Cobalt technology

Growing demand for higher plasticizer alcohols has initiated a revival of the old cobalt technology. New patents about process modifications [86,87] and the construction of new plants underline this. Alone the production of isononanol on the basis of dibutene has been a success story, doubling the production to well beyond 1 million mty-1 within a few years. 

Nevertheless, in comparison with the cobalt technology even the first generation of LPO processes (the expression LPO being coined by BP [266]) proved successful and was promoted by a number of companies (e.g., Celanese, Union Carbide, BASF, Mitsubishi), mostly in parallel. One of the first plants for butanal production belonged to Celanese [192] (later Hoechst-Celanese), closely followed by Union Carbide/Davy Powergas/Johnson Matthey [193] and other companies. 

Cobalt Technologies 2005 Mountain View, CA, USA An immobilized cell technology using a proprietary, nongeneticaUy modified Clostridia strain with high productivity and ability to convert both C5 and C6 sugars into butanol for operation in a continuous fermentation reactor Currently operating a 5000 GPY pilot facility since June 2009. Cobalt is now in the process to commission a 470,000 GPY ceUulosic biobutanol facility... 

An example of a cobalt-based hydroformylation process for long-chain, highly branched olefins is a process developed by Exxon to produce IDA from isomer mixtures of the nonene. There are several recently published patents that describe a further development of this process, thus illustrating that continuous development of the older cobalt technology keeps it competitive for selected challenging hydroformylation processes, such as for complex, highly branched, longer chain olefins. 

Out of all the fuels described in this review (and probably out of all advanced biofuels being developed at the moment), industrial-scale production of butanol is the most realistic to begin in the near future. There are a number of pilot plants around the world, and several companies have shown interest in this biofuel (Gevo, Butamax, Cobalt Technologies, etc.) with much research being performed and many parents published on the topic. 

Process Technology. In a typical oxo process, primary alcohols are produced from monoolefins in two steps. In the first stage, the olefin, hydrogen, and carbon monoxide [630-08-0] react in the presence of a cobalt or rhodium catalyst to form aldehydes, which are hydrogenated in the second step to the alcohols. 

A more extensive comparison of many potential turbine blade materials is available (67). The refractory metals and a ceramic, sHicon nitride, provide a much higher value of 100 h stress—mpture life, normalised by density, than any of the cobalt- or nickel-base aHoys. Several intermetaHics and intermetaUic matrix composites, eg, aHoyed Nb Al and MoSi —SiC composites, also show very high creep resistance at 1100°C (68). Nevertheless, the superaHoys are expected to continue to dominate high temperature aHoy technology for some time. 

K. J. Stmat, ia Proceedings 4th International Workshop on Rare Earth-Cobalt Permanent Magnets, Society Non-Traditional Technology, Tokyo, 1979, p. 8. 

Many competitive programs to perfect a metallic anode for chlorine arose. In one, Dow Chemical concentrated on a coating based on cobalt oxide rather than precious metal oxides. This technology was patented (9,10) and developed to the semicommercial state, but the operating characteristics of the cobalt oxide coatings proved inferior to those of the platinum-group metal oxide. 

D. L. CaldweU and M. J. Hazeltigg, "Cobalt Spiael-Based Chlorine Anodes," paper presented t dnances in Chlor-A.lkali Technology, London, 1979. 

Ocean Basins. Known consohdated mineral deposits in the deep ocean basins are limited to high cobalt metalliferous oxide cmsts precipitated from seawater and hydrothermal deposits of sulfide minerals which are being formed in the vicinity of ocean plate boundaries. Technology for drilling at depth in the seabeds is not advanced, and most deposits identified have been sampled only within a few centimeters of the surface. 

Chevron Chemical Co. began commercial production of isophthahc acid in 1956. The sulfur-based oxidation of / -xylene in aqueous ammonia at about 320°C and 7,000—14,000 kPa produced the amide. This amide was then hydrolyzed with sulfuric acid to produce isophthahc acid at about 98% purity. Arco Chemical Co. began production in 1970 using air oxidation in acetic acid catalyzed by a cobalt salt and promoted by acetaldehyde at 100—150°C and 1400—2800 kPa (14—28 atm). The cmde isophthahc acid was dissolved and recrystallized to yield a product exceeding 99% purity. The Arco technology was not competitive and the plant was shut down in 1974. 

Prior to 1975, reaction of mixed butenes with syn gas required high temperatures (160—180°C) and high pressures 20—40 MPa (3000—6000 psi), in the presence of a cobalt catalyst system, to produce / -valeraldehyde and 2-methylbutyraldehyde. Even after commercialization of the low pressure 0x0 process in 1975, a practical process was not available for amyl alcohols because of low hydroformylation rates of internal bonds of isomeric butenes (91,94). More recent developments in catalysts have made low pressure 0x0 process technology commercially viable for production of low cost / -valeraldehyde, 2-methylbutyraldehyde, and isovaleraldehyde, and the corresponding alcohols in pure form. The producers are Union Carbide Chemicals and Plastic Company Inc., BASF, Hoechst AG, and BP Chemicals. 

Propane, 1-propanol, and heavy ends (the last are made by aldol condensation) are minor by-products of the hydroformylation step. A number of transition-metal carbonyls (qv), eg, Co, Fe, Ni, Rh, and Ir, have been used to cataly2e the oxo reaction, but cobalt and rhodium are the only economically practical choices. In the United States, Texas Eastman, Union Carbide, and Hoechst Celanese make 1-propanol by oxo technology (11). Texas Eastman, which had used conventional cobalt oxo technology with an HCo(CO)4 catalyst, switched to a phosphine-modified Rh catalyst ia 1989 (11) (see Oxo process). In Europe, 1-propanol is made by Hoechst AG and BASE AG (12). 

The oxidation of cyclohexane to a mixture of cyclohexanol and cyclohexanone, known as KA-od (ketone—alcohol, cyclohexanone—cyclohexanol cmde mixture), is used for most production (1). The earlier technology that used an oxidation catalyst such as cobalt naphthenate at 180—250°C at low conversions (2) has been improved. Cyclohexanol can be obtained through a boric acid-catalyzed cyclohexane oxidation at 140—180°C with up to 10% conversion (3). Unreacted cyclohexane is recycled and the product mixture is separated by vacuum distillation. The hydrogenation of phenol to a mixture of cyclohexanol and cyclohexanone is usually carried out at elevated temperatures and pressure ia either the Hquid (4) or ia the vapor phase (5) catalyzed by nickel. 

The total synthesis of ( )-estrone [( )-1 ] by Vollhardt et al. is a novel extension of transition metal mediated alkyne cyclotrimeriza-tion technology. This remarkable total synthesis is achieved in only five steps from 2-methylcyclopentenone (19) in an overall yield of 22%. The most striking maneuver in this synthesis is, of course, the construction of tetracycle 13 from the comparatively simple diyne 16 by combining cobalt-mediated and ort/io-quinodimethane cycloaddition reactions. This achievement bodes well for future applications of this chemistry to the total synthesis of other natural products. 

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