Alcohol formation, pressure

Alcohols are the most frequently formed products of ester hydrogenolysis. The hydrogenation of esters to alcohols is a reversible reaction with alcohol formation favored at high pressure, ester at low pressure (/). Copper chromite is usually the catalyst of choice. Details for the preparation of this catalyst (/7) and a detailed procedure for hydrogenation of ethyl adipate to hexamethylene glycol (/[Pg.80]

As normally practiced in a cobalt process, the aldehyde product contains about 10% alcohol, formed by subsequent hydrogenation. Marko (34) reported that the hydrogenation is more sensitive to carbon monoxide partial pressure than is the hydroformylation reaction and, in the region between 32 and 210 atm, is inversely proportional to the square of the partial pressure. The full kinetic expression for alcohol formation is expressed by Eq. (17). 

The hydrogenation of aldehydes in the absence of amines under more severe reaction conditions was studied extensively by Heil and Marko (16). They found that rates of alcohol formation passed through a maximum with increasing CO partial pressure (> 1000 psi), but at very low pressures CO was inhibiting. 

Normally, the practicing engineer can specify the water-free hydrocarbon composition, and the amount of inhibitor (salts, alcohols, or glycols) in the free water phase, and would like to predict the three-phase (Lw-H-V) hydrate formation pressure, given the lowest temperature of the process (or predict the formation temperature, given the highest pressure in the process). Protection at the extreme conditions (lowest T and highest P) helps ensure hydrate protection at the other process conditions. 

In the case of hydrobromic and hydriodic acids and such olefins as isobutylene and tri methyl ethylene, the rate of alcohol formation may become such that it approaches the rate of hydrolysis of the corresponding alkyl halides, thus supporting the theory that halides are the necessary intermediate product.04 The greater activity of the hydrobromic and hydriodic acids compared with hydrochloric acid toward ethylene is shown by the experiments of Swann, Snow and Keyes.00 At 800 pounds per square inch pressure and a temperature of 150° C. no alkyl chlorides were detected when hydrochloric acid of from 5 to 25 per cent concentration was used. On the other hand, considerable yields of alkyl iodides were obtained under the same conditions when hydriodic acid was used, and alkyl bromides formed in the presence of 40 per cent concentration hydrobromic acid. Alcohol yields were very small. When using propene at 600 to 800 pounds per square inch pressure at 135° C. in the presence of 5 per cent hydrochloric acid solutions and solutions of silver nitrate, yields of alcohol several times that obtained from ethylene were found. The yields were still very low, however, even with times of reaction as long as one hour. 

The proper choice of catalysts for the vapor phase hydration of olefins under pressure to form alcohols is a very important factor. Apparently, catalysts active in promoting the hydration reaction are likewise active toward promotion of the undesirable polymerization reactions since this latter reaction often proceeds at a more rapid rate than that of alcohol formation as evidenced by the high yields of polymers and low yields of alcohols. The use of catalysts to lower the temperature for the reaction is necessitated by the fact that as the temperature is increased to obtain more favorable rates, the equilibrium conversion to alcohol becomes lower, and the tendency to polymerize is increased. Also, the catalyst must not promote dehydrogenation of the alcohol to form hydrogen and aldehyde since at the temperature of operation the equilibrium is very favorable for this reaction as has been pointed out in a previous chapter. Thus, the reaction, isobutanol = isobutyl aldehyde -f hydrogen has an equilibrium constant corresponding to about 72 per cent decomposition at 450° C even with 100 atmospheres of hydrogen pressure. 

Synonyms Amyl formate Formic acid, isopentyl ester Isoamyl methanoate Isopentyl alcohol, formate Isopentyl formate 3-Methylbutyl formate 3-Methylbutyl methanoate Empirical C6H12O2 Formula HCOOCH2CH2CH(CH3)2 Properties Colorless liq., plum-like odor sol. in alcohol, oxygenated soivs. misc. with ether, propylene glycol very si. sol. in water insol. in glycerin m.w. 116.16 dens. 0.859 vapor pressure 10 mm (17.1 C) b.p. 123-124 C flash pt. 86 F ref. index 1.3960-1.40... 

Clean tungsten carbides, a-WC and a-W C, form essentially only hydrocarbons from CO—H2 reactions. At 673 K and atmospheric pressure, the main products on WC, W2C, and W are methane, CO2, and H2O (121). Ethane and propane are also formed at lower temperatures. WC was substantially more active than W2C and W. The nature of the products can be modified by oxide promoters, as for the case of Rh or Pt, or by the carbon vacancies at the surface (122). At 573 K and 5 MPa with 2H2/CO, turnover rates (based on sites titrated by CO chemisorption) of 0.25-0.85 s were reported for hydrocarbon synthesis over bulk and Ti02-supported tungsten carbides. In addition, WC and WC/Ti02 produced alcohols and other oxygenates with 20-50% selectivity. However, W2C of more metallic character did not produce any oxygenates. Coexistence of carbidic and oxidic components on the catalyst surface appeared to be responsible for alcohol formation. 

Some liquids are practically immiscible e.g., water and mercury), whilst others e.g., water and ethyl alcohol or acetone) mix with one another in all proportions. Many examples are known, however, in which the liquids are partially miscible with one another. If, for example, water be added to ether or if ether be added to water and the mixture shaken, solution will take place up to a certain point beyond this point further addition of water on the one hand, or of ether on the other, will result in the formation of two liquid layers, one consisting of a saturated solution of water in ether and the other a saturated solution of ether in water. Two such mutually saturated solutions in equilibrium at a particular temperature are called conjugate solutions. It must be mentioned that there is no essential theoretical difference between liquids of partial and complete miscibility for, as wdll be shown below, the one may pass into the other with change of experimental conditions, such as temperature and, less frequently, of pressure. 

P-Phenylethylamine is conveniently prepared by the hydrogenation under pressure of benzyl cyanide with Raney nickel catalyst (see Section VI,5) in the presence of either a saturated solution of dry ammonia in anhydrous methyl alcohol or of liquid ammonia the latter are added to suppress the formation of the secondary amine, di- P phenylethylamine ... 

Mix 31 g. (29-5 ml.) of benzyl alcohol (Section IV, 123 and Section IV,200) and 45 g. (43 ml.) of glacial acetic acid in a 500 ml. round-bottomed flask introduce 1 ml. of concentrated sulphuric acid and a few fragments of porous pot. Attach a reflux condenser to the flask and boil the mixture gently for 9 hours. Pour the reaction mixture into about 200 ml. of water contained in a separatory funnel, add 10 ml. of carbon tetrachloride (to eliminate emulsion formation owing to the slight difference in density of the ester and water, compare Methyl Benzoate, Section IV,176) and shake. Separate the lower layer (solution of benzyl acetate in carbon tetrachloride) and discard the upper aqueous layer. Return the lower layer to the funnel, and wash it successively with water, concentrated sodium bicarbonate solution (until effervescence ceases) and water. Dry over 5 g. of anhydrous magnesium sulphate, and distil under normal pressure (Fig. II, 13, 2) with the aid of an air bath (Fig. II, 5, 3). Collect the benzyl acetate a (colourless liquid) at 213-215°. The yield is 16 g. 

Under CO pressure in alcohol, the reaction of alkenes and CCI4 proceeds to give branched esters. No carbonylation of CCI4 itself to give triichloroacetate under similar conditions is observed. The ester formation is e.xplained by a free radical mechanism. The carbonylation of l-octene and CCI4 in ethanol affords ethyl 2-(2,2,2-trichloroethyl)decanoate (924) as a main product and the simple addition product 925(774]. ... 

The stringency of the conditions employed in the unmodified cobalt 0x0 process leads to formation of heavy trimer esters and acetals (2). Although largely supplanted by low pressure ligand-modified rhodium-catalyzed processes, the unmodified cobalt 0x0 process is stiU employed in some instances for propylene to give a low, eg, - 3.3-3.5 1 isomer ratio product mix, and for low reactivity mixed and/or branched-olefin feedstocks, eg, propylene trimers from the polygas reaction, to produce isodecanol plasticizer alcohol. 

Amin omethyl-3,5,5-trimethyl cyclohexyl amine (21), commonly called isophoronediamine (IPD) (51), is made by hydrocyanation of (17) (52), (53) followed by transformation of the ketone (19) to an imine (20) by dehydrative condensation of ammonia (54), then concomitant hydrogenation of the imine and nitrile functions at 15—16 MPa (- 2200 psi) system pressure and 120 °C using methanol diluent in addition to YL NH. Integrated imine formation and nitrile reduction by reductive amination of the ketone leads to alcohol by-product. There are two geometric isomers of IPD the major product is ds-(22) [71954-30-5] and the minor, tram-(25) [71954-29-5] (55). 

Ma.nufa.cture. The principal manufacturers of A/-vinyl-2-pyrrohdinone are ISP and BASF. Both consume most of their production captively as a monomer for the manufacture of PVP and copolymers. The vinylation of 2-pyrrohdinone is carried out under alkaline catalysis analogous to the vinylation of alcohols. 2-Pyrrohdinone is treated with ca 5% potassium hydroxide, then water and some pyrroHdinone are distilled at reduced pressure. A ca 1 1 mixture (by vol) of acetylene and nitrogen is heated at 150—160°C and ca 2 MPa (22 atm). Fresh 2-pyrrohdinone and catalyst are added continuously while product is withdrawn. Conversion is limited to ca 60% to avoid excessive formation of by-products. The A/-vinyl-2-pyrrohdinone is distilled at 70-85°C at 670 Pa (5 mm Hg) and the yield is 70-80% (8). 

Reactions of the Side Chain. Benzyl chloride is hydrolyzed slowly by boiling water and more rapidly at elevated temperature and pressure in the presence of alkaHes (11). Reaction with aqueous sodium cyanide, preferably in the presence of a quaternary ammonium chloride, produces phenylacetonitrile [140-29-4] in high yield (12). The presence of a lower molecular-weight alcohol gives faster rates and higher yields. In the presence of suitable catalysts benzyl chloride reacts with carbon monoxide to produce phenylacetic acid [103-82-2] (13—15). With different catalyst systems in the presence of calcium hydroxide, double carbonylation to phenylpymvic acid [156-06-9] occurs (16). Benzyl esters are formed by heating benzyl chloride with the sodium salts of acids benzyl ethers by reaction with sodium alkoxides. The ease of ether formation is improved by the use of phase-transfer catalysts (17) (see Catalysis, phase-thansfer). 

Ethanol can also be obtained by the reaction of methanol with synthesis gas at 185°C and under pressure (6.9—20.7 MPa or 68—204 atm) in the presence of a cobalt octacarbonyl catalyst (177). However, although ethanol was the primary product, methyl formate, methyl, propyl and butyl acetates, propyl and butyl alcohols, and methane were all present in the product. 

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