Ethylene, alcohol from

Reduction with retention of carbon-carbon double bonds—Prim. 2-ethylene-alcohols from ,) -ethylenealdehydes s. 18, 62... 

Prevention of coupling—One-step Barbier-Grignard procedure—4-Ethylene-alcohols from oxido compounds s. 19, 745... 

When dealing with esters of water-soluble, non steam-volatile, poly-hydric alcohols e.g., ethylene glycol or glycerol), the distillate consists of water only (density 1 00). The water soluble, non-volatile alcohol may be isolated by evaporation of the alkahne solution to a thick syrup on a water bath and extraction of the polyhydric alcohol from the salt with cold ethyl alcohol. 

Oxidative Carbonylation of Ethylene—Elimination of Alcohol from p-Alkoxypropionates. Spectacular progress in the 1970s led to the rapid development of organotransition-metal chemistry, particularly to catalyze olefin reactions (93,94). A number of patents have been issued (28,95—97) for the oxidative carbonylation of ethylene to provide acryUc acid and esters. The procedure is based on the palladium catalyzed carbonylation of ethylene in the Hquid phase at temperatures of 50—200°C. Esters are formed when alcohols are included. Anhydrous conditions are desirable to minimize the formation of by-products including acetaldehyde and carbon dioxide (see Acetaldehyde). 

The elimination of alcohol from P-alkoxypropionates can also be carried out by passing the alkyl P-alkoxypropionate at 200—400°C over metal phosphates, sihcates, metal oxide catalysts (99), or base-treated zeoHtes (98). In addition to the route via oxidative carbonylation of ethylene, alkyl P-alkoxypropionates can be prepared by reaction of dialkoxy methane and ketene (100). 

Eour chemical reactions are used to synthesize alcohols from aluminum alkyls and ethylene (qv). 

The product secondary alcohols from paraffin oxidation are converted to ethylene oxide adducts (alcohol ethoxylates) which are marketed by Japan Catalytic Chemical and BP Chemicals as SOFTANOL secondary alcohol ethoxylates. Union Carbide Chemical markets ethoxylated derivatives of the materials ia the United States under the TERGlTOL trademark (23). 

Direct Hydration. The acid-catalyzed direct hydration of propylene is exothermic and resembles the preparation of ethyl alcohol from ethylene (qv). 

There are two main processes for the synthesis of ethyl alcohol from ethylene. The eadiest to be developed (in 1930 by Union Carbide Corp.) was the indirect hydration process, variously called the strong sulfuric acid—ethylene process, the ethyl sulfate process, the esterification—hydrolysis process, or the sulfation—hydrolysis process. This process is stiU in use in Russia. The other synthesis process, designed to eliminate the use of sulfuric acid and which, since the early 1970s, has completely supplanted the old sulfuric acid process in the United States, is the direct hydration process. This process, the catalytic vapor-phase hydration of ethylene, is now practiced by only three U.S. companies Union Carbide Corp. (UCC), Quantum Chemical Corp., and Eastman Chemical Co. (a Division of Eastman Kodak Co.). UCC imports cmde industrial ethanol, CIE, from SADAF (the joint venture of SABIC and Pecten [Shell]) in Saudi Arabia, and refines it to industrial grade. 

Other synthetic methods have been investigated but have not become commercial. These include, for example, the hydration of ethylene in the presence of dilute acids (weak sulfuric acid process) the conversion of acetylene to acetaldehyde, followed by hydrogenation of the aldehyde to ethyl alcohol and the Fischer-Tropsch hydrocarbon synthesis. Synthetic fuels research has resulted in a whole new look at processes to make lower molecular weight alcohols from synthesis gas. 

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). 

The double bond migration which normally occurs on forming ethylene ketals from A -3-ketones has frequently been utilized to form derivatives of the A -system. The related transformation of A -3-ketones into A -3-alcohols is usually accomplished by treatment of the enol acetate (171) (X = OAc) with borohydride. This sequence apparently depends on reduction of the intermediate (172) taking place faster than conjugation ... 

The addition of ethylene oxide to the alcohol causes a decrease in the melting point of the corresponding salt of the alcohol ether sulfate in comparison with the same alcohol sulfate. Weil et al. [65] prepared pure hexadecyl and octadecyl ether alcohols from the corresponding alkyl bromide and glycols with... 

Dioxane forms by the chemical cleavage of two molecules of ethylene oxide from the parent ethoxylated alcohol. Dioxane is the undesirable byproduct. The amount of dioxane ranges from traces to hundreds, even thousands, of ppm (mg/kg) depending on raw material quality and sulfonation/neutralization process conditions. 

Alfol Also called the Conoco process and the Muhlheim process. The same name is used for the products as well. A process for making linear primary alcohols, from C2 to C28, from ethylene. The ethylene is reacted with triethyl aluminum, yielding higher alkyl aluminums These are oxidized with atmospheric oxygen under mild conditions to aluminum alkoxides, which are then hydrolyzed by water to the corresponding alcohols ... 

The various steps introduced in the production of alcohols from ethylene are represented in Fig. 1.11. Similar to the production of a-olefins, in the production of alcohols using the Ziegler process, the final product is a mix showing a typical Poisson distribution with alcohols from C4 up to C2s- Alcohols are also obtained from n-paraffin... 

Nonionic surfactants contain (Fig. 23) no ionic functionalities, as their name implies, and include ethylene oxide adducts (EOA) of alkylphenols and fatty alcohols. Production of detergent chain-length fatty alcohols from both natural and petrochemical precursors has now increased with the usage of alkylphenol ethoxylates (APEO) for some applications. This is environmentally less acceptable because of the slower rate of biodegradation and concern regarding the toxicity of phenolic residues [342]. 

Ethylene glycol from ethylene glycol, propylene glycol, tert-butyl alcohol, water NH4Y, 4A, 5A, NaX Methyl alcohol/ water [202]... 

Uses. As an ethylating agent as an accelerator in the sulfation of ethylene intermediate in the production by one method of ethyl alcohol from ethylene and sulfuric acid... 

Since approximately 2.2 lb of /-butyl alcohol would be produced per 1 lb of propylene oxide, an alternative reactant in this method is ethylbenzene hydroperoxide. This eventually forms phenylmethylcarbinol along with the propylene oxide. The alcohol is dehydrated to styrene. This chemistry was covered in Chapter 9, Section 6 as one of the syntheses of styrene. Thus the side product can be varied depending on the demand for substances such as /-butyl alcohol or styrene. Research is being done on a direct oxidation of propylene with oxygen, analogous to that used in the manufacture of ethylene oxide from ethylene and oxygen (Chapter 9, Section 7). But the proper catalyst and conditions have not yet been found. The methyl group is very sensitive to oxidation conditions. 

The greatest outlet for molasses is of course in alcohol fermentation industries, but since alcohol can be produced from ethylene and from acetylene, which in turn can be produced from methane, research into other fermentations and other uses for molasses would seem to be expedient. 

Only a few of the major developments can be traced here, yet these should give a fair idea of the magnitude and importance of the aliphatic petrochemical growth. It is well to remember that some of the chemistry involved in this industry is old. Four Dutch chemists, otherwise unrecalled today, prepared ethylene dichloride by addition of chlorine to ethylene in 1795, and the synthesis of ethyl alcohol from ethylene via sulfuric acid absorption was studied by Berthelot in 1855 (8). Of course, this was coal-gas ethylene, and the commercial application of this synthesis did not occur until 75 years later, in 1929, when ethylene produced from natural gas was first converted into ethyl alcohol on a practical scale (84). 

Prior to this time, other ventures had already been operating to produce commercial quantities of aliphatic chemicals from petroleum sources. Truly commercial production of ethylene glycol had been achieved by 1925 (10) using natural gas fractions as a starting material, and even earlier (about 1920) there had been the manufacture of isopropyl alcohol from cracking plant propylene (20), which may be termed the pioneer operation on a successful, continuing basis in the sphere of aliphatic synthesis from petroleum. 

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