Abstract
The removal of heteroatoms such as sulphur, nitrogen and metals from oil feedstock by transition metal sulphides has long been one of the major catalytic processes in petroleum industry. The primary driving force for this removal is the protection of catalysts in downstream operations. The growing environmental awareness in the early ‘70s went along with a large research effort in this field resulting in a fair understanding of the structure of these catalysts and the basis of their catalytic activity. Today, the diminishing oil supplies necessitate the processing of heavier feeds containing larger amounts of sulphur, nitrogen and metals. Moreover, legislation on transportation fuels becomes more stringent as can be seen in Table 1. The standard for the sulphur content of diesel fuels will be sharpened in the near future in anticipation of a working deNOx catalyst with a low sulphur tolerance. The total investment costs for the oil industry to produce more advanced fuels according to the EC proposition for the year 2000 will be over 8 billion ECUs over a period of 15 years.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
References
Chianelli, R.R. (1984) Fundamental studies of transition metal sulfide hydrodesulfurization catalysts, Catal. Rev.-Sci. Eng. 26, 361–393.
Prins, R., De Beer, V.H.J., and Somorjai, G.A. (1989) Structure and function of the catalyst and the promoter in Co-Mo hydrodesulfurization catalysts, Catal. Rev.-Sci. Eng. 31, 1–41.
Wiegand, B.C., and Friend, C.M. (1992) Model studies of the desulfurization reactions on metal surfaces and in organometallic complexes, Chem. Rev. 92, 491–504.
Topsoe, H., Clausen, B.S., and Massoth, F.E. (1996) Hydrotreating catalysis, Springer, Berlin.
Pecoraro, T.A., Chianelli, R.R. (1981) Hydrodesulfurization catalysis by transition metal sulfides, J. Catal. 67, 430–445.
Vissers, J.P.R., Groot, C.K., Van Oers, E.M., De Beer, V.H.J., and Prins, R. (1984) Carbon-supported transition metal sulfides, Bull. Soc. Chim. Belg. 93, 813–822.
Ledoux, M.J., Michaux, O., Agostini, G., and Panissod, P. (1986) The influence of sulfide structures on the hydrodesulfurization activity of carbon-supported catalysts, J. Catal. 102, 275–288.
Chianelli, R.R., Pecoraro, T.A., Halbert, T.R., Pan, V.H., and Stiefel, E.I. (1984) Transition metal sulfide catalysts–Relation of the synergic systems to the periodic trends in hydrodesulfurization reactions, J. Catal. 86, 226–230.
Lacroix, M., Boutarfa, N., Guillard, C., Vrinat, M., and Breysse, M. (1989) Hydrogenating properties of unsupported transition metal sulphides, J. Catal. 120, 473–493.
Eijsbouts, S., De Beer, V.H.J., and Prins, R. (1988) Periodic trends in the hydrodenitrogenation of carbon-supported transition metal sulfide catalysts, J. Catal. 109, 217–220.
Eijsbouts, S., De Beer, V.H.J., and Prins, R. (1991) Hydrodenitrogenation of quinoline over carbon-supported transition metal sulfides, J. Catal. 127, 619–630.
Sudhakar, C., Eijsbouts, S., De Beer, V.H.J., and Prins, R. (1987) Hydrodenitrogenation of decahydroquinoline over carbon-supported transition metal sulfide catalysts, Bull. Soc. Chim. Belg. 96, 885–890.
Eijsbouts, S., Sudhakar, C., De Beer, V.H.J., and Prins, R. (1991) Hydrodenitrogenation of decahydroquinoline, cyclohexylamine and O-propylaniline over carbon-supported transition metal sulfides, J. Catal. 127, 605–618.
Sabatier, P. (1911) Hydrogénations et des hydrogénations par catalyse, Ber. Deutsch. Chem. Ges. 44, 1984–2001.
Harris, S. (1982) Study of the electronic structures of 1$` row and 2nd row transition metal sulfides using SCF-SW-Xa cluster calculations, Chem. Phys. 67, 229–237.
Harris, S., and Chianelli, R.R. (1983) Periodic effects in catalysis: the relation between trends in catalytic activity and calculated electronic structure of transition metal sulfides, Chem. Phys. Lett. 101, 603–605.
Harris, S., and Chianelli, R.R. (1984) Catalysis by transition metal sulfides: the relation between calculated electronic trends and HDS activity, J. Catal. 86, 400–412.
Harris, S., and Chianelli, R.R. (1986) Catalysis by transition metal sulfides: a theoretical and experimental study of the relation between the synergic systems and the binary transition metal sulfides, J. Catal. 98, 17–31.
Smit, T.S., and Johnson, K.H. (1993) Hydrodesulphurization of thiophene by transition metal sulphides. A molecular orbital topology study, Chem. Phys. Lett. 212, 525–533.
Smit, T.S., and Johnson, K.H. (1994) The importance of sulphur-sulphur bonding in the hydrodesulphurization process of thiophene, using transition metal sulphide catalysts, J Mol. Catal. 91, 207–222.
Smit, T.S., and Johnson, K.H. (1994) A unified theory of periodic and promotion effects in transition metal sulphide hydrodesulphurization catalysts, Catal. Lett. 28, 361–372.
Zdrazil, M., and Sedlacek, J. (1977) Quantum chemical model of adsorption of thiophenes during hydrodesulphurization, Coll. Chem. Comm. 42, 3133–3143.
Vladov, Ch., Neshev, M., Petrov, L., and Shopov, D. (1983) Quantum-chemical investigation of the active site of CoMo/Al2O3 hydrodesulphurisation catalyst, in Proc. Vth Intern. Symp. On Heterogeneous Catalysis, Part II; Varna, 479–484.
Joffre, J., Geneste, P., and Lerner, D.A. (1986) A quantum-chemical study of site modelling for the adsorption and desulfurization of thiophene, J. Catal. 97, 543–548.
Rong, C., and Qin, X. (1991) Quantum chemical study of MoS2 hydrodesulfurization catalysts, J. Mol. Catal. 64, 321–335.
Rong, C., Qin, X., and Jinglong, H. (1992) Quantum chemical study of hydrodesulfurization catalysts Part II. DV-Xa calculation on clusters of Co9S8 and RuS2, J. Mol. Catal. 75, 253–276.
Zonnevylle, M.C., Hoffmann, R., and Harris, S. (1988) Thiophene hydrodesulfurization on MoS2; theoretical aspects, Surf Sci. 199, 320–360.
Nerskov, J.K., Clausen, B.S., and Topsae, H. (1992) Understanding the trends in hydrodesulfurization activity of the transition metal sulfides, Catal. Lett. 13, 1–8.
Topsee, H., Clausen, B.S., Topsee, N-Y., Hyldtoft, J., and Nerskov, J.K. (1993) Experimental and theoretical studies of periodic trends and promotional behaviours in hydrotreating catalysts.“Symposium Preprints” 38, American Chemical Society, Div. Petr. Chem., 638–641.
Welters, W.J.J., Vorbeck, G., Zandbergen, H.W., De Haan, J.W., De Beer, V.H.J., and Van Santen, R.A. (1994) HDS activity and characterization of zeolite-supported nickel sulfide catalysts, J. Catal. 150, 155–169.
Neurock, M., and Van Santen, R.A. (1994) Theory of carbon-sulfur bond activation by small metal sulfide particles, J. Am. Chem. Soc. 116, 4427–4439.
Topsoe, H., Clausen, B.S., Candia, R., Wivel, C., and Merup, S. (1981) Mössbauer emission-spectroscopy studies of hydrodesulfurization catalysts–evidence for and nature of a Co-Mo-S phase, J. Catal. 68, 433–452.
Wivel, C., Candia, R., Clausen, B.S., Morup, S., and Tops, e, H. (1981) Catalytic significance of a Co-Mo-S phase in Co-Mo-Al2O3 hydrodesulfurization catalysts–combined in situ Mössbauer emission-spectroscopy and activity studies, J. Catal. 68, 453–463.
Crajé, M.W.J., De Beer, V.H.J., and Van der Kraan, A.M. (1991) So-called “Co-Mo-S” phase observed in carbon-supported cobalt sulfide catalysts by Mössbauer emission spectroscopy, Appl. Catal. 70, L7 - L10.
Crajé, M.W.J., De Beer, V.H.J., Van Veen, J.A.R., and Van der Kraan, A.M. (1996) On the identification of “Co-sulfide” species in sulfided supported Co and CoMo catalysts, in M.L. Ocelli and R.R. Chianelli (eds.), Hydrotreating Technology for Pollution Control, Marcel Dekker, New York, pp. 95–113.
Startsev, A.N. (1995) The mechanism of HDS catalysis, Catal. Rev.-Sci. Eng. 37, 353–423.
Vrinat, M.L. (1983) The kinetics of the hydrodesulfurization process–a review, Appl. Catal. 6, 137–158.
Schulz, H., Schon, M., and Rahman, N. (1986) Hydrogenative denitrogenation of model compounds as related to the refining of liquid fuels, Stud. Surf. Sci. Catal. 27, 201–276.
J.R. Jennings (ed.) (1991) Catalytic Ammonia Synthesis Fundamentals and Practice, Plenum, New York.
Van Santen, R.A., and Niemantsverdriet, J.W. (1995) Chemical Kinetics and Catalysis, Plenum, New York.
Kasztelan, S. (1992) Kinetic interpretation of periodic trends in heterogeneous catalysis, Appl. Catal. A 83, L1 - L6.
Hensen, E.J.M., Vissenberg, M.J., De Beer, V.H.J., Van Veen, J.A.R., and Van Santen, R.A. (1996) Kinetics and mechanism of thiophene hydrodesulfurization over carbon-supported transition metal sulfides, J. Catal. 163, 429–435.
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1998 Springer Science+Business Media Dordrecht
About this chapter
Cite this chapter
Hensen, E.J.M., De Beer, V.H.J., Van Santen, R.A. (1998). Chemistry and Reactivity of Transition Metal Sulphides in Relation to Their Catalytic Performance. In: Weber, T., Prins, R., van Santen, R.A. (eds) Transition Metal Sulphides. NATO ASI Series, vol 60. Springer, Dordrecht. https://doi.org/10.1007/978-94-017-3577-3_7
Download citation
DOI: https://doi.org/10.1007/978-94-017-3577-3_7
Publisher Name: Springer, Dordrecht
Print ISBN: 978-90-481-5100-4
Online ISBN: 978-94-017-3577-3
eBook Packages: Springer Book Archive