Bosch

Selective oxidation of secondary alcohols to ketones is usually performed with CrOj/HjSO, I I in acetone (Jones reagent) or with CrOjPyj (Collin s reagent) in the presence of acid-sensitive groups (H.G. Bosche, 1975 C. Djerassi, 1956 W.S. Allen, 1954). As mentioned above, a,)S-unsaturated secondary alcohols are selectively oxidized by MnOj (D.G. Lee, 1969 D. Arndt, 1975) or by DDQ (D. Walker, 1967 H.H. Stechl, 1975). 

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. 

The synthetic ammonia industry of the latter part of the twentieth century employs only the Haber-Bosch process (12—15), developed in Germany just before World War 1. Development of this process was aided by the concurrent development of a simple catalyzed process for the oxidation of ammonia to nitrate, needed at that time for the explosives industry. N2 and H2 are combined direcdy and equiUbrium is reached under appropriate operating conditions. The resultant gas stream contains ca 20% ammonia. 

Fig. 2. The Haber-Bosch process. Gases in parentheses are minor constituents of the mixture.

The mature Haber-Bosch technology is unlikely to change substantiaHy in the foreseeable future. The centers for commercial ammonia production may, however, relocate to sites where large quantities of natural gas are flared from cmde oil production, eg, Saudi Arabia or Venezuela. Relocation would not offset the problems for agriculture of high transportation and storage costs for ammonia production and distribution. Whereas the development of improved lower temperature and pressure catalysts is feasible, none is on the horizon as of this writing. 

Although these other chemical systems ate feasible chemically, there has been httie impetus to solve associated equipment problems. The Bosch reaction appears to be the most promising. 

Bosch and co-workers devised laboratory reactors to operate at high pressure and temperature in a recycle mode. These test reactors had the essential characteristics of potential industrial reactors and were used by Mittasch and co-workers to screen some 20,000 samples as candidate catalysts. The results led to the identification of an iron-containing mineral that is similar to today s industrial catalysts. The researchers recognized the need for porous catalytic materials and materials with more than one component, today identified as the support, the catalyticaHy active component, and the promoter. Today s technology for catalyst testing has become more efficient because much of the test equipment is automated, and the analysis of products and catalysts is much faster and more accurate. 

I. GoriUe, N. Rittmansberger, and P. Werner, Bosch Electronic Fuel Injection with ClosedEoop Control, SAE 750368, Society of Automotive Engineers, Warrendale, Pa., 1975. 

Automotive Handbook, 2nd ed., Robert Bosch GmbH, Stuttgart, Germany, 1986, p. 442. 

C. O. Probst, Bosch Fuel Injection Engine Management, Robert Bentiey, Cambridge, Mass., 1989. 

The results for the tunneling splitting calculated with the use of some of the earlier proposed reaction paths for a single PES (4.40) (with the parameters adopted here) are collected by Bosch et al. [1990]. All of them underestimate by at least an order of magnitude the numerically exact value 10.6 cm which is also given in that paper. The parameters C and Q hit the intermediate region between the sudden and adiabatic approximations, described in sections 2.5 and 4.2, and neither of these approximations is quantitatively applicable to the problem. 

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