SciELO - Scientific Electronic Library Online

 
vol.13 número3Efecto del hidroperóxido de cumeno sobre la desulfuración oxidativaEstudio del efecto de sitios inertes en la reacción CO+O2 en Pt(100) por simulaciones de Monte Carlo dinámico índice de autoresíndice de assuntospesquisa de artigos
Home Pagelista alfabética de periódicos  

Serviços Personalizados

Journal

Artigo

Indicadores

Links relacionados

  • Não possue artigos similaresSimilares em SciELO

Compartilhar


Revista mexicana de ingeniería química

versão impressa ISSN 1665-2738

Rev. Mex. Ing. Quím vol.13 no.3 Ciudad de México Dez. 2014

 

Catálisis, cinética y reactores

 

Caracterización de catalizadores sulfurados W/USY y su actividad en la hidrodesulfuración de gasóleo

 

Characterization of sulfided W/USY catalysis and their activity in hydrodesulfurization of gas oil

 

A. Gutiérrez-Alejandre1*, J. Ramírez1, R. Cid2, A. López-Agudo3, I. Puente Lee

 

1 UNICAT, Departamento de Ingeniería Química, Facultad de Química, Universidad Nacional Autónoma de México, Cd. Universitaria, CP. 04510, México City, D.F. México. * Autor para la correspondencia. E-mail: aidag@unam.mx.

2 Facultad de Ciencias Químicas, Universidad de Concepción, Concepción, Chile.

3 Instituto de Catálisis y Petroleoquímica, CSIC, (Campus Universidad Autónoma, Cantoblanco, 28049 Madrid, España.

 

Recibido 27 de mayo de 2014.
Aceptado 23 de septiembre de 2014.

 

Resumen

Se prepararon dos catalizadores de WS2 soportados en zeolita Y ultra estable mediante impregnación con soluciones acuosas de metatungstato de amonio a pH ácido (2.7) y básico (11). Estos catalizadores se caracterizaron por HRTEM, SEM-EDX y adsorción de NO (FT-IR) para determinar si la localización y dispersión de las especies de sulfuro de W cambia después del proceso de activación y qué consecuencias tiene este cambio en la actividad catalítica para hidrodesulfuración (HDS) de gasóleo. El catalizador W-2.7 mostró una mayor concentración y distribución homogénea de las estructuras laminares de WS2 en la superficie externa de la zeolita, así como una menor dispersión de WS2 dentro de sus cavidades, con respecto a W-11. El catalizador W-2.7 mostró una mayor actividad en la hidrodesulfuración de gasóleo. Los resultados de caracterización indican que debido al tamaño de las moléculas de azufre presentes en el gasóleo, su hidrodesulfuración ocurre predominantemente en la superficie externa de la zeolita, donde este catalizador mostró mayor dispersión de las especies de WS2.

Palabras clave: hidrodesulfuración, gasóleo, USY, zeolita, tungsteno.

 

Abstract

Two catalysts of tungsten sulfide supported on an ultra-stable Y zeolite were prepared by impregnation with aqueous solutions of ammonium metatungstate at acidic (2.7) and basic (11) pH values. The catalysts were characterized by HRTEM, SEM-EDX and FT-IR of adsorbed NO to determine if the location and dispersion of the WS2 particles is changed after the activation of the catalyst, and what consequences this has on the catalyst activity during the HDS of gasoil. W-2.7 catalyst showed a higher concentration and homogeneous distribution of the WS2 structures on the external surface of the zeolite support, and a decreased amount within the zeolite cavities with respect to W-11. The catalyst prepared at pH=2.7 exhibited higher activity in the HDS of gasoil. The characterization results indicate that because of the size of the sulfur molecules present in the gasoil, their hydrodesulfurization occurs mainly on the external surface of the zeolite, where this catalyst displays a superior dispersion of the WS2 species.

Keywords: hydrodesulfurization, gasoil, USY, zeolite, tungsten.

 

DESCARGAR ARTÍCULO EN FORMATO PDF

 

Agradecimientos

Al apoyo financiero de DGICYT, Ministerio de Ciencia y Tecnología, España, proyecto BQU2001-2126, y al Programa de Cooperación Bilateral CSIC (España)/CONACYT (México). A Toural Quiroga por su ayuda en las mediciones de actividad catalítica.

 

Referencias

Alsobaai, A.M., Zakaria, R., Hameed, B.H., (2007). Gas oil hydrocracking on NiW/USY catalyst: Effect of tungsten and nickel loading. Chemical Engineering Journal 132, 77-83.         [ Links ]

Anderson, J.A., Pawelec, B., García Fierro, J.L. (1993). Mo-USY zeolites for hydrodesulphurization. II. Surface properties of sulphided catalysts and activity for thiophene hydrodesulphurization. Applied Catalysis A: General 99, 55-70.         [ Links ]

Atanasova, P., Vladov, Ch., Halachev, T., J. Fierro, L.G, Lopez Agudo, A., (1995). Influence on the phosphorus concentration and the method of preparation on the hydrodesulfurization activity of P-Ni-W/alumina catalysts. Bulletin des Societes Chimiques Belges 104, 219-223.         [ Links ]

Braterman, P. S. (1975) Metal Carbonyl Spectra, Academic Press, London.         [ Links ]

Baes, C.F., Mesmer, R.E. (1986) The Hydrolysis of Cations. John Wiley and Sons, Inc. USA.         [ Links ]

Bendezú, S., Cid, R., Fierro, J.L.G., Loípez Agudo, A., (2000). Thiophene hydrodesulfurization on sulfided Ni, W and NiW/USY zeolite catalysts: effect of the preparation method. Applied Catalysis. A: General 197, 47-60.         [ Links ]

Benitez, A., Ramírez, J., Vázquez, A., Acosta, D., López Agudo, A., (1995). Influence of alumina fluoridation on the dispersion and hydrotreating activity of W/Al2O3 catalysis. Applied Catalysis. A: General 133, 103.119.         [ Links ]

Benitez, A., Ramírez, J., Cruz-Reyes, J., López Agudo, A., (1997). Effect of Alumina Fluoridation on Hydroconversion of n-Heptane on Sulfided NiW/Al2O3 Catalysts. Journal of Catalysis 172, 137-145.         [ Links ]

Cid, R., Neira, J., Godoy, J., Palacios, Mendioroz, J.M., S., Loípez Agudo, A., (1993). Characterization of Tungsten-Modified Ultrastable Y Zeolite Catalysts and Their Activity in Thiophene Hydrodesulfurization. Journal of Catalysis 141, 206-218.         [ Links ]

Cid, R., Atanasova, P., Loípez Cordero, R., Palacios, J.M., Lopez Agudo, A., (1999). Gas Oil Hydrodesulfurization and Pyridine Hydrodenitrogenation over NaY-Supported Nickel Sulfide Catalysts: Effect of Ni Loading and Preparation Method. Journal of Catalysis 182, 328-338.         [ Links ]

Corma, A., Martínez, A., Martínez, C., (1996). The role of extraframework aluminum species in USY catalysts during isobutane/2-butene alkylation. Applied Catalysis. A: General 134, 169-182.         [ Links ]

Cruz Reyes, J., Avalos-Borja, M., Loípez Cordero, R., Lopez Agudo, A., (1994). Influence of phosphorus on the structure and the hydrodesulphurization and hydrodenitrogenation activity of W/Al2O3 catalysts. Applied Catalysis A: General 120, 147-162.         [ Links ]

Dinga, L., Zhenga, Y., Zhangb, Z., Ringc, Z., Chenc, J. (2007). Hydrotreating of light cycle oil using WNi catalysts containing hydrothermally and chemically treated zeolite Y. Catalysis Today 125, 229-238.         [ Links ]

Dinga, L., Zhengb, Y., Yanga, H., Parviza, R ., (2009). LCO hydrotreating with Mo-Ni and W-Ni supported on nano- and micro-sized zeolite beta. Applied Catalysis A: General 353, 17-23.         [ Links ]

Fritz, P.O., Lunsford, J.H., (1989). The effect of sodium poisoning on dealuminated Y-type zeolites. Journal of Catalysis 118, 85-98.         [ Links ]

Hadjiivanov, K., Saussey, J., Frezsz, J.L., Lavalley, J.C., (1998). FT-IR study of NO + O2 co-adsorption on H-ZSM-5: re-assignment of the 2133 cm1 band to NO+ species. Catalysis Letters 52, 103-108.         [ Links ]

Isoda, T., Nagao, S., Xiaolinag, M., Y. Korai, Mochida, I., (1996) Hydrodesulfurization Pathway of 4,6-Dimethyldibenzothiophene through Isomerization over Y-Zeolite Containing CoMo/Al2O3 Catalyst. Energy Fuels 10, 1078-1082        [ Links ]

Isoda,T., Kusakabe, K., Morooka, S., Mochida, I., (1998). Reactivity and Selectivity for the Hydrocracking of Vacuum Gas Oil over Metal-Loaded and Dealuminated Y-Zeolites. Energy and Fuels 12, 493-502.         [ Links ]

Isoda, T., Takase,Y., Kusakabe, K. and Morooka, S. (2000) Changes in Desulfurization Reactivity of 4,6-Dimethyldibenzothiophene by Skeletal Isomerization Using a Ni-Supported Y-Type Zeolite. Energy Fuels 14, 585-590.         [ Links ]

Landau, M.V., Berger, D., Herkowitz, M., (1996). Hydrodesulfurization of Methyl-Substituted Dibenzothiophenes: Fundamental Study of Routes to Deep Desulfurization. Journal of Catalysis 159, 236-245.         [ Links ]

Lecrenay, E., Mochida, I., (1997)a. Catalytic hydrodesulfurization of petroleum middle distillate and model sulfur compounds over a series of catalysts activity and scheme. Studies in Surface Science and Catalysis 106, 333-342.         [ Links ]

Lecrenay, E., Sakanishi, K., Mochida, I, (1997)b. Catalytic hydrodesulfurization of gas oil and model sulfur compounds over commercial and laboratory-made CoMo and NiMo catalysts: Activity and reaction scheme. Catalysis Today 39, 13-20.         [ Links ]

Leglise, J., Manoli, J.M., Potvin, C., Djega-Mariadssou, G., Cornet, D.J., (1995). The Nature of NiMo Phases Encaged in Hy Zeolites. Journal of Catalysis 152, 275-290.         [ Links ]

Mariscal, R., Navarro, R.M., Pawelec, B., Fierro, J.L.G., (2000). Factors affecting Ni-sulfide formation in Y-type zeolites: a combined Fourier transform infrared and X-ray photoelectron spectroscopy study. Microporous and Mesoporous Materials 34, 181-194.         [ Links ]

Michaud, P., Lemberton, J.L., Perot, G., (1998). Hydrodesulfurization of dibenzothiophene and 4,6-dimethyldibenzothiophene: Effect of an acid component on the activity of a sulfided NiMo on alumina catalyst. Applied. Catalysis. A: General 169, 343-353.         [ Links ]

Nakano, K., Syed, A. A., Kim, H., Kim, T. Alhooshani, K. Park, J., Mochida, I., (2013) Deep desulfurization of gas oil over NiMoS catalysts supported on alumina coated USY-zeolite. Fuel Processing Technology 116,44-51.         [ Links ]

Okamoto, Y., (1997). Preparation and characterization of zeolite-supported molybdenum and cobalt-molybdenum sulfide catalysts. Catalysis Today 39, 45-59.         [ Links ]

Portela, L., Grange, P., Delmon, B., (1995). The Adsorption of Nitric Oxide on Supported CoMo Hydrodesulfurization Catalysts: A Review. Catalysis Reviews-Science and Engineering 37, 699-731.         [ Links ]

Reinhoudt, H.R., Crezee, E., van Langeveld, A.D., Kooyman, P.J., van Veen, J.A.R., Moulijn, J.A., (2000). Characterization of the Active Phase in NiW/y-Al2O3 Catalysts in Various Stages of Sulfidation with FTIR (NO) and XPS. Journal of Catalysis 196, 315-329.         [ Links ]

Topsoe, H. Clausen, B.S., Massoth, F.E. (1996). Hydrotreating Catalysis, Editorial Springer-Verlag, Nueva York.         [ Links ]

Welters, W.J.J., Vorbeck, G., Zandbergen, H.W., van de Ven, L.J.M., van Oers, E.M., J.W. de Haan, V.H.J. de Beer, R.A. van Santen, (1996). NaY-Supported Molybdenum Sulfide Catalysts: I. Catalysts Prepared via Impregnation with Ammonium Heptamolybdate. Journal of Catalysis 16, 819-828.         [ Links ]

Zaikovskii, V.I., Shepelin, A.P., Burmistrov, V.A., Startsev, A.N., Yermakov Yu.I., (1984), TEM and XPS studies of Ni/WS2 catalysts for thiophene hydrogenolysis. Reaction Kinetics and Catalysis Letters 25, 17-22.         [ Links ]

Zanella, R., Maturano, J. Cuevas, R., Ramírez, J., Cedeño, L.. (2002) Caracterizacion de Catalizadores Mo, NiMo y Como en su estado sulfurado. Revista Mexicana de Ingeniería Química 1, 13-21.         [ Links ]

Zhang, W., Burckle, E.C., Smirniotis, P.G., (1999). Characterization of the acidity of ultrastable Y, mordenite, and ZSM-12 via NH3-stepwise temperature programmed desorption and Fourier transform infrared spectroscopy. Microporous and Mesoporous Materials 33,173-185.         [ Links ]

Creative Commons License Todo o conteúdo deste periódico, exceto onde está identificado, está licenciado sob uma Licença Creative Commons