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研究生: 李家文
Lee, Chia-Wen
論文名稱: H-ZSM5 型沸石觸媒於催化高酸價大豆油酯化反應之研究
Study on Catalyzed Esterification of High-Acid Soybean Oil with Zeolite H-ZSM5
指導教授: 陳炳宏
Chen, Bing-Hung
學位類別: 碩士
Master
系所名稱: 工學院 - 化學工程學系
Department of Chemical Engineering
論文出版年: 2016
畢業學年度: 104
語文別: 中文
論文頁數: 92
中文關鍵詞: 沸石生質柴油游離脂肪酸酯化兩階段轉酯化
外文關鍵詞: Zeolite, biodiesel, free fatty acids (FFAs), esterification, two-stage transesterification
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  • 生質柴油是對環境友善且環保的再生能源,常見方法是將植物油、動物油脂或廢油與醇類進行轉酯化反應產出生質柴油,轉酯化反應慢,所以會添加觸媒增加反應並提高產率,工業上常用鹼性觸媒催化轉酯化反應,但其缺點是對油料要求較高,若含有過量的游離脂肪酸,會導致皂化反應發生,降低生質柴油產率並使得後續分離純化困難,因此在轉酯化反應前必須先消除游離脂肪酸才能抑制皂化反應發生。
    本研究以高酸價大豆油模擬油料中含過量的游離脂肪酸透過兩階段轉酯化反應來解決此問題,第一階段利用酸觸媒來將油料中的游離脂肪酸酯化,第二階段再以鹼觸媒來進行轉酯化反應生成生質柴油,都使用固相觸媒進行反應,因其容易分離且方便回收再使用。而實驗以H-ZSM5沸石催化酯化反應為主軸,利用高酸價大豆油與過量的甲醇下進行反應,降低油酸含量,探討觸媒使用量與反應溫度對酯化反應的影響,找到合適的反應條件,並進行觸媒耐用性測試及利用XRD、SEM、FTIR、BET、NH3-TPD分析觸媒。
    實驗結果顯示在油 : 觸媒 : 油酸 : 甲醇重量比= 1: 0.5: 0.05: 20及溫度60C情況下反應2小時將油酸含量從5.4wt%降至1.5wt%,而耐用性測試固定反應4小時,在第二次反應能將油酸含量降至2wt%左右,最後在兩階段轉酯化反應得部分,原料為油酸含量為5.4wt%的大豆油,以4小時酯化將油酸含量降至1.2wt%,再進行2小時轉酯化,產率可達90%,可應用在高酸價的油料中。

    In this study, as-synthesized zeolite H-ZSM5 catalysts were chosen to catalyze the esterification of oleic acids spiked in soybean oil or free fatty acids (FFAs) in waste cooking oil. Zeolite H-ZSM5 was synthesized via hydrothermal processes by using fumed silica as a raw material with an addition of proper aluminum hydroxide, ammonium fluoride and tetrapropylammonium bromide as a templating agent at 170C for 1 day. It was characterized with XRD, SEM, BET, FTIR and TPD. The amount of FFAs existing in oil was successfully reduced below to 2 wt% in 2h at 60C from ca. 6 wt% initially present under proper reaction conditions, after which the transesterification can procced with base zeolite catalysts. Besides, the durability test for H-ZSM5 in esterification reaction was conducted. It was revealed that catalysts became inactive after 7th cycle in which its acid strength and quantity decreased significantly according to the NH3-TPD analysis. A two-stage process was devised to facilitate the production of biodiesel from high acid soybean oil or waste cooking oil, in which the yield could achieve above 80% under appropriate conditions.

    摘要 II Abstract III 致謝 XIII 目錄 XIV 表目錄 XVIII 圖目錄 XIX 第一章 緒論 1 1-1前言 1 1-2研究動機與目的 3 第二章 文獻回顧 5 2-1生質柴油之介紹 5 2-1-1 生質柴油的歷史 5 2-1-2 植物油燃料的發展性 7 2-1-3 生質柴油的原料來源與規範 11 2-1-4 油脂原料含酸的前處理 17 2-2 酯化反應 19 2-2-1 勻相酸觸媒 19 2-2-2 非勻相酸觸媒 20 2-3 轉酯化反應 23 2-3-1 勻相鹼性觸媒 23 2-3-2 勻相酸性觸媒 24 2-3-3 非勻相鹼性觸媒 26 2-3-4 非勻相酸性觸媒 26 2-4 沸石觸媒 27 2-4-1 沸石的簡介 27 2-4-2 沸石的結構 28 2-4-3 沸石的特性與應用 31 2-5 ZSM5沸石簡介 33 第三章 實驗 35 3-1實驗架構 35 3-2實驗藥品 36 3-3 實驗設備 38 3-4實驗方法 40 3-4-1 觸媒H-ZSM5的合成 40 3-4-2以含浸法擔載鎢磷酸於商用Modernite型沸石 40 3-4-3 油中含有油離脂肪酸之酸價測試 40 3-4-4 酯化反應 41 3-4-5 轉酯化反應 42 3-4-6 脂肪酸甲酯產率分析 42 3-4-7 觸媒回收再使用 43 3-4-8 兩階段轉酯化反應 43 3-4-9 觸媒鑑定與分析 43 3-4-9-1氣相層析儀 (Gas Chromatography, GC) 43 3-4-9-2掃描式電子顯微鏡 (Scanning Electron Microscope, SEM) 44 3-4-9-3 X光繞射分析儀 (X-ray Diffraction Analyzer, XRD) 44 3-4-9-4 比表面積儀 (Specific Surface Area & Pore Size Distribution Analyzer, BET) 44 3-4-9-5 傅立葉紅外線光譜分析儀 (Fourier transform infrared, FT-IR) 45 3-4-9-6熱重分析儀 (Thermogravimetric Analyzer, TGA) 45 3-4-9-7全自動程式升溫化學吸附儀 (Auto Chemisorption Analyzer) 45 第四章 結果與討論 46 4-1不同商用沸石於酯化反應 46 4-1-1商用H-ZSM5與H-Mordenite酯化效果之比較 46 4-1-2以鎢磷酸改質商用H-Mordenite 48 4-1-2-1 XRD與SEM鑑定 48 4-1-2-2酯化結果之探討 50 4-2 H-ZSM5的鑑定與特性分析 53 4-2-1 H-ZSM5型沸石觸媒XRD鑑定 53 4-2-2 H-ZSM5型沸石觸媒SEM鑑定 55 4-2-3 H-ZSM5型沸石觸媒BET分析 56 4-2-4 H-ZSM5型沸石觸媒FTIR分析 58 4-2-5 H-ZSM5型沸石觸媒TPD分析 59 4-2-5-1 H-ZSM5沸石之NH3-TPD測量 59 4-2-5-2 H-ZSM5沸石之CO2-TPD測量 61 4-2-6 H-ZSM5型沸石觸媒熱重分析 62 4-3-1不同觸媒使用量對酯化反應的影響 63 4-3-2不同溫度對酯化反應的影響與動力學探討 64 4-4商用與自行合成H-ZSM5酯化效果之比較 68 4-5觸媒回收使用測試 69 4-5-1觸媒耐用性測試 69 4-5-2失去活性後的H-ZSM5沸石之鑑定 71 4-5-2-1 XRD與SEM鑑定 71 4-5-2-2 FTIR分析 74 4-5-2-3 BET分析 75 4-5-2-4 NH3-TPD分析 76 4-6兩階段轉酯化反應 78 4-6-1兩階段轉酯化反應高酸價大豆油 78 4-6-2兩階段轉酯化反應廢食用油 80 4-6-3經濟潛力分析 81 第五章 結論 82 參考文獻 83 附錄 89

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