Carbon monoxide hydrogenation catalysis

Chemistry of Hydridoniobium Complexes Approaches to Homogeneous Catalysis of the Carbon Monoxide-Hydrogen Reaction... 

The study of the various reactions of carbon monoxide, hydrogen, and oxygen at oxide surfaces holds a particularly important place in the development of research in heterogeneous catalysis. Not only are the well-established technical aspects of these reactions continuously monitored by those engaged in chemical industry, but the chemist interested in fundamental studies of the interaction of gases with oxides naturally turns to the behavior of these gases because of the combination of high reactivity and molecular simplicity which they afford. Finally, for the chemical physicist,... 

Catalysis by Supported Metal Ousters. Reactions that have received most attention are two highlighted previouslynamely carbon monoxide hydrogenation and the activation of carbon-carbon and carbon-hydrogen bonds of saturated hydrocarbons. 

Catalysis by Metal Ousters in Zeolites. There is an increasing interest in the use of metal clusters stabilized in zeolites. One objective of such work is to utilize the shape and size constraints inherent in these support materials to effect greater selectivities in typical metal-catalysed reactions. Much work has been concerned with carbon monoxide hydrogenation, and although the detailed nature of the supported metals so obtained is not well understood, there is clear evidence of chain limitation in the Fischer-Tropsch process with both RuY zeolites and with HY and NaY zeolites containing Fe3(CO)22- In the former case there is a drastic decline in chain-growth probability beyond C5- or C10-hydrocarbons depending upon the particle size of the ruthenium metal. 

The state and accomplishments of catalysis science are demonstrated through discussions of the ammonia synthesis, carbon monoxide hydrogenation, and hydrocarbon conversion over platinum. 

Carbon monoxide hydrogenation, for hydrocarbon synthesis, 1, 116 Catalysis research, electron diffiraction applicable to, 13, 191 Catalysis,... 

A bottle labelled as 12% acid in aqueous methanol, and probably two years forgotten, exploded in storage, breaking adjacent bottles[l]. Trichloracetic acid is known to be more unstable, with respect to carbon dioxide and chloroform, in aqueous solution than pure. The reaction usually requires either heat or base catalysis [2], Storage of trichloroacetic acid at less than 30% concentration is not advised [3], Hydrolysis of the trichlorogroup is also conceivable, which would yield intermediate oxalyl monochloride, which habitually breaks down to give carbon monoxide, dioxide and hydrogen chloride. 

H. Pichler. 1952. Twenty-five years of synthesis of gasoline by catalytic conversion of carbon monoxide and hydrogen. In Advances in catalysis, ed. W. Frankenburg, E. Rideal, V. Komarewsky. Vol. 4 271. New York Academic Press. 

One approach to promoting the kinetics of hydrogen transfer to bound carbon monoxide is based on maximizing the difference in polarity of the carbon (eg. 6+) and hydrogen (eg. 6-) involved (Jt). This strategy leads naturally to a bimolecular approach, based upon MCO and M H. The additional degree of freedom which follows from employing two different transition metals is noteworthy as an alternative to cluster activation or catalysis. 

Not all C-H activation chemistry is mediated by transition metal catalysts. Many of the research groups involved in transition metal catalysis for C-H activation have opted for alternative means of catalysis. The activation of methane and ethane in water by the hexaoxo-/i-peroxodisulfate(2—) ion (S2O82) was studied and proceeds by hydrogen abstraction via an oxo radical. Methane gave rise to acetic acid in the absence of external carbon monoxide, suggesting a reaction of a methyl radical with CO formed in situ. Moreover, the addition of (external) CO to the reaction mixture led to an increase in yield of the acid product (Equation (ll)).20... 

The reaction between alkenes and synthesis gas (syngas), an equimolar mixture of carbon monoxide and hydrogen, to form aldehydes was discovered in 1938 by Otto Roelen [1,2]. Originally called oxo-reaction , hydroformyla-tion is the term used today. This reflects the formal addition of formaldehyde to the olefinic double bond. Commercially, homogeneous metal complexes based on cobalt and rhodium are used as catalysts. With more than 10 million metric tons of oxo products per year, this reaction represents the most important use of homogeneous catalysis in the chemical industry. 

---