的主要方法，然而這種方法存在許多嚴重的問題，包含產生大量含有氯化鈣的廢渣及廢水，此外該過程還產生極大量的有機氯化物雜質，去除此雜質不僅費力且昂貴。甘油法是另一種合成環氧氯丙烷的方法，但該方法的缺點是轉化率低，且亦形成不少廢渣和廢水。在近期環境意識抬頭和經濟形勢之下，開發綠色環氧氯丙烷製程已是長期的趨勢。

過氧化氫具高的活性氧含量，且是對環境友好、清潔的氧化劑。本研究是在溶劑為甲醇與催化劑為鈦矽沸石狀態下，設計以氯丙烯與過氧化氫進行液相反應產生環氧氯丙烷的整廠製程。在本研究中是使用過量的氯丙烯以增加過氧化氫的轉化率和降低過氧化氫自解產生氧氣的程度。產品於連續攪拌反應器合成後，進入蒸餾塔進行分離，尾氣成份從塔頂的部份冷凝器排出，含有過剩未反應的氯丙烯和溶劑甲醇的塔頂液相產物則循環回至反應器中。主要含有環氧氯丙烷和水的底部餾出物經冷凝後進入分相器形成主要含環氧氯丙烷的有機相液體與主要含水的水相液體，此兩個液體再分別進入兩個氣提塔進行分離，塔底分別可得到高純度的環氧氯丙烷和水，氣提塔的塔頂產物則迴流至分相器。由於過氧化氫自解所產生的氧氣與氯丙烯和甲醇在特定的濃度下會有爆炸的安全疑慮，本研究利用添加氮氣至蒸餾塔的第一板與部份冷凝器的排氣管線內，以避免爆炸的情況發生，所提出的整廠製程不僅可以滿足高純度的產品需求，而且同時可符合製程安全上的要求。在整廠控制方面，本研究在蒸餾塔與兩個氣提塔是以溫度控制間接控制產品的純度，用穩態分析方式設計溫度控制策略。從動態模擬結果顯示，在反應物進料量改變的情況下，經由觸媒量與反應器液位設定點呈相同比例的改變下，環氧氯丙烷和水的純度可穩定控制在操作值，氮氣兩股進料量保持不變或與反應物進料量進行比率控制，皆可使蒸餾塔操作在安全的區域。

Epichlorohydrin (ECH) is an important product in chemical industry. Due to its reactive epoxy group and mobile chlorine atom, ECH can react with many groups of compounds. In addition to the production of epoxy resins, various varnishes, paints, glues, synthetic fibers, ion-exchange resins, and rubbers characterized by high oil and heat resistance and impermeablility to gases are also the products produced from ECH. Nowadays, the chlorohydrin process is the main method to synthesize ECH. However, this process exists many serious problems, including the large amounts of contaminated water containing CaCl2. This process also yields considerable amounts of organochloride impurities, whose removal is laborious and expensive. Another ECH synthesis method is based on glycerol. The disadvantages of this process are low hydrogen chloride and glycerol conversion, and the formation of large amounts of polluted wastewater. Owing to the recently environmental and economic situation, a green ECH synthesis is necessary to be developed for long-term prospects.

In the study, we design a green plant-wide process for ECH synthesis by the liquid-phase epoxidation of allyl chloride with hydrogen peroxide in an organic solvent methanol in the presence of the titanium silicalite. Excess allyl chloride is used in order to increase the reaction conversion of hydrogen peroxide and decrease the reaction extent of the hydrogen peroxide decomposition to oxygen. Products are synthesized in continuous stirred-tank reactors and then separate by a distillation column. The distillate containing mostly allyl chloride and methanol is recycled to the reactor and the bottom product containing mostly ECH and water is decanted into two liquid phases. Liquids of organic and aqueous phases in the decanter are respectively fed into two strippers to obtain high purity ECH and water at the bottoms. Furthermore, nitrogen is fed to distillation column for safety consideration because hydrogen peroxide may generate safety problems from its large exothermic decomposition potential to water and oxygen. Simulations results show that the proposed plant-wide process can achieve high purity products under the safety requirement.

摘要 2
ABSTRACT 4
圖目錄 7
表目錄 8
第一章 緒論 9
1-1 研究背景 9
1-2 研究動機 11
第二章 環氧氯丙烷生產技術現況 12
2-1 丙烯高溫氯化法 12
2-2 醋酸丙烯酯法 14
2-3 甘油法 16
2-4 氯丙烯直接環氧化法 19
2-5 丙烯醛法及丙酮法 21
第三章 整廠製程之設計 22
3-1 前言 22
3-2 熱力學模式 25
3-3 動力學模式 36
3-4 整廠設計 38
3-5 最適化步驟 41
3-6 最適化結果 42
3-7 安全性考慮 46
第四章 整廠製程之控制 48
4-1 穩態分析 48
4-2 動態模擬控制 50
第五章 結論 56
參考文獻 57
附錄A 年度總成本之估算(TURTON ET AL., 2009) 61
附錄B 化工廠成本指數(2015) 74
附錄C 設備成本參數值 75
附錄D 熱交換器規格 76

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