Carbon monoxide olefin hydrogenation effect

DiisononylPhthalate andDiisodeeylPhthalate. These primary plasticizers are produced by esterification of 0x0 alcohols of carbon chain length nine and ten. The 0x0 alcohols are produced through the carbonylation of alkenes (olefins). The carbonylation process (eq. 3) adds a carbon unit to an alkene chain by reaction with carbon monoxide and hydrogen with heat, pressure, and catalyst. In this way a Cg alkene is carbonylated to yield a alcohol a alkene is carbonylated to produce a C q alcohol. Due to the distribution of the C=C double bond ia the alkene and the varyiag effectiveness of certain catalysts, the position of the added carbon atom can vary and an isomer distribution is generally created ia such a reaction the nature of this distribution depends on the reaction conditions. Consequendy these alcohols are termed iso-alcohols and the subsequent phthalates iso-phthalates, an unfortunate designation ia view of possible confusion with esters of isophthaUc acid. 

Transition-metal organometallic catalysts in solution are more effective for hydrogenation than are metals such as platinum. They are used for reactions of carbon monoxide with olefins (hydroformyla-tion) and for some ohgomerizations. They are sometimes immobihzed on polymer supports with phosphine groups. 

From the results of other authors should be mentioned the observation of a similar effect, e.g. in the oxidation of olefins on nickel oxide (118), where the retardation of the reaction of 1-butene by cis-2-butene was greater than the effect of 1-butene on the reaction of m-2-butene the ratio of the adsorption coefficients Kcia h/Kwas 1.45. In a study on hydrogenation over C03O4 it was reported (109) that the reactivities of ethylene and propylene were nearly the same (1.17 in favor of propylene), when measured separately, whereas the ratio of adsorption coefficients was 8.4 in favor of ethylene. This led in the competitive arrangement to preferential hydrogenation of ethylene. A similar phenomenon occurs in the catalytic reduction of nitric oxide and sulfur dioxide by carbon monoxide (120a). 

The composition of the synthesis gas, particularly the concentrations of hydrogen, carbon monoxide, and carbon dioxide, affects the atmosphere throughout the reactor directly, and also indirectly by its effect on the composition of the recycle gas. Synthesis gas, prepared by partial combustion of methane or some less hydrogen-rich carbonaceous material, lacks sufficient hydrogen for the conversion of all the carbon monoxide to hydrocarbons, and in this sense the synthesis gas is deficient in hydrogen. Stoichiometrically methane has sufficient hydrogen to convert all its carbon to olefins by the two-step process ... 

Hydroformylation of linear olefins in a conventional cobalt oxo process (see Section 5.3) produces increasing linear-to-branched aldehyde ratios as the carbon monoxide ratio in the gas stream is increased up to 5 MPa (50 atm), but there is little further effect if the reaction mixture is saturated with carbon monoxide. An increasing partial pressure of hydrogen also increases this ratio up to a hydrogen pressure of 10 MPa. As the reaction temperature is increased, the linear-to-branched aldehyde ratios decreases. Solvents in conventional cobalt-catalyzed hydroformylation affect the isomer distribution. In propylene... 

The effect of trace contaminants on the reaction has been investigated carefully. All uncondensed effiuent gases were recycled to the reactor, except for the amounts present in the streams taken off for analysis or flashed upon depressuring of the organic phase. Aqueous phase from the separator containing the water soluble by-products has been used as the water feed to the reactor. Hydrogen chloride containing chlorinated hydrocarbons and acetylene was used in all operations. In addition, certain possible impurities were tested for their effect on the kinetics and selectivity of the process. Paraffins, carbon monoxide, sulfide, carbon dioxide, alkali, and alkaline earth metals were found to be chemically inert. Olefins, diolefins and acetylenic compounds are chlorinated to the expected products. No deleterious effects of by-product recycle were observed even when some of the main by-products were added extraneously. 

By a similar mechanism to that proposed for the formation of ethyl ether by dehydration of ethanol, it is possible that the reaction occurs stepwise with the intermediate dehydration of one ethanol molecule to form ethylene which then reacts with another ethanol molecule to form butanol. It is thus possible that higher alcohols may be built up by the reaction of olefins with the lower alcohols. Mixed oxide type of catalysts are used in the process of a nature similar to those which have been found effective in alcohol synthesis from hydrogen and carbon monoxide. It should lie noted here that catalysts which promote the union of carbon atoms must be used, and since potassium oxide promoted catalysts composed of mixtures of zinc, copper, or chromium oxides have been found to be effective in the syuthesis of higher alcohols, such catalysts should be useful in promoting the addition of olefins to alcohols or other oxygenated organic molecules.77... 

It has been reported that use of a suitable co-solvent increases the concentration of the olefin in water (catalyst) while retaining the biphasic nature of the system. It has been shown that using co-solvents like ethanol, acetonitrile, methanol, ethylene glycol, and acetone, the rate can be enhanced by several times [27, 28], However, in some cases, a lower selectivity is obtained due to interaction of the co-solvent with products (e.g., formation of acetals by the reaction of ethanol and aldehyde). The hydroformylation of 1-octene with dinuclear [Rh2(/t-SR)2(CO)2(TPPTS)2] and HRh(CO)(TPPTS)3 complex catalysts has been investigated by Monteil etal. [27], which showed that ethanol was the best co-solvent. Purwanto and Delmas [28] have reported the kinetics of hydroformylation of 1-octene using [Rh(cod)Cl]2-TPPTS catalyst in the presence of ethanol as a co-solvent in the temperature range 333-353 K. First-order dependence was observed for the effect of the concentration of catalyst and of 1-octene. The effect of partial pressure of hydrogen indicates a fractional order (0.6-0.7) and substrate inhibition was observed with partial pressure of carbon monoxide. A rate eqution was proposed (Eq. 2). 

The effect of reaction parameters, such as the concentrations of catalyst and olefin and the partial pressures of CO and hydrogen, on the rate of reaction has been studied at 373 K [19]. The rate varies linarly with catalyst concentration, olefin concentration, and partial pressure of hydrogen. Typical substrate-inhibited kinetics was observed with the partial pressure of carbon monoxide. Further, a rate equation to predict the observed rate data has been proposed (Eq. 5). 

Asinger and Berg 12) and workers at the Bureau of Mines 9) have shown that dicobalt octacarbonyl in the presence of carbon monoxide readily catalyzes the isomerization of terminal olefins and that the extent of isomerization increases with temperature and time. The small amount of hydrogen in the carbon monoxide has no marked effect on double-bond isomerization isomerization is not fast even when very large amounts of hydrogen are added. To show that isomerization occurs in the absence of hydrogen, the latter authors 9) refluxed a solution of dicobalt octacarbonyl in 1-hexene until complete conversion to the tricarbonyl, [Co(CO)s]4, took place 5% of the olefin was isomerized after this time. 

The kinetics of hydroformylation of 1-octene using [Rh(COD)Cl]2 as a catalyst precursor with TPPTS as a water-soluble ligand and ethanol as a co-solvent was further studied by Deshpande et al. [15] at different pH values. The rate increased by two- to fivefold when the pH increased from 7 to 10, while the dependence of the rate was found to be linear with olefin and hydrogen concentrations at both pH values. The rate of hydroformylation was foimd to be inhibited at higher catalyst concentrations at pH 7, in contrast to linear dependence at pH 10 (Figure 5). The effect of the concentration of carbon monoxide was linear at pH 7, in contrast to the usual negative-order dependence. At pH 10, substrate-inhibited kinetics was observed with respect to CO (Figure 6). 

---