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研究生:吳育宗
研究生(外文):Yu-Tzong Wu
論文名稱:以反應蒸餾法製備醚類汽油添加劑II.第三戊基乙基醚之合成
論文名稱(外文):Preparation of ethers as fuel additives by reactive distillation II. syunthesis of tert-amyl ethyl ether
指導教授:翁鴻山翁鴻山引用關係
指導教授(外文):Hung-Shan Weng
學位類別:碩士
校院名稱:國立成功大學
系所名稱:化學工程學系碩博士班
學門:工程學門
學類:化學工程學類
論文種類:學術論文
畢業學年度:91
語文別:中文
論文頁數:94
中文關鍵詞:第三戊基醇催化蒸餾乙醇第三戊基乙基醚
外文關鍵詞:Reactive DistillationEthanolTAEETAA
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  本研究室為探討以催化蒸餾技術由具支鏈之五碳烯─2-甲基-2-丁烯與乙醇反應合成醚類汽油添加劑第三戊基乙基醚(tert-amyl ethyl ether , 簡稱TAEE),將研究分為三階段。第一階段由2-甲基-2-丁烯經水合反應製備2-甲基-2-丁醇(或稱第三戊基醇, tert-amyl alcohol, 簡稱TAA) ﹔第二階段則由TAA和乙醇合成TAEE ﹔第三階段將直接以2-甲基-2-丁烯和乙醇合成TAEE。本研究即為第二階段之研究。
首先對於攪拌速率、反應溫度、觸媒用量、觸媒重複使用、反應物不同莫耳比、添加水及壓力等對TAA之反應速率和TAEE之生成分率的影響予以探討。反應是使用Amberlyst 15為觸媒,反應液體積約為445 ml,其中含 250 ml 2-甲基-2-丁醇,134.8 ml乙醇 和60 ml正庚烷。當攪拌速率達到400 rpm以上時,可以忽略外部質傳阻力對反應之影響;當觸媒用量超過20克時,觸媒用量對反應速率與第三戊基乙基醚之生成分率的影響將逐漸減小;同時也發現觸媒可重複使用而活性不會衰減。當乙醇對2-甲基-2-丁醇莫耳數比值增加時,則不管是轉化率或主產物之生成分率都呈現遞增的趨勢;但系統加入水後,水會抑制反應,特別是主反應的進行因而降低反應速率及第三戊基乙基醚的生成分率,而壓力的改變對反應影響並不大。在不同反應溫度下,求出主反應之正向視反應常數,從而求出正向反應之視活化能為60.4 kJ / mole。
  接著探討2-甲基-2-丁醇與乙醇醚化反應之機構。由於反應伴隨著三個副反應,即主反應為2-甲基-2-丁醇(TAA)與乙醇(EtOH)醚化生成第三戊基乙基醚(TAEE)與水 ﹔副反應為TAA脫水生成2-甲基-1-丁烯(2M1B)或2-甲基-2-丁烯(2M2B),以及2M1B轉化為2M2B。我們以初始速率法求取各反應之速率表示式及常數值。得到副反應之正向反應階次對TAA皆為一次,逆向反應之反應階次對2M1B與2M2B及水也各為一次。
最後也就第三階段由2-甲基-2-丁烯與乙醇直接合成TAEE作了初步實驗。分別以使用及不使用共溶劑(丙酮)進行反應,發現在這兩種不同的系統中,皆有TAEE產生。TAEE之生成已經過氣相層析質譜儀測定證實無誤。
除此之外,為了尋求更佳的觸媒,最後又以Amberlyst-31及Amberlyst-36等酸性離子交換樹脂為觸媒進行實驗,確定在相同條件下,這二種樹脂和Amberlyst-15之活性大致相同,但Amberlyst-31的選擇率最高。未來將以它重複第一、二階段之實驗及進行後續之研究。
One of projects in our laboratory is to synthesize a fuel additive, tert-amyl ethyl ether (TAEE), from isoamylenes by catalytic distillation. The study is composed of three steps. In the first step, tert-amyl alcohol (TAA) was prepared from isoamylene by hydration. In the second step, TAEE is synthesized from TAA and ethanol by etherification. And TAEE will be prepared directly from isoamylenes with ethanol in the last step. This thesis deals with the results obtained in the second step.
We investigated the influences of agitation speed, reaction temperature, amount of catalyst , reuse of catalyst, reactant molar ratio, water inhibition, and reaction pressure on the reaction rate and the fractional yield of TAEE. The experimental runs were carried out with Amberlyst 15 as the catalyst, and a liquid of 445 ml containing 250 ml tert-amyl alcohol, 134.8 ml ethanol and 60 ml n-heptane. Experimental results reveal that the influence of external mass transfer resistance can be neglected when the agitation speed is above 400 rpm, and the influence of catalyst loading becomes smaller on the reaction rate and yield of TAEE when the weight of catalyst is beyond 20 gram. It is also found that the catalyst can be reused without activity decay. Both conversion and yield rised when the ethanol/TAA molar ratio is increased. When water is added to the system, the reaction rate and yield decrease greatly due to its inhibition on the reaction, especially on the main reaction. However, the conversion is almost independent of the pressure. The apparent activation energy of the forward reaction is 60.4 kJ/mole.

Subsequently, a kinetic study on the etherification of tert-amyl alcohol with ethanol to produce TAEE and water was carried out. It was found that several side reactions took place simultaneously. Those are the dehydration of tert-amyl alcohol to 2-methyl-1-butene (2M1B) or 2-methyl-2-butene (2M2B), and the isomerization of 2M1B to 2M2B.The initial-rate method was employed to evaluate the rate equations and kinetic parameters. It was found that the side reactions are first order with respect to tert-amyl alcohol of all the forward reactions and are also first order with respect to both 2M1B and 2M2B as well as water in the reverse reactions.

At last, an exploratory study on the third step, the etherification of 2-methyl-2-butene and ethanol to TAEE, was carried out. Acetone was added as a cosolvent to the reactor for comparing with the case without cosolvent. In both systems, the TAEE compound was produced and
was confirmed by the GC/MS.
Besides, in order to find a better catalyst, Amberlyst-31 and Amberlyst -36, were also tested except Amberlyst 15. The reaction rates were almost the same no matter what kinds of catalysts were used, which the yield of TAEE was the highest when Amberlyst-31 was employed. We will repeat the experiments in the first and second steps, and carry out the subsequent studies by using Amberlyst -31 as the catalyst in the future.
中文摘要 I
Abstract IV
誌謝 VII
目錄 VIII
表目錄 XII
圖目錄 XIV
第一章 緒論 1
1-1 前言 1
1-2 MTBE的危機 2
1-3 催化蒸餾的潛力與應用 4
1-4 研究動機 5
第二章 催化蒸餾原理 16
2-1 引言 16
2-2 催化蒸餾的流程設計 17
2-2-1 初步概念可行性的評估 17
2-2-2 概念上的設計 18
2-2-3 硬體設備的選擇與設計 19
2-2-4 實際操作與控制 19
2-3 結語 20
第三章 實驗 22
3-1 實驗裝置 22
3-2 實驗步驟 22
3-2-1 共溶劑的使用 23
3-2-2 氮氣加壓 24
3-3 使用試藥 26
3-4 分析方法 27
3-5 校正曲線 28
第四章 結果與討論 36
4-1 前言 36
4-2 醚化反應之初步探討 36
4-3 攪拌速率對反應之影響 37
4-4 反應溫度之影響 38
4-5 觸媒用量對反應之影響 39
4-6 觸媒重複使用之評估 39
4-7 反應物不同莫耳比對反應之影響 40
4-8 加入水對反應之影響 41
4-9 壓力對反應之影響 41
4-10 不同觸媒對反應之影響 42
4-11 推導反應速率表示式之步驟 42
4-12 副反應(3)速率表示式 44
4-12-1 以積分法求取副反應(3)之反應速率常數 44
4-13 副反應(1)速率表示式 45
4-13-1 以初始速率法求正向反應之階次與反應速率常數 45
4-13-2求取副反應(1)之逆向反應階次與反應速率常數 47
4-14副反應(2)速率表示式 49
4-14-1 以初始速率法求正向反應之階次與反應速率常數 49
4-14-2 以初始速率法求逆向反應之階次與反應速率常數 51
4-15 主反應動力學之探討 52
4-16 以2-甲基-2-丁烯與乙醇合成第三戊基乙基醚之初步探討 58
第五章 總結與未來方向 83
5-1 結論 83
5-2 建議與未來方向 85
參考文獻 87
附錄 92
自述 94
表 目 錄
表1-1 1990年至2000年全球MTBE及TAME之產量 9
表1-2 致癌機率與飲用水含MTBE之濃度關係 9
表1-3 含氧汽油添加劑性質之比較 10
表1-4 酸性離子交換型樹脂觸媒Amberlyst-15特性 11
表1-5 酸性離子交換型樹脂觸媒Amberlyst-31特性 12
表1-6 酸性離子交換型樹脂觸媒Amberlyst-15特性 13
表3-1 反應物與產物之氣相層析儀分析條件 27
表4-1 各成分之生成熱及各反應之反應熱 38
表4-2 利用初始速率代數法所求取之ln k3及α1 46
表4-3 利用初始速率代數法於逆反應所求之ln k4、β1、γ1 49
表4-4 利用初始速率代數法所求取之ln k5及α2 50
表4-5 利用初始速率代數法於逆反應所求之ln k6、β1、γ1 51
表4-6 利用初始速率代數法於主反應求取ln k1、α、β 54
表4-7 各成分之焓值與主反應之焓值 55
表4-8 以初始速率法所求得各反應之反應速率常數 56
表4-9 將各反應之反應速率表示式中反應階次調整為整數後
所求得之反應速率常數 57
表4-10 經調整及模擬所得各反應之反應速率常數 57
圖 目 錄
圖1-1 傳統蒸餾流程與催化蒸餾流程之比較 14
圖1-2 TAEE之醚類合成反應圖 15
圖2-1 催化蒸餾設計流程圖 21
圖3-1 反應設備圖 29
圖3-2 反應物及產物之氣相層析圖 30
圖3-3 TAA與EtOH醚化反應生成TAEE之GC/MS分析結果 31
圖3-4 乙醇對正庚烷的GC校正曲線 32
圖3-5 2-甲基-1-丁烯對正庚烷的GC校正曲線 33
圖3-6 2-甲基-2丁烯對正庚烷的GC校正曲線 34
圖3-7 2-甲基-2丁醇對正庚烷的GC校正曲線 35
圖4-1 2-甲基-2-丁醇與乙醇進行醚化反應之情形 60
圖4-2 攪拌速率對TAA轉化率與TAEE生成分率的影響 61
圖4-3 反應溫度對TAA轉化率與TAEE生成分率的影響 62
圖4-4 ln(-dCA/dt)與1/T的關係圖 63
圖4-5 觸媒添加量對TAA轉化率與TAEE生成分率的影響 64
圖4-6 觸媒重複使用對TAA轉化率與TAEE生成分率的影響 65
圖4-7 不同EtOH/TAA莫耳比對轉化率與生成分率的影響 66
圖4-8 添加水對TAA轉化率與TAEE生成分率的影響 67
圖4-9 壓力對TAA轉化率與TAEE生成分率的影響 68
圖4-10 三種不同觸媒在相同反應條件下之比較 69
圖4-11 2-甲基-1-丁烯轉化生成2-甲基-2-丁烯之反應情形 70
圖4-12 以積分法求反應速率常數k7 71
圖4-13 不同初始濃度2-甲基-2-丁醇進行副反應(1)之反應
情形 72
圖4-14 不同2-甲基-1-丁烯與水之莫耳比例的反應情形 73
圖4-15 不同初始濃度2-甲基-2-丁醇進行副反應(2)之反應
情形 74
圖4-16 不同2-甲基-2-丁烯與水之莫耳比例的反應情形 75
圖4-17 TAA與EtOH進行模擬醚化反應之情形 76
圖4-18 反應速率常數修正後模擬醚化反應之情形 77
圖4-19 以酸性樹脂型觸媒催化2-甲基-2-丁烯之醚化反應 78
圖4-20 2-甲基-2-丁烯與乙醇進行醚化反應初步實驗之
氣相層析圖 79
圖4-21 2-甲基-2-丁烯與乙醇進行初步醚化反應之情形 80
圖4-22 以丙酮為溶劑進行醚化反應初步實驗之氣相層析圖81
圖4-23 以丙酮為溶劑進行初步醚化反應之情形 82
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林裕川, 國立成功大學化工研究所碩士論文, 2002
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