Ethylene acetaldehyde conversion

In the one-stage process (Fig. 2), ethylene, oxygen, and recycle gas are directed to a vertical reactor for contact with the catalyst solution under slight pressure. The water evaporated during the reaction absorbs the heat evolved, and make-up water is fed as necessary to maintain the desired catalyst concentration. The gases are water-scmbbed and the resulting acetaldehyde solution is fed to a distUlation column. The tad-gas from the scmbber is recycled to the reactor. Inert materials are eliminated from the recycle gas in a bleed-stream which flows to an auxdiary reactor for additional ethylene conversion. 

Most of the vinyl acetate produced in the United States is made by the vapor-phase ethylene process. In this process, a vapor-phase mixture of ethylene, acetic acid, and oxygen is passed at elevated temperature and pressures over a fixed-bed catalyst consisting of supported palladium (85). Less than 70% oxygen, acetic acid, and ethylene conversion is realized per pass. Therefore, these components have to be recovered and returned to the reaction zone. The vinyl acetate yield using this process is typically in the 91—95% range (86). Vinyl acetate can be manufactured also from acetylene, acetaldehyde, and the hquid-phase ethylene process (see Vinyl polymers). 

One version of the gas phase process was developed by National Distillers Products (now Quantum Chemical) in the USA and another independently in Germany by Bayer together with Hoechst. In both versions, ethylene is reacted with acetic acid and oxygen on a palladium-containing fixed-bed catalyst at 5-10 bar and 175-200°C to form vinyl acetate and water. The explosion limit restricts the O2 content in the feed mixture so that the ethylene conversion is relatively small ( 10%). The acetic acid conversion is 20-35% with selectivi-ties to vinyl acetate of up to 94% (based on C2H4) and about 98-99% (based on AcOH). The most important side reaction of this process is the total oxidation of ethylene to carbon dioxide and water. Other by-products are acetaldehyde, ethyl acetate and heavy ends. After a multistep distillation the vinyl acetate purity is 99.9% with traces of methyl acetate and ethyl acetate that do not affect the subsequent use in polymerization. 

Ethylene feed and catalyst solution enter the bottom of the cylindrical reactor where the reaction proceeds at 125-130 C (255-265 °F) and 8-9 atm. (100-115 psig). The reactor contains internal distributors to insure good vapor-liquid distribution. Ethylene conversion is 96.7< 7o and selectivity to acetaldehyde is 9B.2 o. Even though there is a high exothermic heat of reaction, the reactor temperature is nearly isothermal because of the large quantity of catalyst solution circulated to the reactor. The reactor effluent is flashed adiabatically. Acetaldehyde product, unreacted ethylene, and flashed steam constitute the overhead vapor from the flash drum, and the catalyst solution is pumped from the bottom. 

High ethylene conversion and acetaldehyde yield were claimed with a heterogeneous catalyst consisting of Pd and Cu or VO as cocatalysts on VO nanotubes [62]. 

Liguras et al. investigated autothermal reforming of ethanol over ruthenium and nickel catalysts on structured supports such as ceramic foams and monoliths [212,213]. Conditions chosen were an O/C ratio of 0.61 and an S/C ratio of 1.5. The reaction was performed at a very high pre-heating temperature of the monoliths and consequently substantial conversion occurred even upstream of the reactor, which created a hot spot of up to 950 °C in the monoliths. A ceramic monolith coated with 5 wt.% ruthenium formed in addition to carbon oxides methane as the main byproduct, but there were also small amounts of acetaldehyde, ethylene and ethane [212]. When the S/C ratio was increased to 2.0, the by-products could be suppressed. Increasing the O/C ratio had a similar effect and also suppressed the methane formation. The ruthenium catalyst showed stable conversion for a 75-h test duration. Nickel/lanthana catalysts containing 13 wt.% nickel on a lanthana carrier showed similar performances with respect to activity, selectivity and stability [213]. 

Chemical production routes for ethanol synthesis use mainly ethylene hydratiza-tion [route (c) in Topic 5.3.1]. The direct ethylene hydratization option uses solid acid catalysts (e.g., H3PO4 on kieselguhr, montmorillonite, or bentonite) in a continuous gas-phase reaction at 60-80bar pressure and 250-300 °C. At an adjusted ethylene conversion of 5%, the selectivity to ethanol is 97%, with diethyl ether and acetaldehyde being the major side products. 

In addition to these principal commercial uses of molybdenum catalysts, there is great research interest in molybdenum oxides, often supported on siHca, ie, MoO —Si02, as partial oxidation catalysts for such processes as methane-to-methanol or methane-to-formaldehyde (80). Both O2 and N2O have been used as oxidants, and photochemical activation of the MoO catalyst has been reported (81). The research is driven by the increased use of natural gas as a feedstock for Hquid fuels and chemicals (82). Various heteropolymolybdates (83), MoO.-containing ultrastable Y-zeoHtes (84), and certain mixed metal molybdates, eg, MnMoO Ee2(MoO)2, photoactivated CuMoO, and ZnMoO, have also been studied as partial oxidation catalysts for methane conversion to methanol or formaldehyde (80) and for the oxidation of C-4-hydrocarbons to maleic anhydride (85). Heteropolymolybdates have also been shown to effect ethylene (qv) conversion to acetaldehyde (qv) in a possible replacement for the Wacker process. 

Equation 1 is referred to as the selective reaction, equation 2 is called the nonselective reaction, and equation 3 is termed the consecutive reaction and is considered to proceed via isomerization of ethylene oxide to acetaldehyde, which undergoes rapid total combustion under the conditions present in the reactor. Only silver has been found to effect the selective partial oxidation of ethylene to ethylene oxide. The maximum selectivity for this reaction is considered to be 85.7%, based on mechanistic considerations. The best catalysts used in ethylene oxide production achieve 80—84% selectivity at commercially useful ethylene—oxygen conversion levels (68,69). 

Other synthetic methods have been investigated but have not become commercial. These include, for example, the hydration of ethylene in the presence of dilute acids (weak sulfuric acid process) the conversion of acetylene to acetaldehyde, followed by hydrogenation of the aldehyde to ethyl alcohol and the Fischer-Tropsch hydrocarbon synthesis. Synthetic fuels research has resulted in a whole new look at processes to make lower molecular weight alcohols from synthesis gas. 

The Wacker process for the oxidation of ethylene to acetaldehyde with PdCb/CuCb at 100°C (212°F) with 95 percent yield and 95 to 99 percent conversion per pass. 

Dehydrogenation processes in particular have been studied, with conversions in most cases well beyond thermodynamic equihbrium Ethane to ethylene, propane to propylene, water-gas shirt reaction CO -I- H9O CO9 + H9, ethylbenzene to styrene, cyclohexane to benzene, and others. Some hydrogenations and oxidations also show improvement in yields in the presence of catalytic membranes, although it is not obvious why the yields should be better since no separation is involved hydrogenation of nitrobenzene to aniline, of cyclopentadiene to cyclopentene, of furfural to furfuryl alcohol, and so on oxidation of ethylene to acetaldehyde, of methanol to formaldehyde, and so on. 

The conversion of ethylene to acetaldehyde using a soluble palladium complex, developed in the late 1950s, was one of the early applications of homogeneous catalysis and the first organo-palladium reaction practised on an industrial scale [40], Typically this reaction requires stoichiometric amounts of CuCl under aerobic conditions. The use of copper represents not only an environmental issue, but often limits the scope of ligands that can be used in conjunction with Pd. 

We have delineated viable coordinated ligand reactions and their attendant intermediates for the stoichiometric conversion of CO ligands selectively to the C2 organics ethane, ethylene, methyl (or ethyl) acetate, and acetaldehyde. We now outline results from three lines of research (1) T -Alkoxymethyl iron complexes CpFe(C0)2CH20R (2) are available by reducing coordinated CO on CpFe(C0)3+ (1) [Cp = r -CsHs]. Compounds 2 then form t -alkoxyacetyl complexes via migratory-insertion (i,e. CO... 

The conversion of a chemical with a given molecular formula to another compound with the same molecular formula but a different molecular structure, such as from a straight-chain to a branched-chain hydrocarbon or an alicyclic to an aromatic hydrocarbon. Examples include the isomerization of ethylene oxide to acetaldehyde (both C2H40) and butane to isobutane (both C4H10). 

Disulfiram is the generic name for Antabuse, a drug used in the treatment of chronic alcoholism. Disulfiram potentiates the toxic and carcinogenic effects of 1,2-dibromoethane in experimental animals. Presumably, this occurs by blocking conversion of the aldehyde metabolite as with acetaldehyde from ethanol. There is no evidence that similar effects occur in humans. Based on animal data, however, Ayerst Laboratories, producers of Antabuse (disulfiram), recommended the following in the package insert "Patients taking Antabuse tablets should not be exposed to ethylene dibromide or its vapors" (PDR 1991). 

Practically all the heavy transition metals can be made to eatalyze olefin isomerization, presumably through transient formation of metal hydrides. A stable platinum hydride has been shown to react with ethylene to form a cT-CjHjPt complex which can eliminate ethylene to regenerate the hydride. The commercially successful processes for the conversion of ethylene to acetaldehyde and ethylene to vinyl acetate via PdClj catalysis have stimulated enormous interest in the mechanism of these reactions, their application to other conversions, and their extension to other catalytic systems. The various stages in the conversion of ethylene are quite well-understood and an important step in the reaction involves hydride migration. The exact role of Pd in the migration has not yet been elucidated. It seems almost certain that the phenomenal interest in the whole area of transition metal isomerization in the last several years will be more than matched by the wealth of work that is certain to pour out of research laboratories in the next few years. 

This cobalamin-dependent enzyme [EC 4.2.1.28] catalyzes the conversion of propane-1,2-diol to propanal and water. The enzyme also dehydrates ethylene glycol to acetaldehyde. 

Extensive experimental and theoretical studies on hydrogen production from SRE have been reported. In the thermodynamic studies carried out by Vasudeva et al. [190], it was reported that in all ranges of conditions considered, there is nearly complete conversion of ethanol and only traces of acetaldehyde and ethylene are present in the reaction equilibrium mixture. Methane formation is inhibited at high water-to-ethanol ratios or at high temperatures [191]. 

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