臺灣博碩士論文加值系統

尋找優良的觸媒進行苯的加氫異構化反應是本論文探討之主題。本研究首先就鎳、鈀及鉑等三種金屬進行篩選，篩選時將此三種金屬分別承載於Hβ上(經一次氫離子交換的β沸石)，製成觸媒篩選出最佳者。然後就最佳之金屬，改變其於觸媒中的含量，找出最佳的金屬承載量；最後探討改質擔體(β沸石)改質的影響，分別製備出Hβ，HHβ，Dβ，DDβ(註：HHβ：二次氫離子交換的β沸石；Dβ：去鋁化4小時的 沸石；DDβ：去鋁化6小時的β沸石)等擔體，測試由這些擔體製成的鉑觸媒在苯的加氫異構化的差異。
本實驗所使用的觸媒皆以臨溼含浸法製備，而以表面積及孔徑分析儀、X射線繞射分析儀、感應耦合電漿原子發射光譜分析儀(ICP-AES)等儀器鑑定之，反應測試於一大氣壓下以連續流動方式進行。
研究結果顯示：在加氫異構化反應方面以10%Ni/Hβ及1%Pt/Hβ觸媒表現較佳，1%Pd/Hβ觸媒的表現則較差的。但是10%Ni/Hβ觸媒衰退的情行很嚴重，因此以鉑觸媒最為適合。以1%Pt/Hβ為觸媒時，甲基環戊烷的產率在240~260℃達到最高，當溫度高於260℃時，反應受到平衡之限制，苯之轉化率反而下降。在鉑含量為0.2~1%的觸媒中，以1%Pt觸媒活性最高，在改變進料組成的實驗中發現，當進料中氫氣增加時，甲基環戊烷產率會隨之提升，但最大產率發生之溫度也會增加。在擔體改質方面，離子交換的程度隨交換的次數增加而效果愈好；去鋁化方面也是隨著去鋁化時間的增加，去鋁的效果愈好，而將去鋁化後的β沸石做氨氣的程式升溫脫附實驗，可發現其總酸量明顯的降低，但其酸強度有顯著的提升。而在表面積及微孔表面積的鑑定中，發現改質的β沸石BET表面積都較原始β沸石低，在微孔表面積部份也如此，顯見改質會造成β沸石結構的破壞，在以各改質擔體製備的觸媒中，以1%Pt/DDβ的活性為最佳，因為DDβ較其他擔體明顯的有較高比例的強酸，因此增加擔體的酸度，尤其是強酸，有助於提升甲基環戊烷的產率。

Searching for a good bifunctional catalyst for hydroisomerization of benzene was the gaol of this investigation. The search started with choosing a proper metal. Nickel, palladium, and platinum were the metals studied. Catalysts of these metals were prepared using Hβ as support. After the metal had been determined, the optimum metal loading was examined. Finally, the effects ofβ-zeolite modifiction were studied. Four modifiedβ-zeolites, designated as Hβ(β-zeolite ion-exchanged with H+ once),HHβ(β-zeolite ion-exchanged with H+ twice), Dβ(β-zeolite dealuminated with HCl for 4 hours), and DDβ(β-zeolite dealuminated with HCl for 6 hours)were prepared. Catalysts of these modified β-zeolite were prepared and their activities in benzene hydroisomerization were investigated.
The catalysts used in this research were all preapred by incipient impregnation. Characterizations of these catalysts were made by BET, XRD, ICP-AES. Activities of these catalysts were tested in a continuous flow tublar reactor under atmospheric pressure.
The results showed 10%Ni/Hβ and 1%Pt/Hβ were more active than 1%Pd/Hβ. Since serious deactivation was found in 10%Ni/Hβ catalysts, the best metal, therefore, was assigned to Pt. The yield of methylcyclopentane on 1%Pt/Hβ reached a maximum at 240-260℃. A further increase in the reaction temperature would lower the conversion of benzene. The reasion for the decrease was the reasion fell in equilibrium region. Activity test of Pt/Hβ catalysts of 0.2-1wt% metal loading showed 1%Pt/Hβ catalyst was the most active one. Increasing the partial pressure of hydrogen could increase the yields of methylcyclopentane but the temperature of maximum yield was also increased. Increasing the number of ion exchange could increase the activity of resulting catalyst. The same effect could be found by the time of dealumination. A significant decrease in the number of acid site was found onβ-zeolite after dealumination. However, the number of strong acid site could be enhanced by dealumination. In the BET measurements, one could found the surface area of β-zeolite was decreased by modifications(ion exchange and dealumination). Since the area of micropores was also decreased, this mean part of theβ-zeolite was destructed by the modification. Among the catalysts prepared from the modifiedβ-zeolite, 1%Pt/DDβ was the most active one. The presence of strong acid sites in 1%Pt/DDβ could be the reason for the catalyst to more active than the others. The result indicated increasing the number of strong acid site could enhance the yield of methylcyclopentane.

第一章 緒 論…………………………………………….1
第二章 文獻回顧………………………………………….5
2.1 氫化異構化觸媒…………………………………..5
2.2 沸石………………………………………………..8
(一)簡介……………………………………………….8
(二) β沸石………………………………………….12
(三)沸石的改質……………………………………..17
第三章 實 驗…………………………………………..18
3.1 實驗試料及氣體………………………………..18
3.1.1 實驗氣體……………………………………18
3.1.2 實驗藥品……………………………………19
3.2 擔體的改質………………………………………21
3.3 觸媒的製備………………………………………22
3.4 觸媒的鑑定………………………………………23
3.4.1 BET表面積………………………………...23
3.4.2 化學吸附……………………………………25
3.4.3 程式升溫脫附……………………………..26
3.4.4 X光繞射分析……………………………….28
3.4.5 感應式耦合電漿原子發射光譜分析儀…...29
3.5 苯的加氫異構化反應…………………………….34
3.5.1 實驗裝置及條件…………………………….34
3.5.2 分析方法與儀器…………………………….36
第四章 結果與討論……………………………………….41
4.1 觸媒鑑定………………………………………….41
4.1.1 擔體的改質………………………………….41
4.1.2 擔體的BET比表面積……………………….44
4.1.3 化學吸附…………………………………….47
4.1.4 X光繞射分析………………………..……..48
4.1.5 氨氣程式升溫脫附………………………….53
4.2 苯的加氫異構化反應…………………………….55
4.2.1 金屬種類的影響…………………………….55
4.2.2 反應溫度的影響…………………………….58
4.2.3 金屬含量的影響…………………………….62
4.2.4 擔體的影響………………………………….66
4.2.5 氫氣進料組成的影響……………………….69
第五章 結 論…………………………….………………71
第六章 參考文獻………………………………………….73
附錄…………………………………………………………78
作者簡介……………………………………………………82

1. Beck L. W. and J. F. Haw, "Multinuclear NMR studies reveal a complex acid function for zeolite beta", J. Phys. Chem., 99, 1995, 1076-1079.
2. Chao, K. J., H. C. Wu, and L. J. Leu, "Hydroisomerization of light normal paraffins over series of platinum-loaded mordenite and beta catalysts", Appl. Catal. A:General 143, 1996, 223-243.
3. Chevalier, F., M. Guisnet, and R. Murel, C. R. Acad. Sci. 282, P3, 1976
4. Corma A., V. Gomez, and A. Martinez, "Zeolite beta as a catalyst for alkylation of isobutane with 2-butene. Influence of synthesis conditions and process variables", Appl. Catal. A : General, 119, 83-96
5. Coughlan Brendan, and M. A. Keane, "The hydrogenation of benzene over nickel-support Y zeolites. Part2. A mechanistic approach", Zeolites, 11, 1991, 483-490.
6. Coughlan Brendan, and M. A. Keane, "Catalyst deactivation during the hydrogenation of benzene over nickel-loaded Y zeolites", Journal of Molecular Catalysis, 71, 1992, 93-109.
7. Dartiques, J. M., A. Chambellan, and F. G. Gault, J. Amer. Chem. Soc. 98, 1976, P856.
8. Das J., Y. S. Bhat, A. I. Bhardwaj, and B. Halgeri, "Zeolite beta catalyzed C7 and C9 aromatics transformation", Appl. Catal. A : General, 116, 1994, 71-79.
9. Elodie Bourgeat-Lami, Pascale Massiani, Francesco Di Renzo, Pierre Espiau and Francois Fajula, "Study of the state of aluminium in zeolite - β", Appl. Catal., 72, 1991, 139-152.
10. Gao, Z., Y. Tang and Y. Zhu, "Effect of Dealumination Defects on the Properties of Zeolite Y", Applied Catalysis, 56, 1989, 83-94.
11. Guisnet, M., J. J. Garcia, F. Chevalier, and R. Maurel, Bull. Soc. Chim. 1657, 1976.
12. Jansen J. C., E. J. Creyghton, S. L. Njo, H. van Koningsveld, H. van Bekkum " On the remarkable behaviour of zeolite Beta in acid catalysis", Catalysis Today 38, 1997, 205-212.
13. Leu L. J. , L. Y. Hou, B. C. Kang, L. Chiuping , S. T. Wu and J. C. Wu, "Synthesis of zeolite β and catalystic isomerization of n-hexane over Pt/Hβ catalysts", Appl. Catal., 69, 1991, 49-63.
14. Martens, J. A., M. Tielen and P. A. Jacobs, H. G. Karge, and J. Weitkamp(Editors), Zeolites as Catalysts, Sorbent and Detergent Builders, Elsevier, Amsterdam, P49, 1989.
15. Moljord Kjell, Hellenes Hilde Gunn, Hoff Anne, Tanem Ingunn, Grande Knut, Holmen Anders, "Effect of reavtion pressure on octane number and reformate and hydrogen yield in catalytic reforming", Industrial & Engineering Chemistry Research 35, 1996, 99-105.
16. Neri G., A. M. Visco, A. Donato, C. Milone, M. Malentacchi, and G. Gubitosa, "hydrogenation of phenol to cyclohexanone over palladium and alkali-doped palladium catalysts", Appl.catal., 110, 1994, 45-59.
17. Nicolaides C. P., M. Wapiennik, K. I. G. Weiss, H. van den Akker, B. van Zalk and P. Wielaaed, "Alkali metal cation exchange of HZSM-5 and the catalytic properties of the alkalized zeolites", Appl. Catal., 68, 1991, 31-39.
18. Nikolopoulos A. A., A. Kogelbauer, J. G. Goodwin, and Jr. G. Marcelin,"Effect of dealumination on the catalytic activity of acid zeolite for the gas phase synthesis of MTBE", Appl. Catal. A : General 119, 1994, 69-81
19. Rao, G. N., R. Kumar, P. Ratnasamy, "Shape selectivity of zeolite EU-1 in reactions of aromatic hydrocarbons", Appl. Catal., 49, 1989, 307-318.
20. Ratnasamy P., R. N. Bhat, S. K. Pokhriyal, S. G. Hegde and R. Kumar, J. Catal., 119, 1989, 65.
21. Reddy K. S. N., B. S. Rao and V. P. Shiralkar, "Alkylation of benzene with isopropanol over zeolite beta", Appl. Catal. A : General, 95, 1993, 53-63.
22. Ribeiro, F., C. Marcilly, and M. Guisnet, "Hydroisomerization of n-Hexane on Platinum-zeolites:Ⅱ. Comparison between the Reaction Mechanisms on Platinum/Y-zeolite and on Platinm/Mordenite", J. Catal. 78, 1982, 267-274.
23. Robb G. M., W. Zhang, P. G. Smirniotis, "Acidity of dealuminated β-zeolites via coupled NH3-stepwise temperature programmed desorption(STPD) and FT-IR spectroscopy", Microporous and Mesoporous Materials, 20, 1998, 307-316.
24. Talukdar, A. K. and K. G. Bhattacharyya., "Hydrogenation of phenol over supported platinum and palladium catalysts.", Appl. Catal. A:General, 96, 1993, 229-239.
25. Weisz, P. B., in"Advanced in Catalysis"(D. D. Eley, H. Pines, and P. B. Weisz, Eds.), Vol. 13, P137. Academic Press, New York, 1963.
26. Yang Chun and Qinhua Xu, "States of aluminum in zeolite β and influence of acidic or basic medium", Zeolites, 19, 1997, 404-410.
27. 趙桂蓉，林建中，"反應壓力對含鉑金屬的絲光沸石和Beta沸石在正庚烷異構化中的影響"，第十五屆台灣區觸媒及反應工程研討會，1997。
28. 財團法人中國技術服務社觸媒研究中心，"油品鍊製觸媒之開發-芳香族氫化觸媒開發"，1997
29. 張祖琰，工業技術，p.25，1985年5月.