Effect of the Fluorine-Addition Order on the Hydrodesulfurization Activity of Fluorinated NiW/Al<sub>2</sub>O<sub>3</sub> Catalysts

Chan Kwak; Sang Heup Moon

Korean Journal of Chemical Engineering, Vol.16, No.5, 608-613, September, 1999

DOI10.1007/BF02708139 Export Citation

Effect of the Fluorine-Addition Order on the Hydrodesulfurization Activity of Fluorinated NiW/Al₂O₃ Catalysts

Chan Kwak, and Sang Heup Moon^†

School of Chemical Engineering and Institute of Chemical Processes, Seoul National University, Seoul, Korea

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Fluorinated NiW/Al₂O₃ catalysts with different orders of fluorine addition have been prepared, tested for hydrodesulfurization (HDS) of thiophene, and characterized using nitric oxide chemisorption and temperature-programmed sulfidation. The catalyst surface area has been affected by fluorine addition but not by the order of fluorination. The fluorine addition-order does not affect the amount of fluorine retained in the catalysts after the calcination and the reaction steps, either. On the other hand, the order of fluorine addition changes the dispersion of the nickel and the tungsten species, incorporation of nickel with the tungsten edge sites, and consequently the HDS activity of the catalysts. The catalyst fluorinated in the last step, i.e., after addition of both tungsten and nickel, shows the highest activity in thiophene HDS, which is supported by other experimental results indicating the most nitric oxide chemisorption and the largest incorporation of nickel with the tungsten species. Accordingly, enhancement of the catalyst activity by fluorination is due to the repartition of the metal species rather than to partial solubilization of alumina in the fluorine-addition step.

Keywords:Hydrodesulfurization;Fluoriantion;Nickel;Tungsten;Thiophene

[References]

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Fierro JLG, Cuevas R, Ramirez J, Agudo AL, Bull. Soc. Chim. Belg., 100, 945 (1991)
Jiratova K, Kraus M, Appl. Catal., 27, 21 (1986)
Kwak C, "Study on the Characteristics of the Fluorine Added Ni-W/Al₂O₃ Catalysts," M.S. Thesis, Seoul National University (1995)
Kwak C, Kim MY, Song CJ, Moon SH, Stud. Surf. Sci. Catal., 121, 283 (1999)
Le Page JF, "Applied Heterogeneous Catalysis," Technip, Paris (1987)
Lewis JM, Kydd RA, Boorman PM, J. Catal., 120, 413 (1989)
Matralis HK, Lycourghiotis A, Grange P, Delmon B, Appl. Catal., 38, 273 (1988)
Matralis H, Papadopoulou C, Lycourghiotis A, Appl. Catal. A: Gen., 116(1-2), 221 (1994)
Muralidhar G, Massoth FE, Shabtai J, J. Catal., 85, 44 (1984)
Okamoto Y, Katoh Y, Mori Y, Imanaka T, Teranishi S, J. Catal., 70, 445 (1981)
Papadopoulou Ch, Lycourghiotis A, Grange A, Delmon B, Appl. Catal., 38, 255 (1988)
Portela L, Grange P, Delmon B, Catal. Rev.-Sci. Eng., 37(4), 699 (1995)
Ramirez J, Cuevas R, Agudo AL, Mendioroz S, Fierro JLG, Appl. Catal., 57, 223 (1990)
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Sarbak Z, Appl. Catal. A: Gen., 164(1-2), 13 (1997)
Scheffer B, Mangnus PJ, Moulijn JA, J. Catal., 121, 18 (1990)
Scokart PO, Selim SA, Damon JP, Rouxhet PG, J. Colloid Interface Sci., 70, 209 (1979)
Spanos N, Vordonis L, Kordulis Ch, Lycourghiotis A, J. Catal., 124, 301 (1990)
Topsoe NY, Topsoe H, J. Catal., 84, 386 (1983)
Van Veen JAR, Wit H, Emeis CA, Hendricks PAJM, J. Catal., 107, 579 (1987)
Vordonis L, Spanos N, Koutsoukos PG, Lycourghiotis A, Langmuir, 8, 1736 (1992)
Weisser O, Landa S, "Sulphide Catalysts: Their Properties and Applications," Frider. Vieweg and Sohn, Braunschweig (1973)

[Referenced By]

[1] Benitez A, Ramirez J, Fierro JL, Agudo AL, Appl. Catal. A: Gen., 144(1-2), 343 (1996)

[2] Fierro JLG, Cuevas R, Ramirez J, Agudo AL, Bull. Soc. Chim. Belg., 100, 945 (1991)

[3] Jiratova K, Kraus M, Appl. Catal., 27, 21 (1986)

[4] Kwak C, "Study on the Characteristics of the Fluorine Added Ni-W/Al₂O₃ Catalysts," M.S. Thesis, Seoul National University (1995)

[5] Kwak C, Kim MY, Song CJ, Moon SH, Stud. Surf. Sci. Catal., 121, 283 (1999)

[6] Le Page JF, "Applied Heterogeneous Catalysis," Technip, Paris (1987)

[7] Lewis JM, Kydd RA, Boorman PM, J. Catal., 120, 413 (1989)

[8] Matralis HK, Lycourghiotis A, Grange P, Delmon B, Appl. Catal., 38, 273 (1988)

[9] Matralis H, Papadopoulou C, Lycourghiotis A, Appl. Catal. A: Gen., 116(1-2), 221 (1994)

[10] Muralidhar G, Massoth FE, Shabtai J, J. Catal., 85, 44 (1984)

[11] Okamoto Y, Katoh Y, Mori Y, Imanaka T, Teranishi S, J. Catal., 70, 445 (1981)

[12] Papadopoulou Ch, Lycourghiotis A, Grange A, Delmon B, Appl. Catal., 38, 255 (1988)

[13] Portela L, Grange P, Delmon B, Catal. Rev.-Sci. Eng., 37(4), 699 (1995)

[14] Ramirez J, Cuevas R, Agudo AL, Mendioroz S, Fierro JLG, Appl. Catal., 57, 223 (1990)

[15] Salvati L, Macovsky LE, Stencel JM, Brown FR, Hercules DM, J. Phys. Chem., 85, 3700 (1985)

[16] Sarbak Z, Appl. Catal. A: Gen., 164(1-2), 13 (1997)

[17] Scheffer B, Mangnus PJ, Moulijn JA, J. Catal., 121, 18 (1990)

[18] Scokart PO, Selim SA, Damon JP, Rouxhet PG, J. Colloid Interface Sci., 70, 209 (1979)

[19] Spanos N, Vordonis L, Kordulis Ch, Lycourghiotis A, J. Catal., 124, 301 (1990)

[20] Topsoe NY, Topsoe H, J. Catal., 84, 386 (1983)

[21] Van Veen JAR, Wit H, Emeis CA, Hendricks PAJM, J. Catal., 107, 579 (1987)

[22] Vordonis L, Spanos N, Koutsoukos PG, Lycourghiotis A, Langmuir, 8, 1736 (1992)

[23] Weisser O, Landa S, "Sulphide Catalysts: Their Properties and Applications," Frider. Vieweg and Sohn, Braunschweig (1973)