Alumina 담지 Molybdenum계 촉매상에서 수소첨가 탈황특성: 촉매상과 활성의 관계

박해경; 이진구; 김경림

HWAHAK KONGHAK, Vol.35, No.2, 276-281, April, 1997

Hydrodesulfurization Characteristics over Alumina-Supported Molybdenum-Based Catalysts: Relation between Catalyst Phase and Activity

박해경, 이진구, 김경림

초록

촉매상에 따른 탈황활성의 변화를 살펴보기 위하여 산화, 환원, 황화, 질화, 탄화 Mo, CoMo, NiMo/γ-Al₂O₃ 촉매상에서 dibenzothiophene 탈황활성을 비교분석하였다. 질소 흡착분석결과 제조방법에 따라 γ-Al₂O₃ 담체 자체의 기하학적인 특성이 변함을 알 수 있었다. 등온 고정층 연속흐름 반응기에서 dibenzothiophene 탈황실험을 하였다. 질화물 및 탄화물의 탈황활성은 비교적 안정되었으나, 산화물, 환원물, 황화물은 반응시간이 경과함에 따라 탈황활성이 저하되었다. 질화물의 경우 Mo/γ-Al₂O₃에 Co와 Ni를 첨가할 경우 활성억제효과를 가져왔으며, 질화물을 전조물로하여 제조한 탄화물은 Co와 Ni를 첨가하였을 때 활성이 우수하였다. 환원물 촉매의 경우 CoMo, NiMo/γ-Al₂O₃ 촉매와 Mo/γ-Al₂O₃ 촉매는 반응변수(온도, 접촉시간)가 변화함에 따라 다른 활성의 변화특성을 보였다. 탈황활성이 우수한 황화 CoMo/γ-Al₂O₃(CoO 3wt%, MoO₃, 12wt%)와 질화 Mo/γ-Al₂O₃(MoO₃, 12wt%)는 반응변수의 변화에 따라 비슷한 활성과 선택도를 보였다.

A number of alumina-supported molybdenum-based catalysts - oxides, metals, sulfides, nitrides and carbides - were prepared and investigated for the relation between catalyst phase and hydrodesulfurization activity. From the N2 adsorption analysis, it was established that the texture properties of γ-Al₂O₃ support were changed by the synthesis method. The hydrodesulfurization of dibenzothiophene over these catalysts was studied in an isothermal fixed-bed continuous-flow reactor. The activities of nitrides and carbides were not significantly changed but oxides, metals and sulfides lost their activities rapidly during the reaction. The addition of cobalt and nickel deteriorated the activities of nitrides but enhanced those of carbides. Among the metals the unpromoted molybdenum showed different reactivity against the promoted one with the variation of reaction parameters(temperature, contact time). Both sulfided CoMo/γ-Al₂O₃(CoO 12 wt%, MoO₃ 12 wt%) and nitrided Mo/γ-Al₂O₃(MoO₃ 12wt%) had shown similar activities and selectivities.

Keywords:Activity;Catalyst Phase;Hydrodesulfurization;Promoter;Stability

[References]

Startserv AN, Catal. Rev.-Sci. Eng., 37(3), 353 (1995)
Chung KS, Massoth FE, J. Catal., 64, 320 (1980)
Colling CW, Thompson LT, J. Catal., 146(1), 193 (1994)
Nagai M, Kusagaya T, Miyata A, Omi S, Bull. Soc. Chim. Belg., 104, 311 (1995)
Schlatter JC, Oyama ST, Metchlfe JE, Lambert JM, Ind. Eng. Chem. Res., 27, 1648 (1988)
Nagai M, Miyao T, Tsuboi T, Catal. Lett., 18, 9 (1993)
Park HK, Lee JK, Yoo JK, Ko ES, Kim DS, Kim KL, Appl. Catal., to be published
Massoth FE, Kibby CL, J. Catal., 47, 300 (1977)
Delmon B, Bull. Soc. Chim. Belg., 104, 173 (1995)
Corrigan TE, Chem. Eng., 199 (1955)
Mears DE, Ind. Eng. Chem. Process Des. Dev., 10(4), 541 (1971)
Lee JS, Boudart M, Appl. Catal., 19, 207 (1985)
Abe H, Cheung TK, Bell AT, Catal. Lett., 21, 11 (1993)
Choi JG, Brenner JR, Thompson LT, J. Catal., 154(1), 33 (1995)
Leclercq G, Kamal M, Lamonier JF, Feigenbaum L, Malfoy P, Leclercq L, Appl. Catal. A: Gen., 121(2), 169 (1995)
Volpe L, Boudart M, J. Solid State Chem., 59, 348 (1985)
Slade RCT, Halstead TK, Dickens PG, Jarman RH, Solid State Commun., 45(5), 459 (1983)
Jaggers CH, Micheals JN, Stacy AM, Chem. Mater., 2, 150 (1990)
Demczyk BG, Choi JG, Thompson LT, Appl. Surf. Sci., 78, 63 (1994)
Walendziewski J, Trawczynski J, Appl. Catal., 96, 163 (1993)
Magai M, Omi S, J. Jpn. Petro. Inst., 38(6), 363 (1995)
Hall WK, J. Catal., 85, 277 (1984)
Topsoe NY, Topsoe H, J. Catal., 139, 631 (1993)
Levy RB, "Properties of Carbides, Nitrides, and Borides: Implications for Catalysis," in Advanced Materials in Catalysis, Academic, New York (1977)
Smit TS, Johnson KH, Catal. Lett., 28(2-4), 361 (1994)
Lee JK, Koh HL, Kim JH, Park HK, Kim KL, J. Korean Ind. Eng. Chem., completed

[Referenced By]

[1] Startserv AN, Catal. Rev.-Sci. Eng., 37(3), 353 (1995)

[2] Chung KS, Massoth FE, J. Catal., 64, 320 (1980)

[3] Colling CW, Thompson LT, J. Catal., 146(1), 193 (1994)

[4] Nagai M, Kusagaya T, Miyata A, Omi S, Bull. Soc. Chim. Belg., 104, 311 (1995)

[5] Schlatter JC, Oyama ST, Metchlfe JE, Lambert JM, Ind. Eng. Chem. Res., 27, 1648 (1988)

[6] Nagai M, Miyao T, Tsuboi T, Catal. Lett., 18, 9 (1993)

[7] Park HK, Lee JK, Yoo JK, Ko ES, Kim DS, Kim KL, Appl. Catal., to be published

[8] Massoth FE, Kibby CL, J. Catal., 47, 300 (1977)

[9] Delmon B, Bull. Soc. Chim. Belg., 104, 173 (1995)

[10] Corrigan TE, Chem. Eng., 199 (1955)

[11] Mears DE, Ind. Eng. Chem. Process Des. Dev., 10(4), 541 (1971)

[12] Lee JS, Boudart M, Appl. Catal., 19, 207 (1985)

[13] Abe H, Cheung TK, Bell AT, Catal. Lett., 21, 11 (1993)

[14] Choi JG, Brenner JR, Thompson LT, J. Catal., 154(1), 33 (1995)

[15] Leclercq G, Kamal M, Lamonier JF, Feigenbaum L, Malfoy P, Leclercq L, Appl. Catal. A: Gen., 121(2), 169 (1995)

[16] Volpe L, Boudart M, J. Solid State Chem., 59, 348 (1985)

[17] Slade RCT, Halstead TK, Dickens PG, Jarman RH, Solid State Commun., 45(5), 459 (1983)

[18] Jaggers CH, Micheals JN, Stacy AM, Chem. Mater., 2, 150 (1990)

[19] Demczyk BG, Choi JG, Thompson LT, Appl. Surf. Sci., 78, 63 (1994)

[20] Walendziewski J, Trawczynski J, Appl. Catal., 96, 163 (1993)

[21] Magai M, Omi S, J. Jpn. Petro. Inst., 38(6), 363 (1995)

[22] Hall WK, J. Catal., 85, 277 (1984)

[23] Topsoe NY, Topsoe H, J. Catal., 139, 631 (1993)

[24] Levy RB, "Properties of Carbides, Nitrides, and Borides: Implications for Catalysis," in Advanced Materials in Catalysis, Academic, New York (1977)

[25] Smit TS, Johnson KH, Catal. Lett., 28(2-4), 361 (1994)

[26] Lee JK, Koh HL, Kim JH, Park HK, Kim KL, J. Korean Ind. Eng. Chem., completed