메탄에 의한 이산화탄소의 환원반응에 관한 연구

홍성수; 양진섭; 김병기; 주창식; 이근대

Journal of the Korean Industrial and Engineering Chemistry, Vol.8, No.4, 685-693, August, 1997

Export Citation

메탄에 의한 이산화탄소의 환원반응에 관한 연구

A Study on the Catalytic Reduction of Carbon Dioxide by Methane

홍성수, 양진섭, 김병기, 주창식, 이근대

초록

여러 종류의 담체에 담지된 니켈 촉매상에서 메탄에 의한 이산화탄소 개질반응에 대해 연구하였다. 여러 가지 담체중에 천연 제올라이트가 가장 높은 활성을 보여주었고, 염기성 담체에 비해 산성 담체에 담지된 니켈 촉매의 활성이 좋았으며 촉매의 비활성화도 느리게 진행되었다. 천연제올라이트에 담지된 니켈 촉매의 담지율이 증가할수록 활성이 증가하였고, 10wt% 이상으로 담지된 경우에는 활성의 변화가 그다지 일어나지 않았다. 반응물중 메탄과 이산화탄소의 비에 따라 전환율과 생성물의 수율이 크게 영향을 받았으며, CH₄/CO₂의 비가 1일 때 가장 높은 수소 및 일산화탄소 수율을 나타내었다. 촉매의 비활성화는 반응중에 생성되는 코크에 침적에 기인하는 것으로 생각되며, 코크는 주로 메탄의 분해에 의해 생성되었고 코크의 형상은 whisker형으로 촉매의 비활성화 속도를 느리게 하였다.

We have studied the reforming of carbon dioxide with methane over various supported nickel catalysts. The nickel supported on natural zeolite showed the highest activity and the nickel on acidic support showed higher activity and slow deactivation compared to nickel on basic support. The activity of nickel on natural zeolite increased with increasing loading ratio and showed almost constant activity above 10wt.% loading of nickel. The conversion and yield of products were affected by the mole ratio of reactants and the highest yields of CO and H₂ were obtained at CH₄/CO₂=1. The deactivation of catalyst was caused by deposition of coke which was formed by the decomposition of methane. The shape of coke was shown to be whisker tripe carbon, and it brought out the slow deactivation of catalyst.

[References]

Park SE, Chang JS, Catalysis, 7, 32 (1992)
Gavin D, Bower C, Proc. 1st Papan-Ec, 96 (1991)
Chubb TA, Sol. Energy, 24, 341 (1980)
Richardson JT, Paripatyadar SA, Appl. Catal., 61, 293 (1990)
Teuner S, Hydrocarb. Process., 64, 106 (1985)
Bibby DM, Chang CD, Howe RF, Yurchak S, Methane Conversion, Elsevier, Amsterdam (1988)
Ayers WM, Catalytic Activation of CO₂, ACS Symp. Ser. American Chemical Society, Washington DC (1988)
Parera JSH, Couves JW, Sanker G, Thomas JM, Catal. Lett., 11, 219 (1991)
Levy M, Rubin R, Rosin H, Revutan R, Energy, 749 (1993)
Rostrup-Nielsen JR, BakHansen JH, J. Catal., 144, 38 (1993)
Ashcroft AT, Cheeltham AK, Green MLH, Vermon DF, Letters to Nature, 352 (1991)
Vermon DF, Green MLH, Cheertham AK, Ashcroft AT, Catal. Today, 13, 417 (1994)
Tang SB, Qiu FL, Lu SJ, Catal. Today, 24(3), 253 (1995)
Swaan HM, Kroll VCH, Martin GA, Mirodatos C, Catal. Today, 21, 571 (1994)
Fujimoto K, Shikada L, Appl. Catal., 31, 13 (1987)
Chang JS, Park SE, Chon HZ, Appl. Catal. A: Gen., 145(1-2), 111 (1996)
Masai M, Stud. Surf. Sci. Catal., 36, 67 (1984)
Huder K, Chem. Ing. Tech., 63, 376 (1991)
Guerrero-Ruiz A, Sepulveda-Escribano A, Rodriguez-Ramos I, Catal. Today, 21, 545 (1994)
Hu YH, Ruckenstein E, Catal. Lett., 43(1-2), 71 (1997)
Zhang Z, Verykios XE, J. Chem. Soc.-Chem. Commun., 71 (1995)
Vannice MA, J. Catal., 44, 152 (1976)
Gadalla AM, Bower B, Chem. Eng. Sci., 43, 3049 (1988)
Richard JT, "Principles of Catalyst Development," Plenum Press, New York, 221 (1989)
Yamazaki O, Nozaki T, Omata K, Fujimoto K, Chem. Lett., 1953 (1992)
Kim GJ, Cho DS, Kim KH, Kim JH, Catal. Lett., 28, 41 (1994)
Claridge JB, Green MLH, Tsang SC, York APE, Ashcroft AT, Battle PD, Catal. Lett., 22, 299 (1993)

[Referenced By]

[1] Park SE, Chang JS, Catalysis, 7, 32 (1992)

[2] Gavin D, Bower C, Proc. 1st Papan-Ec, 96 (1991)

[3] Chubb TA, Sol. Energy, 24, 341 (1980)

[4] Richardson JT, Paripatyadar SA, Appl. Catal., 61, 293 (1990)

[5] Teuner S, Hydrocarb. Process., 64, 106 (1985)

[6] Bibby DM, Chang CD, Howe RF, Yurchak S, Methane Conversion, Elsevier, Amsterdam (1988)

[7] Ayers WM, Catalytic Activation of CO₂, ACS Symp. Ser. American Chemical Society, Washington DC (1988)

[8] Parera JSH, Couves JW, Sanker G, Thomas JM, Catal. Lett., 11, 219 (1991)

[9] Levy M, Rubin R, Rosin H, Revutan R, Energy, 749 (1993)

[10] Rostrup-Nielsen JR, BakHansen JH, J. Catal., 144, 38 (1993)

[11] Ashcroft AT, Cheeltham AK, Green MLH, Vermon DF, Letters to Nature, 352 (1991)

[12] Vermon DF, Green MLH, Cheertham AK, Ashcroft AT, Catal. Today, 13, 417 (1994)

[13] Tang SB, Qiu FL, Lu SJ, Catal. Today, 24(3), 253 (1995)

[14] Swaan HM, Kroll VCH, Martin GA, Mirodatos C, Catal. Today, 21, 571 (1994)

[15] Fujimoto K, Shikada L, Appl. Catal., 31, 13 (1987)

[16] Chang JS, Park SE, Chon HZ, Appl. Catal. A: Gen., 145(1-2), 111 (1996)

[17] Masai M, Stud. Surf. Sci. Catal., 36, 67 (1984)

[18] Huder K, Chem. Ing. Tech., 63, 376 (1991)

[19] Guerrero-Ruiz A, Sepulveda-Escribano A, Rodriguez-Ramos I, Catal. Today, 21, 545 (1994)

[20] Hu YH, Ruckenstein E, Catal. Lett., 43(1-2), 71 (1997)

[21] Zhang Z, Verykios XE, J. Chem. Soc.-Chem. Commun., 71 (1995)

[22] Vannice MA, J. Catal., 44, 152 (1976)

[23] Gadalla AM, Bower B, Chem. Eng. Sci., 43, 3049 (1988)

[24] Richard JT, "Principles of Catalyst Development," Plenum Press, New York, 221 (1989)

[25] Yamazaki O, Nozaki T, Omata K, Fujimoto K, Chem. Lett., 1953 (1992)

[26] Kim GJ, Cho DS, Kim KH, Kim JH, Catal. Lett., 28, 41 (1994)

[27] Claridge JB, Green MLH, Tsang SC, York APE, Ashcroft AT, Battle PD, Catal. Lett., 22, 299 (1993)