Acetaldehydes propylene derivatives

Propylene. 2-Ethylhexanol is now produced almost entirely from propylene, with the exception of a minor portion that comes from ethylene-derived acetaldehyde. 

Acetic acid (qv) can be produced synthetically (methanol carbonylation, acetaldehyde oxidation, butane/naphtha oxidation) or from natural sources (5). Oxygen is added to propylene to make acrolein, which is further oxidized to acryHc acid (see Acrylic acid and derivatives). An alternative method adds carbon monoxide and/or water to acetylene (6). Benzoic acid (qv) is made by oxidizing toluene in the presence of a cobalt catalyst (7). 

Direct Oxidation. Direct oxidation of petroleum hydrocarbons has been practiced on a small scale since 1926 methanol, formaldehyde, and acetaldehyde are produced. A much larger project (29) began operating in 1945. The main product of the latter operation is acetic acid, used for the manufacture of cellulose acetate rayon. The oxidation process consists of mixing air with a butane-propane mixture and passing the compressed mixture over a catalyst in a tubular reaction furnace. The product mixture includes acetaldehyde, formaldehyde, acetone, propyl and butyl alcohols, methyl ethyl ketone, and propylene oxide and glycols. The acetaldehyde is oxidized to acetic acid in a separate plant. Thus the products of this operation are the same as those (or their derivatives) produced by olefin hydration and other aliphatic syntheses. 

Acetic Anhydride. Other products recovered from the oxidation of light hydrocarbons (6) are acetic acid and acetic anhydride as well as acetaldehyde, acetone, and isopropyl alcohol, all of which may be converted to acetic acid or the anhydride. The direct oxidation process supplements the production of acetic anhydride from acetone derived from propylene, which has been the principal commercial source of the anhydride. The increasing production of cellulose acetate within recent years has been attributed to the low cost of acetic anhydride from the latter process (44). 

The end product of the acetylene process was a high purity monomer that contained some water-derived impurities such as acetaldehyde but was free of some of the organic impurities such as butadiene, ethylene, and propylene which are often associated with other processes. 

Although acetylene still is used in a number of organic syntheses on an industrial scale, its use on a high-tonnage basis has diminished because of the lower cost of other starting materials, such as ethylene and propylene. Acetylene has been widely used in the production of halogen derivatives, acrylonitrile, acetaldehyde, and vinyl chloride. Within recent years, producers of acrylonitrile switched to propylene as a starting material. 

Process Economics Program Report SRI International. Menlo Park, CA, Isocyanates IE, Propylene Oxide 2E, Vinyl Chloride 5D, Terephthalic Acid and Dimethyl Terephthalate 9E, Phenol 22C, Xylene Separation 25C, BTX, Aromatics 30A, o-Xylene 34 A, m-Xylene 25 A, p-Xylene 93-3-4, Ethylbenzene/Styrene 33C, Phthalic Anhydride 34B, Glycerine and Intermediates 58, Aniline and Derivatives 76C, Bisphenol A and Phosgene 81, C1 Chlorinated Hydrocarbons 126, Chlorinated Solvent 48, Chlorofluorocarbon Alternatives 201, Reforming for BTX 129, Aromatics Processes 182 A, Propylene Oxide Derivatives 198, Acetaldehyde 24 A2, 91-1-3, Acetic Acid 37 B, Acetylene 16A, Adipic Acid 3 B, Ammonia 44 A, Caprolactam 7 C, Carbon Disulfide 171 A, Cumene 92-3-4, 22 B, 219, MDA 1 D, Ethanol 53 A, 85-2-4, Ethylene Dichloride/Vinyl Chloride 5 C, Formaldehyde 23 A, Hexamethylenediamine (HMDA) 31 B, Hydrogen Cyanide 76-3-4, Maleic Anhydride 46 C, Methane (Natural Gas) 191, Synthesis Gas 146, 148, 191 A, Methanol 148, 43 B, 93-2-2, Methyl Methacrylate 11 D, Nylon 6-41 B, Nylon 6,6-54 B, Ethylene/Propylene 29 A, Urea 56 A, Vinyl Acetate 15 A. 

The direct oxidation of ethylene is used to produce acetaldehyde (qv) in the Wacker-Hoeclist process. The catalyst system is an aqueous solution of palladium chloride and cupric chloride. Under appropriate conditions an olefin can be oxidized to form an unsaturated aldehyde such as the production of acrolein [107-02-8] from propylene (see Acrolein and derivatives). 

CAS 104-76-7. CH3(CH2)3CHC2H5CH2OH. Properties Colorless liquid. D 0.83 (20C), bp 183.5C, fp -76C, vap press 0.36 (20C), refr index 1.4300 (20C), bulk d 6.9 lb/gal (20C), flash p 178F (81.1C). Miscible with most organic solvents, slightly soluble in water. Combustible. Derivation (a) Oxo process from propylene and synthesis gas (b) aldolization of acetaldehyde or butyraldehyde, followed by hydrogenation (c) from fermentation alcohol. 

The Wacker process, the oxidation of ethylene to acetaldehyde, lost its original importance over the past 30 years. While at the beginning more than 40 factories with a total capacity of more than 2 million tons of acetaldehyde per year were installed, acetaldehyde as an industrial intermediate was replaced successively by other processes. For example, compounds such as butyraldehyde/butanol are produced by the oxo process from propylene, and acetic acid by the Monsanto process from methanol and CO or by direct oxidation of ethane. The way via acetaldehyde to these products is dependent on the price of ethylene. Petrochemical ethylene from cracking processes became considerably more expensive during these years. Thus, only few factories would be necessary to meet the demand for other derivatives of acetaldehyde such as alkyl amines, pyridines, glyoxal, and pentaerythritol. 

Ethylhexanol is derived as follows in Figure 9.6 from propylene, acetaldehyde, or butyraldehyde. 

Figure 9.6 2-Ethylhexanol derived from propylene (Process 1) or acetaldehyde (Process 2)...

Feedstock dependency is based on 2-ethylhexanol and sebacic acid. As previously shown, 2-ethylhexanol is derived as follows from propylene, acetaldehyde, or butyr-aldehyde see Figure 9.14. 

When this vork was first done, the mechanism of vinyl polymerization had not been established and we were interested in finding out the exact structure of the polymers formed from an unsymmetrical olefin. Propylene-polysulfone was selected for study of the structure. It was fo md that this polymer was hydrolyzed readily by alkali to yield a four-carbon two-sulfur derivative and a polymer of acetaldehyde. The two potential polymer structures were I and II. 

Main products acetic acid, water, CO, CH4, Hz, CO2 minor products ketene, acetaldehyde, acetone, acetylene, ethylene, ethane, propylene, and C4, C5 and Cg hydrocarbons Acetic acid, acetyl derivatives of D-glucose H2O, CO, CO2, C2H4,C2H6, C2H5OH, CH3CHO. aliphatic compounds, fiiran derivatives... 

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