Metal supported cobalt catalysts from

Several groups have reported deactivation of silica-supported cobalt catalysts. Holmen and coworkers19 30 have reported increased deactivation due to added (external) water in the feed to silica-supported Co catalysts. Kogelbauer et al 1 reported the formation of silicates. Catalysts recovered from FTS as well as catalysts deactivated by steam-treatment both showed fractions of non-reducible cobalt in TPR. The presence of metallic cobalt was a prerequisite for the silicate formation. 

Cobalt-based catalysts are effective in the ethanol reformation to hydrogen. Many oxides have been used to prepare supported cobalt catalysts of low cobalt content (circa 1 wt%) by impregnation from a solution of Co2(CO)8 catalysts were used in the ethanol reformation as prepared [156]. The performance of the catalysts in the steam reforming of ethanol was related with the presence, under reaction conditions, of metallic (ferromagnetic) cobalt particles and oxidized cobalt species. An easy exchange between small metallic cobalt particles and oxidized cobalt species was found. Comparison of Co/ZnO catalysts prepared from Co2(CO)8 or from nitrate precursor indicated that the catalyst prepared from the carbonyl precursor was highly stable and more selective for the production of CO-free hydrogen... 

Supported Cobalt Catalysts. Experiments were conducted with [Co(PC)]/Si02 at 340°C to determine the important variables for the catalysis of a typical [M(PC)]. Table IV gives the results for runs which were conducted for varying periods of time. It is seen that even at 100 hr. the conversion only reached 36%. The equilibrium conversion at 342°C can be estimated to be 97%. (9) Thus, the reaction is quite far from equilibrium even at long times. This may be taken as evidence for product inhibition of the catalysis. This might be expected since tetrahydroquinoline is a stronger Lewis base than quinoline. Thus, the product could bind to the metal center and prevent activation of the substrate and/or hydrogen. One important conclusion is that the reaction is not over in 24 hours and it can be assumed that the difference in conversions noted in Table I with different [M(PC)] are due to differences in inherent activity of the [M(PC)]. 

Silica-supported cobalt catalysts are accessible by ALE, after chemisorption onto silica of Co(acac)3 from the gas phase with a metal loading between 5.7 and 19. 5 wt% . The catalysts were tested for gas-phase toluene hydrogenation in a microreactor system. 

Silica-supported cobalt catalysts were prepared from cobalt nitrate (Co(N03)2), lanthanum nitrate (La(N03)3) and commercially available silica gel (Fuji Davison, ID gel, 270 m /g) using conventional methods of impregnation [14]. The composition of the catalyst was Co La Si02 = 20 6 87 by weight. The catalyst precursor was dried in air at 120°C and then calcined at 450 °C for 3 h to form supported metal oxides. It was then exposed to hydrogen at 400 °C for 12 h. The mean pore diameter of the catalyst was 8.7 nm. 

Llorca, J. Ramirez de la Piscina, P Dalmon, J.A., Sales, J. and Homs, N, (2003) CO-free hydrogen from steamreforming of bioethanol over ZnO-supported cobalt catalyst. Effect of the metallic precursor. Appl. Catal. B, 43, 355-369. 

The oxidation of cobalt metal to inactive cobalt oxide by product water has long been postulated to be a major cause of deactivation of supported cobalt FTS catalysts.6 10 Recent work has shown that the oxidation of cobalt metal to the inactive cobalt oxide phase can be prevented by the correct tailoring of the ratio Ph2cJPh2 and the cobalt crystallite size.11 Using a combination of model systems, industrial catalyst, and thermodynamic calculations, it was concluded that Co crystallites > 6 nm will not undergo any oxidation during realistic FTS, i.e., Pi[,()/I)i,2 = 1-1.5.11-14 Deactivation may also result from the formation of inactive cobalt support compounds (e.g., aluminate). Cobalt aluminate formation, which likely proceeds via the reaction of CoO with the support, is thermodynamically favorable but kinetically restricted under typical FTS conditions.6... 

TOF-SIMS images (Figs. 13.5 and 13.6) illustrate the ability to detect changes in the dispersion (uniform or presence of metal clusters) of the active phase in supported-oxide catalysts. Figure 13.5 shows nearly uniform distribution of molybdenum. The surface contamination with NH4+ ions coming from a precursor, which were not removed during the catalyst preparation process, is also observed. Cobalt clusters in the range of several micrometers are clearly visible in Fig. 13.6. 

Scope of the Review Paper. - From the above reasoning it is clear that over the past decades a large number of studies have been reported on supported cobalt F-T catalysts. All these studies indicate that the number of available surface cobalt metal atoms determines the catalyst activity and attempts to enhance the catalytic activity have been focusing on two interconnected issues (1) to reduce the cobalt-support oxide interaction and (2) to enhance the number of accessible cobalt atoms available for F-T reaction. It has been shown that the number of catalytically active cobalt atoms as well as their selectivity can be largely enhanced by the addition of small amounts of various elements, called promoters, to the catalyst material. The exact role of these promoters - as is the case for many other heterogeneous catalysts as well -remains often, however, unclear. 

A simple but effective means of preparing supported metal ion catalysts is to employ ion exchange resins. For example, a cobalt-exchanged H-type resin (Dowex 50) was shown43 to be an effective solid catalyst for the autoxidation of acetaldehyde to acetic acid at 20°C. No leaching of cobalt ions from the resin was observed and the catalyst was used repeatedly (5x) without any significant loss of activity. More recently the use of weak acid resins exchanged with cobalt ions as catalysts for the autoxidation of cyclohexane... 

According to Eidus (90) carbides formed on cobalt or nickel catalysts are neither intermediate products nor catalysts promoting the formation of hydrocarbons from carbon monoxide and hydrogen. In the absence of hydrogen carbon monoxide poisoned the cobalt catalyst. Despite Eidus results, Braude and Bruns (42) supported Craxford s assumption that the carbide is formed by reaction of the metal (iron) with carbon monoxide and hydrogen. It was pointed out by Eidus (84a) that Braude and Bruns did not clearly distinguish between the carbide and free carbon... 

The metal catalysts mentioned above may be supported on polymers to facilitate the recovery of the catalyst from reaction mixtures. Rh and Pt can be complexed with a polymer phosphine such as [—COC6H4CONH(CH2)mN(PPh2)—] or Si02(=SiCH2CH2PPh2). Cobalt carbonyl adsorbed on silica gel or alumina is also reported. 

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