Ru/C 촉매를 이용한 p-Toluidine의 선택적 수소화 반응에 있어서 공정변수의 최적화연구

홍범의; 이종민; 박융호; Bum-eui Hong; Jong-min Lee; Yeung-ho Park

Journal of the Korean Industrial and Engineering Chemistry, Vol.19, No.4, 432-438, August, 2008

Export Citation

Ru/C 촉매를 이용한 p-Toluidine의 선택적 수소화 반응에 있어서 공정변수의 최적화연구

Optimization of Process Variables in the Hydrogenation of p-Toluidine on Ru/C Catalyst

홍범의, 이종민, 박융호 ^†

한양대학교 재료화학공학부

Bum-eui Hong, Jong-min Lee, and Yeung-ho Park^†

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

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초록

Ru/C 촉매를 이용한 p-toluidine (TLD) 선택적 수소화 반응의 특성을 파악하기 위하여 반응 온도, 수소 압력, 촉매량, 반응 용매 및 알카리 첨가제와 같은 공정변수들을 변화시켜가면서 반응속도와 생성물 분포에 미치는 영향을 조사하였다. TLD 수소화 반응에서 4-methylcyclohexylamine (MCHA)이 주된 생성물로 얻어졌으며 부반응물로는 bis(4-methyl cyclohexyl) amine (BMCHA)이 주로 생성되었다. MCHA는 온도와 압력의 증가에 따라 감소하였지만, 촉매량에 따라서는 증가함을 나타내었다. 용매의 변화에서는 isopropanol (IPA)에서 가장 좋은 선택도를 나타내었다. 이로부터 TLD 선택적 수소화에 대한 반응 기구를 제시하였다. 알카리염의 첨가는 BMCHA의 생성률을 낮게 하여 MCHA로의 선택도를 증가시켰으며 반응속도 또한 증가시켜주는 효과를 나타내었다.

Hydrogenation reactions of p-toluidine over Ru/C were performed while varying reaction temperature, the hydrogen pressure, catalyst loading, solvent, and alkali additive and the effects on the reaction rates and product distribution were examined. 4-Methylcyclohexylamine was generated as a main product and bis(4-methyl cyclohexyl)amine was obtained as a resentative side-product for the hydrogenation reaction of p-toluidine. The selectivity of MCHA decreased with reaction temperature and the hydrogen pressure while increased with catalyst loading. IPA was the best solvent for MCHA. A mechanism of hydrogenation reaction of p-toluidine was suggested from the results. It was found that the presence of alkali salt increased MCHA by reducing BMCHA and rates of hydrogen reaction increased.

Keywords:p-Toluidine;Ru/C catalyst;hydrogenation;process variables;alkali additive

[References]

U. S. Patent 5,219,546 (1993)
Francesco Siclari. U. S. Patent 3,632,558 (1988)
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U. S. Patent 2,606,925 (1952)
Greenfield H, J. Org. Chem., 29, 3082 (1964)
Kim HS, Seo SH, Lee HJ, Lee SD, Kwon YS, Lee IM, J. Mol. Catal. A-Chem., 132, 267 (1998)
Guraya M, Sprenger S, Rarog-Pilecka W, Szmigiel D, Kowalczyk Z, Muhler M, Appl. Surf. Sci., 238(1-4), 77 (2004)

[Related Articles]

[1] U. S. Patent 5,219,546 (1993)

[2] Francesco Siclari. U. S. Patent 3,632,558 (1988)

[3] Minoru T, Sachiko F, Michiya M, J. Biochem., 117, 719 (1995)

[4] U. S. Patent 491,429 (1990)

[5] Rylander PN, Steele DR, Engelhard Ind. Tech. Bull., 9, 19 (1962)

[6] Rylander PN, Steele DR, Engelhard Ind. Tech. Bull., 12, 20 (1963)

[7] Nishimura S, Shu T, Hara T, Bull. Chem. Soc. Jpn., 39, 329 (1966)

[8] Nishimura S, Shu T, Hara T, Bull. Chem. Soc. Jpn., 44, 240 (1971)

[9] Barkdoll AE, England DC, Gray HW, Kirk W, Whitman GM, J. Am. Chem. Soc., 75, 1156 (1953)

[10] U. S. Patent 2,606,924 (1952)

[11] U. S. Patent 2,606,925 (1952)

[12] Greenfield H, J. Org. Chem., 29, 3082 (1964)

[13] Kim HS, Seo SH, Lee HJ, Lee SD, Kwon YS, Lee IM, J. Mol. Catal. A-Chem., 132, 267 (1998)

[14] Guraya M, Sprenger S, Rarog-Pilecka W, Szmigiel D, Kowalczyk Z, Muhler M, Appl. Surf. Sci., 238(1-4), 77 (2004)