Cobalt-based hydrogenation catalysts

Practically, natural gas following partial oxidation gives essentially the desired H2 CO ratio of 2 1 and water-gas shift inactive cobalt-based FT catalysts can be used to produce these hquid fuels. However, in the case of coal, water-gas shift is effected in situ using an iron-based catalyst Alternatively, the hydrogen fraction in the syngas feed can be maximized by subsequently applying the exothermic water-gas shift reaction (7.9) ... 

Jacobsen GM, Yang JY, Twamley B, Wilson AD, Bullock RM, DuBois MR, DuBois DL (2008) Hydrogen production using cobalt-based molecular catalysts containing a proton relay in the second coordination sphere. Energy Environ Sci 1(1) 167-174. doi 10.1039/B805309J... 

An example of such recychng in a parallel reaction system is in the Oxo process for the production of C4 alcohols. Propylene and synthesis gas (a mixture of carbon monoxide and hydrogen) are first reacted to ra- and isobutyraldehydes using a cobalt-based catalyst. Two parallel reactions occur ... 

Hydrogenation Catalysts. The key to catalytic hydrogenation is the catalyst, which promotes a reaction which otherwise would occur too slowly to be useful. Catalysts for the hydrogenation of nitro compounds and nitriles are generally based on one or more of the group VIII metals. The metals most commonly used are cobalt, nickel, palladium, platinum, rhodium, and mthenium, but others, including copper (16), iron (17), and tellurium... 

Currently the reaction is carried out using cobalt based catalysts with severe penalties in terms of harsh operating conditions (80 bar CO/H2, 200°C). In addition, substantial loss of substrate (ca. 10%) to hydrogenation makes the overall selectivity to the linear alcohol ca. 80% [15]. Rhodium based systems are capable of giving higher selectivities (>90%) to the desired linear aldeyde product under milder conditions (20 bar, 100°C) [13]... 

E. van Steen and H. Schulz, Polymerisation kinetics of the Fischer-Tropsch CO hydrogenation using iron and cobalt based catalysts, Appl. Catal. A, 1999, 186, 309-320. 

F-T Catalysts The patent literature is replete with recipes for the production of F-T catalysts, with most formulations being based on iron, cobalt, or ruthenium, typically with the addition of some pro-moter(s). Nickel is sometimes listed as a F-T catalyst, but nickel has too much hydrogenation activity and produces mainly methane. In practice, because of the cost of ruthenium, commercial plants use either cobalt-based or iron-based catalysts. Cobalt is usually deposited on a refractory oxide support, such as alumina, silica, titania, or zirconia. Iron is typically not supported and may be prepared by precipitation. 

The hydroformylation of olefins discovered by Otto Roelen [ 151 ] is one of the most important industrial homogeneously catalyzed reactions [152,153] for the synthesis of aldehydes with an estimated production of more than 9.2 million t in 1998 [ 153]. Hydroformylation is the addition of hydrogen and carbon monoxide to a C,C double bond. Industrial processes are based on cobalt or rhodiiun catalysts according to Eq. 1. The desired products are linear (n-) and branched (i-) aldehydes, in which the hnear products are generally favored for subsequent processing. 

Recently another family of dendrimers has become commercially available. These polyamines were developed by Meijer and de Brabander-van den Berg of DSM Research and are based on Vogtle s initial synthesis [7]. In this case the troublesome reduction step was performed using a Raney cobalt hydrogenation catalyst and other process improvements have permitted this synthesis to be continued up to the fifth generation with multikilogram quantities available. 

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... 

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