Catalyst BASF process

Patents claiming specific catalysts and processes for thek use in each of the two reactions have been assigned to Japan Catalytic (45,47—49), Sohio (50), Toyo Soda (51), Rohm and Haas (52), Sumitomo (53), BASF (54), Mitsubishi Petrochemical (56,57), Celanese (55), and others. The catalysts used for these reactions remain based on bismuth molybdate for the first stage and molybdenum vanadium oxides for the second stage, but improvements in minor component composition and catalyst preparation have resulted in yields that can reach the 85—90% range and lifetimes of several years under optimum conditions. Since plants operate under more productive conditions than those optimum for yield and life, the economically most attractive yields and productive lifetimes maybe somewhat lower. 

Reppe s work also resulted in the high pressure route which was estabUshed by BASF at Ludwigshafen in 1956. In this process, acetylene, carbon monoxide, water, and a nickel catalyst react at about 200°C and 13.9 MPa (2016 psi) to give acryUc acid. Safety problems caused by handling of acetylene are alleviated by the use of tetrahydrofuran as an inert solvent. In this process, the catalyst is a mixture of nickel bromide with a cupric bromide promotor. The hquid reactor effluent is degassed and extracted. The acryUc acid is obtained by distillation of the extract and subsequendy esterified to the desked acryhc ester. The BASF process gives acryhc acid, whereas the Rohm and Haas process provides the esters dkecdy. 

The first CO route to make adipic acid is a BASF process employing CO and methanol in a two-step process producing dimethyl adipate [627-93-0] which is then hydroly2ed to the acid (43—46). Cobalt carbonyl catalysts such as Co2(CO)g are used. Palladium catalysts can be used to effect the same reactions at lower pressures (47—49). 

Catalyst A process for treating industrial off-gases by catalytic oxidation over a titania/vanadia catalyst. Offered by BASF. 

The high catalyst loading typical of sol gel entrapped catalysts ensures a desirably high substrate/catalyst (S/C) ratio as the major part of the heterogeneous catalyst weight originates from the silicate matrix. For example, in a preparative-scale reaction of the alcohol raol-(2-naphthyl)-ethanol only 250 mg of sol-gel CaLB immobilizate could be used per 10 g of substrate. For comparison, all this makes the process based on sol-gel immobilized lipase very competitive with the commercial BASF process using lipase immobilized on Amberlite to produce the amine at a scale of 1000 tons per year. 

The industrial catalytic Reppe process is usually applied in the production of acrylic acid. The catalyst is NiBr2 promoted by copper halides used under forcing conditions. The BASF process, for example, is operated at 225°C and 100 atm in tetrahydrofuran solvent.188 Careful control of reaction conditions is required to avoid the formation of propionic acid, the main byproduct, which is difficult to separate. Small amounts of acetaldehyde are also formed. Acrylates can be produced by the stoichiometric process [Eq. (7.20)], which is run under milder conditions (30-50°C, 1-7 atm). The byproduct NiCl2 is recycled ... 

In contrast, high-molecular-weight (up to 500,000) elastomeric materials are formed by lowering the polymerization temperature. Two important continuous slurry processes are used the Exxon (Vistanex) process with A1C13 catalyst and the BASF process (Oppanol), which polymerizes isobutylene dissolved in ethylene (in a ratio about 1 2) in the presence of BF3. Ethylene serves as the internal cooler. 

In the classical oxo process the catalyst cohalt carbonyl is formed in situ by introducing divalent cobalt into the reactor. High temperature is required for this catalyst formation that gives a mixture of aldehydes and alcohols containing only 60-70% of linear product. A new BASF process using cobalt carbonyl hydride shows improved selectivity and efficient catalyst recovery. The catalyst is prepared by passing an aqueous solution of cobalt salt over a promoter and extracting the catalyst from the water phase with olefin. 

The first-generation catalyst, a cobalt carbonyl ligand, was employed in the BASF process. In the next generation, phosphine species were added to milden the reaction conditions and to optimize the linear to branched ratio. In the third... 

BASF s original acid scavenger, triethylamine, created viscosity and work-up problems because of the need to maintain anhydrous conditions. BASF s use of 1-methylimidazole instead of triethylamine, at their reaction temperature of 80°C, led to the formation of two liquid phases, an upper diethoxyphenylphosphine phase, and a lower methylimidazolium chloride phase (fortuitously, this ionic liquid melts at 75°C ). Moreover, methylimidazolium chloride proved to be a nucleophilic catalyst. The processing revolution generated by these discoveries enabled creation of a high-productivity continuous process for diethoxyphenylphosphine manufacture and created a whole new business in acid scavenging technology. 

The Inventa-NO process is similar to the BASF process in that the first source of by-product ammonium sulfate is eliminated. Like the BASF process the Inventa process prepares hydroxylamine sulfate by the reduction of nitric oxide with hydrogen over a noble metal catalyst suspended in sulfuric acid. The differences between the BASF and Inventa processes are ... 

In this chapter we discuss the mechanistic and other details of a few industrial carbonylation processes. These are carbonylation of methanol to acetic acid, methyl acetate to acetic anhydride, propyne to methyl methacrylate, and benzyl chloride to phenyl acetic acid. Both Monsanto and BASF manufacture acetic acid by methanol carbonylation, Reaction 4.1. The BASF process is older than the Monsanto process. The catalysts and the reaction conditions for the two processes are also different and are compared in the next section. Carbonylation of methyl acetate to acetic anhydride, according to reaction 4.2, is a successful industrial process that has been developed by Eastman Kodak. The carbonylation of propyne (methyl acetylene) in methanol to give methyl methacrylate has recently been commercialized by Shell. The Montedison carbonylation process for the manufacture of phenyl acetic acid from benzyl chloride is noteworthy for the clever combination of phase-transfer and organometallic catalyses. Hoechst has recently reported a novel carbonylation process for the drug ibuprofen. 

The CO used for the carbonylation reaction always contains some hydrogen. The side products in the BASF carbonylation process arise due to Fischer-Tropsch reaction catalyzed by the cobalt catalyst. The high temperatures and pressures used in the BASF process are conditions under which the Fischer-Tropsch reaction with soluble cobalt catalyst can take place. In the Monsanto process the reaction conditions are much milder, and the side-product-forming Fischer-Tropsch reaction is avoided. 

In the BASF process the 1,2-diacetate is the substrate for the hydroformylation step. It can be prepared either directly via oxidative acetoxylation of butadiene using a selenium catalyst or via PtCl4-catalyzed isomerization of the 1,4-diacetate (see above). The latter reaction affords the 1,2-diacetate in 95% yield. The hydroformylation step is carried out with a rhodium catalyst without phosphine ligands since the branched aldehyde is the desired product (phosphine ligands promote the formation of linear aldehydes). Relatively high pressures and temperatures are used and the desired branched aldehyde predominates. The product mixture is then treated with sodium acetate in acetic acid to effect selective elimination of acetic acid from the branched aldehyde, giving the desired C5 aldehyde. 

As far as large ale industrial application is concerned, the major Reppepropionic acid from ethylene. This was carried out by a BASF process (plant of about 30000 l/a) under 240 atm at 2 0 C with NKCO) as the catalyst. It also appears that Monsanto has a rhodium-catalyzed process on stream, which operates under milder conditions. 

In the BASF process this is reduced with hydrogen to hydroxylamine on a platinum catalyst on carbon substrates suspended in dilute sulfuric acid. In the Inventa process palladium is used. 

Precious metal or oxide catalysts are used. In the BASF process a vanadium(V) oxide catalyst is utilized and the process operates at a temperature of 230 to 350°C at the... 

Structure 4 is an intermediate for manufaeturing vitamin A (Scheme 2). The annual demand for vitamin A is about 3000 tons. Major producers are BASF, Hoffmann-La Roche and Rhone-Poulenc Animal Nutrition [55]. At an early stage in the synthesis BASF and Hoffmann-La Roche are using a hydroformylation step to synthesize 4 starting from l,2-diacetoxy-3-butene (5) and 1,4-di-aeetoxy-2-butene (6), respectively [56, 57]. The selectivity toward the branched product in the BASF process is achieved by using an unmodified rhodium carbonyl catalyst at a high reaction temperature. The symmetry of 6 in La Roche s process does not lead to regioselectivity problems. Elimination of acetic acid and isomerization of the exo double bond (La Roche) yields the final product 4 in both processes. 

Developed nearly in parallel with the UCC s LPO process, the BASF process also makes use of a gas recycle to separate aldehydes and catalyst solution [216]. The latter also consists of aldehyde condensation products [217] with TPP and the corresponding rhodium complex dissolved therein [218, 219]. With about 3-5 wt. % the concentration of TPP is rather low, thus limiting the rhodium concentration to a level below 200 ppm in order to establish a P/Rh ratio of about 100 1 (mol/g-at). Accordingly, the n/i ratio is somewhere in the range of 84 16. With a temperature of about 110°C, the pressure is limited to about 1.5-1.7 MPa to avoid too large a recycle. 

G. H. Grosch, U. Muller, M. Schulz, N. Richer, H. Wurz, Oxidation catalyst and process for the production of epoxides from olefines, hydrogen and oxygen using said oxidation catalyst, U.S. Patent No. 6,008,389,1999, Assigned to BASF Corporation. 

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