Carbon monoxide from acetaldehyde

From the amount of carbon monoxide and acetaldehyde produced, a minimum value of the quantum yield of the reaction has been estimated to be 0.04 at 25°C and 0.07 at 50°C. 

About half of the wodd production comes from methanol carbonylation and about one-third from acetaldehyde oxidation. Another tenth of the wodd capacity can be attributed to butane—naphtha Hquid-phase oxidation. Appreciable quantities of acetic acid are recovered from reactions involving peracetic acid. Precise statistics on acetic acid production are compHcated by recycling of acid from cellulose acetate and poly(vinyl alcohol) production. Acetic acid that is by-product from peracetic acid [79-21-0] is normally designated as virgin acid, yet acid from hydrolysis of cellulose acetate or poly(vinyl acetate) is designated recycle acid. Indeterrninate quantities of acetic acid are coproduced with acetic anhydride from coal-based carbon monoxide and unknown amounts are bartered or exchanged between corporations as a device to lessen transport costs. 

The changeover from ROO radicals to HOO radicals and the switch from organic peroxides to HOOH has been shown as temperature is increased in propane VPO (87,141). Tracer experiments have been used to explore product sequences in propane VPO (142—145). Propylene oxide comes exclusively from propylene. Ethylene, acetaldehyde, formaldehyde, methanol, carbon monoxide, and carbon dioxide come from both propane and propylene. Ethanol comes exclusively from propane. 

Acetic acid (qv) can be produced synthetically (methanol carbonylation, acetaldehyde oxidation, butane/naphtha oxidation) or from natural sources (5). Oxygen is added to propylene to make acrolein, which is further oxidized to acryHc acid (see Acrylic acid and derivatives). An alternative method adds carbon monoxide and/or water to acetylene (6). Benzoic acid (qv) is made by oxidizing toluene in the presence of a cobalt catalyst (7). 

Acetic acid is also produced hy the oxidation of acetaldehyde and the oxidation of n-hutane. However, acetic acid from the carhonylation route has an advantage over the other commercial processes because both methanol and carbon monoxide come from synthesis gas, and the process conditions are quite mild. 

North American producers of, 7 129t physical properties of, 7.T15-117 5 29t production from acetaldehyde, 7 102, 111 production from acetylene, 7 219 production from carbon monoxide, 5 4-5 production of, 76 299 24 265... 

Photolytic. Major products reported from the photooxidation of butane with nitrogen oxides under atmospheric conditions were acetaldehyde, formaldehyde, and 2-butanone. Minor products included peroxyacyl nitrates and methyl, ethyl and propyl nitrates, carbon monoxide, and carbon dioxide. Biacetyl, tert-butyl nitrate, ethanol, and acetone were reported as trace products (Altshuller, 1983 Bufalini et al, 1971). The amount of sec-butyl nitrate formed was about twice that of n-butyl nitrate. 2-Butanone was the major photooxidation product with a yield of 37% (Evmorfopoulos and Glavas, 1998). Irradiation of butane in the presence of chlorine yielded carbon monoxide, carbon dioxide, hydroperoxides, peroxyacid, and other carbonyl compounds (Hanst and Gay, 1983). Nitrous acid vapor and butane in a smog chamber were irradiated with UV light. Major oxidation products identified included 2-butanone, acetaldehyde, and butanal. Minor products included peroxyacetyl nitrate, methyl nitrate, and unidentified compounds (Cox et al., 1981). 

Photolytic. Major products reported from the photooxidation of 2,3-dimethylbutane with nitrogen oxides are carbon monoxide and acetone. Minor products included formaldehyde, acetaldehyde and peroxyacyl nitrates (Altshuller, 1983). Synthetic air containing gaseous nitrous acid and exposed to artificial sunlight (A. = 300-450 nm) photooxidized 2,3-dimethylbutane into acetone, hexyl nitrate, peroxyacetal nitrate, and a nitro aromatic compound tentatively identified as a propyl nitrate (Cox et al., 1980). 

In a separate investigation MargeHs and Roginekii1107 carried nut catalytic oxidation of ethylene at 350° over vanadium pentoxidc. reportedly similar to metallic silver in catalytic properties. TVv asoertainod that carbon dioxide was formed faster from, ethylene oxide, or from acetaldehyde under comparable conditions, than from ethylene itself. Further, they noted the formation of carbon monoxide, and determined that its rate of formation was considerably greater than that of carbon dioxide, increasing still more in the presence of adtk-d ethylene oxide. The addition of ethylene oxide also appeared to depro both ethylene oxide and acetaldehyde formation. They concluded that reactions leading to carbon dioxide and water did not proceed by wav of ethylene oxide, but by way of some other intermediates, and tlmt-this process could occur either on the catalyst surface or in the gas phase. 

Formaldehyde, acetaldehyde, acetone, and carbon monoxide were common combustion products of the four hexanes. Propionaldehyde, n-butyraldehyde, acrylic aldehyde, crotonic aldehyde, and methyl ethyl ketone were all found as intermediates in the combustion of n-hcxane. Acetaldehyde and acetone were prominent and propionaldehyde and acrylic aldehyde were present among the intermediates from 2-methylpentane. Acetaldehyde and methyl ethyl ketone were peculiarly characteristic of 3-methyl-pentane and acetaldehyde, acetone, and pivalic aldehyde were characteristic of 2,2-dimethylbutane. In other words, the intermediate monocarbonyl combustion products... 

Catalysts used to convert ethylene to vinyl acetate are closely related to those used to produce acetaldehyde from ethylene. Acetaldehyde was first produced industrially by the hydration of acetylene, but novel catalytic systems developed cooperatively by Farbwerke Hoechst and Wacker-Chemie have been used successfully to oxidize ethylene to acetaldehyde, and this process is now well established (7). However, since the largest use for acetaldehyde is as an intermediate in the production of acetic acid, the recent announcement of new processes for producing acetic acid from methanol and carbon monoxide leads one to speculate as to whether ethylene will continue to be the preferred raw material for acetaldehyde (and acetic acid). 

Few chemicals have experienced as long and as successful a career us acetic acid, Acetic acid reluins its importance in (he production of vinyl and cellulose acetates Acetic acid is made industrially by oxidation of acetaldehyde or butane in air, or from methanol and carbon monoxide. 

The recent dramatic increase in the price of petroleum feedstocks has made the search for high selectivities more urgent. Several new processes based on carbon monoxide sources are currently competing with older oxidation processes.103,104 The more straightforward synthesis of acetic acid from methanol carbonylation (Monsanto process) has made the Wacker process obsolete for the manufacture of acetaldehyde, which used to be one of the main acetic acid precursors. Several new methods for the synthesis of ethylene glycol have also recently emerged and will compete with the epoxidation of ethylene, which is not sufficiently selective. The direct synthesis of ethylene... 

As many as 70 products were at one time produced commercially from ethanol. Some of these downstream products are butanol, 2-ethyl hexanol, crotonaldehyde, butyraldehyde, acetaldehyde, acetic acid, butadiene, sorbic acid, 2-ethylbutanol, ethyl ether, many esters, ethanol-glycol ethers, acetic anhydride, vinyl acetate, ethyl vinyl ether, even ethylene gas. Many of these products are now more economically made from other feedstocks such as ethylene for acetaldehyde and methanol-carbon monoxide for acetic acid. Time will tell when a revival of biologically-oriented processes will offer lower-cost routes to at least the simpler products. 

Other oxidation products, in addition to those above, have been reported for the oxidation of DMS (I, 2, 16, 22, 23, 28, 35) formic acid, carbon dioxide, carbon monoxide, silanols (Si—OH), cyclic siloxanes, hydrogen, and methanol. Analogously, acetaldehyde and acetic acid are reported as the oxidation products from diethyl silicone at 160°—190° C. 

More reoently, Jolley71 has extended the data (Tables III and IV) in the region from 35 to 150°C. with a wide range of intensities. Filters restricted the chief absorbed wavelengths to 2537, 2650, and 3130 A. At 150 °C., using carbon-14 in the carbonyl group, the carbon monoxide, carbon dioxide, and acetaldehyde were found to be 93, 77, and 4% radioactive, respectively. 

Reactions involving abstraction from acetaldehyde are just as likely in diethyl ketone oxidation as reactions involving abstraction from formaldehyde in acetone oxidation. The acetyl radical so produced will oxidize as in the oxidation of acetone to give mostly carbon dioxide (from the -carbon atom of diethyl ketone71), but a little decomposition seems to occur since some carbon monoxide does not come from the original carbonyl group of the ketone.71... 

Calvert and Hanst88 using infrared analysis, have also re-investigated the photooxidation of acetaldehyde at 20°C. using 3130 A. radiation. Acetaldehyde pressures were chiefly about 42.5 nun., but the oxygen pressure was varied from 0 to 745 mm. Analyses were made for carbon monoxide, carbon dioxide, formic acid, methanol, acetic acid, peracetic acid, acetyl peroxide, methyl hydroperoxide, and unreacted acetaldehyde (Table X). Chains were short. Although they do not detect methyl hydroperoxide or diacetyl peroxide, the non-observance of a peroxide does not necessarily mean it is not formed. The decomposition of hydroperoxides on the smallest particle of catalyst is remarkably fast. 

This is probably because 0 atoms produced in primary process (45) react much more rapidly with C2H6 than with N20. Several products are formed including ethylene, butane, carbon monoxide, hydrogen, methane, and probably ethanol and acetaldehyde. More ethylene is formed than one would expect from the amount of butane. It was found that 0 atoms react rapidly with ethylene, which is one of the photolytic products. The reaction-rate constant of O atoms with ethylene is estimated to be about 330 times as rapid as that with ethane.82 Complete elucidation of the mechanism of O-atom reaction with ethane is complicated because of the rapid reaction of O atoms with one or more of the products. 

Using the catalyst system known from the Monsanto process, Dumas et at. have been able to direct the reaction towards ethanol formation using syngas mixtures extremely rich in hydrogen [87]. As is shown in Table XII, no acetic acid and only minor amounts of acetates are formed at an H3/CO ratio of 60. Ethanol and acetaldehyde aie the main products along with considerable amounts of methyl ethyl ether. Unfortunately, the Dumas c/ at. based the yields and conversion on carbon monoxide and not on methanol. This makes the data of this interesting process difficult to compare with those of other catalyst systems. 

FIGURE 1. Examples of reactions catalyzed by molybdenum containing enzymes. From top to bottom, hydroxylation of xanthine, hydroxylation of acetaldehyde, dehydrogenation of carbon monoxide, transhydroxylation of pyrogallol, oxidation of sulfite, reduction of nitrate, reduction of dimethylsulfoxide, oxidation of formate, reduction of polysulfide and formation of formylmethanofuran. 

---