Cobalt molybdates

Alternative means for removal of carbonyl sulfide for gas streams iavolve hydrogenation. For example, the Beavon process for removal of sulfur compounds remaining ia Claus unit tail gases iavolves hydrolysis and hydrogenation over cobalt molybdate catalyst resulting ia the conversion of carbonyl sulfide, carbon disulfide, and other sulfur compounds to hydrogen sulfide (25). 

Hydrogen sulfide has been produced in commercial quantities by the direct combination of the elements. The reaction of hydrogen and sulfur vapor proceeds at ca 500°C in the presence of a catalyst, eg, bauxite, an aluminosihcate, or cobalt molybdate. This process yields hydrogen sulfide that is of good purity and is suitable for preparation of sodium sulfide and sodium hydrosulfide (see Sodium compounds). Most hydrogen sulfide used commercially is either a by-product or is obtained from sour natural gas. 

When the Claus reaction is carried out in aqueous solution, the chemistry is complex and involves polythionic acid intermediates (105,211). A modification of the Claus process (by Shell) uses hydrogen or a mixture of hydrogen and carbon monoxide to reduce sulfur dioxide, carbonyl sulfide, carbon disulfide, and sulfur mixtures that occur in Claus process off-gases to hydrogen sulfide over a cobalt molybdate catalyst at ca 300°C (230). 

Reduction of sulfur dioxide by methane is the basis of an Allied process for converting by-product sulfur dioxide to sulfur (232). The reaction is carried out in the gas phase over a catalyst. Reduction of sulfur dioxide to sulfur by carbon in the form of coal has been developed as the Resox process (233). The reduction, which is conducted at 550—800°C, appears to be promoted by the simultaneous reaction of the coal with steam. The reduction of sulfur dioxide by carbon monoxide tends to give carbonyl sulfide [463-58-1] rather than sulfur over cobalt molybdate, but special catalysts, eg, lanthanum titanate, have the abiUty to direct the reaction toward producing sulfur (234). 

Carbon monoxide has been found to poison cobalt molybdate catalysts. It causes not only instantaneous deactivation but a cumulative deactivation as well. It should be removed from treat gas entirely or at least reduced to a very low value. Carbon dioxide also must be removed since it is converted to CO in the reducing atmosphere employed in Hydrofining. Liquid water can damage the structural integrity of the catalyst. Water, in the form of steam does not necessarily hurt the catalyst. In fact 30 psig steam/air mixtures are used to regenerate the catalyst. Also, steam appears to enhance the catalyst activity in... 

Effect of Catalyst The catalysts used in hydrotreating are molybdena on alumina, cobalt molybdate on alumina, nickel molybdate on alumina or nickel tungstate. Which catalyst is used depends on the particular application. Cobalt molybdate catalyst is generally used when sulfur removal is the primary interest. The nickel catalysts find application in the treating of cracked stocks for olefin or aromatic saturation. One preferred application for molybdena catalyst is sweetening, (removal of mercaptans). The molybdena on alumina catalyst is also preferred for reducing the carbon residue of heating oils. 

In treating cracked stocks such as steam cracked naphtha or visbreaker naphtha, which are highly olefinic in nature, nickel molybdate or nickel tungstate catalysts are generally employed. These catalysts have much higher activity for olefin samration reactions than does cobalt molybdate. 

Lapidus (LI) described liquid residence-time distribution studies for air-water and air-hydrocarbon in cocurrent, downward flow through a column of 2-in. diameter and 3-ft height. Spherical glass beads of 3.5. mm diameter and cobalt molybdate catalyst cylinders of -in. diameter were used as packing materials. 

Johnston, K. P., Hydrogenation-Dehydrogenation of Pyrenes Catalyzed by Sulphided Cobalt-Molybdate at Coal Liquefaction Conditions. Fuel, 1984. 63 pp. 463 168. 

The process temperature is approximately 600°C the catalyst is based on cobalt/molybde-num. Developed by the Union Oil Company of California. 

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 ... 

Kinetic studies ( ) of such systems Indicate that the Initial stages of liquefaction Involve conversion of the coal Into a more or less completely pyrldlne-soluble solid and thereafter Into a benzene-soluble material which Is gradually transformed Into a viscous liquid as increasing amounts of hydrogen combine with It. This process can be catalyzed by, e.g., cobalt molybdate, but proceeds rapidly even in the absence of catalysts. At 775 F (A00°C), total py-solubi1ity (and vSO per cent solubility In benzene) can be attained within less than 10 minutes. 

These cracking and H-addition processes also require catalysts, and a major engineering achievement of the 1970s was the development of hydroprocessing catalysts, in particular cobalt molybdate on alumina catalysts. The active catalysts are metal sulfides, which are resistant to sulfur poisoning. One of the major tasks was the design of porous pellet catalysts with wide pore structures that are not rapidly poisoned by heavy metals. 

Heating hydrogen and sulfur vapor at 500°C in the presence of a catalyst, such as, bauxite or cobalt molybdate, which produces a high purity H2S ... 

Reduction with carbon monoxide at high temperatures can form either carbonyl sulfide or sulfur depending on the catalyst used. With cobalt molybdate, COS is the primary product. On the other hand, lanthanum titanate catalyzes the reaction to form sulfur. 

In a recent work we were able to show that an electronic effect was detected between Bi2Mo30i2 and a mixed iron and cobalt molybdate with an enhancement of the electrical conductivity of the cobalt molybdate with the substitution of the cobaltous ions by the ferrous ions (7). However this effect alone cannot explain the synergy effect and we have investigated the influence of both the de ee of subtitution of the cobalt with the iron cations in the cobalt molybdate and the ratio of the two phases (for a given substituted cobalt molybdate) on the catalytic propert cs of the mixture.We have tried to characterize by XPS and EDX-STEM the catalysts before and after the catalytic reaction in order to detect a possible transformation of the solid. The results obtained are presented and discussed in this study. 

Since a polymorphic transition (a/p) of the mixed iron and cobalt molybdate occurs in the temperature range of the catalytic reaction (10,13,14), and since the high temperature form (p) can metastably be maintained at low temperature,... 

The analysis by X-ray diffraction after catalysis showed only the presence of the a or p phase of the mixed iron and cobalt molybdates depending upon heat treatment, 380 or 430 C respectively. No phase suspected to be present in the conditions of the catalysis reaction have been detected. This was confirmed by IR spectroscopy and EPR which did not detected any new ferric species (9). 

XPS has been used to characterize the three mixtures containing respectively 7,25, and 50 weight % of Bi2Mo30i2 (Table II samples J,K and L). These samples have been characterized before and after catalytic reaction (table III). Bi, Mo, Fe, Co and O have been analyzed. The Mo/0 ratio remains equal to 0.25 for all the samples, before and after catalysis which confirms that no new phase was formed since the molybdates suspected to have formed, have a much lower Mo/0 ratio (0.17 for Bi2Mo06 and Bi3FeMo20i2). Concerning the Bi/(Fe+Co) ratio, it can first be observed that before catalysis this ratio was always lower than that calculated from chemical analysis. This can be explained by the difference between the particles size of the bismuth molybdate and the iron and cobalt molybdates which is in a ratio of more than 30 as calculated from differences in surface area values, 0.3 and 9 to 22 m. g Secondly the Bi/(Fe+Co) ratio increased systematically after catalysis which could be explained by the decrease in size of the bismuth molybdate particles or by the covering of the iron and cobalt molybdate particles by the bismuth molybdate or by both effects. 

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