Production of Acetate

The lipolytic activity associated with the myceha was stable for more than 8 months when the lyophilized biocatalyst was maintained under dry conditions over P2O5. 

The carboxylesterases involved in the esterification of geraniol and butyric acid have been partially purified they are tightly membrane bound and only the use of a surfactant such as 3-[(3-cholamidopropyl)dimethylammonium]-l-propanesulfo-nate (CHAPS) allowed their removal from cellular membranes. From a biocatalytic point of view, this situation can be seen as if the enzymes were immobilized into a hydrophobic carrier. 

Many acetate esters (such as those of isoamyl, benzyl, citroneUyl, and geranyl alcohols) are components of natural flavors. They can be obtained by Upase-cata-lyzed esteriflcation in organic solvents, but the major problem with enzymatic acetylations is deactivation of lipases by acetic acid [8, 9]. Most of the Upase-catalyzed syntheses of esters have been carried out by transesterification to avoid free acid toxicity and water formation. Claon and Akoh [10] found that immobilized lipases from Candida antarctica promote highly effective direct esterification of geraniol and citronellol with acetic acid. 

Dry mycelia of A. oryzae MIM efficiently catalyzed the esterification between free acetic acid and primary alcohols in organic solvent [11] (Table 6.2). 

The most relevant features of this biotransformation are the following. 

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Homogeneous catalysts. With a homogeneous catalyst, the reaction proceeds entirely in the vapor or liquid phase. The catalyst may modify the reaction mechanism by participation in the reaction but is regenerated in a subsequent step. The catalyst is then free to promote further reaction. An example of such a homogeneous catalytic reaction is the production of acetic anhydride. In the first stage of the process, acetic acid is pyrolyzed to ketene in the gas phase at TOO C ... 

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. 

Commercial production of acetic acid has been revolutionized in the decade 1978—1988. Butane—naphtha Hquid-phase catalytic oxidation has declined precipitously as methanol [67-56-1] or methyl acetate [79-20-9] carbonylation has become the technology of choice in the world market. By-product acetic acid recovery in other hydrocarbon oxidations, eg, in xylene oxidation to terephthaUc acid and propylene conversion to acryflc acid, has also grown. Production from synthesis gas is increasing and the development of alternative raw materials is under serious consideration following widespread dislocations in the cost of raw material (see Chemurgy). 

Trioxane and Tetraoxane. The cycHc symmetrical trimer of formaldehyde, trioxane [110-88-3] is prepared by acid-catalyzed Hquid- or vapor-phase processes (147—151). It is a colorless crystalline soHd that bods at 114.5°C and melts at 61—62°C (17,152). The heats of formation are — 176.9 kJ/mol (—42.28 kcal/mol) from monomeric formaldehyde and —88.7 kJ/mol (—21.19 kcal/mol) from 60% aqueous formaldehyde. It can be produced by continuous distillation of 60% aqueous formaldehyde containing 2—5% sulfuric acid. Trioxane is extracted from the distillate with benzene or methylene chloride and recovered by distillation (153) or crystallization (154). It is mainly used for the production of acetal resins (qv). 

Formic acid was a product of modest industrial importance until the 1960s when it became available as a by-product of the production of acetic acid by hquid-phase oxidation of hydrocarbons. Since then, first-intent processes have appeared, and world capacity has climbed to around 330,000 t/yr, making this a medium-volume commodity chemical. Formic acid has a variety of industrial uses, including silage preservation, textile finishing, and as a chemical intermediate. 

Butane. Butane LPO has been a significant source for the commercial production of acetic acid and acetic anhydride for many years. At various times, plants have operated in the former USSR, Germany, Holland, the United States, and Canada. Only the Hoechst-Celanese Chemical Group, Inc. plants in Pampa, Texas, and Edmonton, Alberta, Canada, continue to operate. The Pampa plant, with a reported aimual production of 250,000 t/yr, represents about 15% of the 1994 installed U.S. capacity (212). Methanol carbonylation is now the dominant process for acetic acid production, but butane LPO in estabhshed plants remains competitive. 

The production of acetic acid from butane is a complex process. Nonetheless, sufficient information on product sequences and rates has been obtained to permit development of a mathematical model of the system. The relationships of the intermediates throw significant light on LPO mechanisms in general (22). Surprisingly, ca 25% of the carbon in the consumed butane is converted to ethanol in the first reaction step. Most of the ethanol is consumed by subsequent reaction. 

Production of maleic anhydride by oxidation of / -butane represents one of butane s largest markets. Butane and LPG are also used as feedstocks for ethylene production by thermal cracking. A relatively new use for butane of growing importance is isomerization to isobutane, followed by dehydrogenation to isobutylene for use in MTBE synthesis. Smaller chemical uses include production of acetic acid and by-products. Methyl ethyl ketone (MEK) is the principal by-product, though small amounts of formic, propionic, and butyric acid are also produced. / -Butane is also used as a solvent in Hquid—Hquid extraction of heavy oils in a deasphalting process. 

Uses. The lowest member of this class, ketene itself, is a powerful acetylating agent, reacting with compounds containing a labile hydrogen atom to give acetyl derivatives. This reaction is used only when the standard acetylation methods with acetic anhydride or acetyl chloride [75-36-5] do not work weU. Most of the ketene produced worldwide is used in the production of acetic anhydride. Acetic anhydride is prepared from the reaction of ketene and acetic acid. 

This process is one of the three commercially practiced processes for the production of acetic anhydride. The other two are the oxidation of acetaldehyde [75-07-0] and the carbonylation of methyl acetate [79-20-9] in the presence of a rhodium catalyst (coal gasification technology, Halcon process) (77). The latter process was put into operation by Tennessee Eastman in 1983. In the United States the total acetic anhydride production has been reported to be in the order of 1000 metric tons. 

World methanol consumption for 1992 is shown in Figure 10 (27). The principal use of methanol has traditionally been in the production of formaldehyde [50-00-0] where typically around 40% of the world methanol market is consumed. In the United States, an increasing role for methanol has been found in the oxygenated fuels market from the use of MTBE. Another significant use of methanol is in the production of acetic acid other uses include the production of solvents and chemical intermediates. 

In 1973, a multistage surface-fermentation process was patented in Japan for the production of acetic acid (42) eight surface fermenters were connected in series and arranged in such a way that the mash passed slowly through the series without disturbing the film of yAcetobacter on the surface of the medium. This equipment is reported to produce vinegar of 5% acidity and 0.22% alcohol with a mean residency time in the tanks of 22 h. 

The PVA process is highly capital-iatensive, as separate faciUties are required for the production of poly(viayl acetate), its saponification to PVA, the recovery of unreacted monomer, and the production of acetic acid from the ester formed during alcoholysis. Capital costs are far in excess of those associated with the traditional production of other vinyl resins. 

A primary use for iodine is as a catalyst in the production of acetic acid (qv) (39). Iodine is converted to compounds used in mbber, stabilizers, animal feed supplements, colorants, pharmaceuticals, sanitary products, and photographic products. 

In 1996, consumption in the western world was 14.2 tonnes of rhodium and 3.8 tonnes of iridium. Unquestionably the main uses of rhodium (over 90%) are now catalytic, e.g. for the control of exhaust emissions in the car (automobile) industry and, in the form of phosphine complexes, in hydrogenation and hydroformylation reactions where it is frequently more efficient than the more commonly used cobalt catalysts. Iridium is used in the coating of anodes in chloralkali plant and as a catalyst in the production of acetic acid. It also finds small-scale applications in specialist hard alloys. 

An alternative route to acrylic esters is via a (3-propiolactone intermediate. The lactone is obtained by the reaction of formaldehyde and ketene, a dehydration product of acetic acid ... 

The production of acetic acid from n-butene mixture is a vapor-phase catalytic process. The oxidation reaction occurs at approximately 270°C over a titanium vanadate catalyst. A 70% acetic acid yield has been reported. The major by-products are carbon oxides (25%) and maleic anhydride (3%) ... 

Acetic acid is a versatile reagent. It is an important esterifying agent for the manufacture of cellulose acetate (for acetate fibers and lacquers), vinyl acetate monomer, and ethyl and butyl acetates. Acetic acid is used to produce pharmaceuticals, insecticides, and dyes. It is also a precursor for chloroacetic acid and acetic anhydride. The 1994 U.S. production of acetic acid was approximately 4 billion pounds. 

The production of acetic anhydride from acetic acid occurs via the intermediate formation of ketene where one mole of acetic acid loses one mole of water ... 

The balanced equation for production of acetic acid from ethanol is... 

In fermentation for the production of acetic acid, ethyl alcohol is used in an aerobic process. In an ethanol oxidation process, the biocatalyst Acetobacter aceti was used to convert ethanol to acetic acid under aerobic conditions. A continuous fermentation for vinegar production was proposed for utilisation of non-viable A. aceti immobilised on the surface of alginate beads. 

Although most industrial catalysts are heterogeneous, a growing number of industrial reactions use homogeneous catalysts. One example is the production of acetic acid. Most of the 2.1 billion kilograms of acetic acid produced annually is used in the polymer industry. The reaction of methanol and carbon monoxide to form acetic acid is catalyzed by a rhodium compound that dissolves in methanol ... 

Several other important commercial processes need to be mentioned. They are (not necessarily in the order of importance) the low pressure methanol process, using a copper-containing catalyst which was introduced in 1972 the production of acetic add from methanol over RhI catalysts, which has cornered the market the methanol-to-gasoline processes (MTG) over ZSM-5 zeolite, which opened a new route to gasoline from syngas and ammoxidation of propene over mixed-oxide catalysts. In 1962, catalytic steam reforming for the production of synthesis gas and/or hydrogen over nickel potassium alumina catalysts was commercialized. 

The same mechanism proposed for the combustion catalyst Mg-chromite apply also to catalysts that allow significant yields in acetic acid from n-butane, like vanadia-titania, that accordingly also show a medium-high Brpnsied acidity. Being acetate ions intermediates in the combustion way, it is easily rationalized that the production of acetic acid is favored by the addition of steam in the reactant mixture and by adjusting the reaction conditions. 

The formation of C-C bonds is of key importance in organic synthesis. An important catalytic methodology for generating C-C bonds is provided by carbonylation. In the bulk chemicals arena this is used for the production of acetic acid by methanol carbonylation (Eqn. (9)) in the presence of rhodium- or, more recently, iridium-based catalysts (Maitlis et al, 1998). 

The rate of production of acetic acid (kg acid/kg charge sec) is... 

Increased fat content in milk The sow has responded to increased fibre in the diet, like the dairy cow, by increasing the production of acetate, which has then beneficially increased the fat content of the milk. 

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