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Language: korean

Conflict of Interest: In relation to this article, we declare that there is no conflict of interest.

Publication history: Received September 19, 2011
Accepted October 10, 2011

This is an Open-Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License (http://creativecommons.org/licenses/bync/3.0) which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.

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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

김정권 최정호 이종협 송인규^†

Jeong Kwon Kim Jung Ho Choi Jongheop Yi In Kyu Song^†

서울대학교 공과대학 화학생물공학부, 151-744 서울특별시 관악구 관악로 599

School of Chemical and Biological Engineering, College of Engineering, Seoul National University, 599 Gwanak-ro, Gwanak-gu, Seoul 151-744, Korea

inksong@snu.ac.kr

Korean Chemical Engineering Research, April 2012, 50(2), 251-256(6), NONE Epub 30 March 2012

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Abstract

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-_x000D_ 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.

Keywords

Etherification Di-n-Butyl Ether Heteropolyacid Catalyst Niobium Acidity

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