Ethylene partial oxidation

Finally, some authors [31,130,131] employed 7-AI2O3 thin supported layers (pore size 4 nm) for ethylene partial oxidation in membrane reactors with separate feed of reactants. In such cases the membrane material had a specific surface area high enough to guarantee a direct catalyst support. 

Ethylene partial oxidation Metallic silver 13.00 Bond (1962)... 

When propylene was used for a fuel instead of ethylene, partial oxidation of propylene to acrolein was performed with a 96 % selectivity under short circuit conditions. Acrolein is a Jt-allyl oxidation product at a Pd° catalyst and is not a Wacker oxidation product at a Pd catalyst. When the oxidation rate of propylene was accelerated by an apphed voltage, acetone was produced with 90 % selectivity [5]. The anode potentials in operation were lower than a redox potential of Pd (+0.74 V (Ag/AgCl)) under short circuit conditions. On the other hand, the potentials were higher than the redox potential under applying voltage conditions [6, 7]. The oxidation state of Pd at the anode was Pd° under the former conditions and was Pd " under the latter conditions. The product selectivities to acrolein and acetone were able to control in the propylene oxidation by tuning anode potentials in operation. 

Acetaldehyde, first used extensively during World War I as a starting material for making acetone [67-64-1] from acetic acid [64-19-7] is currendy an important intermediate in the production of acetic acid, acetic anhydride [108-24-7] ethyl acetate [141-78-6] peracetic acid [79-21 -0] pentaerythritol [115-77-5] chloral [302-17-0], glyoxal [107-22-2], aLkylamines, and pyridines. Commercial processes for acetaldehyde production include the oxidation or dehydrogenation of ethanol, the addition of water to acetylene, the partial oxidation of hydrocarbons, and the direct oxidation of ethylene [74-85-1]. In 1989, it was estimated that 28 companies having more than 98% of the wodd s 2.5 megaton per year plant capacity used the Wacker-Hoechst processes for the direct oxidation of ethylene. 

Since 1960, the Hquid-phase oxidation of ethylene has been the process of choice for the manufacture of acetaldehyde. There is, however, stiU some commercial production by the partial oxidation of ethyl alcohol and hydration of acetylene. The economics of the various processes are strongly dependent on the prices of the feedstocks. Acetaldehyde is also formed as a coproduct in the high temperature oxidation of butane. A more recently developed rhodium catalyzed process produces acetaldehyde from synthesis gas as a coproduct with ethyl alcohol and acetic acid (83—94). 

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. 

Partial oxidation of natural gas or a fuel oil using oxygen may be used to form acetylene, ethylene (qv) and propylene (qv). The ethylene in turn may be partially oxidi2ed to form ethylene oxide (qv) via advantages (/) and (5). A few of the other chemicals produced using oxygen because of advantages (/) and (5) are vinyl acetate, vinyl chloride, perchloroethylene, acetaldehyde (qv), formaldehyde (qv), phthaHc anhydride, phenol (qv), alcohols, nitric acid (qv), and acryhc acid. 

Ethylene Oxidation to Ethylene Oxide. A thoroughly investigated reaction catalyzed by a supported metal is the commercially appHed partial oxidation of ethylene to give ethylene oxide (90). The desired reaction is the formation of ethylene oxide, ie, epoxidation the following reaction scheme is a good approximation ... 

Partial Oxidation of Ethylene to Ethylene Oxide. About 3.3 million metric tons of ethylene oxide were produced worldwide in 1988. Of this, about 70% was converted into ethylene glycol, and the balance went into detergents and other appHcations. An excellent review of ethylene oxide synthesis has been written (66). 

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). 

As an alternate to LNG, natural gas can be chemically converted to methanol, chemical feedstocks (such as ethylene), gasoline, or diesel fuel. Most processes start with the conversion of methane to synthesis gas, a mixture of carbon monoxide and hydrogen. This can be done partial oxidation, an exothermic reaction ... 

Most of the inhibitors in use are organic nitrogen compounds and these have been classified by Bregman as (a) aliphatic fatty acid derivatives, b) imidazolines, (c) quaternaries, (d) rosin derivatives (complex amine mixtures based on abietic acid) all of these will tend to have long-chain hydrocarbons, e.g. CigH, as part of the structure, (e) petroleum sulphonic acid salts of long-chain diamines (preferred to the diamines), (/) other salts of diamines and (g) fatty amides of aliphatic diamines. Actual compounds in use in classes (a) to d) include oleic and naphthenic acid salts of n-tallowpropylenediamine diamines RNH(CH2) NH2 in which R is a carbon chain of 8-22 atoms and x = 2-10 and reaction products of diamines with acids from the partial oxidation of liquid hydrocarbons. Attention has also been drawn to polyethoxylated compounds in which the water solubility can be controlled by the amount of ethylene oxide added to the molecule. 

The effect of Pc2H4 and Uwr on the rate of C2H4 oxidation is shown in Fig. 8.5. Increasing UWr causes a pronounced decrease in the ethylene partial pressure, pc2H4> necessary to reduce the surface Rh oxide and thus a dramatic, up to 100-fold, increase in reaction rate for intermediate PC2H4 values (p=100). 

Figure 8.79. Steady-state kinetics of C2H4 oxidation on Pt/Ce02 as a function of catalyst potential, UWR, and ethylene partial pressure (a) catalyst A, T=500°C, pO2=5.0 kPa (b) catalyst C, T=510°C, Pc2h4=4-8 kPa.71 Reprinted by permission of The Electrochemical Society.

If tars are formed (which happened in the trial with mixed PVC waste), it is necessary to apply a partial oxidation to convert these tars into gaseous products. Via a quench, HCl is recovered from the product stream which consists of fuel gas and HCl. After purification the HCl can be used for producing ethylene dichloride (EDC) via oxychlorination. The recovery of CI2 is more then 90%, in general 94%-97%. Inert materials in the feed, such as the chalk and metal stabilisers present in a PVC-formulation, are separated from the flue gas as fly ash or will be set free as a bleed from the circulating sand. 

A packed-bed nonpermselective membrane reactor (PBNMR) is presented by Diakov et al. [31], who increased the operational stability in the partial oxidation of methanol by feeding oxygen directly and methanol through a macroporous stainless steel membrane to the PB. Al-Juaied et al. [32] used an inert membrane to distribute either oxygen or ethylene in the selective ethylene oxidation. By accounting for the proper kinetics of the reaction, the selectivity and yield of ethylene oxide could be enhanced over the fixed-bed reactor operation. 

Small olefins, notably ethylene (ethene), propene, and butene, form the building blocks of the petrochemical industry. These molecules originate among others from the FCC process, but they are also manufactured by the steam cracking of naphtha. A wealth of reactions is based on olefins. As examples, we discuss here the epoxida-tion of ethylene and the partial oxidation of propylene, as well as the polymerization of ethylene and propylene. 

When a calcined Cr(VI)/Si02 catalyst is fed with ethylene at 373-423 K, an induction time is observed prior to the onset of the polymerization. This is attributed to a reduction phase, during which chromium is reduced and ethylene is oxidized [4]. Baker and Garrick obtained a conversion of 85-96% to Cr(II) for a catalyst exposed to ethylene at 400 K formaldehyde was the main by-product [44]. Water and other oxidation products have been also observed in the gas phase. These reduction products are very reactive and consequently can partially cover the surface. The same can occur for reduced chromium sites. Consequently, the state of sihca surface and of chromium after this reduction step is not well known. Besides the reduction with ethylene of Cr(Vl) precursors (adopted in the industrial process), four alternative approaches have been used to produce supported chromium in a reduced state ... 

T. Ito and J. H. Lunsford, Synthesis of ethylene and ethane by partial oxidation of methane over lithium-doped magnesium oxide, Nature, 1985, 314, 721. 

Scheme 5 Proposed reaction pathway for the partial oxidation of ethanol. The dehydration into ethylene intermediate is not included. 

Note that processes involving partial oxidation, such as conversion of ethylene to ethylene oxide, can pose significantly different hazards than the combustion systems described above. As such, processes involving partial oxidation should answer NO to Question 5. 

Numerous chemical intermediates are oxygen rich. Methanol, acetic acid and ethylene glycol show a O/C atomic ratio of 1, as does biomass. Other major chemicals intermediates show a lower O/C ratio, typically between 1/3 and 2/3. This holds for instance for propene and butene glycols, ethanol, (meth)acrylic acids, adipic acid and many others. The presence of some oxygen atoms is required to confer the desired physical and chemicals properties to the product. Selective and partial deoxygenation of biomass may represent an attractive and competitive route compared with the selective and partial oxidation of hydrocarbon feedstock. 

These values of A Hr are standard state enthalpies of reaction (aU gases in ideal-gas states) evaluated at 1 atm and 298 K. 7VU values of A are in kilojoules per mole of the first species in the equation. When A Hr is negative, the reaction hberates heat, and we say it is exothermic, while, when A Hr is positive, the reaction absorbs heat, and we say it is endothermic. Tks Table 2-2 indicates, some reactions such as isomerizations do not absorb or liberate much heat, while dehydrogenation reactions are fairly endothermic and oxidation reactions are fairly exothermic. Note, for example, that combustion or total oxidation of ethane is highly exothermic, while partial oxidation of methane to synthesis gas (CO + H2) or ethylene (C2H4) are only slightly exothermic. 

The selective oxidation of alkanes is cuiTently one of the most widely studied classes of catalytic reactions. This work mainly concentrates on the oxidative dehydrogenation of methane, with some attention paid to the partial oxidation of the product of this reaction, ethane. As regards the latter reaction, higher yields of pai tial oxidation products (acetaldehyde and ethylene) were achieved when N2O was used instead of O2 (1-6). 

Rb2Mo04 This catalyst was found to be much more active and selective than the divalent metal molybdates. As shown in Figure 2, very little decay was obsei ved in the conversion of ethane. In contrast with the previous catalysts, acetaldehyde was the main product of partial oxidation at 823 K it was fornied with a selectivity of 23-24%. The selectivity for ethylene was 10-13%. As it appears from Figure 2, the yield of acetaldehyde formation was about 5 times higher than on Mo03/Si02... 

With decrease of the reaction temperature, no change was experienced in the selectivity for ethylene, but there was an increase in the selectivity of acetaldehyde formation. The oxidation of ethane has been also investigated on Mo03/Si02. Under these conditions, this catalyst was found to be very active for the total oxidation of ethane. At 510 K, the conversion of ethane was 21%, the products of partial oxidation were formed only in trace amount. 

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