고체 염기촉매에 의한 아세톤의 Aldol 부가반응:Ca(OH)2, KOH-Ca(OH)2, NaOH-Ca(OH)2

허진목; 권혁회; 이호인; Jin Mok Hur; Heock Hoi Kwon; Ho In Lee

Journal of the Korean Industrial and Engineering Chemistry, Vol.11, No.6, 667-671, October, 2000

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고체 염기촉매에 의한 아세톤의 Aldol 부가반응:Ca(OH)2, KOH-Ca(OH)2, NaOH-Ca(OH)2

Aldol Addition of Acetone over Solid Base Catalysts: Ca(OH)2, KOH-Ca(OH)2, and NaOH-Ca(OH)2

허진목, 권혁회 ¹, 이호인 ^†

서울대학교 응용화학부, 서울 151-744
¹숭실대학교 환경/화학공학과, 서울 156-743

Jin Mok Hur, Heock Hoi Kwon¹, and Ho In Lee^†

School of Chemical Engineering, Seoul National University, Seoul 151-744, Korea
¹Department of Chemical and Environmental Engineering, Soongsil University, Seoul 156-743, Korea

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초록

아세톤의 aldol 부가반응을 모델반응으로 하여서, Ca(OH)2, KOH-Ca(OH)2, NaOH-Ca(OH)2 등의 고체 염기촉매로서의 특성을 연구하였다. Ca(OH)2를 소성하여 제조한 촉매의 경우, 촉매활성은 촉매의 BET 표면적에 강하게 의존하였다. Ca(OH)2에 KOH와 NaOH를 함침시키고 소성하여 제조한 KOH-Ca(OH)2와 NaOH-Ca(OH)2 촉매의 경우, Ca(OH)2와 KOH 그리고 Ca(OH)2와 NaOH 사이에 고체·고체 상호작용이 있음을 XRD와 DTA를 이용하여 확인할 수 있었으며, 이로 인한 Ca(OH)2보다 강염기인 CaO 구조 생성에 따른 촉매의 표면 염기도 증가, 그리고 반응물인 아세톤에 의한 촉매피독의 저항성 증가에 의해서 Ca(OH)2만을 소성하여 제조한 촉매에 비해서 촉매활성이 뛰어났다.

The properties of Ca(OH)2, KOH-Ca(OH)2, and NaOH-Ca(OH)2 as solid base catalysts for acetone aldol addition reaction were studied. For the calcined Ca(OH)2 catalysts, the catalytic activities depended strongly on the BET surface areas. For the KOH-Ca(OH)2 and NaOH-Ca(OH)2 catalysts, XRD and DTA showed that there was solid-solid interaction between Ca(OH)2 and impregnated species. These impregnated catalysts exhibited higher catalytic activities than the calcined Ca(OH)2 catalyst. We believe that the increased activities are due to the increased surface basicity by the formation of CaO structure which is more basic than Ca(OH)2 structure, and by the increased resistance to acetone poisoning of the impregnated catalysts.

Keywords:Acetone;Diacetone alcohol;Solid base catalysts;Aldol addition

[References]

Tanabe K, "Catalysis by Acids and Bases," 1, Elsevier (1985)
Hattori H, "Heterogeneous Catalysis and Fine Chemicals III," 35, Elsevier (1993)
Hattori H, Chem. Rev., 95(3), 537 (1995)
Zhang G, Hattori H, Tanabe K, Appl. Catal., 36, 189 (1988)
Zhang G, Hattori H, Tanabe K, Appl. Catal., 40, 183 (1988)
Raso AG, Sinisterra JV, Marinas JM, React. Kinet. Catal. Lett., 18, 33 (1981)
Sinisterra JV, Blanco FG, Iglesias M, Marinas JM, React. Kinet. Catal. Lett., 25, 277 (1984)
Tanabe K, Misono M, Ono Y, Hattori H, "New Solid Acids and Bases," 39, Kodanshi-Elsevier (1989)
Busca G, Escribano VS, Forzatti P, Lietti L, Ramis G, "New Developments in Selective Oxidation II," 777, Elsevier (1994)
Maiti GC, Baerns M, Thermochim. Acta, 261, 69 (1995)
Klyucharev VV, Sinel'nikov SM, Razumova AP, Sasnovskaya VD, Russ. Chem. Bull., 45, 26 (1996)
Aramendia MA, Borau V, Jimenez C, Marinas JM, Porras A, Urbano FJ, J. Catal., 161(2), 829 (1996)

[Related Articles]

[1] Tanabe K, "Catalysis by Acids and Bases," 1, Elsevier (1985)

[2] Hattori H, "Heterogeneous Catalysis and Fine Chemicals III," 35, Elsevier (1993)

[3] Hattori H, Chem. Rev., 95(3), 537 (1995)

[4] Zhang G, Hattori H, Tanabe K, Appl. Catal., 36, 189 (1988)

[5] Zhang G, Hattori H, Tanabe K, Appl. Catal., 40, 183 (1988)

[6] Raso AG, Sinisterra JV, Marinas JM, React. Kinet. Catal. Lett., 18, 33 (1981)

[7] Sinisterra JV, Blanco FG, Iglesias M, Marinas JM, React. Kinet. Catal. Lett., 25, 277 (1984)

[8] Tanabe K, Misono M, Ono Y, Hattori H, "New Solid Acids and Bases," 39, Kodanshi-Elsevier (1989)

[9] Busca G, Escribano VS, Forzatti P, Lietti L, Ramis G, "New Developments in Selective Oxidation II," 777, Elsevier (1994)

[10] Maiti GC, Baerns M, Thermochim. Acta, 261, 69 (1995)

[11] Klyucharev VV, Sinel'nikov SM, Razumova AP, Sasnovskaya VD, Russ. Chem. Bull., 45, 26 (1996)

[12] Aramendia MA, Borau V, Jimenez C, Marinas JM, Porras A, Urbano FJ, J. Catal., 161(2), 829 (1996)