Isopropyl alcohol, from acetone

For reductive amination of acetone with ammonia two types of catalysts were designed (i) skeletal Ni catalyst prepared form a Ni-Al alloy and Ci) its tin modified versions. Both types of catalysts were used in a continuous flow gas phase reactor. The requirements for these catalysts were as follows high thermal and mechanical stability, high rates for the formation of both primary and secondary amines and suppression of the formation of isopropyl alcohol from acetone. 

Although the selectivity of isopropyl alcohol to acetone via vapor-phase dehydrogenation is high, there are a number of by-products that must be removed from the acetone. The hot reactor effluent contains acetone, unconverted isopropyl alcohol, and hydrogen, and may also contain propylene, polypropylene, mesityl oxide, diisopropyl ether, acetaldehyde, propionaldehyde, and many other hydrocarbons and carbon oxides (25,28). 

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). 

Isopropyl Ether. Isopropyl ether is manufactured by the dehydration of isopropyl alcohol with sulfuric acid. It is obtained in large quantities as a by-product in the manufacture of isopropyl alcohol from propylene by the sulfuric acid process, very similar to the production of ethyl ether from ethylene. Isopropyl ether is of moderate importance as an industrial solvent, since its boiling point Hes between that of ethyl ether and acetone. Isopropyl ether very readily forms hazardous peroxides and hydroperoxides, much more so than other ethers. However, this tendency can be controlled with commercial antioxidant additives. Therefore, it is also being promoted as another possible ether to be used in gasoline (33). 

Ellis A process for making isopropyl alcohol from light olefin mixtures by treatment with concentrated sulfuric acid. Operated in World War I by the Melco Chemical Company, as an intermediate for the production of acetone for airplane dope. ... 

In 1992, industrial wastewater containing isopropyl alcohol and acetone from the Kennedy Air Force Base was treated using at 5-gpm Perox-Pure unit. Total O M costs for the system were 3.60 per 1,000 gallons of wastewater treated. These costs included 2.00 for electricity priced at 0.06 per kW-hour, 0.60 for hydrogen peroxide priced at 0.35 per pound, and 1.00 for maintenance (D10057S, p. 59 60 D19079Y, p. 3-21 D17231G, p. 410). 

Fig. 9. The independence of the heats of exchange on the temperature (a) alcohols on oxide catalyst SB), Reading from left to right allyl, w-propyl, ethyl, i-propyl, i-amyl, n-butyl, phenyl ethyl alcohols, (b) Curve 1—isopropyl alcohol with acetone, curve 2—isopropyl alcohol with hydrogen on MnO (SB).

In 2001, negative ion ESl-MS studies suggested that monoper-oxovanadium species are responsible for the vanadium-catalyzed oxidation of Isopropyl alcohol to acetone [30]. Fragmentation studies conducted In the gas phase showed loss of acetone from the species [0V(02)(0 Pr)2] (Fig. 2A, m/z 217), confirming that the reaction occurs within the Inner sphere of the metal. In a follow-up study, positive Ion ESl-MS lead to the observation of the intermediate [VO(OH2)(OH)(OBr)] " (Fig. 2B, m/z 197/199), which was implicated as a potential Intermediate in the vanadium-catalyzed oxidation of bromide by hydrogen peroxide [32]. 

Acetone is obtained by fermentation as a by-product of -butyl alcohol manufacture, or by chemical synthesis from isopropyl alcohol from cumene as a by-product in phenol manufacture or from propane as a by-product of oxidation-cracking. 

The first totally synthetic route to a solvent in the United States was the synthesis of isopropyl alcohol from propylene by Melco Chemical Corporation in 1917. In 1928 Union Carbide made acetone from isopropyl alcohol the synthesis of acetone in the cumene-to-phenol process came much later and now is the source of about 85% of acetone production. In 1927 Du Pont began the synthesis of methanol. Synthetic ethyl alcohol was made from ethylene by Union Carbide in 1929. Specialized books on ethyl alcohol (14. 15) and isopropyl alcohol (16) give many details on the manufacture, properties, and uses of these major products. 

Miscible solvents can significantly enhance PAH desorption and solubilization from the environment. According to Li, Cheung, and Reddy (2000), each of three cosolvents, n-butylamine, acetone, and tetrahydrofuran, increased phenanthrene solubility by more than five orders of magnitude, compared to a cosolvent-free control. Moreover, Peters and Luthy (1993) found that n-butylamine more readily solubilized coal tar into the cosolvent-water phase than did isopropyl alcohol or acetone. This indicates that cosolvents of higher molecular weight, and with few polar... 

Acetone is used to extract fats, oils, waxes, and resins from natural products, to dewax lubricating oils, and to extract certain essential oils. The pharmaceutical industry uses acetone to extract B-vitamin complexes, alkaloids, antibiotics and enzymes. Methyl ethyl ketone is used to dewax lube oil. Methyl isobutyl ketone is used to dewax mineral oil, refine tall oil, and in extractive distillation and separation of isopropyl alcohol from ethyl and butyl alcohols. The extraction and purification of antibiotics and other pharmaceutical products utilize MIBK. Methyl isobutyl ketone is used in the extraction of rosin from pine wood and the extraction of heavy metal ion complexes from water solutions. 

Secondary Alcohols. In addition to reporting that primary alcohols cause an increased excretion of glucuronic acid, Neubauer (299) claimed a similar effect after administration of isopropyl, sec-butyl and sec-octyl alcohols. In contradiction, Neymark (310) has reported the quantitative transformation of isopropyl alcohol to acetone in the dog. Neuberg and Gott-schalk (303) claimed that in rabbits acetoin (3-hydroxy-2-butanone) forms a glucuronoside, either from acetoin itself or from its metabolite, 2,3-butylene glycol. 

The DKR procedure described above was improved by Meijer and coworkers in 2007 [87]. The protocol was improved both in terms of reaction time (26 h instead of 72 h) and the required amount of acyl donor (the excess acyl donor could be reduced to 1.1 equiv). This was accomplished using a more effective acyl donor isopropyl 2-methoxyacetate for the enzymatic acylation. CALB was used for the kinetic resolution, and the para-methoxyphenyl derivative of the Shvo catalyst was used for racemization (22). All the DKR reactions were performed under reduced pressure (750 mbar) to eliminate the isopropyl alcohol from the reaction mixture. The isopropyl alcohol can be oxidized to acetone, and the latter can in subsequent reaction steps form unwanted condensation products with the amine substrates. The revised protocol afforded the products with excellent selectivity (96-99% ee). The yields were slightly lower (56-80%) than those obtained with the Backvall protocol [86], mainly due to problems with purification. 

An example of a reaction which does produce a byproduct is the production of acetone from isopropyl alcohol, which produces a hydrogen byproduct ... 

Place 35 ml. of a M solution of aluminium tsopropoxide or 7 g. of solid aluminium tsopropoxide, 450 ml. of dry isopropyl alcohol and 21 g. of purified benzaldehyde (Section IV,115) in a 1 litre round-bottomed flask. Fit a short reflux condenser (no water in the cooling jacket) or better a Hahn condenser (2) (containing a 1 cm. layer of ethyl alcohol in the iimer tube) to the flask and arrange for slow distillation from a water bath at the rate of 3-6 drops per minute. Continue the heating until a negative test for acetone is obtained after 5 minutes of total reflux (6-9 hours) if the volume of the mixture falls below 200 ml. during the reduction, add more isopropyl alcohol. Remove the reflux or Hahn condenser and distil off (Fig. II, 13, 3) most of the isopropyl alcohol under atmospheric pressure from a suitable oil bath. Hydrolyse the... 

Until World War 1 acetone was manufactured commercially by the dry distillation of calcium acetate from lime and pyroligneous acid (wood distillate) (9). During the war processes for acetic acid from acetylene and by fermentation supplanted the pyroligneous acid (10). In turn these methods were displaced by the process developed for the bacterial fermentation of carbohydrates (cornstarch and molasses) to acetone and alcohols (11). At one time Pubhcker Industries, Commercial Solvents, and National Distillers had combined biofermentation capacity of 22,700 metric tons of acetone per year. Biofermentation became noncompetitive around 1960 because of the economics of scale of the isopropyl alcohol dehydrogenation and cumene hydroperoxide processes. 

Production of acetone by dehydrogenation of isopropyl alcohol began in the early 1920s and remained the dominant production method through the 1960s. In the mid-1960s virtually all United States acetone was produced from propylene. A process for direct oxidation of propylene to acetone was developed by Wacker Chemie (12), but is not beheved to have been used in the United States. However, by the mid-1970s 60% of United States acetone capacity was based on cumene hydroperoxide [80-15-9], which accounted for about 65% of the acetone produced. 

Dehydrogenation of isopropyl alcohol accounts for most of the acetone production not obtained from cumene. The vapor is passed over a brass, copper, or other catalyst at 400—500°C, and a yield of about 95% is achieved (1.09 unit weight of alcohol per unit of acetone) (13). 

Almost 95% of the acetone produced in the United States in 1987 and 1988 was made from cumene and 4% from isopropyl alcohol (13). 

The economics of acetone production and its consequent market position are unusual. Traditional laws of supply and demand cannot be appHed because supply depends on the production of phenol and demand is controUed by the uses of acetone. Therefore, coproduct acetone from the cumene to phenol process will continue to dominate market supply. DeHberate production of acetone from isopropyl alcohol accommodates demand in excess of that suppHed by the phenol process. More than 75% of world and 90% of U.S. production comes from the cumene to phenol process. 

---