New Catalyst Developments

Of course, the pharmaceutical industry is not the only sector in which process engineering is needed to enhance national security and homeland defense. Also, other areas of process engineering such as model development, optimization schemes, on-line control, catalyst development, new separation methods, biomass conversion, and models using multiple length scales are equally important to include in research efforts. 

Richardson, J.T. (1989) Principles of Catalyst Development. New York Plenum Press. 

Lyondell and Sun Oil Co. are the main producers of benzene by disproportionation. Eiaa Oil Co. of Texas has developed the Eiaa T2BX process for toluene disproportionation usiag a proprietary catalyst. The new catalyst is claimed to reduce hydrogen consumption and is suitable for feeds containing small amounts of moisture (53). A commercial production unit was started up ia the fall of 1985. 

A thorough list of references is given in J. T. Richardson, Principles of Catalyst Development, Plenum Press, New York, 1989. 

From a historical perspective it is interesting to note that the Nozaki experiment was, in fact, a mechanistic probe to establish the intermediacy of a copper carbe-noid complex rather than an attempt to make enantiopure compounds for synthetic purposes. To achieve synthetically useful selectivities would require an extensive exploration of metals, ligands and reaction conditions along with a deeper understanding of the reaction mechanism. Modern methods for asymmetric cyclopropanation now encompass the use of countless metal complexes [2], but for the most part, the importance of diazoacetates as the carbenoid precursors still dominates the design of new catalytic systems. Highly effective catalysts developed in... 

To reduce pollution, Dow developed a new catalyst system from the mor-denite-zeolite group to replace phosophoric acid or aluminum chloride catalysts. The new catalysts eliminates the disposal of acid wastes and handling corrosive materials. 

Catalysts developed in the titanium-aluminum alkyl family are highly reactive and stereoselective. Very small amounts of the catalyst are needed to achieve polymerization (one gram catalyst/300,000 grams polymer). Consequently, the catalyst entrained in the polymer is very small, and the catalyst removal step is eliminated in many new processes. Amoco has introduced a new gas-phase process called absolute gas-phase in which polymerization of olefins (ethylene, propylene) occurs in the total absence of inert solvents such as liquefied propylene in the reactor. Titanium residues resulting from the catalyst are less than 1 ppm, and aluminum residues are less than those from previous catalysts used in this application. 

The chapter by Hausberger et al. deals with catalyst development, and the performance of several new high-nickel catalysts in bench-scale and large pilot tests with high carbon oxide concentrations. Kinetics of the reaction over these catalysts are developed. 

The discovery that Lewis acids can promote Diels-Alder reactions has become a powerful tool in synthetic organic chemistry. Yates and Eaton [4] first reported the remarkable acceleration of the reactions of anthracene with maleic anhydride, 1,4-benzoquinone and dimethyl fumarate catalyzed by aluminum chloride. The presence of the Lewis-acid catalyst allows the cycloadditions to be carried out under mild conditions, reactions with low reactive dienes and dienophiles are made possible, and the stereoselectivity, regioselectivity and site selectivity of the cycloaddition reaction can be modified [5]. Consequently, increasing attention has been given to these catalysts in order to develop new regio- and stereoselective synthetic routes based on the Diels-Alder reaction. 

There are comparable incentives to develop new process-related materials that are more selective as catalysts, extractants, or separation membranes and more effective in controlling flow in porous media. In addition, the development of materials that are less energy intensive in terms of production and use is a goal equivalent to other means of energy conservation. 

Ghosh et al. [70] reviewed a few years ago the utihty of C2-symmetric chiral bis(oxazoline)-metal complexes for catalytic asymmetric synthesis, and they reserved an important place for Diels-Alder and related transformations. Bis(oxazoline) copper(II)triflate derivatives have been indeed described by Evans et al. as effective catalysts for the asymmetric Diels-Alder reaction [71]. The bis(oxazoline) Ugand 54 allowed the Diels-Alder transformation of two-point binding N-acylimide dienophiles with good yields, good diastereos-electivities (in favor of the endo diastereoisomer) and excellent ee values (up to 99%) [72]. These substrates represent the standard test for new catalysts development. To widen the use of Lewis acidic chiral Cu(ll) complexes, Evans et al. prepared and tested bis(oxazoHnyl)pyridine (PyBOx, structure 55, Scheme 26) as ligand [73]. 

Both new catalysts and new processes need to be developed for a complete exploitation of the potential of CO2 use [41]. The key motivation to producing chemicals from CO2 is that CO2 can lead to totally new polymeric materials and also new routes to existing chemical intermediates and products could be more efficient and economical than current methods. As a case in point, the conventional method for methanol production is based on fossil feedstock and the production of dimethyl carbonate (DMC) involves the use of toxic phosgene or CO. A proposed alternative production process involves the use of CO2 as a raw material (Figure 7.1)... 

Please note that the approach taken to find a solution for carbon deposition started with leads from surface science and computational chemistry and led to the straightforward development of a new catalyst a good example of rational catalyst development based on fundamental knowledge ... 

Understanding the kinetics of the SCR process helps greatly in developing new and better catalysts. For efficient operation, one important issue is to maximize NO con-... 

Transition metal oxides represent a prominent class of partial oxidation catalysts [1-3]. Nevertheless, materials belonging to this class are also active in catalytic combustion. Total oxidation processes for environmental protection are mostly carried out industriaUy on the much more expensive noble metal-based catalysts [4]. Total oxidation is directly related to partial oxidation, athough opposes to it. Thus, investigations on the mechanism of catalytic combustion by transition metal oxides can be useful both to avoid it in partial oxidation and to develop new cheaper materials for catalytic combustion processes. However, although some aspects of the selective oxidation mechanisms appear to be rather established, like the involvement of lattice catalyst oxygen (nucleophilic oxygen) in Mars-van Krevelen type redox cycles [5], others are still uncompletely clarified. Even less is known on the mechanism of total oxidation over transition metal oxides [1-4,6]. 

Gezdhmte Chemie im Mikroreaktor, VDI Nachrichten, June 2000 Micro-reactor enterprises shape and material variety of micro reactors selectivity gains and new project regimes direct fluorination faster process development BASF investigations safety increase speed-up of catalyst development production for fine chemistry and pharmacy numbering-up first industrial examples for micro-reactor production [215]. 

The outstanding performances of five-membered NHC ligands in organometallic chemistry and catalysis prompted Grubbs and co-workers to develop a novel stable four-membered NHC [64]. Following their interest in developing new ruthenium olefin metathesis catalysts, they synthesised and fully characterised complex 51 to study the impact of the architecturally unique NHC ligand on the activity of the Ru-based catalyst [65] (Fig. 3.20). In the RCM of 1 at 40°C in CH Cl with 51 (5 mol% catalyst), the reaction reached completion within 20 min, whereas less than 10 min are required for standard catalysts 14 and 16. It should be noted that catalysts 14 and 16 are able to complete the RCM of 1 with only 1 mol% catalyst at 30°C. 

Many parallel developments in organometallic chemistry focusing on various transition metals have eventually led to the use of A-heterocyclic carbenes in metathesis catalysts. A new episode of a successful story has been started. 

The large molecular size and ambient operation of enzymes means that they are likely to be more suited to niche applications rather than to high-power devices, but there are important lessons to be leamt from biological catalysis that occurs in conditions under which conventional metal catalysts would fail. Development of synthetic catalysts inspired by the chemistry (although not necessarily the stmctures) of enzyme active sites may lead to future catalysts with new and improved properties. 

In 1997, Chelucci et al. developed new chiral 2-(l-p-tolylsulfinyl)alk-ylpyridines and assessed these ligands in the enantioselective addition of ZnEt2 to benzaldehyde." This produced in all cases catalysts in good yields but with low enantioselectivities (< 19% ee). An examination of the results collected in Scheme 3.33 indicates that the enantioselectivity and the configuration of the resulting carbinol were independent of both the substituent and the configuration at the carbon centre. Therefore, this suggests that the stereochemical... 

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