Acetone, large-scale production

Fermentative Manufacture. Throughout the years, riboflavin yields obtained by fermentation have been improved to the point of commercial feasibiUty. Most of the riboflavin thus produced is consumed in the form of cmde concentrates for the enrichment of animal feeds. Riboflavin was first produced by fermentation in 1940 from the residue of butanol—acetone fermentation. Several methods were developed for large-scale production (41). A suitable carbohydrate-containing mash is prepared and sterilised, and the pH adjusted to 6—7. The mash is buffered with calcium carbonate, inoculated with Clostridium acetohutylicum and incubated at 37—40°C for 2—3 d. The yield is ca 70 mg riboflavin/L (42) (see Fermentation). 

In the modified Raschlg process , used by Bayer A.G. and by Mobay Chem. Co. for large scale production of hydrazine, the intermediacy of an oxaziridine could be clearly evidenced (81MI50800). In this process ammonia and hypochlorite are reacted in the presence of acetone to form ketazine (302). Nitrogen-nitrogen bond formation is faster by a factor of about 1000 in the presence of acetone than in its absence. Thus acetone does not merely trap hydrazine after formation, but participates in the N —N bond forming reaction. Very fast formation of oxaziridine (301), which is isolable, is followed by its likewise fast reaction with ammonia. 

Autoxidation may in some cases be of preparative use thus reference has already been made to the large-scale production of phenol+ acetone by the acid-catalysed rearrangement of the hydroperoxide from 2-phenylpropane (cumene, p. 128). Another example involves the hydroperoxide (94) obtained by the air oxidation at 70° of tetrahydro-naphthalene (tetralin) the action of base then yields the ketone (a-tetralone, 95), and reductive fission of the 0—0 linkage the alcohol (a-tetralol, 96) ... 

The other change that needed to be made in the synthesis of RSR 13 for in vivo administration was the method of purification. RSR 13 is used in vivo as the sodium salt. I prepared the first batch for in vivo toxicology by triturating RSR 13 sodium salt with acetone to remove any vestiges of water. However, the first industrial scale-up procedure called for crystallization of the salt from ethanol-water. The ethanol-water crystals were not as soluble as the acetone triturated method and could not be formulated at a reasonable volume. We performed the crystal structure determination of the ethanol-water crystals and found that it was a heptahydrate (Figure 17.5) [50]. The problem for large-scale production of RS R13 was solved eventually by the industrial producers of RSR 13. 

More recently, a simple synthetic route for a large scale production of 12 (2,3-0-isopropylidene-L-lyxonolactone) was described [27]. The chosen starting material was D-ribose (13), which was oxidized to the corresponding lactone 14 (Scheme 5). The latter was submitted in situ to acetonation to provide the 2,3-0-isopropylidene derivative 9, which was then mesylated at OH-5. Treatment of the crude 5-0-mesylate 15 with potassium hydroxide led to 12 according to the mechanism proposed in Scheme 5. 

Fermentation has been used in the production of foods and drinks since the days of antiquity. A recent application is the large-scale production of yogurt. Before the advent of cheap petroleum, a variety of other commodity chemicals were produced by fermentation. Acetone and n-butyl alcohol were produced by Clostridium aceto-butylicum.17 Ethanol, which was all made from fermentation, is now made in part by the hydration of ethylene. Acetic acid is now made largely by the carbonylation of methanol (9.2) using a rhodium catalyst in the presence of iodide ion.18... 

Cumene is an important intermediate in the industrial production of phenol, acetone and a-methylstyrene. The large-scale production of cumene is based on the alkylation of benzene with propene over Friedel-Crafts [1] or phosphoric acid on silica catalysts [2]. Zeolites, namely ZSM-5 and ZSM-11, have also been shown to be potential catalysts for this process [3, 4]. However, the formation of cumene (isopropylbenzene. IPB) on this catalysts is accompanied by its isomerization to n-propylbenzene (NPB). The latter is considered as an undesired by-product with respect to further processing of cumene to phenol and acetone. Therefore, preventing the formation of NPB would enable the substitution of the current catalysts used in the industrial process by ZSM-5 or ZSM-11 type solid acids which have major advantages in terms of environmental protection, safety, and avoidance of corrosion. 

A comparative study of six different strains of the organism commonly concerned in large-scale production of butyl alcohol and acetone by the biological process. / BacterioL, 14, 399-424. 

Yeasts, molds, and bacteria are used commercially for the large-scale production of various organic compounds. An important example, in addition to ethanol production, is the anaerobic fermentation of starch by certain bacteria to yield 1-butanol, acetone, ethanol, carbon dioxide, and hydrogen. 

Organic solvents snch acetone, chloroform, or methanol can also be used to extract enzymes. These chemicals liberate the enzyme by creating pores and channels in the cell membrane. However, organic solvents use is limited in large-scale production due to their toxicity, flammability, high costs, and possible protein dena-turation effects (Ghosal and Srivastava, 2009). 

Some strains of Clostridium aurantibutyricum and C. beijerinckii have the capacity to reduce acetone to isopropanol, and in these organisms, isopropanol may supercede acetone as the second most abundant neutral end product after butanol (George et al. 1983). The butanol- and isopropanol-producing organism Clostridium toanum Baba (Prescott and Dunn 1959c) was used in large-scale production of butanol and isopropanol in Taiwan between 1942 and 1958 (see the section O Industrial Solvent Fermentation in this chapter), but this organism is not available from any major culture collection. 

Weyer ER, Rettger LF (1927) A comparative study of six different strains of the organism commonly concerned in large-scale production of butyl alcohol and acetone by the biological proass. J Bacteriol 14 399-424 Whitfield CD, Mayhew SG (1974) Purification and properties of electron-transferring flavoprotein from P tostr tococcus elsdenii J Biol Chem 249 2801-2810... 

The problem of selective oxidation of alkylarens to hydroperoxides is economically sound. Hydroperoxides are used as intermediates in the large-scale production of important monomers. For instance, propylene oxide and styrene are synthesized from a-phenyl ethyl hydroperoxide (PEH), and cumyl hydroperoxide is the precursor in the synthesis of phenol and acetone. The method of modifying the Ni" and Fe° complexes used in the selective oxidation... 

Dehydrogenation. Before the large-scale availabiUty of acetone as a co-product of phenol (qv) in some processes, dehydrogenation of isopropyl alcohol to acetone (qv) was the most widely practiced production method. A wide variety of catalysts can be used in this endothermic (66.5 kj/mol (15.9 kcal/mol) at 327°C), vapor-phase process to achieve high (75—95 mol %) conversions. Operation at 300—500°C and moderate pressures (207 kPa (2.04 atm)) provides acetone in yields up to 90 mol %. The most useful catalysts contain Cu, Cr, Zn, and Ni, either alone, as oxides, or in combinations on inert supports (see Catalysts, supported) (13-16). 

Other Processes. Isopropyl alcohol can be prepared by the Hquid-phase oxidation of propane (118). It is produced iacidentaHy by the reductive condensation of acetone, and is pardy recovered from fermentation (119). Large-scale commercial biological production of isopropyl alcohol from carbohydrate raw materials has also been studied (120—123). 

The Hock process includes the oxidation of cumene by air to hydroperoxides using large bubble columns and the cleavage of the hydroperoxide via acid catalysis, which is reaction [OS 82]. This process is used for the majority of world-wide phenol production and, as a secondary product, also produces large quantities of acetone [64]. Phenol is used, e.g., for large-scale polymer production when reacted in a polycondensation with formaldehyde. 

Ketene gas is the product of acetone pyrolysis with copper at temperatures higher than 700°C [112]. These harsh reaction conditions require tremendous technical setup, thus this interesting route is not feasible for large scale industrial purposes. 

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