Acetone from

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

This oxidation process for olefins has been exploited commercially principally for the production of acetaldehyde, but the reaction can also be apphed to the production of acetone from propylene and methyl ethyl ketone [78-93-3] from butenes (87,88). Careflil control of the potential of the catalyst with the oxygen stream in the regenerator minimises the formation of chloroketones (94). Vinyl acetate can also be produced commercially by a variation of this reaction (96,97). 

The yield of acetone from the cumene/phenol process is beUeved to average 94%. By-products include significant amounts of a-methylstyrene [98-83-9] and acetophenone [98-86-2] as well as small amounts of hydroxyacetone [116-09-6] and mesityl oxide [141-79-7]. By-product yields vary with the producer. The a-methylstyrene may be hydrogenated to cumene for recycle or recovered for monomer use. Yields of phenol and acetone decline by 3.5—5.5% when the a-methylstyrene is not recycled (21). 

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. 

E. Graedel, D. T. Hawkins, and L. D. Cld,si.toQ., Atmospheric Chemical Compounds, Academic Press, Odando, Fla., 1986, p. 263, cited in Hazardous Substances Data Bank, Acetone from Toxicology Data Network (TOXNET), National Library of Medicine, Bethesda, Md., Jan. 1990, NATS section in the review. 

Yields of excited states from 1,2-dioxetane decomposition have been determined by two methods. Using a photochemical method (17,18) excited acetone from TMD is trapped with /n j -l,2-dicyanoethylene (DCE). Triplet acetone gives i7j -l,2-dicyanoethylene with DCE, whereas singlet acetone gives 2,2-dimethyl-3,4-dicyanooxetane. By measuring the yields of these two products the yields of the two acetone excited states could be determined. The yields of triplet ketone (6) from dioxetanes are determined with a similar technique. 

The selectivity of pervaporation membranes varies considerably and has a critical effect on the overall separation obtained. The range of results that can be obtained for the same solutions and different membranes is illustrated in Figure 41 for the separation of acetone from water using two types of membrane (89). The figure shows the concentration of acetone in the permeate as a function of the concentration in the feed. The two membranes shown have dramatically different properties. The siUcone mbber membrane removes acetone selectively, whereas the cross-linked poly(vinyl alcohol) (PVA) membrane removes water selectively. This difference occurs because siUcone mbber is hydrophobic and mbbery, thus permeates the acetone preferentially. PVA, on the other hand, is hydrophilic and glassy, thus permeates the small hydrophilic water molecules preferentially. 

Fig. 41. The pervaporation separation of acetone—water mixtures achieved with a water-selective poly(vinyl alcohol) (PVA) membrane and with an acetone-selective siUcone mbber membrane. The PVA membrane is best suited to removing small amounts of water from a concentrated acetone solution, whereas the siUcone mbber membrane is best suited to removing small amounts of acetone from a dilute acetone stream (89).

Another method of manufacture involves the oxidation of 2-isopropylnaphthalene ia the presence of a few percent of 2-isopropylnaphthalene hydroperoxide/i)ti< 2-22-(y as the initiator, some alkaU, and perhaps a transition-metal catalyst, with oxygen or air at ca 90—100°C, to ca 20—40% conversion to the hydroperoxide the oxidation product is cleaved, using a small amount of ca 50 wt % sulfuric acid as the catalyst at ca 60°C to give 2-naphthalenol and acetone in high yield (70). The yields of both 2-naphthalenol and acetone from the hydroperoxide are 90% or better. 

In the mid-1980s a convenient and relatively safe procedure was developed for vacuum codistillation of dimethyldioxirane and acetone from acetone—caroate systems (107). The resulting acetone solution of dimethyldioxirane could be used in subsequent oxygenation reactions (92). 

Production of a-methylstyrene (AMS) from cumene by dehydrogenation was practiced commercially by Dow until 1977. It is now produced as a by-product in the production of phenol and acetone from cumene. Cumene is manufactured by alkylation of benzene with propylene. In the phenol—acetone process, cumene is oxidized in the Hquid phase thermally to cumene hydroperoxide. The hydroperoxide is spHt into phenol and acetone by a cleavage reaction catalyzed by sulfur dioxide. Up to 2% of the cumene is converted to a-methylstyrene. Phenol and acetone are large-volume chemicals and the supply of the by-product a-methylstyrene is weU in excess of its demand. Producers are forced to hydrogenate it back to cumene for recycle to the phenol—acetone plant. Estimated plant capacities of the U.S. producers of a-methylstyrene are Hsted in Table 13 (80). 

In a study on dewatering methods for peat, displacement dewatering was done using acetone, a polar solvent having a lower heat of vapori2ation than water. Dewatering was improved in terms of both the pressure filtering step and the quantity of heat required. Less heat was required to dry the cake and recover the acetone from the filtrate by distillation (31). 

Example 6 Solvent Rate for Absorption Let us consider the absorption of acetone from air at atmospheric pressure into a stream of pure water fed to the top of a packed absorber at 25 C. The inlet gas at 35 C contains 2 percent by volume of acetone and is 70 percent saturated with water vapor (4 percent H2O by volume). The mole-fraction acetone in the exit gas is to be reduced to 1/400 of the inlet value, or 50 ppmv. For 100 kmol of feed-gas mixture, how many Idlomoles of fresh water should be fed to provide a positive-driving force throughout the pacldug How many transfer units will be needed according to the classical adiabatic method What is the estimated height of pacldug required if Hqq = 0.70 m ... 

Example 1 Partition Ratios Let us estimate the partition ratio in weight fractions K for extracting low concentrations of acetone from water into chloroform. The solute is acetone, the feed solvent is water, and the extraction solvent is chloroform in this case. 

Finally, select acetone from the molecules on screen. Here, both the LUMO and the LUMO map are available under the Surfaces menu. First, select LUMO and display it as a Solid. It describes a 7U-type antibonding ( i ) orbital concentrated primarily on the earbonyl carbon and oxygen. Next, turn off this surface (select None under the LUMO sub-menu), and then seleet LUMO Map under the Surfaces menu. Display the map as a transpareni solid. Note the blue spot (maximum value of the LUMO) directly over the carbonyl carbon. This reveah the most likely site for nucleophilic attack. 

Related and equally important reactions are the acetoacetic ester synthesis and the eyanoaeetie ester synthesis Here too the initial substituted product can be hydrolyzed and decarboxylated, to yield a ketone 11 (i.e. a substituted acetone) from acetoacetic ester 10, and a substituted acetonitrile 14 from eyanoaeetie ester 13 respectively. Furthermore a substituted acetoacetic ester can be cleaved into a substituted acetic ester 12 and acetate by treatment with strong alkali ... 

Obtain free -poly(L-malic acid) after passage over Amberlite IR 120 (H -form) (20 ml bed volume/1 g of polymer salt). Lyophylize, dissolve powder in acetone, remove insoluble material by centrifugation, and evaporate acetone from the supernatant. 

A direct route for acetone from propylene was developed using a homogeneous catalyst similar to Wacker system (PdCl2/CuCl2). The reaction conditions are similar to those used for ethylene oxidation to acetaldehyde. ... 

Chemicals Based on Benzene, Toluene, and Xylenes 271 Phenol and Acetone from Cumene... 

Figure 10-6. The Mitsui Petrochemical Industries process for producing phenol and acetone from cumene (1) autooxidatlon reactor, (2) vacuum tower, (3) cleavage reactor, (4) neutralizer, (5-11 ) purification train.

After an initial distillation to split the coproducts phenol and acetone, each is purified in separate distillation and treating trains. An acetone finishing column distills product acetone from an acetone/water/oil mixture. The oil, which is mostly unreacted cumene, is sent to cumene recovery. Acidic impurities, such as acetic acid and phenol, are neutralized hy caustic injection. Figure 10-7 is a simplified flow diagram of an acetone finishing column, and Table 10-1 shows the feed composition to the acetone finishing column. 

In the mass spectrum (Figure 6) of 3-deoxy-l,2 5,6-di-0-isopropyli-dene-D-xt/Zo-hexofuranose (9) the fragmentations described above are found at m/e 229, 171, 143, 111, and 101. The fragments at m/e 143 and 101 arise by cleavage of C-4-C-5 with charge retention on C-4 and C-5, respectively (see Equations 17 and 18). Scheme 2 summarizes the losses of a methyl group, acetone from the second cyclic ketal function, and... 

FIGURE 7.17 Storage modulus and loss factor—temperature plots of the chameleon arhPIB-h-P(p-MeSt) block copolymer. = precipitated into methanol, = precipitated into acetone. (From Puskas, J.E., Dos Santos, L., and Kaszas, G., J. Polym. Set Chem. A., 44, 6494, 2006. With permission.)... 

Pyriminobac-methyl in plant samples (rice grains and rice straw) and soil is recovered by refluxing with aqueous acetone. After removing acetone from the extract, pyriminobac-methyl in the aqueous solution is transferred into n-hexane. The n-hexane layer is dried and evaporated under reduced pressure. The residue from soil... 

Nitenpyram and its metabolites. The metabolites of nitenpyram, CPMA and CPMF, are determined by HPLC under the same conditions as for the parent nitenpyram. The retention times of nitenpyram, CPMA, and CPMF are 9.2,7.9 and 5.3 min, respectively. However, these compounds are unstable and need to be derivatized to a more stable compound, CPF, prior to analysis. It is necessary to remove acetone from the extract before derivatization, because a by-product can be formed in the presence of acetone thus impacting the recovery of CPF. Nitenpyram is more effectively determined using HPLC, whereas CPF, as the analyte of nitenpyram and its metabolites, is more effective by gas chromatography/flame thermionic detection (GC/FTD). 

The procedure for setting up the equations and assigning suitable values to the split-fraction coefficients is best illustrated by considering a short problem the manufacture of acetone from isopropyl alcohol. 

A column is required to recover acetone from an aqueous solution. The feed contains 5 mol per cent acetone. A product purity of 99.5 per cent w/w is required and the effluent water must contain less than 100 ppm acetone. 

A process for the production of cellulose acetate fiber produces a waste stream containing mainly air but with a small quantity of acetone vapor. The flowrate of air is 300 kmol h-1 and that of acetone is 4.5 kmolh-1. It is proposed to recover the acetone from the air by absorption into water followed by distillation of the acetone-water mixture. The absorber requires a flow of water 2.8 times that of the air. 

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