Cobalt molybdates, hydrodesulfurization catalysts

Chemical vapor deposition, nanowires, 179 Cluster structures change in grain size, 5 ion-bombardment technique, 7-8 Cobalt molybdates, hydrodesulfurization catalysts, 2-3... 

Trickle-bed reactors are used in catalytic hydrotreating (reaction with H2) of petroleum fractions to remove sulfur (hydrodesulfurization), nitrogen (hydrodenitrogena-tion), and metals (hydrodemetallization), as well as in catalytic hydrocracking of petroleum fractions, and other catalytic hydrogenation and oxidation processes. An example of the first is the reaction in which a sulfur compound is represented by diben-zothiophene (Ring and Missen, 1989), and a molybdate catalyst, based, for example, on cobalt molybdate, is used ... 

The so-called cobalt molybdate catalyst has been used much in the petroleum industry for hydrotreating and hydrodesulfurization. More recently, these catalysts have been employed in coal liquefaction and synthoil upgrading. The latter probably accounts for the recent rash of publications on this very interesting catalyst system. Indeed, of the papers surveyed for this review, the majority have been published in the past 5 years with no letup in sight. 

Molybdenum oxide - alumina systems have been studied in detail (4-8). Several authors have pointed out that a molybdate surface layer is formed, due to an interaction between molybdenum oxide and the alumina support (9-11). Richardson (12) studied the structural form of cobalt in several oxidic cobalt-molybdenum-alumina catalysts. The presence of an active cobalt-molybdate complex was concluded from magnetic susceptibility measurements. Moreover cobalt aluminate and cobalt oxide were found. Only the active cobalt molybdate complex would contribute to the activity and be characterized by octahedrally coordinated cobalt. Lipsch and Schuit (10) studied a commercial oxidic hydrodesulfurization catalyst, containing 12 wt% M0O3 and 4 wt% CoO. They concluded that a cobalt aluminate phase was present and could not find indications for an active cobalt molybdate complex. Recent magnetic susceptibility studies of the same type of catalyst (13) confirmed the conclusion of Lipsch and Schuit. 

Over the past 30 years, our laboratory has examined the synthesis of nanostructured materials for advanced catalysts. The first process for the synthesis of fine grains of cobalt molybdates for hydrodesulfurization catalysis... 

A detailed description of a chromia-on-alumina catalyst prepared by impregnation has been given elsewhere . Another supported nonmetallic catalyst widely used commercially is cobalt molybdate-on-alumina. The preparation of this catalyst using an alumina support with controlled pore-size distribution is as follows. Silica-stabilized alumina, with greater than 50% of its surface area in 3-8 nm pores and at least 3% of the total pore volume in pores greater than 200 nm in diameter, is impregnated with an aqueous solution of cobalt and molybdenum. The finished oxysulfide catalyst was tested for hydrodesulfurization of petroleum residuum at 370°C and 100 atm for 28 days and compared with a convential cobalt-molybdate catalyst having a major portion of the surface area in 3-7 nm pores. The latter catalyst and controlled pore catalyst maintained 57 and 80% activity, respectively. 

Kolboe, S. and C.H. Amberg. "Catalytic Hydrodesulfurization of Thiophene. VI. Comparisons over Molybdenum Disulfide Cobalt Molybdate, and Chromia Catalysts. Can, J. Chenu 44 (1966) 2623. 

Carbon-supported Co-Mo catalysts used in terpene hydrodesulfurization (SM = sodium molybdate, AHM = ammonium heptamolybdate, CN = cobalt nitrate). All the catalysts contain 7 wt.-% CoO and 4.4 wt.-% M0O1 corresponding to a Co-to-Co+Mo atomic ratio of 0.75. J... 

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