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研究生: 林彥儒
Yan-Ru Lin
論文名稱: 微通道反應器應用於1,4丁二醇氧化為丁二酸之研究
Study on Oxidation of 1,4-Butanediol to Succinic Acid with Using Microchannel Reactor
指導教授: 曾堯宣
Yao-Hsuan Tseng
口試委員: 劉志成
Jhy-Chern Liu
李豪業
Hao-Yeh Lee
何郡軒
Jinn-Hsuan Ho
曾堯宣
Yao-Hsuan Tseng
學位類別: 碩士
Master
系所名稱: 工程學院 - 化學工程系
Department of Chemical Engineering
論文出版年: 2021
畢業學年度: 109
語文別: 中文
論文頁數: 88
中文關鍵詞: 微化工技術微反應器1,4-丁二醇的氧化丁二酸
外文關鍵詞: Microchemical Technology, Microreactor, Oxidation of 1,4-Butanediol, Succinic Acid
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  • 微化工技術歷經多年發展,已開始建立完整的基礎理論和程序設計,微反應器也廣泛應用於各種領域,逐漸成為化工業界中的生產程序。本研究以1,4-丁二醇作為反應物,應用微反應器將其製備成丁二酸。此研究目的為解決1,4-丁二醇市場供過於求的問題,也滿足丁二酸的市場需求,故具有經濟應用潛力。本研究使用微反應器系統,進行新的製程開發與設計,以瞭解微反應器應用於不同的製程條件與反應模組配置方式對反應速率與選擇率產生的影響。
    本研究第一階段使用MMRS模組化微反應器系統,以Miprowa微反應器為主體和不同混合的模塊組合而成。使用雙氧水為氧化劑進行1,4-丁二醇氧化反應,通過反應條件的測試,得到最佳的操作條件為:反應溫度為160℃、滯留時間為6 min、1,4-丁二醇/雙氧水流速的比例為 1:9、系統壓力為10 bar,此條件下可達成97.5%以上的1,4-丁二醇轉化率,丁二酸的選擇率可達到14.0%。實驗結果顯示雙氧水氧化能力會影響產物選擇率與反應速率,其太強會導致產物被分解,而太弱時則反應停留在中間產物4-羥基丁酸。以氣相層析質譜儀分析產物與副產物,並觀察在微反應器系統中不同操作條件下,對反應結果的影響,以推測雙氧水氧化1,4-丁二醇為丁二酸的反應途徑。
    在第二階段中,本研究通過MMRS系統模組的更換、多段進料的設計和反應器串連等微反應器系統的設計與改良,成功改善第一階段遇到的問題,在進一步優化反應結果的同時,更加深入的了解微反應系統在不同製程中系統設計的方式,並對其製程開發的可行性與使用時的安全性進行評估,本研究可作為後續微反應器系統設計與應用的參考依據。


    The complete basic theory and process design of microchemical technology were developed during decades. It was also widely applied in various fields and gradually used as the mass production process in the chemical industry. In this study, the reactant, 1,4-butanediol, was converted to succinic acid via microreactor system. The goal of this research was reduce the oversupply of 1,4-butanediol and also meet the demand for succinic acid. It thus exhibited economic potential. In this study, a microreactor system was used to develop and design a new process. The effects of process parameters and allocation of reactor module on reaction rate and selectivity were investigated in detail.
    The MMRS modular microreactor (MRT) system used in the first stage is a major reactor, Miprowa, equipped with different mixing modules. The hydrogen peroxide was used as the oxidant for 1,4-butanediol. A series of systematic test indicated the optima operating conditions were 160°C of reaction temperature, 6 min of residence time, and 1/9 of flow-rate ratio for 1,4-butanediol/H2O2, and 10 bar of system pressure, resulting in over 97.5% of conversion for 1,4-butanediol with 14.0% of selectivity for succinic acid. The oxidizing ability of hydrogen peroxide affected reaction rate and selectivity significantly. The product was decomposed under strongly oxidative condition, and the reaction was only reached to intermediate product, 4-Hydroxybutanoic acid, under mild condition. The analysis of the products and by-products were carried out with using a gas chromatography mass spectrometer. The effects of operation parameters in the microreactor system were observed to find out the reaction pathway of 1,4-butanediol to succinic acid with using hydrogen peroxide as oxidant.
    In the second stage, the problems encountered in the first stage were successfully improved through the replacement of the MMRS system modules, multi-stage feed and the connection of reactors in series. The reaction design was further optimized and the system design concept of the micro-reactor system for different processes was realized. the feasibility and safety design of MRT process were evaluated. t is hoped that this process will be used as an example to demonstrate the micro-reactor system Flexible applicability.

    中文摘要 i ABSTRACT ii 致謝 iii 圖目錄 vi 表目錄 viii 第一章 緒論 1 1.1前言 1 1.2 1,4-丁二醇 3 1.3丁二酸 4 1.4研究動機與目的 5 第二章 文獻回顧 6 2.1丁二酸的製備方式 6 2.1.1傳統製程 6 2.1.2 由1,4-丁二醇直接氧化 8 2.1.3 由1,4-丁二醇脫氫後氧化 10 2.1.4 由1,4-丁二醇脫水後氧化 11 2.1.5不同方法之比較 12 2.2 微化工技術與微反應器系統 14 2.2.1微化工技術之發展 14 2.2.2微化工技術之基本原理 17 2.2.3微反應器系統之特點 18 2.2.4 微反應器應用的限制 19 2.2.5 微反應器合成二酸類化合物 20 第三章 實驗方法與步驟 22 3.1實驗設計 22 3.2實驗藥品 24 3.3實驗設備與分析儀器 25 3.3.1實驗設備 25 3.3.2分析儀器 27 3.4微反應器系統 29 3.5實驗步驟 33 3.5.1微反應器系統操作流程 33 3.5.2以雙氧水氧化1,4-丁二醇 35 3.5.3以空氣/氧氣氧化1,4-丁二醇 36 3.5.4進料系統設計 37 第四章 結果與討論 38 4.1溫度對反應的影響 38 4.2滯留時間對反應的影響 43 4.3進料比例對反應的影響 46 4.4 壓力對反應的影響與主要副產物的分析 50 4.5系統優化設計 56 4.5.1混合器更換對反應的影響 56 4.5.2多段進料設計 58 4.5.3反應器串聯結合多段進料設計 60 4.5.4氧化系統調整 63 第五章 結論與未來展望 65 5.1結論 65 5.1.1反應條件的測試 65 5.1.2系統優化與安全性評估 66 5.2未來展望 67 5.2.1反應器串聯結合多段進料設計系統的改良 67 5.2.2產物純化與試量產 67 5.2.3氣相氧化劑系統的改良 68 5.2.4反應器材質的改良 68 參考文獻 69

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