Homogeneous catalysts industrial applications

Homogeneous catalysts industrial applications Homogeneous catalyst development... 

Homogeneous catalytic reduction of N2 to NH3 Homogeneous catalysts industrial applications Homogeneous catalyst development... 

T he six years since the first Advances in Chemistry Series volume, Homogeneous Catalysis—Industrial Applications and Implications, (Number 70) have been a period of mushrooming activity in the field. Not only has this activity been marked by the discovery of new types of catalysts and new insights into reaction mechanisms, but several major commercial processes based on homogeneous catalysts have been developed. 

In contrast to heterogeneous catalysis, industrial applications of homogeneous catalysis are relatively scarce, largely being restricted to the speciality and pharmaceutical sectors. Homogeneous catalysts have been well researched, since their catalytic centres can be relatively easily... 

In this brief review we illustrated on selected examples how combinatorial computational chemistry based on first principles quantum theory has made tremendous impact on the development of a variety of new materials including catalysts, semiconductors, ceramics, polymers, functional materials, etc. Since the advent of modem computing resources, first principles calculations were employed to clarify the properties of homogeneous catalysts, bulk solids and surfaces, molecular, cluster or periodic models of active sites. Via dynamic mutual interplay between theory and advanced applications both areas profit and develop towards industrial innovations. Thus combinatorial chemistry and modem technology are inevitably intercoimected in the new era opened by entering 21 century and new millennium. 

Table 3.12 surveys current industrial applications of enantioselective homogeneous catalysis in fine chemicals production. Most chiral catalyst in Table 3.12 have chiral phosphine ligands (see Fig. 3.54). The DIP AMP ligand, which is used in the production of L-Dopa, one of the first chiral syntheses, possesses phosphorus chirality, (see also Section 4.5.8.1) A number of commercial processes use the BINAP ligand, which has axial chirality. The PNNP ligand, on the other hand, has its chirality centred on the a-phenethyl groups two atoms removed from the phosphorus atoms, which bind to the rhodium ion. Nevertheless, good enantio.selectivity is obtained with this catalyst in the synthesis of L-phenylalanine. 

As already mentioned, the most important industrial application of homogeneous hydrogenation catalysts is for the enantioselective synthesis of chiral compounds. Today, not only pharmaceuticals and vitamins [3], agrochemicals [4], flavors and fragrances [5] but also functional materials [6, 7] are increasingly produced as enantiomerically pure compounds. The reason for this development is the often superior performance of the pure enantiomers and/or that regulations demand the evaluation of both enantiomers of a biologically active compound before its approval. This trend has made the economical enantioselective synthesis of chiral performance chemicals a very important topic. 

The cost of the catalysts represents a major hurdle on the road to the industrial application of homogeneous catalysis, and in particular for the production of fine chemicals [1, 2], This is particularly true for chiral catalysts that are based on expensive metals, such as rhodium, iridium, ruthenium and palladium, and on chiral ligands that are prepared by lengthy total syntheses, which often makes them more expensive than the metals. In spite of this, the number of large-scale applications for these catalysts is growing. Clearly, these can only be economic if the substrate catalyst ratio (SCR) can be very high, often between 103 and 105. 

On the other hand thermomorphic solvent systems can be used for industrial applications within existing equipment. In principal, it is also possible to use unmodified ligands and catalyst complexes for homogeneously catalyzed reactions. Therefore, the economic hurdles to use the system in industrial practice are not very high. 

From an industrial point of view, homogeneous catalysis has significant advantages concerning selectivities and due to mild reaction conditions [47]. In fact, there is only a limited munber of processes established in industrial applications because of the disadvantageous separabihty of the catalyst from substrate and product. A possible and convenient solution for this limitation can be the application of supercritical carbon dioxide as part of a reaction system due to the following ... 

In particular the recent investigation as part of the project Smart Sol-vents/Smart ligands of the SLPC with PEG and ionic Hquids ( SILP ) as the catalyst carrier opened up new possibihties for the immobihzation of homogeneous catalysts. By increasing the stabihty of the catalytic performance, this concept may have the potential to be kept in mind for industrial catalysis in combination with environmentally benign supercritical or compressed carbon dioxide. In addition, this methodology is able to provide access to some chemical applications and processes because of the easy and facile preparation of the coated materials. 

For the production of chemicals, food additives and pharmaceutical products, homogeneous catalysis offers some attractive features such as a high selectivity and activity, e.g. in asymmetric synthesis. However, since most homogeneous catalysts are relatively expensive, their current industrial application is limited [3]. On the other hand, heterogeneous catalysts can easily be separated from the products and can be recycled efficiently. Membrane separations with emphasis on nanofil-tration and ultrafiltration will allow for a similar recyclability of homogeneous catalysts, which is important both from an environmental as well as a commercial... 

Zeolites and other mesoporous materials are excellent catalysts for industrial and laboratory applications. Favourable characteristics are their capacity to immobihze homogenous catalysts rendering them heterogeneous, their thermal stability, and the ease of separation from the reaction products and reuse in hquid- and gas-phase conditions. The pore size and Brpnsted and Lewis acidic properties are determinant for their use as catalyst in the Beckmann rearrangement. Recently, a review on the use of zeolites and mesoporous materials in the Beckmann rearrangement was published. ... 

Oxidation of carbohydrates can be achieved by either chemical or biochemical processes [98, 99]. Owing to their cation sequestering properties, the resulting carboxylic derivatives find potential applications in the detergent industries [100, 101]. Although homogeneous catalysts are often used in oxidation processes, utilization of solid catalysts has proved to be a feasible alternative [102]. 

---