臺灣博碩士論文加值系統

中文摘要
在前期的研究中,Pd/SDB(Styrene divinyl-benzene copolymer)觸媒巳知能將含水酒精氧化，轉化成乙酸乙酯。然而由於Pd/SDB觸媒上金屬與擔體之交互作用力甚弱，使得鈀極易和中間產物醋酸形成醋酸鈀( Pd(CH3COO)2 )，而有金屬流失現象。另一方面此情形也造成金屬Pd聚集的現象而使得Pd/SDB觸媒的活性減退。
為了解決觸媒活性嚴重衰退的問題，在此加入了固體酸性觸媒來改善。不過效果並不加預期的好。因此便發展出一系列以Zeolite為擔體之雙功能金屬觸媒Pd-x/Zeolite,其中X為第二種金屬包括(鉑，銀，鎳)等等以此來做為含水酒精生產乙酸乙酯製程的觸媒。
藉由改變觸媒配製方法和改變操作條件，希望能達到提高酯化反應的選擇性、觸媒穩定性、和使產品的雜質減至最低等的目標。主要研究有(1)Zeolite觸媒擔體矽鋁比對酯化反應的影響:在此可得知增加擔體矽鋁比可以增高酯化反應選擇性但相對的也會降低乙醇的轉化率。因此其有個極限值。(2)溫度效應:當溫度改變，使得整個反應系統由液相反應變成氣相反應時，乙醇轉化率會提昇將近10%。(3)進料氧氣/乙醇之間比率:進料之間的比率對於整個酯化反應是有相當的影響的。當進料比太低時乙醇的轉化率便會太低，相反的此時燃料氣產生量和乙酸的選擇率亦會隨著進料比增加而增高。除了觸媒本身的設計外，也希望能考慮到未來製程的設計。在實驗結果中可看出生成的產物中跟以催化蒸餾製程所產生的產物非常相近，這也表示出未來製程上的一些成本將藉由特殊的觸媒設計而降低許多。

Abstract
In early study, we found that ethyl-acetate can be formed directly from water-containing ethonal(5%H2O) with Pd/SDB (Styrene divinyl benzene compolymer) catalyst. However, because of the low affinity between metal clusters and hydrophobic support, the catalyst deactivated rapidly by the extraction of Pd(CH3COO)2, which is formed from the reaction of palladium with acetic acid, a byproduct and intermediate of the reaction.
Since the water adsorption can greatly be decreased by hydrophobic catalyst, combined Amberlyst 35 with Pd/SDB was thus be used.
It’s have several problems like metal aggregating, low eaterification selectivity etc. Besides, Amberlyst 35 is a polymer which has low heat resistance and hardly regenerition. To remedy the drawbacks of the catalysts, zeoilte-supports bimetallic catalysts Pd-X(Pt, Ag, Ni)/Zeolite have been developed. By controlling operation conditions ,we wish to get the goals of high esterification selectivity, stability maintenance, and low ipurity. The major study is (1)The influence of Si(silicon)/Al(aluminum) ratio of the Zeolite catalyst to esterification reaction: Si/Al ratio will be effect to acidity strength of Zeolite catalyst to make differ to ability of esterificaton reaction. When Si/Al ratio becomes higher, the acidity becomes stronger and the ability of esterification reaction becomes better.
But the catalyst will produce too few acid to proceed the esterification reaction. (2) Temperature factor: When reactant changes from liquid phase to gas phase, the ethanol conversion will raise 10% by using the catalyst prepared by our lab. (3) O2 /ethonal ratio: The reaction will be best in a specific range of ratio. If the ratio of O2 /ethonal is too high, the selectivity to fuel gas and acetic acid will be increase. Otherwise the can’t react completely and selectivity to acetaldehyde will increase.(4) Character of catalysts: By experiment, the result of reaction in fixed bed reactor is the same with catalytic distillation. It show that our catalyst will have quality of catalytic distillation. Now we change temperature, pressure and feed ratio to find best operation conditions. In the future, we hope we can be promising for industrial application.

目 錄
圖目錄I
表目錄III
第一章 緒論1
1.1 乙酸乙酯製程介紹1
1.2 問題發生與研究動機5
1.3 一般性的分析5
1.4各製程優缺點的比較………………………………………..6
1.5研究目的……………………………………………………..7
第二章 觸媒製備、催化反應與特性分析12
2.1 觸媒製備12
2.2 藥品及氣體12
2.3 以離子交換法製備不同擔體離子交換金屬觸媒12
2.4 反應設備13
2.5 觸媒媒床填裝14
2.6 實驗步驟與產物分析14
2.7 觸媒特性分析16
2.7.1 一氧化碳化學吸附分析16
2.7.2 程溫還原分析17
2.7.3 延伸X光吸附細微結構光譜分析18
第三章 雙功能金屬觸媒25
3.1 疏水性金屬觸媒Pd/SDB在氧化反應之優點25
3.2 疏水性觸媒在酯化反應的現象26
3.3 EXAFS 特性分析27
3.4 雙功能金屬觸媒29
第四章 實驗結果與討論37
4.1 觸媒的選擇37
4.2 擔體在不同操作條件下對酯化反應的影響39
4.2.1 溫度對Zeoilte擔體酯化反應的影響39
4.2.2 壓力對Zeoilte擔體酯化反應的影響40
4.3 氧氣對Pd-X/Zeolite 擔體在乙酸乙酯製程下的影響41
4.4 進料比對Pd-X/Zeolite 擔體在乙酸乙酯製程下的影響43
4.5與催化製程之比較………………………………………….43
4.6與不同商業觸媒之比較…………………………………….44
4.7生產其它的酯類…………………………………………….45
第五章 總結與未來展望68
參考文獻70

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