Acetone from ethylene

Most by-product acetylene from ethylene production is hydrogenated to ethylene in the course of separation and purification of ethylene. In this process, however, acetylene can be recovered economically by solvent absorption instead of hydrogenation. Commercial recovery processes based on acetone, dimetbylform amide, or /V-metby1pyrro1idinone have a long history of successfiil operation. The difficulty in using this relatively low cost acetylene is that each 450, 000 t/yr world-scale ethylene plant only produces from 7000 9000 t/yr of acetylene. This is a small volume for an economically scaled derivatives unit. 

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). 

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. ... 

George, K.M., On the extraction of oleoresin from turmeric comparative performance of ethanol, acetone and ethylene dichloride, Indian Spices, 18, 7, 1981. 

In the area of extracting solutes from aqueous solutions, many systems have been screened in feasibility tests that have used carbon dioxide as a solvent. A partial list of the solutes includes ethanol, acetic acid, dioxane, acetone, and ethylene glycol. The reason for these efforts has been potential low energy costs compared with distillation and the environmental advantages of using carbon dioxide. 

The important derivatives of benzene are shown in Table 8.8. Ethylbenzene is made from ethylene and benzene and then dehydrogenated to styrene, which is polymerized for various plastics applications. Cumene is manufactured from propylene and benzene and then made into phenol and acetone. Cyclohexane, a starting material for some nylon, is made by hydrogenation of benzene. Nitration of benzene followed by reduction gives... 

A later method proposed by Oehman [26] produces glycol nitrate and diethylene glycol from ethylene by electrolysis. A platinum wire mesh submerged in an acetone solution of calcium nitrate acts as anode, ethylene being blown through the solution continuously. The cathode space behind the aluminium cathode is filled with a solution of calcium nitrate in nitric acid. At the anode the nitrate ion forms a free radical N03 which combines partially with ethylene to produce nitroglycol (6) ... 

Tetrapentaerythritol was isolated by the same author from technical pentaerythritol by fractional crystallization. It was nitrated with 98% nitric acid at —5 to +5°C. It is readily soluble in acetone and ethylene dichloride. It has been suggested as a coating agent and sensitizer for ammonium nitrate. 

Diethyizinc is changed to an active catalyst for the polymerization of ethylene oxide and propylen oxide by reacting it with an appropriate amount of water, alcohol, acetone, amine, nitro compound, or nitroso compound. This type of catalyst gives high molecular weight (over one million) polymers from ethylene oxide and propylene oxide. 

Close examination of the products from irradiation of 2-pentanone, (Formula 255) (R = H) in cyclohexane reveals that in addition to the expected equimolar amounts of acetone and ethylene a third product, 1-methylcyclobutanol (Formula 256) (R = H), is formed in 12% yield... 

Donald Cram attempted synthesis of cyclophane charge transfer complexes with (NC)2C=C(CN)2 1961 - N.F. Curtis first Schiff s base macrocycle from acetone and ethylene diamine 1964 - Busch and Jager Schiff s base macrocycles... 

Liquid phase oxidation of hydrocarbons by molecular oxygen forms the basis for a wide variety of petrochemical processes,3 "16 including the manufacture of phenol and acetone from cumene, adipic acid from cyclohexane, terephthalic acid from p-xylene, acetaldehyde and vinyl acetate from ethylene, propylene oxide from propylene, and many others. The majority of these processes employ catalysis by transition metal complexes to attain maximum selectivity and efficiency. 

This seems somewhat inconsistent with the value of 17 3 Kcal estimated from the earlier work on formation of /-BuOH relative to acetone from dtBP photolysis in the presence of ethylene imine by Brinton and Volman, loc. cit. 

Acrylonitrile and methacrylonitrile can be obtained from petro-chemical olefins [2] by the noncatalytic reactions of HCN with acetaldehyde, acetone (cyanohydrin is the intermediate in these processes) or oxiranes (Z-cyanoetltanol being the intermediate in the acrylonitrile synthesis from ethylene oxide). 

The photochemical formation of cyclobutanols is substantially favored if the ethylene that would be formed in a type II elimination must have a bridgehead double bond.120) Jn 1-adamcUitylacetone, 77, the strain is sufficient to substantially inhibit the elimination of acetone from the molecule ion. 12 ) Cyclobutanol formation is the virtually exclusive photochemical pathway for 71 and related bridgehead acetone derivative. 

Problem 27.4 The following compounds are of great industrial importance for the manufacture of polymers acrylonitrile (for Orion), methyl acrylate (for Acryloid), methyl methacrylate (for Lucite and Plexiglas). Outline a possible industrial synthesis of (a) acrylonitrile from ethylene (b) methyl acrylate from ethylene (c) methyl methacrylate from acetone and methanol. 

Under most assay conditions, ADH is reasonably specific for ethanol. Interference, relative to ethanol, is generahy about 7% for isopropanol, 3% for methanol, and 4% for ethylene glycol. Reagent kits for use with manual spectrophotometers or automated analyzers are available from several manufacturers. Some manufacturers (Dade-Behring [flcfl], Abbott [TDx], Dade-Behring [EMIT]) claim interference from isopropanol, methanol, acetone, and ethylene glycol to be less than 1%. 

Into a dry tube fitted with a Youngs tap and a Quickfit joint (ofthe type used to polymerize butyl acrylate in Protocol 1) is placed a small piece of sodium (about the size of a match-head). The tube is connected to the manifold or a vacuum line, evacuated and a sodium mirror formed (as for potassium above.) The tube is then cooled ( 78°C, dry ice/acetone) and ethylene oxide (ca. 8 mL) is added from the cylinder. The tube is then held at -10°C for 24 h. After this time the liquid is once again connected to the gas-line, frozen (liquid nitrogen), and the tube evacuated. An identical tube containing a sodium mirror is also prepared on the same line and cooled to 78°C. The first tube is allowed to return to room temperature and ethylene oxide is then transferred by virtue of its low vapour pressure. The second tube is then isolated from the system and once again allowed to stand under vacuum for 24 h. 

The growth of synthetic fibers has led to the devising of syntheses from petroleum of the chemical intermediates required for this new industry. Leaving aside acetic anhydride from ethylene via synthetic ethanol and from propylene via acetone, already established and used for cellulose acetate in the 193O s, nylon has called for the isolation of petroleum cyclohexane and for the discovery of a route from butadiene to nylon salt Dacron for the isolation of p-xylene from petroleum xylene, and the nitrile fibers for the synthesis of acrylonitrile from ethylene or acetylene. 

Process From ethylene From propylene Esterification Esterification From acetone and hydrogen cyanide From t-butyl alcohol... 

Zosel s explanation is generally accurate concerning the ratio of the hydrocarbon radical to the hydroxyl group. However, ethanol can be extracted from ethanol-water solutions by supercritical ethylene (Paulaitis, Gilbert, and Nash, 1981) and so can acetone from acetone-water solution (Elgin and Weinstock, 1959) a few such inaccuracies still do not detract from the vast amount of data that Zosel provides. 

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. 

Paramagnetic species, generated in the vapor phase in a crossed-beam experiment by irradiation with 1 Mev. He ions, have been trapped at 77 °K. and detected by electron spin resonance (ESR). This paper describes the results obtained from irradiated methyl-, ethyl-, and tert-butyl alcohol, acetone, and ethylene. Trapped electrons together with the radicals CH2OH, CHsCHOH, and (CHa)2C(OH)CH2- and (CH i).tC are formed in methyl-, ethyl-, and tert-butyl alcohol respectively. Ethyl radicals are formed from ethylene. Acetone gives rise to CHjCOCH, and CHS radicals and appears to form trapped electrons in the deposit. The results are compared with the radiation chemistry of these systems in the solid and vapor phase. 

A soln. of l-methyl-l,2-cyclohexanediol in acetone treated at ca. 0 with 1-2 gin. portions of KMn04 - 6-ketoheptanoic acid. Y 84% based on reacted starting material.—In general, better yields from, ethylene derivatives were obtained by first preparing and then oxidizing the corresponding glycols. (F. e. s. H. Adkins, A. K. Roebuck, Am. Soc. 70, 4041 (1948).)... 

Hydrochloride, C H ClNjS, Dibulil, Lysivane, Pardisol, Parphezein, Parphezm, Parsidoi, Parsitan, Parsotil, Rodipal. Crystals from ethylene dichloride, mp 223-225° (some decompn). Lower melting points reported are caused by admixture with 10-(2-diethylamino-I -methylethyl)pheno-thiazine-HCI which melts at 166-168°. One gram dissolves in 400 m] water at 20", in 20 m] water at 40°. Sol in ethanol, chloroform. Soly in abs ethanol at 25° = 1.0 g/30 ml. Sparingly sol in acetone. Practically insol in ether, benzene. pH of a 5% aq soln is about 5.3. 

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