Homogeneously Catalyzed Industrial Processes

Homogeneous hydrogenation is used in polymer synthesis, the hydrogenation of aldehydes to alcohols (oxo process), in asymmetric hydrogenation (L-dopa, Monsanto), and for the hydrogenation of benzene to cyclohexane (Procatalyse). 

Industrial Catalysis A Practical Approach, Second Edition. Jens Hagen Copyright 2006 WILEY- VCH Verlag GmbH Co. KGaA, Weinheim ISBN 3-527-31144-0 

The most important industrial application of homogeneous catalysts is the oxidation of hydrocarbons with oxygen or peroxides. Mechanistically, a distinction is made between  

Homol5dic processes the transition metals react with formation of radicals, and the oxidation or reduction steps are one-electron processes 

Ohgomerization reactions involve mono-olefins and dienes polymerization reactions are mechanistically similar. Polymerization or copolymerization with soluble or insoluble transition metal catalysts is used to produce  

---

Hydroformylation is the oldest and in production volume the largest homogeneously catalyzed industrial process. The hydroformylation reaction was discovered by Otto Roelen in 1938 the reaction is also called oxosynthesis and Roden s reaction [1-13]. 

I 3 Homogeneously Catalyzed Industrial Processes Jacobsen Epoxidation [22]... 

Although progress has been made with zeolite and non-zeolitic molecular sieves, these alternatives cannot compete with the current, homogeneously catalyzed industrial process the catalyst lives are still much too short. In contrast to that, the oximation of cyclohexanone might be carried out on industrial scale in the near future a pilot plant in Italy is already under construction or running. 

T,he hydroformylation reaction or oxo synthesis has been used on an industrial scale for 30 years, and during this time it has developed into one of the most important homogeneously-catalyzed technical processes (I). A variety of technical processes have been developed to prepare the real catalyst cobalt tetracarbonyl hydride from its inactive precursors, e.g., a cobalt salt or metallic cobalt, to separate the dissolved cobalt carbonyl catalyst from the reaction products (decobaltation) and to recycle it to the oxo reactor. The efficiency of each step is of great economical importance to the total process. Therefore many patents and papers have been published concerning the problem of making the catalyst cycle as simple as possible. Another important problem in the oxo synthesis is the formation of undesired branched isomers. Many efforts have been made to keep the yield of these by-products at a minimum. 

Within this context carbon monoxide is not the inert molecule so frequently depicted on the basis of its formal triple bond and the remarkable similarity of its physical properties to those of the isoelectronic molecule dinitrogen. (Indeed, if it were, atmospheric carbon monoxide would present no hazard ) It is, in fact, a fairly readily activated molecule the industrial process for the production of methyl formate (1) is well known, but it is less widely appreciated that this process is an example of a homogeneous, selective, base-catalyzed, activation of carbon monoxide which has for its net chemistry... 

This section addresses a wide variety of systems that all, in a direct or indirect way, involve the activation of small molecules. The treated systems are of biological, environmental, or industrial interest and form the basis of homogeneously catalyzed processes. 

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. 

Another example is butene dimerization catalyzed by nickel complexes in acidic chloroaluminates 14). This reaction has been performed on a continuous basis on the pilot scale by IFF (Difasol process). Relative to the industrial process involving homogeneous catalysis (Dimersol process), the overall yield in dimers is increased. Similarly, selective hydrogenation of diene can be performed in ionic liquids, because the solubility of dienes is higher than that of monoene, which is higher than that of paraffins. In the case of the Difasol process, a reduction of the volume of the reaction section by a factor of up to 40 can be achieved. This new Difasol technology enables lower dimer (e.g., octenes) production costs 14). 

An important development in the past 15 years in hydroformylation technology was the introduction of biphasic homogeneous catalysis. Kuntz (62) expressed the basic idea of a new generation of water-soluble oxo catalysts with triphenylphosphane trisulfonate (tppts as the sodium salt) as a ligand for a rhodium-complex-catalyzed hydroformylation process. Ruhrchemie AG adapted the idea on the basis of research done at Rhone-Poulenc and developed it into an industrially viable process, which was... 

The hydroformylation of alkenes to give linear aldehydes constitutes the most important homogeneously catalyzed process in industry today [51]. The hydroformylation of propene is especially important for the production of n-bu-tyraldehyde, which is used as a starting material for the manufacture of butanol and 2-ethylhexanol. Catalysts based on cobalt and rhodium have been the most intensively studied for the hydroformylation of alkenes, because they are industrially important catalysts. While ruthenium complexes have also been reported to be active catalysts, ruthenium offers few advantages over cobalt or... 

For homogeneous base catalyzed processes, reaction conditions are generally at ambient or slightly higher pressure, and a temperature of 65 °C-70 °C, in the presence of approximately 0.5% catalyst, with a 6 1 molar ratio of methanol to oil (Freedman et al, 1986). The process can be operated continuously (Noureddini et al, 1998) or in batch mode. Examples of continuous industrial processes include Ballestra, Connemann CD, and the Lurgi PSI process. 

---