산화물에 담지된 금 나노입자에 의한 1,3-부타디엔의 수소화

안호근; 히로오 니이야마; Ho Geun Ahn; Hiroo Niiyama

Journal of the Korean Industrial and Engineering Chemistry, Vol.12, No.8, 920-926, December, 2001

Export Citation

산화물에 담지된 금 나노입자에 의한 1,3-부타디엔의 수소화

Hydrogenation of 1,3-Butadiene over Supported Gold Nanoparticle

안호근 ^†, 히로오 니이야마¹

순천대학교 공과대학 화학공학과, 나노기술센터, 순천 540-742
¹동경공업대학 화학공학과, O-okayama, Meguro-ku, Tokyo 152

Ho Geun Ahn^†, and Hiroo Niiyama¹

Department of Chemical Engineering and Nanotechnology Center, Sunchon National Univ, Sunchon 540-742, Korea
¹Department of Chemical Engineering, Tokyo Institute of Technology, O-okayama, Meguro-ku, Tokyo 152, Japan

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초록

침착법에 의하여 나노크기로 Al2O3, SiO2와 TiO2에 담지된 금입자에 부타디엔 수소화에 대한 활성 및 생성물 분포를 유통식 반응기에서 조사하였다. 함침법으로 제조한 금 촉매 및 Co/Al2O3촉매와 활성을 비교하고 속도론적 고찰을 통하여 반응 메카니즘을 검토하였다. 침착법으로 제조한 담지 금촉매가 가장 높은 수소화 활성을 나타내었고, 부텐의 선택성은 부타디엔 수소화가 완전히 진행되어 부타디엔이 존재하지 않는 조건에서도 거의 100%이었다. 전화율이 높아 부타디엔이 없어지면 1-부텐이 2-부텐으로 이성화됨을 알았다. 담지 금 촉매는 코발트 촉매와는 달리 수소와 부타디엔과 적절한 친화력을 가졌다. Co/Al2O3촉매의 부타디엔에 대한 반응차수는 부타디엔의 강한 흡착 때문에 음수이지만, Au/oxides 촉매는 양수를 가졌다. 결과적으로, 담지 금 촉매는 코발트 촉매와는 달리 부분 수소화에 적절한 흡착력을 가지며, 금입자와 담체와의 경계에 존재하는 금원자는 수소의 해리흡착을 촉진하는 것으로 생각되었다.

The activity and products distribution for the hydrogenation of 1,3-butadiene over supported gold nanoparticles, prepared by deposition or impregnation, were investigated using a flow-type reactor. The effect of gold particles on the reaction and the reaction mechanism were studied by comparing the kinetics of gold catalyst with that of the supported cobalt catalyst. The results showed that the activity of gold catalyst prepared by the deposition method was the best; the selectivity to butene was nearly 100% even at 100% conversion level. In the absence of butadiene, due to depletion in the stream, 1-butene isomerized to 2-butene. Different from the colbalt catalyst, the gold catalyst possessed a good affinity for both hydrogen and butadiene. Dut to a strong adsorption of butadiene, the reaction order of butadiene on Co/Al2O3 catalyst was negative, but the order on Au/oxide catalysts was positive. Therefore, the supported gold catalyst had an adsorption characteristic suitable for partial hydrogenation; the gold atoms existed at the interface between gold particles and the support promoted the dissociative adsorption of hydrogen.

Keywords:gold catalyst;nanoparticle;butadiene;hydrogenation;kinetics

[References]

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Haruta M, Kobayashi T, Iijima S, Delannary F, Proc. 9th ICC, 1206 (1988)
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Ahn HG, Niiyama H, J. Korean Ind. Eng. Chem., 5(2), 285 (1994)
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Ahn HG, Niiyama H, J. Korean Ind. Eng. Chem., 10(7), 1003 (1999)
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Bond GC, Webb G, Wells PB, Winterbattom JM, J. Chem. Soc., A3218 (1965)
Wells PB, Bates AJ, J. Chem. Soc., A3064 (1968)
Phillipson JJ, Wells PB, Wilson GR, J. Chem. Soc., A1351 (1969)
Webb G, "Catalysis," ed. by D.A. Dowden and C. Kemball, Vol. 2, Chem. Soc., 145 (1978)
Hub S, Hilaire L, Touroude R, Appl. Catal., 35, 307 (1988)
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Smith GV, Burwell RL, J. Am. Chem. Soc., 84, 925 (1962)
Nudel JN, Umansky BS, Piagentini RO, Lombardo EA, J. Catal., 89, 362 (1984)
Oudar J, Pinol S, Pradier CM, Berthier Y, J. Catal., 107, 445 (1987)

[Related Articles]

[1] Haruta M, Kobayashi T, Sano H, Yamada N, Chem. Lett., 405 (1987)

[2] Haruta M, Kobayashi T, Iijima S, Delannary F, Proc. 9th ICC, 1206 (1988)

[3] Haruta M, Yamada N, Kobayashi T, Iijima S, J. Catal., 115, 301 (1989)

[4] Haruta M, Kageyama H, Kamijo N, Kobayashi T, Delannay F, U.S.-Japna Catal. Seminar, Philadelphia, 5 July (1988)

[5] Fukushima T, Kikuta T, Shindo K, Hattori Y, Catal. Sci. Technol., (Proc. TOCAT 1), ed. by S. Yoshida, N. Takezawa, and T. Ono, Vol. 1, Kodansha, 483 (1991)

[6] Haruta M, Catal. Today, 36(1), 153 (1997)

[7] Ahn HG, Niiyama H, J. Korean Ind. Eng. Chem., 5(2), 285 (1994)

[8] Ahn HG, Park DA, Jung SC, Chung MC, Kim BH, J. Korean Ind. Eng. Chem., 11(5), 529 (2000)

[9] Ahn HG, Niiyama H, J. Korean Ind. Eng. Chem., 10(7), 1003 (1999)

[10] Okuhara M, Akita T, Haruta M, Proc. of 8th Japan-Korea Symp. on Catal. Osaka(Japan), 13 (2001)

[11] Bond GC, Webb G, Wells PB, Winterbattom JM, J. Chem. Soc., A3218 (1965)

[12] Wells PB, Bates AJ, J. Chem. Soc., A3064 (1968)

[13] Phillipson JJ, Wells PB, Wilson GR, J. Chem. Soc., A1351 (1969)

[14] Webb G, "Catalysis," ed. by D.A. Dowden and C. Kemball, Vol. 2, Chem. Soc., 145 (1978)

[15] Hub S, Hilaire L, Touroude R, Appl. Catal., 35, 307 (1988)

[16] Boitiaux JP, Cosyns J, Robert E, Appl. Catal., 32, 145 (1987)

[17] Smith GV, Burwell RL, J. Am. Chem. Soc., 84, 925 (1962)

[18] Nudel JN, Umansky BS, Piagentini RO, Lombardo EA, J. Catal., 89, 362 (1984)

[19] Oudar J, Pinol S, Pradier CM, Berthier Y, J. Catal., 107, 445 (1987)