Maleic Acid의 Pd/C 촉매상 저압 수소화 반응의 반응 기구에 관한 연구

홍도영; 박융호; 홍범의; Do-Young Hong; Yeung-Ho Park; Bum-Eui Hong

Journal of the Korean Industrial and Engineering Chemistry, Vol.14, No.5, 541-548, August, 2003

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Maleic Acid의 Pd/C 촉매상 저압 수소화 반응의 반응 기구에 관한 연구

Mechanism of Low Pressure Hydrogenation of Maleic Acid over Pd/C Catalyst in Aqueous Solution

홍도영, 박융호 ^†, 홍범의

한양대학교 재료화학공학부, 안산 425-791

Do-Young Hong, Yeung-Ho Park^†, and Bum-Eui Hong

Division of Material and Engineering, Hanyang University, Ansan 425-791, Korea

E-mail:

초록

Pd/C 촉매를 이용한 maleic acid의 수용액 중 저압 수소화 반응의 특성을 파악하기 위하여 수소압력, 반응온도, 반응물 농도, 촉매량 및 교반속도 등의 공정변수를 변화시켜 가면서 반응 속도와 생성물 분포에 미치는 영향을 조사하였다. maleic acid의 수소화 반응에서 succinic acid, fumaric acid 및 malic acid가 얻어졌고 산업적 공정조건에서 물질전달의 제한을 받는 것으로 나타났다. 본래적인 반응특성을 보면, maleic acid의 수소화 반응에서 succinic acid와 fumaric acid의 생성속도가 수소압, 촉매양, 온도와 반응물 농도에 비례하여 증가하였으나 malic acid의 생성속도는 이와 다른 경향을 보였으며, 이로부터 maleic acid의 저압 수소화 반응에 대한 반응기구를 제시하였다.

Hydrogenation reactions of maleic acid over Pd/C at a lower pressure were performed in aqueous solution while varying the hydrogen pressure, reaction temperature, reactant concentration, catalyst loading, and agitation speed and the effects on the reaction rate and product distribution were examined. Intrinsic reaction characteristics were studied from the results of reaction performed at higher agitation speed than that of industrial reaction condition. Succinic acid, fumaric acid and malic acid were abtained from the reaction. Both rates of formation of succinic acid and fumaric acid increased with hydrogen pressure and catalyst amount while that of malic acid a showed different trend, from which a mechanism for hydrogenation of maleic acid was suggested.

Keywords:maleic acid;catalytic hydrogenation;mass transfer;fumaric acid;reaction mechanism

[References]

Edward ER, Byrne MJ, Hydrogenation Catalyst and Method for Preparing Tetrahydrofuran, W.O. Patent, 9202298 (1992)
Herrmann U, Emig G, Ind. Eng. Chem. Res., 36(8), 2885 (1997)
Pallassana V, Neurock M, Coulston G, Catal. Today, 50(3-4), 589 (1999)
Mabry MA, Prichard WW, Ziemecki SB, Process for Making Tetrahydrofuran and 1,4-butanediol using Pd/Re Hydrogenation Catalyst, U.S. Patent, 4,550,185 (1985)
Mabry MA, Prichard WW, Ziemecki SB, Pd/Re Hydrogenation Catalyst for Making Tetrahydrofuran and 1,4-butanediol, U.S. Patent, 4,609,636 (1986)
Messori M, Vaccari A, J. Catal., 150(1), 177 (1994)
Weiss JM, Downs CR, J. Chem. Soc., 44, 1118 (1922)
Kroschwitz JI, Maleic Anhydride, Maleic Acid and Fumaric Acid, Kirk-Othmer Concise Encyclopedia of Chemical Technology, 4th Ed., 26, 1242, Wiley, New York (1999)
Lohbeck K, Haferkorn H, Fuhrmann W, Aktienge-scellschaft H, Maleic and Fumaric Acids, Ullmann's Encyclopedia of Industrial Chemistry, Ed. B. Elvers, S. Hawkins, and G. Schulz, A16, 53 (1990)
Souichi Y, Hidefumi H, Shoichi M, Yoji A, Production of Succinic Acid, Japan Patent, 09-031011 (1997)
Katsumi M, Seiji I, Maso N, Production of Succinic Acid, Japan Patent, 61-204148 (1986)
Katsumi M, Seiji I, Maso N, Production of Succinic Acid, Japan Patent, 61-204149 (1994)
Fogler HS, Elements of Chemical Reaction Engineering, 771, Prentice Hall, New Jersey (1999)
Boitiaux JP, Consyns J, Robert E, Appl. Catal. A: Gen., 35, 193 (1987)

[Referenced By]

[Related Articles]

[1] Edward ER, Byrne MJ, Hydrogenation Catalyst and Method for Preparing Tetrahydrofuran, W.O. Patent, 9202298 (1992)

[2] Herrmann U, Emig G, Ind. Eng. Chem. Res., 36(8), 2885 (1997)

[3] Pallassana V, Neurock M, Coulston G, Catal. Today, 50(3-4), 589 (1999)

[4] Mabry MA, Prichard WW, Ziemecki SB, Process for Making Tetrahydrofuran and 1,4-butanediol using Pd/Re Hydrogenation Catalyst, U.S. Patent, 4,550,185 (1985)

[5] Mabry MA, Prichard WW, Ziemecki SB, Pd/Re Hydrogenation Catalyst for Making Tetrahydrofuran and 1,4-butanediol, U.S. Patent, 4,609,636 (1986)

[6] Messori M, Vaccari A, J. Catal., 150(1), 177 (1994)

[7] Weiss JM, Downs CR, J. Chem. Soc., 44, 1118 (1922)

[8] Kroschwitz JI, Maleic Anhydride, Maleic Acid and Fumaric Acid, Kirk-Othmer Concise Encyclopedia of Chemical Technology, 4th Ed., 26, 1242, Wiley, New York (1999)

[9] Lohbeck K, Haferkorn H, Fuhrmann W, Aktienge-scellschaft H, Maleic and Fumaric Acids, Ullmann's Encyclopedia of Industrial Chemistry, Ed. B. Elvers, S. Hawkins, and G. Schulz, A16, 53 (1990)

[10] Souichi Y, Hidefumi H, Shoichi M, Yoji A, Production of Succinic Acid, Japan Patent, 09-031011 (1997)

[11] Katsumi M, Seiji I, Maso N, Production of Succinic Acid, Japan Patent, 61-204148 (1986)

[12] Katsumi M, Seiji I, Maso N, Production of Succinic Acid, Japan Patent, 61-204149 (1994)

[13] Fogler HS, Elements of Chemical Reaction Engineering, 771, Prentice Hall, New Jersey (1999)

[14] Boitiaux JP, Consyns J, Robert E, Appl. Catal. A: Gen., 35, 193 (1987)