臺灣博碩士論文加值系統

添加鈀膜於傳統觸媒反應器中可使反應轉化率高於熱力學平衡值，多數文獻將此現象歸咎於氫氣產品在反應進行中立即由觸媒床經由鈀膜移出，減少反應器中的氫氣分壓因而降低逆向反應速率。然而，經由實驗發現，鈀膜管的添加，氫氣分壓反而增加亦會增加正向反應速率。
本研究以正己烷為原料做為汽油或輕油蒸汽重組的模型，在400∼530℃進行正己烷蒸汽重組反應。為補充降低反應溫度所要的觸媒活性，我們重新設計大表面積及抗積碳的改質觸媒（Y1、Y2、Y3）並與商用觸媒（G-56H-1、FCR-4-02）進行性能的比較實驗。在反應性方面，較大表面積的改質觸媒轉化率雖沒有商用觸媒好，但卻能減少了反應所需活化能。而鉀的添加會遮蔽表面積而降低反應速率，氧化鎂的添加對反應速率提升效果不佳。
在觸媒積碳的改善方面，以大表面積的γ-Al2O3為主仿造商用觸媒成分進行改質。結果發現，添加1％鉀的Y2觸媒對積碳現象的改善最為明顯（3.2mgC/gCat-h），積碳速率較商用觸媒G-56H-1（13.29mgC/gCat-h）表現好，然而，添加了5％氧化鎂的Y3觸媒則對積碳速率無明顯改善（7.7mgC/gCat-h）。
實驗使用具有高表面積的改質觸媒Y2（1%K2O, 15%Ni/γ-Al2O3, 133.6M2/gm）以增加觸媒反應性使對鈀膜反應器有所助益。在一般觸媒反應器（RCR）及添加鈀膜管（9.525mmO.D. × 30mmL ，表面積=8.9 cm2）的鈀膜反應器（CMR）來比較反應速率，並使轉化率分別低於42％及27％。結果發現，在500℃、9大氣壓下的反應速率常數分別為3.26×10-3mol/g-sec 及 5.49×10-3mol/g-sec，添加鈀膜進行反應使轉化率提升170％。造成速率提升的原因是由於在蒸汽重組反應生成氫氣的同時，氫氣原子由觸媒表面活性位置溢滑至鈀膜表面而滲透至反應床外，帶動反應速率的提升。
添加鈀膜管於反應器中不只可在較低的溫度下提升轉化率（54.00% 至72.09%），且在反應產物中會有較高之氫氣分率（19.10%至27.09%），在反應性較佳的高碳氫化合物的蒸汽重組中，常生成反應性較低的甲烷，甲烷的生成會牽制氫氣的生成，故上述兩優點在使用鈀膜反應器進行現場氫氣純化的程序及減少甲烷的生成具有重要的價值。

Incorporation of a palladium membrane in a catalytic reactor is known to increase reaction conversion beyond its thermodynamic equilibrium. Most of literature reports attributed these phenomena to the intrinsic removal of hydrogen from the reaction mixture bringing about an decrease of backward reaction to make up the reduced hydrogen partial pressure in the product side. However, we also found the rate enhancement of forward reaction incorporation a palladium membrane in a catalytic reactor in this experiment.
As a simpler model compound for gasoline, h-Hexane studied for the steam reforming on modified catalysts (Y1,Y2,Y3) which had higher surface area and anti-coking property for better catalyst reactivity in lower reaction temperature and compared with industrial catalysts (G-56H-1、FCR-4-02) between 400℃ and 530℃. On the reactivity of catalyst, modified catalysts of higher surface area showed lower conversion rates, but they reduced the activation energy of the reaction. The addition of potassium may cover up the catalyst surface to reduce the rate constant, the addition of magnesium oxide showed no enhancement of rate constant.
On the improvement of coking phenomenon, we use high surface area support of γ-Al2O3 to follow the composition of industrial catalyst G-56H-1 as a model to produce our modified catalysts. The results showed there is a significant reduction of coking phenomenon of Y2 catalyst having 1% of potassium, its coking rate (3.2mgC/gCat-h) is profoundly reduced from that of G-56H-1 (13.29 mgC/gCat-h); however, Y3 catalyst which has 5% of magnesium oxide shows no significant improvement of the coking rate.
We report here our high surface area steam reforming catalyst Y2 (1%K2O, 15%Ni/γ-Al2O3, 133.6M2/gm) to boost the catalytic reactivity to take advantage of the membrane reactor at a lower reaction temperature of 400 to 530℃. With this catalyst, we measured the forward reaction rate by keeping conversion level below 42% in a regular catalytic reactor (RCR) and below 27% in a catalytic membrane reactor (CMR) incorporating a palladium membrane tube (9.525mmO.D.×30mmL with S.A.=8.9 cm2). The reaction rates in RCR and in CMR at 9atm and 500℃ were 3.26×10-3mol/g-sec and 5.49×10-3mol/g-sec, respectively; There was an increase of almost 170% by the use of Pd-membrane in the reactor. The result is attributed to the hydrogen spillover of the nascent hydrogen atoms from the catalytic site to the membrane surface and irreversibly permeating out of the system right after the formation of hydrogen atom from the steam reforming reaction.
The incorporation of a palladium membrane tube in the CMR enables one to enjoy not only a higher conversion level at relatively low reaction temperature (72.09% vs 54.00%) but also a higher hydrogen partial pressure in the product mixture (27.09 vs. 19.10 mole fraction). This is a very important value for taking advantage of in situ hydrogen separation by a Pd-membrane and minimizing the formation of lower reactive methane which ties up primary hydrogen product from the steam reforming reaction of the more reactive higher hydrocarbons.

目錄
誌謝 i
中文摘要 ii
Abstract iv
目錄 vi
圖目錄 ix
表目錄 xi
第一章 緒論 1
1.1 簡介 1
1.2 研究目的 3
第二章 文獻回顧 6
2.1 蒸汽重組反應 6
2.1.1 甲烷蒸汽重組 6
2.1.2 高級烷類（C-2以上）蒸汽重組 10
2.2 觸媒選擇 14
2.2.1 鎳觸媒之選擇 14
2.2.2 衰退與毒化 14
2.2.3 鎳觸媒之積碳現象 15
2.2.4 硫化現象 20
2.3 觸媒改質對反應之影響 22
2.3.1貴重金屬（Precious metals）對溢滑現象（Spillover）之效應 22
2.3.2 添加促進劑（Promoters）之效應 24
2.4 鈀及鈀銀薄膜之特性 26
2.5 支撐式鈀膜反應器之構造 30
2.6 薄膜之製備方法 33
2.6.1無電電鍍法（Electroless-Plating） 33
2.6.2真空濺鍍法（Sputtering） 36
第三章 實驗方法與步驟 40
3.1 觸媒之製備 40
3.1.1 觸媒種類與性質 40
3.1.2 觸媒改質方法 41
3.1.3 觸媒改質步驟 41
3.2 分析儀器及方法 43
3.2.1 BET表面積與孔徑大小分析儀 43
3.2.2 程溫脫附系統（Temperature Programmed Desorption） 46
3.2.3 熱重分析儀TGA（Thermogravimetric Analysers） 48
3.3 實驗材料、設備、步驟與分析方法 49
3.3.1 實驗藥品 49
3.3.2 實驗氣體 49
3.3.3 實驗設備 50
3.3.4 實驗步驟 56
3.3.5 產物分析方法 59
第四章 結果與討論 60
4.1 質量平衡與空白實驗 60
4.1.1 質量平衡 60
4.1.2 空白實驗 60
4.2正己烷蒸汽重組機制討論 61
4.3 速率常數k及反應活化能Ea之計算 64
4.3.1 速率常數（Rate constant，k）之計算 64
4.3.2反應活化能（Activation energy，Ea）之計算 65
4.4 兩種商業觸媒G-56H-1及FCR-4-02比較 66
4.4.1 G-56H-1及FCR-4-02之反應性比較 66
4.4.2 G-56H-1及FCR-4-02之積碳量比較 70
4.5 各參數對重組反應的影響 73
4.5.1 空間速度VHSV對正己烷重組反應的影響 73
4.5.2 溫度對反應的影響 75
4.5.3 壓力對反應的影響 75
4.6 觸媒改質 78
4.6.1改質觸媒與商用觸媒G-56H-1之反應性討論 79
4.6.2 改質觸媒積碳量討論 81
4.7 添加鈀膜對反應的影響 86
第五章 結論 91
參考文獻 93
附件 97
附件A FCR-4-02觸媒動力學數據 97
附件B G-56H-1觸媒動力學數據 98
附件C Y1觸媒動力學數據 100
附件D Y2觸媒動力學數據 101
附件E Y3觸媒動力學數據 103
附件F 鈀膜管基本特性 104
附件G n-Hexane與Methane之平衡轉化率計算 105
附件H 發表著作 106
圖目錄
圖1.1 不同燃料的體積能量密度 3
圖2.1 穩定狀態下蒸汽與鎳觸媒之互動關係 11
圖2.2 電子顯微鏡下Whisker carbon結構[36] 17
圖2.3 Whisker碳在鎳觸媒顆粒表面經由擴散成長 19
圖2.4 比值對硫含量之影響[33,45] 21
圖2.5 物質溢滑示意圖與其能量變化情形 22
圖2.6 添加鹼金屬對重組反應之影響[33,45] 25
圖2.7 氫氣滲透鈀薄膜的機制 28
圖2.8 Equilibrium solubility isotherms of PdHn at different temperatures[61] 29
圖2.9 支撐式鈀合金膜反應器示意圖 31
圖2.10 無電電鍍法流程示意圖[67] 38
圖2.11 濺鍍腔體與原理示意圖[69] 39
圖3.1 BET總表面積極孔隙測定儀 45
圖3.2 程溫脫附系統（TPD） 47
圖3.3 排氣集水裝置圖 53
圖3.4 反應裝置圖 54
圖3.5 固定床反應器結構及內部填充情形 55
圖3.6 正己烷蒸汽重組反應流程圖 58
圖4.1 正己烷重組反應流程示意圖a.反應經由R1進行；b.反應經由R2進行 63
圖4.2 正己烷蒸汽重組反應以FCR-4-02於500℃下之速率常數k 67
圖4.3 正己烷蒸汽重組反應以FCR-4-02於450℃下之速率常數k 67
圖4.4 正己烷蒸汽重組反應以FCR-4-02於400℃下之速率常數k 68
圖4.5 正己烷蒸汽重組反應於FCR-4-02觸媒之活化能Ea作圖 68
圖4.6 G-56H-1及FCR-4-02在TGA分析之積碳量比較 71
圖4.7 G-56H-1及FCR-4-02在VHSV=20,000h-1、1atm、500℃下反應1hr後之積碳平均速率比較 72
圖4.8 G-56H-1在9atm進行正己烷蒸汽重組反應不同溫度下產物中H2/CH4比例及轉化率與空間速度之關係 74
圖4.9 G-56H-1在VHSV為20,000h-1不同壓力下轉化率與溫度的關係 76
圖4.10 G-56H-1在空間速度為20,000h-1下反應產物中H2/CH4比例 77
圖4.11 正己烷蒸汽重組速率常數表示 80
圖4.12 四種觸媒在VHSV=20,000h-1、1atm、500℃下反應6hr後積碳之TGA圖 82
圖4.13 四種觸媒在VHSV=20,000h-1、1atm、500℃下反應6hr後之積碳平均速率比較 83
圖4.14 四種觸媒在VHSV=20,000h-1、1atm、500℃下反應6hr之轉化率變化比較 85
圖4.15 Y2觸媒在500℃進行正己烷蒸汽重組含/不含鈀膜之轉化率與空間速度關係 88
表目錄
表1.1 氫氣與天然氣發熱量比較 3
表2.1 各種碳氫化合物的反應級數[24] 13
表2.2 碳氫化合物蒸汽重組不同形式之積碳現象[34] 18
表2.3 鈀金屬薄膜製備方法的比較[65] 33
表2.4 鍍膜參數對膜的影響*[68] 37
表3.1 兩種商用觸媒及三種改質觸媒成分及性質 40
表4.1 碳氫化合物C-C及C-H鍵能比較（298K）[73] 61
表4.2 9atm下G-56H-1及FCR-4-02速率常數與活化能比較 69
表4.3 G-56H-1與FCR-4-02在VHSV=20,000h-1、1atm、500℃下反應1hr後積碳及不純物重量百分比與積碳平均速率 71
表4.4 四種觸媒在9atm下各溫度之反應速率常數值 80
表4.5 四種觸媒在VHSV=20,000h-1、1atm、500℃下反應6hr後積碳及不純物重量百分比與積碳速率 83
表4.6 四種觸媒在VHSV=20,000h-1、1atm、500℃下轉化率變化值 84
表4.7 Y2觸媒在500℃、空間速度為10,000∼30,000h-1下含/不含鈀膜進行正己烷蒸汽重組結果比較 88
表4.8 Y2觸媒在含/不含鈀膜進行正己烷蒸汽重組反應速率常數k值比較 89

1. Eliasson, B., Bssel, U., Montana Associated Technology Roundtables (2002)
2. Barreto, L., Makihira, A., Riahi, K., International J. of Hydrogen Energy. March, (2002) 1-10
3. Grasshoff, G. J., Pilkington, C. E., Corti, C.W., Platinum Met. Rev., 27 (1983) 157
4. Lin, Y. M., Rei, M. H., International J. of Hydrogen Energy 25 (2000) 211-219
5. Balandin, A. A., Slovokhotova, T. A., Sholin, A. F., and Ugol’tseva, L. A., Kinet. Katal. 6 (1965) 115
6. Guczi, L., Gudkov, B. S., Tetenyi, P., J. Catal. 24 (1972) 187
7. Sinfelt, J. H., Catal. Rev. 3 (1969) 175
8. Blayden, H. E., Riley, H. L., & Shaw, F., Fuel 22 (1943) 64
9. Lin, Y. M., Lee, G. L., Rei, M. H., Catal. Today 44 (1998) 343-349
10. Shu, J., Grandjean, B.P.A., Kaliaguine, S., Ciavarella, P., Giroir-Fendler, A., Dalmon, J.A., Can. J. Chem. Eng. 75 (1997) 712
11. 潘建文, “鈀膜反應器對甲醇水蒸氣重組反應之動力學研究”, 長庚大學化工與材料工程研究所碩士論文 (2002)
12. Davy, H., Phil. Trans. Roy. Soc. London, 107 (1817) 77
13. Tessie du Motay, M., Marechal, M., Bull. Soc. Chim. France 9 (1868) 334
14. DRP 51572, 1889(Mond, L. and Langer, C.), Chem. Zentralbl. Ⅱ(1890) 32
15. Lang, J., Z. Phys. Chem. 2 (1888) 161
16. Neumann, B., Jacob, K., Z. Elektrochem. 30 (1924) 557
17. Fraser, O. B. J., Trans. Electrochem. Soc. 71 (1937) 425
18. Byrne, Jr. P. J., Gohr, R. J., Haslam, R. T., Ind. Eng. Chem. 24 (1932) 1129
19. Gard, N. R., Nitrogen 39 (1966) 25
20. Linkins, M. R., Diss. Abstr. Int. B 31(6) (1970) 3359
21. Ross, J. R. H., Steel, M. C. F., & Zeini-Isfahani, A., J. Catal. 21 (1971) 171
22. Bodrov, I. M., Apel'baum, L. O., & Temkin, M. I., Kinet. Katal. 5 (1964) 696
23. Boudart, M., AIChE J. 18 (1972) 465
24. Rostrup-Nielsen, J. R., "Catalysis Science and Technology", edited by Anderson, J. R., Boudart, M., Springer-Verlag, Berlin, Heidelberg 1984, vol 5, Chapter 1.
25. Bodrov, I. M., Apel'baum, L. O., & Temkin, M. I., Kinet. Katal. 9 (1968) 1065
26. Bhatta, K. S. M., Dixon, G. M., Ind. Eng. Chem. Prod. Res. Develop. 8 (1969) 324
27. Saito, M., Tokuno, M., Ichiro, A., Morita, Y., Kogyo Kagaku Zasshi 73 (1970) 2405
28. Kato, A., Ogino, Y., Bull. Jap. Petrol. Inst. 15 (1973) 115
29. Hougen, O. A., Watson, K. M., “Chemical Process Principles”, Part 3, p.964, Wiley, New York (1959)
30. Satterfield, Charles N., “Heterogeneous Catalysis in Industrial Practice” second edition, McGraw-Hill (1991)
31. 蘇天寶, “含羥基化合物的蒸汽重組反應”, 國立台灣大學化學工程研究所博士論文 (1987)
32. Borowiecki, T., Appl. Catal. 4 (1982) 223
33. Rostrup-Nielsen, J.R., Steam Reforming Catalysts, Danish Technical Press Copenhagen (1975)
34. Rostrup-Neilsen, J. R., Tottrup, P. B., Symposium on Science of Catalysis and its Application in Industry FPDIL, Sindri (1979)
35. Baker, R. T. K., Barber, M., Harris, P., Feates, F., Waite, R., J. Catal. 26 (1972) 51
36. Rostrup-Neilsen, J. R., J. Catal. 27 (1972) 343
37. Davies, H. S., Humphries, K. J., Hebden, D., Percy, D. A., Inst. Gas Eng. J. 7 (1967) 708
38. Trimm, D. L., Catal. Rev.-Sci. Eng. 16 (1977) 155
39. Forment, G. F., Chem. Eng. Sci. 36 (1981) 1271
40. Lahaye, J., Badie, P., Ducret, V., Carbon (Oxford) 15 (1977) 87
41. Mizuno, K., Ikeda, M., Imokawa, T., Take, J., Yoneda, Y., Bull. Chem. Soc. Japan 49 (1976) 1788
42. Figueiredo, J. L., Trimm, D. L., J. Catal. 40 (1975) 154
43. Bernardo, C., Trimm, D. L., Carbon(Oxford) 17 (1979) 115
44. Baker, R. T. K., Sherwood, R. D., J. Catal. 70 (1981) 198
45. Rostrup-Neilsen, J. R., J. Catal. 21 (1971) 171
46. Conner, W.C., Teichner, S. J., Pajonk, G. M., Adv. Catal. Eley, D., Pines, H., Weisz, P., Eds. (1986)
47. Emmett, P. H., Twelfth Report of the Committee on catalyst (National Research Council), John Wiley and Sons, New York (1940) 64
48. Pajonk, G. M., Teichner, S., Spillover of Adsorbed Species: Studies in Surface Catalysis 17, J. Germ. Eds, Elsevier: Amsterdam 17 (1983)
49. Cevallos Candau, J. F., Conner, W. C., J. Catal. 106 (1987) 378-385
50. Chen, S. Sun, Yuhan Sun and Shaoyi Peng, “The role of irreversible and reversible spillover hudrogen in reforming reactions” T. Inui et al. New Aspects of Spillover Effect in Catalysis (1993)
51. Conner, W. C., Jr., Falcorer, J. L., “Spillover in Heterogeneous Catalysis”, Chem. Rev 95 (1995) 759-788
52. Baumgarten E., Maschke, L., Appl. Catal. A: General 202 (2000) 171-177
53. Andrew, S. P. S., Ind. Eng. Chem. Prod. Res. Develop. 8 (1969) 321
54. Saito, M., Tokuno, M., Morita, Y., Kogyo Kagaku Zasshi 74 (1971) 687
55. Barrer, R.M., “Diffusion in and through Solids”, Cambridge University Press, London (1951)
56. Grashoff, G.J., Pilkington, C.E., Corti, C.W., Platinum Met. Rev., 27 (1983) 157
57. Lewis, F.A., AIChE Symp. Ser., 256 (85) (1989) 53
58. Tong, X.Q., Kandasamy, K., Lewis, F.A., Scripta Metall. Mater, 24 (1990) 1923
59. Shu, J., Bongondo, B.E.W., Grandjean, B.P.A., Kaliaguiine, S., J. Mater. Sci. Letters, 16 (1997) 294
60. Ohira, K., Sakamoto, Y., Flanagan, T.B., J. Alloys Comp. 236 (1996) 42
61. Fort, D., Farr, J.P.G., Harris, I.R., J. Less-Common Met. 39 (1975) 293
62. E. Kikuchi, Catal. Today 25 (1995) 333
63. Lin, Y. M., Rei, M. H., Catal. Today 67 (2001) 77-84
64. Lin, Y. M., Rei, M. H., Separ. Purif. Methods 28 (1999) 51
65. 邱博文, "鈀銀合金氫分離薄膜之製備與其滲氫特性之研究", 國立清華大學材料科學工程研究所碩士論文 (1998)
66. Cheng, Y. S., Yeung, K. L., J. Membr. Sci. 182 (2001) 195-203
67. Yeung, K. L., Christiansen, S. C., Varma, A., J. Membr. Sci. 159 (1999) 107-122
68. Ritter E., Appl. Opt. 20 (1981) 21-25.
69. Wasa, K., Hayakawa, S., "Handbook of Sputter Deposition Technology", Noyes Publications (1992)
70. Singh, C. P. P., Saraf, D. N., Ind. Eng. Chem. Process Des. Dev. 18 (1979) 1
71. Yarze, J. C., Lockerbie, T. E., Proc. 137th Meeting of the Amer. Chem. Soc. Ohio (1960)(Chem. Abstr. 57 (1962) 6209)
72. Hyman, M. H., Hydrocarbon Processing., July 47 (1968) 131
73. David R. Lide, “Handbook of chemistry and physics”, 75th Edtion, CRC Press, (1994~1995) 9-65
74. Rostrup-Neilsen, J. R., J. Catal. 33 (1974) 184
75. Borowiecki, T., Giecko, G., Panczyk, M., Appl. Catal. A: General 230 (2002) 85—97
76. Takeguchi, T., Kani, Y., Yano, T., J. Power Sources 112 (2002) 588-595
77. Trimm, D. L., Catal. Today 49 (1999) 3-10