Silver epoxidation

Supported catalysts in which a metal oxide is supported on a different metal oxide find tremendous use in commercial chemical production, petroleum refining, and environmental remediation [7], Table 2.1 lists a number of important industrial reactions that are catalyzed by supported metal oxides. The active phase consists of single metal oxides, metal oxide mixtures, or complex metal oxides. Some supported metal catalysts can, technically, be considered supported metal oxide catalysts if the metal is partially oxidized under reaction conditions, such as alumina-supported silver epoxidation catalysts and palladium-on-stabilized alumina combustion catalysts. Clearly, supported metal oxide compositions are diverse, especially considering that the range of relative amounts of the active phase to the support is large, and that additional metal oxides and modifiers can be introduced. 

Flaul R, Floge D, Neubauer G and Zeeck U 1982 Ethene epoxidation on silver oxide surface layers Surf. Scl. 122 L622-8... 

Bromine is used in the manufacture of many important organic compounds including 1,2-dibromoethane (ethylene dibromide), added to petrol to prevent lead deposition which occurs by decomposition of the anti-knock —lead tetraethyl bromomethane (methyl bromide), a fumigating agent, and several compounds used to reduce flammability of polyester plastics and epoxide resins. Silver(I) bromide is used extensively in the photographic industry... 

Selectivity of propylene oxide from propylene has been reported as high as 97% (222). Use of a gas cathode where oxygen is the gas, reduces required voltage and eliminates the formation of hydrogen (223). Addition of carbonate and bicarbonate salts to the electrolyte enhances ceU performance and product selectivity (224). Reference 225 shows that use of alternating current results in reduced current efficiencies, especiaHy as the frequency is increased. Electrochemical epoxidation of propylene is also accompHshed by using anolyte-containing silver—pyridine complexes (226) or thallium acetate complexes (227,228). 

The selective oxidation is catalyzed by silver, which is the only good catalyst. Other olefins are not converted selectively to the epoxides in the presence of silver. However, propylene epoxidation is appHed commercially the catalysts are either molybdenum complexes in solution or soHd Ti02—Si02 (see... 

Dehydrochlorination to Epoxides. The most useful chemical reaction of chlorohydrins is dehydrochlotination to form epoxides (oxkanes). This reaction was first described by Wurtz in 1859 (12) in which ethylene chlorohydria and propylene chlorohydria were treated with aqueous potassium hydroxide [1310-58-3] to form ethylene oxide and propylene oxide, respectively. For many years both of these epoxides were produced industrially by the dehydrochlotination reaction. In the past 40 years, the ethylene oxide process based on chlorohydria has been replaced by the dkect oxidation of ethylene over silver catalysts. However, such epoxides as propylene oxide (qv) and epichl orohydrin are stiU manufactured by processes that involve chlorohydria intermediates. 

For many years ethylene chlorohydrin was manufactured on a large iadustrial scale as a precursor to ethylene oxide, but this process has been almost completely displaced by the direct oxidation of ethylene to ethylene oxide over silver catalysts. However, siace other commercially important epoxides such as propylene oxide and epichlorohydrin cannot be made by direct oxidation of the parent olefin, chlorohydrin iatermediates are stiU important ia the manufacture of these products. 

Epoxides are normally hydrogenated in preference to saturated ketones but double bonds are usually reduced under these conditions. It is possible in some cases to selectively cleave an epoxide without saturating double bonds by the use of the deactivated catalysts recommended for the partial reduction of acetylenes (see section IV) or by the addition of silver nitrate to the palladium-catalyzed reaction mixture. " ... 

Rearrangement of fluorine with concomitant ring opening takes place in fluorinated epoxides Hexafluoroacetone can be prepared easily from perfluo-ropropylene oxide by isomerization with a fluorinated catalyst like alumina pre treated with hydrogen fluoride [26, 27, 28] In ring-opening reactions of epoxides, the distribution of products, ketone versus acyl fluoride, depends on the catalyst [29] (equation 7) When cesium, potassium, or silver fluoride are used as catalysts, dimenc products also are formed [29]... 

It seems that silver is a unique epoxidation catalyst for ethylene. All other catalysts are relatively ineffective, and the reaction to ethylene is limited among lower olefins. Propylene and butylenes do not form epoxides through this route. ... 

Ethylene oxide, the simplest epoxide, is an intermediate in the manufacture of both ethylene glycol, used for automobile antifreeze, and polyester polymers. More than 4 million tons of ethylene oxide is produced each year in the United States by air oxidation of ethylene over a silver oxide catalyst at 300 °C. This process is not useful for other epoxides, however, and is of little value in the laboratory. Note that the name ethylene oxide is not a systematic one because the -ene ending implies the presence of a double bond in the molecule. The name is frequently used, however, because ethylene oxide is derived pom ethylene by addition of an oxygen atom. Other simple epoxides are named similarly. The systematic name for ethylene oxide is 1,2-epoxyethane. 

Epoxides such as ethylene oxide and higher olefin oxides may be produced by the catalytic oxidation of olefins in gas-liquid-particle operations of the slurry type (S7). The finely divided catalyst (for example, silver oxide on silica gel carrier) is suspended in a chemically inactive liquid, such as dibutyl-phthalate. The liquid functions as a heat sink and a heat-transfer medium, as in the three-phase Fischer-Tropsch processes. It is claimed that the process, because of the superior heat-transfer properties of the slurry reactor, may be operated at high olefin concentrations in the gaseous process stream without loss with respect to yield and selectivity, and that propylene oxide and higher... 

The effect of alkali presence on the adsorption of oxygen on metal surfaces has been extensively studied in the literature, as alkali promoters are used in catalytic reactions of technological interest where oxygen participates either directly as a reactant (e.g. ethylene epoxidation on silver) or as an intermediate (e.g. NO+CO reaction in automotive exhaust catalytic converters). A large number of model studies has addressed the oxygen interaction with alkali modified single crystal surfaces of Ag, Cu, Pt, Pd, Ni, Ru, Fe, Mo, W and Au.6... 

The preparation of Pans-1,2-cyclohexanediol by oxidation of cyclohexene with peroxyformic acid and subsequent hydrolysis of the diol monoformate has been described, and other methods for the preparation of both cis- and trans-l,2-cyclohexanediols were cited. Subsequently the trans diol has been prepared by oxidation of cyclohexene with various peroxy acids, with hydrogen peroxide and selenium dioxide, and with iodine and silver acetate by the Prevost reaction. Alternative methods for preparing the trans isomer are hydroboration of various enol derivatives of cyclohexanone and reduction of Pans-2-cyclohexen-l-ol epoxide with lithium aluminum hydride. cis-1,2-Cyclohexanediol has been prepared by cis hydroxylation of cyclohexene with various reagents or catalysts derived from osmium tetroxide, by solvolysis of Pans-2-halocyclohexanol esters in a manner similar to the Woodward-Prevost reaction, by reduction of cis-2-cyclohexen-l-ol epoxide with lithium aluminum hydride, and by oxymercuration of 2-cyclohexen-l-ol with mercury(II) trifluoro-acetate in the presence of ehloral and subsequent reduction. ... 

DL-Valiolamine (205) was synthesized from the exo-alkene (247) derived from 51 with silver fluoride in pyridine. Compound 247 was treated with a peroxy acid, to give a single spiro epoxide (248, 89%) which was cleaved by way of anchimeric reaction in the presence of acetate ion to give, after acetylation, the tetraacetate 249. The bromo group was directly displaced with azide ion, the product was hydrogenated, and the amine acety-lated, to give the penta-A, 0-acetyl derivative (250,50%). On the other hand. 

Ethylene oxide is an important intermediate for ethylene glycol (antifreeze) and for plastics, plasticizers, and many other products [R.A. van Santen and H.P.C.E. Kui-pers, Adv. Catal. 35 (1987) 265]. In Chapter 1 we explained that the replacement of the traditional manufacturing process - which generated 1.5 mole of byproducts per 1 mole of epoxide - by a catalytic route based on silver catalysts is a major success story with respect to clean chemistry (Fig. 9.16). 

Figure 9.16. Ethylene hardly adsorbs on clean silver, but it does interact with preadsorbed oxygen atoms. At low coverages, the O atoms preferably interact with the C-H bond of ethylene, leading to its decomposition into fragments that oxidize to CO2 and H2O but at higher coverages the oxygen atoms become electrophilic and interact with the n-system of ethylene to form the epoxide. [After R.A. van Santen and H.P.C.E. Kuipers, Ac/v, Catal. 35 (1987) 265.]...

Figure 24. Size of metal particles and support pores in silver and gold catalysts for gas-phase propylene epoxidation.

The effect of microwave irradiation on the catalytic properties of a silver catalyst (Ag/Al203) in ethane epoxidation was studied by Klimov et al. [91]. It was found that on catalyst previously reduced with hydrogen the rates of both epoxidation and carbon dioxide formation increased considerably on exposure to a microwave field. This effect gradually decreased or even disappeared as the catalyst attained the steady state. It was suggested that this was very likely because of modification of electronic properties of the catalyst exposed to microwave irradiation. 

The catalytic epoxidation of ethylene on silver has been studied extensively over the last thirty years. The literature in this area is very broad and has been reviewed by several authors (2>2 3). In recent years considerable progress has been made towards a satisfactory understanding of the mechanism of this important and complex catalytic system. 

When oxygen is pumped to the catalyst the activity of oxygen on the silver catalyst-electrode increases considerably because of the applied voltage. It thus becomes possible to at least partly oxidize the silver catalyst electrode. In a previous communication it has been shown that the phenomenon involves surface rather than bulk oxidation of the silver crystallites (17). The present results establish the direct dependence of the change in the rates of epoxidation and combustion Ari and Ar2 on the cell overvoltage (Equations 2,3, and 5) which is directly related to the surface oxygen activity. 

If the activation energies for the epoxidation and combustion reactions on silver oxide equal E, then the rate coefficients k in equations (14) can be expressed as... 

The relative increase Ar /r Q in the rates of epoxidation (i=l) and combustion (i=2) is proportional to A/S, where A is the electrolyte surface area and S is the surface area of the silver catalyst electrode. Thus with a reactor having a low value of S (reactive oxygen uptake Q =.4 10 7 mol O2) a threefold increase in ethylene oxide yield was observed with a corresponding 20% increase in selectivity. 

II 0 H Rate constant for ethylene epoxidation (i=l and deep oxidation (i=2) on reduced silver, s bar... 

Scheme 8.27. Silver-mediated reaction of alkylzirconocenes with epoxides.

This epoxide to aldehyde rearrangement was postulated to be the first step in the silver-mediated reaction of alkylzirconocene chlorides with epoxides, in which the aldehyde is subsequently alkylated by the alkylzirconocene species (cf. Scheme 8.44) [56], In a control experiment, it was shown that zirconocene dichloride (1 equivalent or less) and silver (catalytic amounts) do indeed induce the rearrangement of an epoxide to an aldehyde very quickly. 

While chlorine is a poison for the ammonia synthesis over iron, it serves as a promoter in the epoxidation of ethylene over silver catalysts, where it increases the selectivity to ethylene oxide at the cost of the undesired total combustion to C02. In this case an interesting correlation was observed between the AgCl27Cl ratio from SIMS, which reflects the extent to which silver is chlorinated, and the selectivity towards ethylene oxide [16]. In both examples, the molecular clusters reveal which elements are in contact in the surface region of the catalyst. 

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