Cobalt catalyst carbon monoxide hydrogenation

TI Carbon monoxide hydrogenation over cobalt catalyst in a tube-wall reactor Part II Modeling studies KW Fischer Tropsch synthesis modeling, carbon monoxide hydrogenation cobalt catalyst, tube wall reactor Fischer Tropsch reaction IT Hydrogenation catalysts... 

TI Non-Flory product distributions in Fischer - Tropsch synthesis catalyzed by ruthenium, cobalt. and iron KW Fischer Tropsch synthesis hydrocarbon distribution. Flory kinetics carbon monoxide hydrogenation, chain growth carbon monoxide hydrogenation, ruthenium catalyst carbon monoxide hydrogenation, cobalt iron catalyst hydrocarbon distribution IT Hydrocarbons, preparation... 

In the reaction of aHyl alcohol with carbon monoxide using cobalt carbonyl, Co(CO)g as the catalyst, in the presence of a small amount of hydrogen and carbon monoxide under pressure, 9.8 MPa (1420 psi), at 100°C, intramolecular hydroesterification takes place, yielding y-butyrolactone [96-48-0] (16). 

Lee, D.-K., Lee, J.-H., and Ihm, S.-K. 1988. Effect of carbon deposits on carbon monoxide hydrogenation over alumina-supported cobalt catalysts. Appl. Catal. 36 199-207. 

Lahtinen, J., Anraku, T., and Somotjai, G. A. 1993. Carbon monoxide hydrogenation on cobalt foil and on thin cobalt film model catalysts. J. Catal. 142 206-25. 

Hydroformylation (0.xo process). Production of aldehydes by catalytic reaction of an olefm with carbon monoxide and hydrogen. Cobalt catalysts are often used. 

Addition of carbon monoxide and hydrogen to an alkene linkage in the presence of cobalt catalysts gives aldehydes in an average yield of 50%. The reactions may be carried out in the usual hydrogenation apparatus. The poisonous properties of carbon monoxide and cobalt carbonyls call for considerable care. Compounds made by hydroformylation include cyclopentanealdehyde from cyclopentene (65%), /3-carbethoxy-propionaldehyde from ethyl acrylate (74%), and ethyl /3-formylbutyrate from ethyl crotonate (71%). 

The selective production of methanol and of ethanol by carbon monoxide hydrogenation involving pyrolysed rhodium carbonyl clusters supported on basic or amphoteric oxides, respectively, has been discussed. The nature of the support clearly plays the major role in influencing the ratio of oxygenated products to hydrocarbon products, whereas the nuclearity and charge of the starting rhodium cluster compound are of minor importance. Ichikawa has now extended this work to a study of (CO 4- Hj) reactions in the presence of alkenes and to reactions over catalysts derived from platinum and iridium clusters. Rhodium, bimetallic Rh-Co, and cobalt carbonyl clusters supported on zinc oxide and other basic oxides are active catalysts for the hydro-formylation of ethene and propene at one atm and 90-180°C. Various rhodium carbonyl cluster precursors have been used catalytic activities at about 160vary in the order Rh4(CO)i2 > Rh6(CO)ig > [Rh7(CO)i6] >... 

The yields of liquid products in one throughput amounted to 20-25 cc,/m.3 carbon monoxide-hydrogen mixture with iron (Fe Cu = 4 1 + 0.2% K2C03) and cobalt (Co Cu = 9 1, no alkali) as catalysts. Thirty grams of oxides were used for the conversion of 4 liters of synthesis gas per hour. 

Synthesis of Liquid Hydrocarbons by the Reduction of Carbon Mon-dxide. When carbon monoxide-hydrogen mixtures are passed over cobalt, iron, nickel, and some copper catalysts that are promoted with certain metallic oxides, particularly oxides of the alkali mietals, at temperatures in the range frmn about 200-300°C and pressures from about 1-25 atm, various hydrocarbons are formed according to the following type of reactions ... 

Investigations into these topics are presented in this volume. Iron, nickel, copper, cobalt, and rhodium are among the metals studied as Fischer-Tropsch catalysts results are reported over several alloys as well as single-crystal and doped metals. Ruthenium zeolites and even meteo-ritic iron have been used to catalyze carbon monoxide hydrogenation, and these findings are also included. One chapter discusses the prediction of product distribution using a computer to simulate Fischer-Tropsch chain growth. 

The identification of catalytically active species in FTS is of fundamental importance, as an improved understanding could enable the development of catalysts with increased activity and selectivity. In cobalt- and ruthenium-catalysed FTS, metallic cobalt and ruthenium function as active catalysts. However, in iron-catalysed FTS there are several distinct species generated during the reaction. Due to the lower, or similar, activation energy for iron carbide formation in comparison to carbon monoxide hydrogenation, iron-carbide formation is typically observed in FTS. The formation of several iron-carbide phases have been observed -Fe2C/8 -Fe2.2C (hexagonal... 

In the Fischer-Tropsch process, partial combustion in oxygen-steam mixtures occurs in the presence of cobalt or nickel catalysts. A carbon monoxide-hydrogen mixture is primarily formed from the carbon and water. The carbon monoxide is then polymerized with simultaneous hydrogenation to higher hydrocarbons. The process was used up to the end of the Second World War in Germany, and is now only used in South Africa. 

Chen AA, Kaminsky M, Geoffrey GL, Vannice MA. Carbon monoxide hydrogenation over carbon-supported iron-cobalt and potassium-ironicobalt carbonyl cluster-derived catalysts. 

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 ... 

Cobalt has an odd number of electrons, and does not form a simple carbonyl in oxidation state 0. However, carbonyls of formulae Co2(CO)g, Co4(CO)i2 and CoJCO),6 are known reduction of these by an alkali metal dissolved in liquid ammonia (p. 126) gives the ion [Co(CO)4] ". Both Co2(CO)g and [Co(CO)4]" are important as catalysts for organic syntheses. In the so-called oxo reaction, where an alkene reacts with carbon monoxide and hydrogen, under pressure, to give an aldehyde, dicobalt octacarbonyl is used as catalyst ... 

Process Technology. In a typical oxo process, primary alcohols are produced from monoolefins in two steps. In the first stage, the olefin, hydrogen, and carbon monoxide [630-08-0] react in the presence of a cobalt or rhodium catalyst to form aldehydes, which are hydrogenated in the second step to the alcohols. 

The 0X0 and aldol reactions may be combined if the cobalt catalyst is modified by the addition of organic—soluble compounds of 2inc or other metals. Thus, propylene, hydrogen, and carbon monoxide give a mixture of aldehydes and 2-ethylhexenaldehyde [123-05-7] which, on hydrogenation, yield the corresponding alcohols. 

The mixture of carbon monoxide and hydrogen is enriched with hydrogen from the water gas catalytic (Bosch) process, ie, water gas shift reaction, and passed over a cobalt—thoria catalyst to form straight-chain, ie, linear, paraffins, olefins, and alcohols in what is known as the Fisher-Tropsch synthesis. 

Goal Upgrading via Fischer-Tropsch. The synthesis of methane by the catalytic reduction of carbon monoxide and hydrogen over nickel and cobalt catalysts at atmospheric pressure was reported in 1902 (11). 

Hydroformylation. Esters of maleate and fumarate are treated with carbon monoxide and hydrogen in the presence of appropriate catalysts to give formyl derivatives. Dimethyl fumarate [624-49-7] is hydroformylated in 1 1 CO/H2 at 100°C and 11.6 MPa pressure with a cobalt [7440-48-4] catalyst to give an 83% yield of dimethyl formylsuccinate [58026-12-3] product (72). 

Ruthenium. Ruthenium, as a hydroformylation catalyst (14), has an activity signiftcandy lower than that of rhodium and even cobalt (22). Monomeric mthenium carbonyl triphenylphosphine species (23) yield only modest normal to branched regioselectivities under relatively forcing conditions. For example, after 22 hours at 120°C, 10 MPa (1450 psi) of carbon monoxide and hydrogen, biscarbonyltristriphenylphosphine mthenium [61647-76-5] ... 

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). 

With Unsaturated Compounds. The reaction of unsaturated organic compounds with carbon monoxide and molecules containing an active hydrogen atom leads to a variety of interesting organic products. The hydroformylation reaction is the most important member of this class of reactions. When the hydroformylation reaction of ethylene takes place in an aqueous medium, diethyl ketone [96-22-0] is obtained as the principal product instead of propionaldehyde [123-38-6] (59). Ethylene, carbon monoxide, and water also yield propionic acid [79-09-4] under mild conditions (448—468 K and 3—7 MPa or 30—70 atm) using cobalt or rhodium catalysts containing bromide or iodide (60,61). 

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