Industrial Application of Hydroformylation

The main industrial application of hydroformylation is in the production of butanal from propene (CH3CH = CH2 -------- CH3CH2CH2CHO). Subsequent hydro-... 

The main industrial application of hydroformylation is in the production of butanal... 

Metal-catalysed hydrocarboxylation of olefins (Equation 3) is the poor relative of the more famous hydroformylation. It generally requires forcing reaction conditions and suffers from mediocre activities and selectivities (n/i ratio). Moreover, the same products can be made via hydroformylation and oxidation of the aldehyde product.431 Consequently, there are few industrial applications of hydrocarboxylation e.g. Ni(CO)4-catalysed production of propionic acid by hydrocarboxylation of ethylene.432,433... 

The application of hydroformylation is not limited to unfunctionalized petrochemicals. Also, renewables are of interest for industrial applications. One good available resource is oleocompounds which possess C=C-double bonds [16]. Ucciani and Lai first investigated the hydroformylation of unsaturated fatty acid esters using cobalt catalysts such as cobalt laurate or dicobalt octacarbonyl (Scheme 6) [17, 18]. 

This reaciion was discovered in the late 1930s by Otto Roelen of Ruhrehemie, who was working on Fischer-Tropsch4ype chemistry. He found that alkencs can be converted to aldehydes by treatment with CO and H2 in the presence of a cobalt catalyst at elevated temperatures and pressures 12—14]. Today, in terms of product volume, hydroformylation represents one of the largest industrial applications of soluble transition metal catalysts. 

New functionalizing reactions with carbon monoxide to give carbonyl compounds, in addition to hydroformylation, have been developing rapidly during the past ten years, but mainly for laboratory-scale synthesis. Industrial applications of carbon monoxide in the synthesis of fine chemicals have been until now rare. In this section, applications of the carbonylation of benzyl-, aryl-, and related vinyl-and allyl-X compounds are discussed [1]. Emphasis is given especially to a fundamental understanding and to technically interesting developments. 

As far as is known, the only industrial application of the water-soluble catalyst for the hydroformylation of 5 -functionalized alkenes has been developed by Kura-ray [17]. In this process, 7-octen-l-al is hydroformylated into nonane-1,9-dial, a precursor of nonene-l,9-diol, by using a rhodium catalyst and the monosulfonated tri-phenylphosphine as water-soluble ligand in a 1 1 sulfolane/water system. At the completion of reaction, the aldehydes are extracted from the reaction mixture with a primary alcohol or a mixture of primary alcohol and saturated aliphatic hydrocarbon (cf. Section 6.9). 

The catalytic addition of CO and H2 (synthesis gas) to olefins (hydroformylation or oxo-synthesis) is one of the major industrial applications of homogeneous catalysis. Over 6 million metric tons of aldehydes or alcohols (oxo-products) are produced worldwide per year. Commodities based on the C4 oxygenates currently have... 

As mentioned earlier, supercritical fluids have a broad potential for application in new processes. In recent years a number of publications reviewed the role of supercritical fluids in technical applications [9-16], and more industrial applications of sc-fluids were established in the synthesis of fine chemicals. In a variety of reactions such as hydrogenations, hydroformylations and Friedel-Crafts reactions, the advantageous use of sc-fluids as solvents has been demonstrated with respect to yield, selectivities, and no work-up procedure [17]. 

Indeed, sulfonated phosphine ligands appear to have been first developed and studied for industrial application in hydroformylation. An early example of hydroformylation in a two-phase system (1-hexene-water) with the TPPMS analogue of the Wilkinson complex appeared in the public-domain literature in the 1970s [126]. 

The hydroformylation of olefins is a type of CO insertion reaction that is one of the most important industrial applications of homogeneous catalysis with transition metal complexes (208,209). Conventional industrial processes (e.g., the Oxo process) typically use either cobalt- or rhodium-based catalysts and conduct the reaction in two-phase gas-liquid reactors. Efficient transfer of the reactants from the gas phase into the liquid phase is of primary importance to minimize inherent mass transfer limitations (208). Reactor design thus focuses on optimizing this mass transfer rate by maximizing the interfacial area between phases. An SCE process eliminates this transport restriction since the hydrogen... 

Biphasic catalysis in the presence of water-soluble catalysts has been the most significant development in recent years. After the report of Kuntz on the synthesis of sulfonated triarylphosphine TPPTS (Figure 14.1) and its successful industrial application in Rh-catalyzed hydroformylation of propene, great attention has been focused on the scientific study and industrial application of water-soluble catalysts, especially on water-soluble phosphines [6, 7], phosphites, and other phosphide compounds as well as their rhodium complexes [8]. Among them, TPPTS is the most widely studied and applied. Other important phosphine hgands will he introduced later. 

The main use of rhodium is with platinum in catalysts for oxidation of automobile exhaust emissions. In the chemical industry, it is used in catalysts for the manufacture of ethanoic acid, in hydroformylation of alkenes and the synthesis of nitric acid from ammonia. Many applications of iridium rely on... 

If cobalt carbonylpyridine catalyst systems are used, the formation of unbranched carboxylic acids is strongly favored not only by reaction of a-olefins but also by reaction of olefins with internal double bonds ( contrathermo-dynamic double-bond isomerization) [59]. The cobalt carbonylpyridine catalyst of the hydrocarboxylation reaction resembles the cobalt carbonyl-terf-phos-phine catalysts of the hydroformylation reaction. The reactivity of the cobalt-pyridine system in the hydrocarboxylation reaction is remarkable higher than the cobalt-phosphine system in the hydroformylation reaction, especially in the case of olefins with internal double bonds. This reaction had not found an industrial application until now. 

Regioselective reactions belong to the most important applications of homogeneous catalysis. An example is the hydroformylation of alkenes, which is a very important industrial reaction ... 

The hydroformylation of alkenes, which was originally discovered by Otto Roelen in 1938 [1], has developed into one of the most important applications of homogeneous catalysis in industry (Scheme 1) [2,3]. Today, more than 9 million tons of so-called oxo-products are produced per year, a number which is still rising continuously. The majority of these oxo-products stem... 

Amidocarbonylation converts aldehydes into amido-substituted amino acids, which have many important industrial applications ranging from pharmaceuticals to detergents and metal-chelating agents.588 Two catalyst systems have been developed, a cobalt-based system and, more recently a palladium-based system. In the cobalt system, alkenes can be used as the starting material, thus conducting alkene-hydroformylation, formation of hemi-amidal and carbonylation in one pot as... 

The ionic liquid investment could be further reduced if future research enables the application of ammonium based alkylsulfate or arylsulfonate ionic liquids. For these systems bulk prices around 15 /kg are expected. Ammonium based alkylsulfate or arylsulfonate ionic liquids usually show melting points slightly above room temperature but clearly below the operating temperature of the hydroformylation reaction. Therefore these systems may be less suitable for the liquid-liquid biphasic process in which the ionic liquid may be involved in process steps at ambient temperature (e.g. phase separation or liquid storage). In contrast, for the SILP catalyst a room temperature ionic liquid is not necessarily required as long as the film becomes a liquid under the reaction conditions. Assuming an ammonium based SILP catalyst, the capital investment for the ionic liquid for the industrial SILP catalyst would add up to 105,000 . 

The principal product of the hydroformylation which is most desired in industrial applications is a linear aldehyde. The unmodified, cobalt-catalyzed processes produce a mixture of linear and branched aldehydes, the latter being mostly an a-methyl isomer. For the largest single application—propylene to butyraldehydes—the product composition has an isomer ratio (ratio of percent linear to percent branched) of (2.5 t.0)/l. The isobutyraldehyde cannot be used to make 2-ethylhexanol, and iso-... 

Optically active aldehydes are important precursors for biologically active compounds, and much effort has been applied to their asymmetric synthesis. Asymmetric hydroformylation has attracted much attention as a potential route to enantiomerically pure aldehyde because this method starts from inexpensive olefins and synthesis gas (CO/H2). Although rhodium-catalyzed hydrogenation has been one of the most important applications of homogeneous catalysis in industry, rhodium-mediated hydroformylation has also been extensively studied as a route to aldehydes. 

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