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Korean Chemical Engineering Research,
Vol.50, No.2, 251-256, 2012
Vol.50, No.2, 251-256, 2012
Keggin형 H3+xPW12-xNbxO40 (x=0, 1, 2, 3) 및 Wells-Dawson형 H6+xP2W18-xNbxO62 (x=0, 1, 2, 3) 헤테로폴리산 촉매를 이용한 n-Butanol로부터 Di-n-Butyl Ether의 제조
Etherification of n-Butanol to Di-n-Butyl Ether over H3+xPW12-xNbxO40 (x=0, 1, 2, 3) Keggin and H6+xP2W18-xNbxO62 (x=0, 1, 2, 3) Wells-Dawson Heteropolyacid Catalysts
Keggin형 H3+xPW12-xNbxO40(x=0, 1, 2, 3) 및 Wells-Dawson형 H6+xP2W18-xNbxO62(x=0, 1, 2, 3) 헤테로폴리산(Heteropolyacid) 촉매를 이용하여 n-Butanol의 에테르화(Etherification) 반응을 통한 Di-n-Butyl Ether의 제조를 수행하였다. 먼저 Niobium이 서로 다른 비율로 치환된 Keggin형 및 Wells-Dawson형 헤테로폴리산 촉매를 제조하였다. FTIR, ICP-AES 및 31P NMR 분석을 통하여 촉매가 잘 제조되었음을 확인하였다. NH3-TPD(Temperature-Programmed Desorption) 분석을 통해 헤테로폴리산 촉매의 산특성을 측정하였다. 두 계열의 촉매군에서 헤테로폴리산 촉매는 Niobium의 함량에 따라 다른 산특성을 나타내었다. 이후, 헤테로폴리산 촉매를 에테르화 반응에 적용하고 촉매의 반응활성과 산특성 간의 상관관계를 분석하였다. Keggin형 H3+xPW12-xNbxO40 및 Wells-Dawson형 H6+xP2W18-xNbxO62 헤테로폴리산 촉매의 Acidity는 Keggin형과 Wells-Dawson형 모두에서 Niobium의 치환량이 증가함에 따라 감소하였으며, n-Butanol의 전환율과 Di-n-Butyl Ether로의 수율은 헤테로폴리산 촉매의 구조와 관계없이 Acidity가 증가함에 따라 선형적으로 증가하였다. 이처럼 헤테로폴리산의 Acidity는 n-Butanol의 에테르화(Etherification) 반응을 통한 Di-n-Butyl Ether의 제조 반응에서 촉매 활성을 결정하는 중요한 요소로 작용하였다.
Etherification of n-butanol to di-n-Butyl Ether was carried out over Keggin H3+xPW12-xNbxO40 (x=0, 1, 2, 3) and H6+xP2W18-xNbxO62 (x=0, 1, 2, 3) Wells-Dawson heteropolyacid catalysts. Niobium-substituted Keggin and Wells-Dawson heteropolyacid catalysts with different niobium content were prepared. Successful preparation of the catalysts was confirmed by FT-IR, ICP-AES, and 31P NMR analyses. Their acid properties were determined by NH3-TPD (Temperature-
Programmed Desorption) measurements. Heteropolyacid catalysts showed different acid properties depending on niobium content in both series. The correlation between acid properties of heteropolyacid catalysts and catalytic activity was then established. Acidity of Keggin and Wells-Dawson heteropolyacid catalysts decreased with increasing niobium content, and conversion of n-butanol and yield for di-n-butyl ether increased with increasing acidity of the catalysts, regardless of the identity of heteropolyacid catalysts (without heteropolyacid structural sensitivity). Thus, acidity of heteropolyacid catalysts served as an important factor determining the catalytic performance in the etherification of n-butanol to di-n-Butyl Ether.
[References]
- Tejero J, Fite C, Iborra M, Izquierdo JF, Cunill F, Bringue R, Microporous Mesoporous Mater., 117(3), 650, 2009
- Patrini R, Marchinonna M, US Patent 0159341, 2003
- Golibkov A, WO Patent 01/018154, 2001
- Alaoui FEM, Montero EA, Bazile JP, Aguilar F, Bonded C, J. Chem. Eng. Data., 56(3), 595, 2011
- Xu MT, Lunsford JH, Goodman DW, Bhattacharyya A, Appl. Catal. A: Gen., 149(2), 289, 1997
- Woodhouse, J. C., US Patent 2014408, 1935
- Golay S, Kiwi-Minsker L, Doepper R, Renken A, Chem. Eng. Sci., 54(15-16), 3593, 1999
- Patrini R, Marchinonna M, US Patent 6218583, 2001
- Makarova MA, Paukshtis EA, Thomas JM, Williams C, Zamaraev KI, J. Catal., 149(1), 36, 1994
- Makgoba NP, Sakuneka TM, Koortzen JG, van Schalkwyk C, Botha JM, Nicolaides CP, Appl. Catal. A: Gen., 297(2), 145, 2006
- Berteau P, Checkiewicz S, Delmon B, Appl. Catal., 31(2), 361, 1987
- Mizuno N, Misono M, Chem. Rev., 98(1), 199, 1998
- Youn MH, Park DR, Jung JC, Kim H, Barteau MA, Song IK, Korean J. Chem. Eng., 24(1), 51, 2007
- Song IK, Barteau MA, Korean J. Chem. Eng., 19(4), 567, 2002
- Shikata S, Okuhara T, Misono M, J. Mol. Catal. A: Chem., 100(1-3), 49, 1995
- Baronetti G, Thomas H, Querini CA, Appl. Catal. A: Gen., 217(1-2), 131, 2001
- Pope MT, Heteropoly and Isopoly Oxometalates, Springer-Verlag, Berlin Heidelberg, New York, 15, 1983
- Park DR, Song SH, Hong UG, Seo JG, Jung JC, Song IK, Catal. Lett., 132(3-4), 363, 2009
- Park DR, Choi JH, Park S, Song IK, Appl. Catal. A: Gen., 394(1-2), 201, 2011
- Okumura K, Yamashita K, Yamada K, Niwa M, J. Catal., 245(1), 75, 2007
- Massart R, Contant R, Fruchart JM, Ciabrini JP, Fournier M, Inorg.Chem., 16(11), 2196, 1977
- Hornstein BJ, Finke RG, Inorg. Chem., 41(10), 2720, 2002
- Choi JH, Kim JK, Park DR, Park SY, Yi JH, Song IK, Catal. Commun., 14(1), 48, 2011
- Rocchiccioli-Deltcheff C, Thouvenot R, Franck R, Spectrochim. Acta., 32(3), 587, 1976
- Comuzzi C, Dolcetti G, Trovarelli A, Cavani F, Trifiro F, Llorca J, Finke RG, Catal. Lett., 36(1-2), 75, 1996
- Okuhara T, Mizuno N, Misono M, Adv. Catal., 41, 113, 1996
- Lee KY, Arai T, Nakata S, Asaoka S, Okuhara T, Misono M, J. Am. Chem. Soc., 114(8), 2836, 1992
- Himeno S, Takamoto M, Ueda T, Bull. Chem. Soc. Jpn., 78, 1463, 2005
- Okuhara T, Kasai A, Hayakawa N, Misono M, Yoneda Y, Chem. Lett., 391, 1981
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