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以作者查詢圖書館館藏 、以作者查詢臺灣博碩士 、以作者查詢全國書目 、勘誤回報 、線上人數：66 、訪客IP：18.188.62.10
姓名 吳國卿(Kuo-Ching Wu) 查詢紙本館藏 畢業系所 化學工程與材料工程學系 論文名稱 高效率醋酸乙酯生產製程研究
(Efficient Catalytic Processes for the Preparation of Ethyl Acetate)相關論文 檔案 [Endnote RIS 格式]
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摘要(中) 醋酸乙酯為重要工業成品，廣泛應用於各種工業領域。目前商業化醋酸酯化製程大多採行液相酯化反應，然液相酯化反應受熱力學平衡限制，等莫耳醋酸和乙醇進行酯化反應所得之醋酸乙酯產率低於67 mol%，亦即有30 mol%以上的醋酸與乙醇未完全反應，而其中乙醇會和產物中的醋酸乙酯與水形成乙醇-水、乙醇-醋酸乙酯之二成分共沸，及乙醇-水-醋酸乙酯之三成分共沸，所以欲分離產物中之乙醇-水-醋酸乙酯需耗用很多能源，因此傳統之醋酸乙酯製程約有90%的能源是消耗在分離乙醇-水-醋酸乙酯的程序上，而其中最重要的分離關鍵為乙醇的存在，因為乙醇的存在除了導致多重共沸外，其三成分共沸組成為均勻互溶相，無法利用蒸餾直接分離，先需採用加水萃取法降低醋酸乙酯產物中之乙醇含量，才可利用共沸蒸餾純化醋酸乙酯與水。所以開發一高效率的酯化製程以提高乙醇轉化率，將可提升製程的能源使用效率。本研究成功的在不改變傳統酯化製程的流程下，利用製程技術將等莫耳酯化反應的one-pass乙醇轉化率由67 mol%提高至85 mol%以上，使產物流中之乙醇含量由14wt%降低至6.5wt%，產物流中之乙醇含量降低將有助於後端之醋酸乙酯分離純化，此新製程之關鍵技術為所採用之反應溫度，控制反應溫度介於傳統之液相酯化和氣相酯化反應之間，並允許反應組成於反應器中由液相轉換成氣相，因為液相反應所需之反應器較小和反應物與觸媒接觸時間較長，而氣相酯化反應之平衡常數高於液相酯化反應可獲得較高之乙醇轉化率，所以控制反應起始於液相，終於氣相，如此可同時解決液相酯化反應產率低及氣相反應需要較大反應器之缺點，且使用之HZSM-5沸石觸媒已完成570小時之壽命實驗，經過製程評估此製程之可降低一半製程廢水、及節省1/3純化所需之蒸汽耗用量。 摘要(英) Ethyl acetate (EAc) is an important feedstock in chemical industry. Most of the commercial processes for EAc production are via liquid-phase esterification. Owing to the thermodynamics limitation, the overall yields of EAc are confined to 67% with equimolar reactants feed of acetic acid and ethanol. Consequently, there are 30% of unreacted reactants with azeotropic by-products of ethanol-water, ethanol-EAc and ethanol-water-EAc. To separate these impurities is laborious and energy consuming. Over 90% of overall energy supply of EAc production is consumed by the separation of ethanol-water-EAc azeotropes. The key factor is ethanol. Owing to its difficulty in separating by direct distillation, the most plausible way is water extraction to reduce the ethanol content in EAc followed by azeotropic distillation for purification. In order to improve the EAc distillation process, a high-efficiency, low energy-consuming esterification process has been developed. In this study, the one-pass ethanol conversion was successfully improved from 67mol.% to 85mol.% while the ethanol concentration was decreased from 14wt.% to 6.5wt% without changing the flow sheet of traditional esterification process. One of the critical parameters in this novel EAc synthesis process is the reaction (esterification) temperature. By keeping it between the liquid-phase and gas-phase operation regimes during which parts of the reacting composition were vaporized. The major consideration is based on the equilibrium constants in the gas-phase reaction which are higher than those in the liquid-phase. The initial reaction stage in the liquid-phase has the advantage of smaller reactor size and more efficient contacting with the catalysts. As the equilibrium had been achieved in the final gas-phase, a higher conversion of ethanol was obtained due to the equilibrium constant constraints. Consequently, either of the equilibrium conversion constraint for the liquid-phase regime and larger reactor volume requirement for the gas-phase reaction has been overcome. In addition, the solid acid catalysts used in this novel process has low impact to the environment without corrosion to the reactor wall. These catalysts had been passed for performance after 2200 h of duration. Evaluation also shows that half of the process water and one-third of consumption of purification steam can be saved 關鍵字(中) ★ 沸石
★ 酯化反應
★ 醋酸乙酯
★ 氣液相關鍵字(英) ★ esterification
★ zeolite
★ gas-liquid phase
★ ethyl acetate論文目次 頁次
第一章 緒言 1
1.1前言 1
1.2 文獻回顧 3
1.3 理論背景 5
1.3.1 化學平衡 5
1.3.2 反應機構 6
1.4 商業製程回顧 7
1.4.1 Tishchenko法（乙醛法） 7
1.4.2 直接酯化法 9
1.4.3丁烷液相氧化製備醋酸之副產物 11
1.4.4 其他製程 11
1.5 用途 12
1.6 研究目的與目標 13
第二章 實驗 14
2.1 原料和產品的主要性質與規格 14
2.2 觸媒合成 16
2.3 觸媒改質 17
2.4 實驗裝置圖 18
2.4.1 高壓批式酯化反應器 18
2.4.2 固定床連續式酯化反應器 19
2.5 觸媒性質分析 20
2.5.1 比表面積 20
2.5.2 孔洞量測 20
2.5.3 沸石酸性分析 21
2.5.4 HZSM-5沸石之晶相分析 21
2.5.5 HZSM-5沸石之矽與鋁之組態分析 21
2.6 產物分析 22
第三章 沸石改質 23
3.1概述 23
3.2 實驗結果與討論 24
3.2.1 酸種類對沸石孔洞的影響 24
3.2.2 酒石酸處理對沸石結晶結構的影響 25
3.2.3 酒石酸濃度對沸石孔洞的影響 29
3.2.4 酒石酸處理時間對沸石孔洞的影響 31
3.2.5 酒石酸處理溫度對沸石孔洞的影響 33
3.3 HZSM-5沸石經酒石酸處理後之酸性變化 35
3.4 HZSM-5沸石經酒石酸處理後之酯化活性變化 39
3.5 小結 40
第四章 醋酸乙酯之氣液相酯化製程 41
4.1概述 41
4.2 反應之動力學探討 46
4.3 以HZSM-5沸石為觸媒之醋酸乙酯液相酯化反應探討 49
4.4 以HZSM-5沸石為觸媒之醋酸乙酯氣相酯化反應探討 51
4.5醋酸乙酯之氣液相共存酯化製程 52
4.6 伴隨化學反應的相平衡 54
4.7 伴隨氣液相平衡之酯化反應模擬 60
4.7.1 NRTL和NRTL-HOC熱力學模組之差異 61
4.7.2 添加惰性氣體對氣相酯化反應的影響 61
4.7.3 添加惰性氣體對氣液共存酯化反應的影響 63
4.7.4氣液相共存下之組成分佈 65
4.7.5氣液相共存對酯化平衡常數的影響 67
4.8 酸醇莫耳比對氣液相酯化反應的影響 69
4.9 反應溫度對氣液相酯化反應的影響 72
4.10空間流速對氣液相酯化反應的影響 74
4.11 進料中含水量對氣液相酯化反應之影響 78
4.12 觸媒粒徑對氣液相酯化反應之影響 80
4.13固定床連續式醋酸酯化觸媒壽命測試 82
4.14 小結 85
第五章 醋酸乙酯之反應蒸餾製程 86
5.1概述 86
5.2 反應蒸餾實驗裝置 90
5.3 觸媒裝填方式探討 92
5.3.1觸媒裝填於降液管中 93
5.3.2觸媒粒子放入金屬波紋絲網與平板絲網的夾層 95
5.3.3觸媒粒子放入噴射塔盤中 96
5.4 醋酸乙酯反應蒸餾之實驗結果與討論 97
5.4.1 自身催化和醇酸莫耳比之影響 97
5.4.2迴流比之影響 98
5.4.3 塔上下進料比之影響 100
5.4.4 塔底溫度(加熱量)之影響 102
5.4.5 進料中乙醇含量之影響 104
5.5 Bench Scale反應蒸餾系統 106
5.5.1 塔底溫度(加熱量)之影響 106
5.5.2系統穩定性測試 108
5.5.3 進料中乙醇含量之影響 110
5.5.4 塔上下進料比之影響 112
5.5.5 觸媒填充量之影響 114
5.5.6觸媒填充方法之影響 116
5.6 醋酸乙酯純化塔進料中乙醇含量對純化塔蒸汽耗用之影響 118
5.7 小結 119
第六章 醋酸乙酯製程之比較 120
6.1概述 120
6.2氣液相共存之改良式酯化製程 121
6.2.1 氣液相共存之改良式酯化製程之PFD圖 122
6.2.2 氣液相共存之改良式酯化製程模擬結果說明 123
6.2.3氣液相共存之改良式酯化製程分析總結 128
6.3以無水酒精為原料之反應蒸餾製程 129
6.3.1 以無水酒精為原料之反應蒸餾製程之PFD圖 130
6.3.2 以無水酒精為原料之反應蒸餾製程模擬結果說明 131
6.3.3 以無水酒精為原料之反應蒸餾製程分析 136
6.4 以95%乙醇為原料之反應蒸餾製程 137
6.4.1 以95%乙醇為原料之反應蒸餾製程之PFD圖 138
6.4.2 以95%乙醇為原料之反應蒸餾製程之stream line說明 139
6.4.3 以95%乙醇為原料之反應蒸餾製程分析 144
6.5 純酯迴流之反應蒸餾製程 145
6.5.1 純酯迴流之反應蒸餾製程之PFD圖 146
6.5.2 純酯迴流之反應蒸餾製程之stream line說明 147
6.5.3 純酯迴流之反應蒸餾製程分析 152
6.6 小結 153
第七章 氣液相共存之酯化製程 154
7.1概述 154
7.2甲基丙烯酸甲酯之氣液相共存酯化製程 155
7.2.1反應溫度的影響 155
7.2.2空間流速的影響 156
7.2.3甲醇/甲基丙烯酸莫耳比的影響 157
7.2.4 觸媒失活原因探討 159
7.2.5 觸媒壽命促進之研究 161
7.3六氫苯二甲酸二異丁酯之氣液相共存酯化製程 162
7.3.1 實驗方法 163
7.3.2分析方法：酸價滴定法 164
7.3.3 反應溫度的影響 166
7.3.4異丁醇/六氫苯二甲酸酐莫耳比的影響 167
7.3.5空間流速的影響 168
7.3.6六氫苯二甲酸酐酯化反應之觸媒壽命測試 169
7.4醋酸丁酯之氣液相共存酯化製程 171
7.4.1操作程序 171
7.4.2實驗結果 172
7.5馬林酸二乙酯之氣液相共存酯化製程 173
7.5.1操作程序 173
7.5.2實驗結果 174
7.6小結 175
第八章 結論 176
參考文獻 179
圖目錄 頁次
圖1.1 乙醛法生產醋酸乙酯流程圖 8
圖1.2 直接酯化法生產醋酸乙酯之流程圖 10
圖2.1 高壓批式酯化反應器 18
圖2.2 固定床連續式酯化反應器 19
圖2.3 醋酸乙酯之GC校正曲線 22
圖3.1 經有機酸處理之HZSM-5沸石的29Si-MASNMR圖譜 26
圖3.2 經有機酸處理之HZSM-5沸石的27Al-MASNMR圖譜 27
圖3.3 經有機酸處理之HZSM-5沸石的XRD圖譜 28
圖3.4 酒石酸處理濃度對沸石孔洞的影響 30
圖3.5 酒石酸處理時間對沸石孔洞的影響 32
圖3.6 酒石酸處理溫度對沸石孔洞的影響 34
圖3.7 酒石酸處理對沸石酸強度的影響 37
圖3.8 酒石酸處理對沸石酸量的影響 38
圖4.1 反應溫度對沸石觸媒酯化活性的影響 49
圖4.2 觸媒用量對沸石觸媒酯化活性的影響 50
圖4.3 模擬結果與文獻數據比較 60
圖4.4 氮氣稀釋對氣相反應平衡常數的影響 62
圖4.5 氮氣稀釋對氣液相反應平衡常數的影響 64
圖4.6 氣液共存對酯化平衡常數的影響 68
圖4.7 酸醇莫耳比對平衡常數的影響 70
圖4.8 醇酸莫耳比對氣相組成莫耳分率的影響 71
圖4.9 不同反應溫度下實驗結果與模擬結果之比較 73
圖4.10 空間流速的影響 77
圖4.11 氣液相存醋酸酯化之壽命測試(Lab scale) 83
圖4.12 氣液相存醋酸酯化之壽命測試(bench Scale) 84
圖5.1 反應蒸餾裝置圖 90
圖5.2 反應蒸餾塔之實體裝置設備圖 91
圖5.3 降液管的觸媒裝填構造圖 93
圖5.4 降液管的觸媒裝填實體圖 94
圖5.5 觸媒粒子放入金屬波紋絲網與平板絲網夾層之實體圖 95
圖5.6 觸媒粒子放入噴射塔盤之構造圖 96
圖6.1 氣液相共存之改良式酯化製程之PFD圖 122
圖6.2 以無水酒精為原料之反應蒸餾製程之PFD圖 130
圖6.3 以95%乙醇為原料之反應蒸餾製程之PFD圖 138
圖6.4 純酯迴流之反應蒸餾製程之PFD圖 146
圖7.1 反應溫度的影響 155
圖7.2 空間流速的影響 156
圖7.3 甲醇/甲基丙烯酸莫耳比的影響 158
圖7.4 觸媒失活與甲基丙烯酸未反應量的關係 160
圖7.5 觸媒壽命測試 161
圖7.6 醋酸正丁酯之觸媒壽命測試 172
圖7.7 馬林酸二乙酯之觸媒壽命測試 174
表目錄 頁次
表2.1 反應物及產物之主要性質 14
表2.2 藥品規格 15
表2.3 沸石觸媒改質之處理條件對照表 17
表2.4 醋酸乙酯之GC校正曲線配比表 22
表3.1 酸種類對沸石二次孔洞的影響 24
表3.2 有機酸對沸石的影響 26
表3.3 酒石酸濃度對沸石孔洞的影響 29
表3.4 酒石酸處理時間對沸石孔洞的影響 31
表3.5 酒石酸溫度對沸石孔洞的影響 33
表3.6 HZSM-5 沸石觸媒的物性 36
表3.7 酒石酸處理對酯化反應活性的影響 39
表4.1 醋酸乙酯平衡常數之文獻資料 43
表4.2 醋酸乙酯之氣相酯化反應 51
表4.3 the NRTL model 參數 57
表4.4 在1atm下,不同反應轉化率下之氣相莫耳分率 66
表4.5 醇酸莫耳比的影響 69
表4.6 空間流速的影響 75
表4.7 酯化反應之正向反應速率 76
表4.8 進料中含水量之影響 79
表4.9 觸媒粒徑之影響 81
表5.1 醋酸乙酯反應蒸餾系統沸點、共沸點物性資料 89
表5.2 常見的觸媒裝填方式 92
表5.3 不同醇酸進料莫耳比之結果 97
表5.4 迴流比對醋酸乙酯反應蒸餾的影響 99
表5.5 進料體積比對醋酸乙酯反應蒸餾的影響 101
表5.6 塔底溫度對醋酸乙酯反應蒸餾的影響 103
表5.7 進料中乙醇含量對醋酸乙酯反應蒸餾的影響 105
表5.8 塔底溫度對醋酸乙酯反應蒸餾的影響 107
表5.9 醋酸乙酯反應蒸餾穩定性測試 109
表5.10 進料中乙醇含量對醋酸乙酯反應蒸餾的影響 111
表5.11 塔上下進料比對醋酸乙酯反應蒸餾的影響 113
表5.12 觸媒填充量對醋酸乙酯反應蒸餾的影響 115
表5.13 觸媒填充方法對醋酸乙酯反應蒸餾的影響 117
表5.14 乙醇含量對醋酸乙酯純化之影響 118
表6.1 氣液相共存之改良式酯化製程R-1單元之stream line說明 123
表6.2 氣液相共存之改良式酯化製程block B1之stream line說明 124
表6.3 氣液相共存之改良式酯化製程block C-2之stream line說明 125
表6.4 氣液相共存之改良式酯化製程block B4之stream line說明 126
表6.5 氣液相共存之改良式酯化製程block C-4之stream line說明 127
表6.6 氣液相共存之改良式酯化製程R-1之stream line說明 131
表6.7 以無水酒精為原料之反應蒸餾製程 block C-1之stream line說明 132
表6.8 以無水酒精為原料之反應蒸餾製程 block B-1之stream line說明 133
表6.9 以無水酒精為原料之反應蒸餾block C-3之stream line說明 134
表6.10 以無水酒精為原料之反應蒸餾block C-2之stream line說明 135
表6.11 氣液相共存之改良式酯化製程R-1之stream line說明 139
表6.12 以95%乙醇為原料之反應蒸餾製程 block C-1之stream line說明 140
表6.13 以95%乙醇為原料之反應蒸餾製程 block B-1之stream line說明 141
表6.14 以95%乙醇為原料之反應蒸餾block C-3之stream line說明 142
表6.15 以95%乙醇為原料之反應蒸餾block C-2之stream line說明 143
表6.16 氣液相共存之改良式酯化製程R-1之stream line說明 147
表6.17 純酯迴流之反應蒸餾製程 block C-1之stream line說明 148
表6.18 純酯迴流之反應蒸餾製程 block B-1之stream line說明 149
表6.19 純酯迴流之反應蒸餾製程block C-3之stream line說明 150
表6.20 純酯迴流之反應蒸餾製程block C-2之stream line說明 151
表6.21 製程經濟評估結果比較表 153
表7.1 原料酸價滴定 165
表7.2 反應溫度的影響 166
表7.3 異丁醇/六氫苯二甲酸莫耳比的影響 167
表7.4 空間流速的影響 168
表7.5 觸媒壽命測試 170參考文獻 1. Eversole, A.R. Ethyl Acetate –United States. Chemical economics handbook – SRI International, 643.5000A, Menlo Park, CA, USA (1992)
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