臺灣博碩士論文加值系統

摘 要
異蒲勒醇（IPG）乃是製造薄荷腦（Menthol）的一個重要中間物質，它可廣泛的使用在藥物與特用化學品上。本研究利用X射線繞射儀、表面積測試儀、溫度程控脫附儀與固態核磁共振儀，測量觸媒結構，表面積，觸媒的酸性等。結果顯示，隨著矽/鋁莫爾比的增加，Al-MCM-41分子篩的晶體結構提高，表面積增加，但酸量隨之減少。而Al-MCM-41經過鍛燒後，骨架中的鋁會產生脫鋁的現象。沸石矽/鋁比值增加時，其表面積變化不大，而酸量則下降。
使用固定床流動反應器於一大氣壓與220℃下，研究香茅醛經由不同矽/鋁比值的沸石(HZSM-5，Hβ與HY)與Si-和Al-MCM-41中孔型分子篩催化反應合成異蒲勒醇。研究結果發現，這些觸媒都具有良好的催化活性，且異蒲勒醇的選擇率會隨矽/鋁比值的增加而增加。然而Si-MCM-41具有最佳的穩定性，載流時間經25小時後，其催化活性與異蒲勒醇選擇率分別為91.9%與63.8%。
使用攪拌批次反應器於一大氣壓與40~60℃下，研究香茅醛經催化反應合成異蒲勒醇。實驗結果顯示，在溶劑效應下催化活性大小為甲苯>乙酸乙酯>環己烷>苯，因此極性溶劑有較好之催化活性。所以在反應溫度60℃下，選擇甲苯為溶劑，反應時間2小時其催化活性依序為Al-MCM-41≒HY>Hβ>HZSM-5。發現Al-MCM-41(50)與HY(80)催化獲得最佳的異蒲勒醇產率(56%)。Al-MCM-41(100)催化香茅醛產生競爭型一級反應，生成異蒲勒醇，menthone和p-menth-4(8)-en-3-ol之初級產物，其反應活化能分別為64.9，67.5和89.3 kJ/mol。

Abstract
Isopulegol (IPG) is an important intermediate for the synthesis of menthol, a raw material for the manufacture of pharmaceuticals, perfumery and flavors. The catalysts were characterized by the methods of XRD, BET surface area measurement, 27Al and 29Si MAS-NMR and TPD of ammonia. Increasing SiO2/Al2O3 mol ratio of MCM-41 catalysts results in the enhancement of both crystalinity and surface area with concomitant decrease of acid amount. Dealumination occurs after calcinations of Al-MCM-41. For zeolites, an increase of SiO2/Al2O3 mol ratio causes the decrease of acid amount and only small change in the surface area.
The reaction of citronellal was performed at 220℃ and atmospheric pressure in a fixed-bed, integral-flow reactor by using zeolites HZSM-5, HY and Hβ as well as Si- and Al-MCM-41 molecular sieves.The effects of different catalysts with various SiO2/Al2O3 molar ratios on the catalytic results were investigated; all catalysts attain quite high activity and the isopulegol selectivity increases markedly with such ratios.Among all catalysts, Si-MCM-41 exhibits the best catalytic performance; the conversion and IPG yield are 91.9 and 58.6%, respectively, after at least 25 h process time.
IPG was synthesized from citronellal at 40℃~60℃ and atmospheric pressure in a stirred batch reactor. The effect of solvents on the catalytic activity follows the decreasing order : toluene > ethyl acetate > cyclohexane > benzene. Therefore, polar solvents exhibit better catalytic performance. The catalytic activity decreases in the order of Al-MCM-41≒HY>Hβ>HZSM-5 for the reaction in toluene at 60℃ and 2 h reaction time. Both Al-MCM-41(50) and HY(80) exhibit the best IPG selectivity of 56%. Competitive first order reactions of citronellal product primary products of IPG, menthone and p-meth-4(8)-en-3-ol with corresponding activation energies 64.9, 67.5 and 89.3 kJ/mol.

第一章 緒 論
1.1觸媒簡介……………………………………… 1
1.2沸石結構及分類……………………………… 2
1.3MCM-41觸媒生成機制推測圖………………… 10
1.4MCM-41觸媒合成機構………………………… 12
1.5論文動機與目的……………………………… 14
第二章 實 驗
2.1觸媒簡寫代號………………………………… 16
2.2實驗試劑……………………………………… 16
2.2.1反應試劑……………………………………… 16
2.2.2觸媒原料、製備及處理……………………… 16
2.2.3鑑定產物的試劑……………………………… 18
2.2.4其它實驗試劑………………………………… 19
2.3實驗儀器……………………………………… 19
2.4觸媒性質的測定……………………………… 21
2.4.1沸石晶體測定………………………………… 21
2.4.2觸媒表面積的測定…………………………… 21
2.4.3觸媒酸性質的測定…………………………… 22
2.5催化反應……………………………………… 24
2.5.1固定床反應器………………………………… 24
2.5.2批次反應器…………………………………… 27
2.5.3固定床反應器產物的鑑定…………………… 28
2.5.4批次反應器產物的鑑定……………………… 30
第三章 結果與討論
3.1觸媒的物理性質……………………………… 32
3.1.1觸媒晶體的測定……………………………… 32
3.1.227Al及29Si的MAS NMR圖譜………………… 37
3.1.3觸媒表面積與酸性…………………………… 41
3.2固定床反應器之香茅醛的催化反應………… 48
3.2.1觸媒對催化反應的影響……………………… 49
3.2.2接觸時間對催化反應的影響………………… 55
3.3批次反應器之香茅醛的催化反應…………… 65
3.3.1攪拌轉速對催化反應的影響………………… 66
3.3.2觸媒重對催化反應的影響…………………… 66
3.3.3溶劑效應對催化反應的影響………………… 66
3.3.4反應溫度對催化反應的影響………………… 70
3.3.5觸媒對催化反應的影響……………………… 70
3.3.6香茅醛在酸觸媒之反應途徑………………… 71
3.3.7香茅醛在Al-MCM-41(100)催化下之反應動力學
…………………………………………………………… 82
第四章 結 論……………………………………… 86
參考文獻………………………………………………… 88
附錄……………………………………………………… 91

參 考 文 獻
1.M. Estermann, L. B. McCusker, C. Baerlocher, A. Merouche, and H. Kessler, Nature, 352 ( 1991 ) 320.
2.X. S. Zhao, G. Q. Lu, and G. J. Millar, Ind. Eng. Chem. Res. 35 ( 1996 ) 2075.
3.陳郁文、黃朝男，觸媒與製程 5 ( 1996 ) 14.
4.J. S. Beck, J. C. Vartuli, W. J. Roth, M. E. Leonowicz, C. T. Kreshe, K. D. Schmitt, C. T-W. Chu, D. H. Olson, E. W.Sheppard, S. B. McCullin, J. B. Higgins, and J. L. Schlenker, J. Am. Chem. Soc. 114 ( 1992 ) 10834.
5.H. P. Lin, S. Cheng, and C. Y. Mou, J. Chin. Chem. Soc, 43 ( 1996 ) 375.
6.R.Schmidt, D. Akporiaye, M. Stocker, and O. H. Ellestad, J. Chem. Soc., Chem. Commun. ( 1994 ) 1493.
7.K. M. Reddy, I. Moudrakovski, and A. Sayari, J. Chem. Soc., Chem. Commun. ( 1994 ) 1059.
8.A. Corma, M. T. Navarro, and J. Perez Pariente, J. Chem. Soc. Chem. Commun., ( 1994 ) 147.
9.A. Sayari, C. Danumah, and I. L. Moudrakovski, Chem. Mater. 7 ( 1995 ) 813.
10.D. Zhao, and D. Goldfarb, J. Chem. Soc., Chem. Commun. ( 1995 ) 875.
11.A. Corma, V Fornes, M. T. Navarro, and J. Perez-Pariente, J. Catal. 148 ( 1994 ) 569.
12.C. Y. Chen, H. X. Li, and M. E. Davis Microporous Mater (1993) 17
13.A. Corma, A. Martinez, V. Martinez-Soria, and J. B. Monton, J. Catal. 153 ( 1995 ) 25.
14.I. V. Kozhevnikov, A. Sinnema, R. J. J. Jansen, K. Pamin, and H. van Bekkum, Catal. Lett. 30 ( 1995 ) 241.
15.E. Armengol, M. L. Cano, A. Corma, H. Garcia, and M. T. Navaro, J. Chem. Soc. , Chem. Commun. ( 1995 ) 519.
16.K. R. Kloetstra, and H. van Bekkum, J. Chem. Res. ( 1995 ) 26.
17.C. T. Kresge, M. E. Leonowicz, W. J. Roth, J. C. Vartuli and J. S. Beck, Nature 359 ( 1992 ) 710.
18.H. P. Lin and C. Y. Mou, Science 273 ( 1996 ) 765.
19.林弘萍、牟中原，科學月刊 5 ( 1997 ) 360.
20.Lin, H. P.; Cheng, Y, R.; Mou, C. Y. Chem. Mater. 1998, 10, 581.
21.C.-Y. Chen, S.L.Brudett, H.-X.Li,M. E.Davis, Microporous Mater.,2 (1993) 27.
22.余瑞益，東海大學應用化學所碩士論文，”利用固體鹼觸媒製備特用化學品”, 1999.
23.周志宇，東海大學應用化學所碩士論文，”Al-MCM-41之備製、修飾、鑑定及運用”, 1998.
24.陳立文，東海大學應用化學所碩士論文，”β-萘酚和甲醇在中孔型分子篩Al-MCM-41催化下有效合成β-萘甲基醚”, 1998.
25.D.Trong On, S.M.J. Zaidi, S. Kaliguine, Micro. and Meso. Mater. 22 (1998) 211-224.
26.Akihiko Matsumoto, Hui Chen, Kazuo Tsutsumi, Michael Grun, Klaus Unger, Micro, and Meso. Mater. 32 (1999) 55-62.
27.翁和傑，石油季刊 33 (1997) 73.
28.蔡啟馨，觸媒與製程 5 (1996) 1.
29.吳榮中，工業觸媒概論.
30.K. Arata and C. Matsuura, Chem. Lett. 1797 (1989).
31.N. Ravasio, M. Antenori, F. Babudri; and M. Gargano, Stud. Surf. Sci. Catal. 108 (1997) 625.
32.Y. Nakatani and K. Kawashima, Communications, 147 (1978).
33.Naves, Y. R. and Ochsner, P., Helv. Chim. Acta. 47, 51 (1964).
34.Fuentes, M., Magraner, J., Pozas, C. D. L. and Roque-Malherbe, R., Appl. Catal. 47, 367 (1989).
35.Yadav, G. D. and Nair, J. J. Langmuir, 16, 4072 (2000).
36.Ko, A.-N., Hung, C.-C., Chen, C.-W. and Ouyang, K.-H., Catal. Lett. 71, 219 (2001).
37.歐陽光浩，東海大學應用化學所碩士論文，”環己酮在固體酸觸媒生成己內醯胺的貝克曼重排反應”, 1997.