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研究生:蔡龍德
研究生(外文):Lung-De Tsai
論文名稱:乳酸和醋酸酯化反應之觸媒的研究
論文名稱(外文):Catalyst Studies For The Esterification Of Lactic Acid And Acetic Acid
指導教授:李國禎李國禎引用關係
指導教授(外文):Kuo-Tseng Li
口試委員:王奕凱吳榮宗
口試委員(外文):I-kai WangRung-Tzung Wu
口試日期:2012-07-26
學位類別:碩士
校院名稱:東海大學
系所名稱:化學工程與材料工程學系
學門:工程學門
學類:化學工程學類
論文種類:學術論文
論文出版年:2012
畢業學年度:100
語文別:中文
論文頁數:110
中文關鍵詞:混合金屬氧化物酸性點
外文關鍵詞:mixed metal oxideacid site
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乳酸酯具有無毒、溶解性好、不易揮發、有果香味等特點,同時可生物降解,因此極具開發與應用前景,其消費的增長很快,是理想的”綠色溶劑 ”,主要用於微電子工廠作為電路板和電子原料的清洗劑。此外,醋酸酯及乳酸酯是油漆、塗料、塑料等工廠中的溶劑。乳酸酯還可用於天然樹脂、油漆、印刷油墨、乾洗液、黏著劑等。

本論文使用共沉澱法製備不同莫耳比的TiO2-SiO2觸媒、TiO2-Al2O3觸媒以及ZrO2-Al2O3觸媒催化乳酸及醋酸與醇類間的酯化反應以製造乳酸丁酯和醋酸丁酯。ZrO2-Al2O3觸媒催化乳酸酯化反應的性能最好(在170◦C及8hr下,乳酸丁酯產率可達94.11%),而在催化醋酸酯化反應中,以TiO2-Al2O3觸媒催化之性能最好(在220◦C及6hr下醋酸丁酯產率可達97.63%)。

我們利用X射線繞射儀(XRD)、熱場發射掃描式電子顯微鏡(TFSEM)、熱重分析儀(TGA)、表面積與孔洞分析儀(BET)、能量散射光譜儀(EDS)對混合雙金屬氧化物觸媒作特性分析,並探討酯化反應之活性和觸媒酸性之間關聯性,當reaction rate(轉化頻率*酸性密度*比表面積)越高,產率越大。

Esters of lactic acid are non-toxic、soluble、non-volatile and have fruit flavor. It is also biodegradable and has wide applications, particularly as regulations and consumer preferences increase the demand for “green” chemicals. They are ideal green solvents which are used as the cleaning agents for the circuit board and electronic raw material. In addition,esters of lactic acid and acetic acid are solvents for paint and plastics. Esters of lactic acid also can be used to produce natural resins, paints, printing inks, dry lotion, adhesives and so on.

This thesis prepared mixed metal oxide catalysts with a co-precipitation method and catalyze the esterification of lactic acid and acetic acid with the prepared catalysts. ZrO2-Al2O3 catalysts had the best ester yield(butyl lactate yield was 94.11% at 150◦C and 8hr) For the esterification of acetic acid, TiO2-Al2O3 catalysts had the best ester yield(butyl acetate yield was 97.63% at 220◦C and 6hr).

We used XRD、TFSEM、TGA、BET and EDS to characterise the mixed metal oxide catalysts. The correlation between esterification activity and catalyst acidic properties were investigated. The higher reaction rate(turnover frequency * acid site density * specific surface area) is, the higher yield is.

目錄
第一章 緒論 1
1.1 背景 1
1.1.1 乳酸 1
1.1.2 醋酸 3
1.2 研究動機 3
第二章 文獻回顧 5
2.1 乳酸介紹 5
2.1.1 乳酸生產方法 6
2.2 醋酸介紹 8
2.2.1 醋酸生產方法 8
2.3 酯化介紹 10
2.3.1 乳酸正丁酯 11
2.3.2 醋酸正丁酯 12
2.4 觸媒原理 13
2.4.1 觸媒擔體種類 14
2.4.2 觸媒之合成方法 14
2.5 固體酸觸媒介紹 16
2.6 混合金屬氧化物觸媒 17
2.6.1 各金屬氧化物觸媒介紹 19
第三章 觸媒製備與實驗設備 24
3.1 實驗材料 24
3.1.1 實驗藥品 24
3.1.2 實驗氣體 25
3.1.3 實驗設備 26
3.2 觸媒製備 27
3.2.1 TiO2-SiO2的製備 27
3.2.2 ZrO2-Al2O3的製備 28
3.3 酯化反應實驗步驟 29
3.4 儀器設定與反應物產物定性、定量分析 31
3.4.1 氣相層析分析法 31
3.4.2 定性分析 33
3.4.3 定量分析(內部標準品法) 35
3.4.3.1 乳酸酯化反應校正線整理 36
3.4.3.2 醋酸酯化反應校正線整理 37
3.5 熱場發射掃描式電子顯微鏡(TFSEM) 38
3.6 X射線繞射實驗(XRD) 39
3.7表面積與孔洞分析實驗(BET) 40
3.7.1 BET表面積之測定原理 40
3.7.2 BET表面積及孔徑大小之測定實驗 46
3.8熱重分析儀原理 47
第四章 實驗結果與討論 48
4.1 金屬氧化物觸媒與陽離子樹脂優劣之比較 49
4.2 乳酸酯化反應 50
4.2.1 TiO2-SiO2催化乳酸酯化反應 51
4.2.2 TiO2-SiO2催化乳酸酯生成 51
4.2.3 ZrO2-Al 2O3催化乳酸酯化反應 55
4.2.4 ZrO2-Al 2O3催化乳酸酯生成 55
4.3 醋酸酯化反應 58
4.3.1 TiO2-SiO2催化醋酸酯之合成 58
4.3.2 ZrO2-Al 2O3催化醋酸酯之合成 61
4.3.3 TiO2- Al 2O3催化醋酸酯生成 63
4.3.4 反應時間對混合金屬氧化物觸媒催化醋酸酯化反應之影響 64
4.3.5 反應溫度對混合金屬氧化物觸媒催化醋酸酯化之影響 65
4.3.6 提高醋酸酯化反應之產率 66
4.4 觸媒之XRD分析 68
4.4.1 TiO2-SiO2觸媒之XRD分析 68
4.4.2 ZrO2-Al2O3觸媒之XRD分析 69
4.5 觸媒之EDS分析 71
4.5.1 TiO2-SiO2觸媒之EDS分析 71
4.5.2 ZrO2-Al2O3觸媒之EDS分析 72
4.6 觸媒之BET分析 73
4.6.1 TiO2-SiO2觸媒之BET分析 73
4.6.2 ZrO2-Al2O3觸媒之BET分析 74
4.7 觸媒之SEM分析 76
4.7.1 TiO2-SiO2觸媒之SEM分析 76
4.7.2 ZrO2-Al2O3觸媒之SEM分析 84
4.8 觸媒之總酸量分析 92
4.8.1 TiO2-SiO2之總酸量分析 92
4.8.2 ZrO2-Al2O3之總酸量分析 93
4.9 觸媒之TOF、酸性點密度分析 94
第五章 結論與建議 97
5-1 結論 97
5-2 建議 99
第六章 參考文獻 100

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