Kuraray process, hydroformylation

On the industrial level, aqueous two-phase systems are used more often than nonaqueous two-phase systems. The Kuraray Co. operates a pilot plant for the hydrodimerization of 1,3-butadiene in a two-phase system with a Pd/tppms catalyst (140). The reaction is carried out in sulfolane-water, from which the products, the octadienols, separate. The final products can be octanol or nonanediol made by subsequent isomerization and hydroformylation. The capacity of the Kuraray process is about 5000 tons/year. 

In the Kuraray process for the production of nonane-1,9-diol two steps involve the use of aqueous biphasic catalysis Pd/tppms catalyzed telomerization of butadiene with water as a reactant and Rh/tppms catalyzed hydroformylation (Fig. 7.14) [51]. 

Two process variants have been described. A type n process [91] resembles the Union Carbide process for butenes hydroformylation (see 8.6.1). Rapid oxidation of the diphosphite ligands by air ingress in vacuum distillation columns is mitigated by addition of an excess of sacrificial ligand (tri-orthotolylphosphine). In a type IVA process, very much like the Kuraray process (see 8.6.4.1), apolar and polar solvents are applied to effect the desired combinahon of one-phase reachon fohowed by phase separation, with most Rh/diphosphite catalyst in the apolar layer [92,93]. 

Functional Olefin Hydroformylation. There has been widespread academic (18,19) and industrial (20) interest in functional olefin hydroformylation as a route to polyfiinctional molecules, eg, diols. There are two commercially practiced oxo processes employing functionalized olefin feedstocks. Akyl alcohol hydroformylation is carried out by Arco under Hcense from Kuraray (20,21). 1,4-Butanediol [110-63 ] is produced by successive hydroformylation of aHyl alcohol [107-18-6] aqueous extraction of the intermediate 2-hydroxytetrahydrofuran, and subsequent hydrogenation. 

An example of the application of a water-soluble hydroformylation catalyst other than in the Ruhrchemie/Rhone-Poulenc process is the synthesis of 1,9- non-anediol according to Kuraray [58]. Hydrodimerization of butadiene (also cata-... 

The aqueous biphasic processes require a minimum solubility of the reactants S in the catalyst phase [196, 205]. Therefore, hydroformylation of higher olefins (approx. > Cg) or functionally substituted olefins is more difficult but offers various advantages, such as the simplification of reaction sequences and reduced expenditure for the catalyst cycle. So far, work on these biphasic processes for the conversion of higher olefins, except for Kuraray s recent devel-... 

Aqueous, two-phase catalysis is also utilized industrially in a number of other processes apart from hydroformylation. The hydrodimerization of butadiene and water, a telomerization variant yielding 1-octanol or 1,9-nonanediol (cf. Section 6.9), is carried out at a capacity of 5000 tonnes per annum by the Kuraray Corporation in Japan. Rhone-Poulenc is operating two-phase, aqueous, catalytic C—C coupling processes (using TPPTS obtained from Ruhrchemie) for small-scale production of various vitamin precursors such as geranylacetones. Moreover, TPPTS-modified Ru catalysts have been proposed for the homogeneously catalyzed hydrogenation to convert unsaturated ketones into saturated ones. 

To our knowledge, the only industrial application of the water-soluble catalyst for the hydroformylation of ( functionalized olefins has been developed by Kuraray [11]. In this process, oct-7-en-Tal is hydroformylated into 1,9-nonanedial by using a rhodium catalyst and the monosulfonated triphenylphosphine (cf. also Section 2.4.4.2). 

Accompanying Ruhrchemie/Rhone-Poulenc s industrial realization of the aqueous biphasic hydroformylation reaction (cf Sections 2.4.1.1.3 and 2.5.1) and Kuraray s hydrodimerization process (see Section 2.4.4.2), there are some other minor processes for the production of fine chemicals. 

The Type IV concept has been commercialized for the first time in the Rh-catalyzed hydroformylation of polar feed to polar product allyl alcohol (AA) conversion to 4-hydroxybutanal (for production of 1,4-butanediol (BDO)) [46]. This process was developed by Kuraray and Daicel Chemical Industries [47, 48] and commercialized in 1990 by Arco (Lyondell since 1998) [49], and is described in Figure 6. 

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