Hydrodesulfurization catalyst

Interestingly, the Mo2S " 4 (Fig- 3f) core stmcture can be viewed as occupying six of the eight vertices of a distorted cube. Reaction of the dinuclear complexes having the Mo2S " 4 core with appropriate metal ions leads to the plaimed assembly of M2M02S4 thiocubane stmctures (19,20). When M = Co (Fig. 3h) the compounds are potential precursors for hydrodesulfurization catalysts (15). 

Figure 4.23. Infrared spectra of NO probe molecules on sulfided Mo, Co, and Co-Mo hydrodesulfurization catalysts. The peak assignments are supported by the IR spectra of organometallic model compounds. These spectra allow for a quantitative titration of Co and Mo sites in the Co-Mo catalyst.

Explain why hydrodesulfurization catalysts are used in the sulfidic form. Would it be possible to use metal catalysts for this process ... 

Delmon, B. "Recent Approaches To The Anatomy and Physiology of Cobalt Molybdenum Hydrodesulfurization Catalysts" in preprints of Third International Conference on the Chemistry and Uses of Molybdenum, Univ. of Michigan, Ann Arbor, 1979 (Climax Molybdenum Company). 

Coulier, L. Kishan, G. van Veen, J. A. R., and Niemantsverdriet, J. W., Surface science models for CoMo hydrodesulfurization catalysts Influence of the support on hydrodesulfurization activity. Journal of Vacuum Science Technology A Vacuum, Surfaces, and Films, 2001. 19(4) pp. 1510-1515. 

Perez De la Rosa, M., Trader, S. Berhault, G., et al., Structural studies of catalytically stabilized model and industrial-supported hydrodesulfurization catalysts. J. Catal., 2004. 225 pp. 288-299. 

Zhang, P. W. Inoue, K. Tsuyama, H. Recovery of metal values from spent hydrodesulfurization catalysts by liquid-liquid extraction. Energy Fuels 1995, 9, 231-239. 

Autofining A fixed-bed catalytic process for removing sulfur compounds from petroleum distillates. This process uses a conventional cobalt/molybdenum hydrodesulfurization catalyst but does not require additional hydrogen. Developed by The Anglo-Iranian Oil Company in 1948. 

If reaction (2-13) follows reaction (2-12) instantaneously, the effect will not be noticeable in the H2 signal [12]. In spite of these limitations, we conclude that TPS with mass spectrometric detection is a highly useful technique for studying the sulfidation of hydrotreating catalysts. We shall return to the sulfidation of molybdenum oxides in the chapters on photoemission (Chapter 3), ion spectroscopy (Chapter 4), and in a case study on hydrodesulfurization catalysts in Chapter 9. 

We illustrate the use of RBS with a study on the sulfidation of molybdenum hydrodesulfurization catalysts supported on a thin layer of Si02 on silicon [21], As explained in connection with the SIMS experiments on this model system (Fig. 4.8), the catalyst is sulfided by treating the oxidic Mo03/Si02 precursor in a mixture of H2S and H2. RBS is used to determine the concentrations of Mo and S. 

LEIS has been applied to study the surface composition of Co-Mo and Ni-Mo hydrodesulfurization catalysts [46-48], Fe-based Fischer-Tropsch [49] and ammonia synthesis catalysts [50], and model systems such as Pt evaporated on Ti02 [51]. The review of Horrell and Cocke [52] describes several applications. 

Measurements of supported catalysts in diffuse reflection and transmission mode are in practice limited to frequencies above those where the support absorbs (below about 1250 cm-1). Infrared Emission Spectroscopy (IRES) offers an alternative in this case. When a material is heated to about 100 °C or higher, it emits a spectrum of infrared radiation in which all the characteristic vibrations appear as clearly recognizable peaks. Although measuring in this mode offers the attractive advantage that low frequencies such as those of metal-oxygen or sulfur-sulfur bonds are easily accessible, the technique has hardly been explored for the purpose of catalyst characterization. An in situ cell for IRES measurements and some experiments on Mo-O-S clusters of interest for hydrodesulfurization catalysts have been described by Weber etal. [11],... 

The use of infrared spectroscopy of adsorbed molecules to probe oxide surfaces has been reviewed by Davydov and Rochester [23], This approach works on sulfide catalysts as well. The infrared signal of NO has been successfully used to identify sites on the surface of a hydrodesulfurization catalyst, as the following example shows [24]. 

Supported Rhodium Catalysts Alkali Promoters on Metal Surfaces Cobalt-Molybdenum Sulfide Hydrodesulfurization Catalysts Chromium Oxide Polymerization Catalysts... 

What is the structure of this Co-Mo-S phase A model system, prepared by impregnating a MoS2 crystal with a dilute solution of cobalt ions, such that the model contains ppms of cobalt only, appears to have the same Mossbauer spectrum as the Co-Mo-S phase. It has the same isomer shift (characteristic of the oxidation state), recoilfree fraction (characteristic of lattice vibrations) and almost the same quadrupole splitting (characteristic of symmetry) at all temperatures between 4 and 600 K [71]. Thus, the cobalt species in the ppm Co/MoS2 system provides a convenient model for the active site in a Co-Mo hydrodesulfurization catalyst. 

Irrespective of the exact configuration around the promoter atom, we have a detailed picture of the Co-Mo-S phase on the atomic scale. Figure 9.23 summarizes schematically what a working Co-Mo/A1203 hydrodesulfurization catalyst looks like. It contains MoS2 particles with dimensions of a few nanometers, decorated with cobalt to form the catalytically highly active Co-Mo-S phase. It also contains cobalt ions firmly bound to the lattice of the alumina support, and it may contain crystallites of the stable bulk sulfide Co9S8, which has a low activity for the HDS reaction [49]. 

Microphonic Fourier transform infrared photoacoustic spectroscopy (FT-IR/PAS) has emerged as a useful tool for characterizing fractions of a monolayer of organic species adsorbed on opaque, high surface area samples. Such a study of calcined and sulfided hydrodesulfurization catalysts will be discussed. 

Electron-transfer and intramolecular redox reactions (related to 82 complexes). The redox behavior of 82 complexes is of particular interest because it can probably provide a foundation for understanding the course of reactions involved in relevant enzymes and catalysts (especially hydrodesulfurization catalysts). Intramolecular redox reactions related to type la 82 ligands can be summarized as follows ... 

Data from tests at 250,275,300, and 325 C were used to calculate pseudo-first order rate constants for the formation of H2S. These data are expressed on a standard Arriienius plot (Fig. 2) for which the linear least squares coefficient of determination, r, is 0.98. The apparent activation energy calculated from the slope is 28.5 kcal/mol. This result is in excellent agreement with the recent work of Abotsi, who studied the performance of carbon-supported hydrodesulfurization catalysts (10). Using Ambersorb XE-348 carbon lo ed with sulfided ammonium molybdate (3% Mo loading) prepared by the same procedure reported here, Abotsi hydrotreated a coal-derived recycle solvent The apparent activation energy for... 

Mo(CO)6 and Co(CO)3NO NaY zeolite Adsorption from vapor phase and H2S treatment Intrazeolite Co2Mo2S i clusters, model hydrodesulfuration catalyst [25]... 

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