Acetaldehyde/acetic anhydride route

Figure 3 shows the production of acetaldehyde in the years 1969 through 1987 as well as an estimate of 1989—1995 production. The year 1969 was a peak year for acetaldehyde with a reported production of 748,000 t. Acetaldehyde production is linked with the demand for acetic acid, acetic anhydride, cellulose acetate, vinyl acetate resins, acetate esters, pentaerythritol, synthetic pyridine derivatives, terephthaHc acid, and peracetic acid. In 1976 acetic acid production represented 60% of the acetaldehyde demand. That demand has diminished as a result of the rising cost of ethylene as feedstock and methanol carbonylation as the preferred route to acetic acid (qv). 

In 1953 the Celanese Corporation of America introduced a route for the production of vinyl acetate from light petroleum gases. This involved the oxidation of butane which yields such products as acetic acid and acetone. Two derivatives of these products are acetic anhydride and acetaldehyde, which then react together to give ethylidene diacetate (Figure 14.2.)... 

In fact, a plant may still be operated by Celanese which produces EDA by this reaction of acetaldehyde and acetic anhydride, each prepared through independent routes ( ). 

C. Acetaldehyde via Acetic Anhydride Reduction. Another route to... 

In the mid-l O s, it was found that acetic acid itself could be catalytically dehydrated to ketene, which when absorbed in fresh acid gave the anhydride. Soon after this process became commercially established, the older processes of making the anhydride were discontinued. By this time synthetic acetic acid was being made from acetylene via acetaldehyde oxidation, from synthetic ethyl alcohol also via acetaldehyde, and by the direct oxidation of fermentation ethyl alcohol. The ketene route to acetic anhydride, in addition to starting from acetic acid, later employed acetone as raw material. 

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. 

Acetic Anhydride. A total of 1.9 billion lb of acetic anhydride was produced in the United States in 1999. Commercial production of acetic anhydride is currently accomplished through two routes, one involving ketene and the other methyl acetate carbonylation. A former route based on liquid phase oxidation of acetaldehyde is now obsolete. 

The processes for the manufacture of acetic anhydride have included, initially, the distillation of wood pulp, which was followed by the ketene route from acetic acid or acetone and finally the ethylene based oxidation of acetaldehyde. The carbonylation of CH3OAC to acetic anhydride has in part replaced anhydride capacity from the more expensive processes. 

Subsequent developments of Eastman carbonylation technology are yet to be commercialized production routes to acetaldehyde, propionic acid, propionic anhydride, methacrylates, and acrylates (29). It is also relevant to note that dimethyl ether, readily available from methanol by dehydration, has recently achieved some prominence as a suitable raw material in carbonylation technology, via the intermediacy of methyl acetate and acetic anhydride in the case of acetic anhydride manufacture. It also offers the advantage of processing under totally anhydrous conditions. 

In subsequent developments, Eastman has reported two new alternative manufacturing routes to vinyl acetate (38). The first uses the carbonylation of dimethyl ether to acetic anhydride, followed by the reaction between acetic anhydride and acetaldehyde in a reactive distillation column to 3ueld vinyl acetate, whereas the second involves the intermediacy of ketene. Here ketene is hydrogenated to acetaldehyde, and the acetaldehyde is reacted with a second equivalent of ketene to produce vinyl acetate. Both of these routes are claimed to avoid the problematic and expensive acetic acid recycle. 

The cyanides 1408-1412 have all been synthesized by dehydrating their carbox-aldoximes with acetic anhydride [1070-1074]. A pteridine synthesis yielded 75% of 6-cyano-l,3-dimethyUumazine 1408 [1070]. N-Acetyl (3-phenyl-l,2,4-triazolo-5-yl)-thiolacetonitrile 1409 was obtained as the condensation product from a triazole derivative and chloro acetaldehyde, followed by oximation and dehydration, in 79% yield [1071]. endo-l-Cyano-3-acetoxy-8-oxabicyclo[3.2.1]oct-6-ene 1410 (89%) is an intermediate in the synthesis of ll-oxatricyclo[5.3.1.0 Jundecane [1072]. A synthesis of loi,25-dihydroxY-18-norvitamin Dj and la,25-dihydroxy-18,19-dinorvitamin Dj requires the 8j8-acetoxy-des-A,B-cholestane-18-nitrile 1411 (86%) [1073]. A new route to spirooxindoles, a tricyclic system found in a number of interesting natural products, requires the cyanide 1412 (72%) as a key intermediate [1074]. 

In the second step of the above synthetical route, acetaldehyde is oxidized to acetic anhydride by air at 30—60°C a mixture of copper and cobalt acetates serves as catalyst. A complex series of reactions is involved and acetic acid is also a major product. The overall process may be represented simply as follows ... 

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