INDUSTRIAL AND ENGINEERING CHEMISTRY
September 1948
(152) Parks, W. S., and Kats, J., OPRD Research Rhode Island State College (1944). (153) Pearce, J.A., Can. J.Research, 24F, 369-79 (1946). (154) Pease, R. N., and Walz;, A. T., J. Am. Chem. SOC.,53, 3728 (1931). (155) Perrine, J. H., U. S. Patent 2,394,871 (Feb. 12, 1946). (156) Pie, P. F., U. S.Patent 2,280,928(April 28, 1942). (157) Pinkston, J. T., Jr., IND. ENG.CHEM.,39,255 (1947). (158) Pokorny, R., J.Am. Chem. Soc., 63,1768 (1941). (159) Priest, H. F., and Grosse,A.V., IND. ENG.CHEM.,39,279 (1947). (160) Ibid., 39, 431-3 (1947). (161) Priest, H. F., and Grosse, A. V., U. S.Patent 2,419,915 (April 29, 1947). (162) Prins, H. J., Rec. trav. chim., 65,455-67 (1946). (163) Rahrs, E. J., U. S.Patent 2,235,562 (March 18, 1941). (163A) Raasch, M. S.,U. 8.Patent 2,424,667 (July 29, 1947). (164) Ramage, H. S., U. S. Patent 2,441,287 (May 11, 1948). (165) Renfrew, M. M., and Lewis, E. E., IND. ENG.CHEM.,38, 870 (1946). Renoll, M. W., U. S.Patent 2,414,330 (Jan. 14, 1947). Rust, F. F., and Vaughan, W. E., British Patent 542,913 (Feb. 2, 1942). Rust, F. F., and Vaughan, W. E., U. 8. Patent 2,278,527 (April 7, 1942). Ibid., 2,284,479 (May 26, 1942). Salisbury, L. F., U. S. Patent 2,437,307 (March 9, 1948). Ibid., 2,437,308 (March 9, 1948). Sayward, J. M., U. 5.Patent 2,391,745 (Dee. 25, 1945). Schubart, F. C., U. 5. Patent 2,389,088 (Nov. 13,1945), Schumb, W. C., IND.ENG.CHEM.,39,421 (1947). Schumb, W. C., and Stevens, A. J., U. 8. Patent 2,422,590 (June 17, 1947). Schumb, W. C., Young, R. C., and Radimer, K. J., IND. ENG. CHEM.,39,244 (1947). Sconce, J. S., Rucher, J. T., Whitmine, S. E., apd Schoonover, W. R., U. S.Patent 2,385,475 (Sept. 25,1945). Shilov, E. A., and Kupinskaya, G. V., J . Applied Chem. (U.S.S.R.), 18, 121-6 (1945). Shoemaker, B. H., and D'Ouville, E. L., U. S. Patent 2,390,621 (Dee. 11, 1945). Slade, R. E., Chemistry &Industry, 64,314-19 (1945). Soday, F. J., U. S.Patent 2,374,711 (May 1, 1945). Spence, L. V., and Haas, F. O . , U. S.Patent 2,379,759 (July 3, 1945).
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(183) Standard Oil Development Co., British Patent 539,416 (Sept. 10, 1939). (184) Ibid., 562,194 (June 22, 1944). (185) Ibid., 562,195 (June 22, 1944). (186) Stanley, H. M., U. S.Patent 2,407,039 (Sept. 23, 1947). (187) Stanley, H. M., and Philip, T. B., U. S. Patent 2,329,795 (Sept. 21, 1944). (188) Stern, G., and Friedrichsen, W., German Patent 703,067 (Jan. 30, 1941). (189) Stilmar, F. B., Struve, W. S., and Wirth, W.V., IND. ENQ.. CHEM.,39, 348-50 (1947). (190) Stratton. G. B.. U. S.Patent 2.420.801 (Mav 20, 1947). Stsuve, W. S., Benning, A. F., Downing, F. B., Lulek, R. N., and Wirth, W. V., IND. ENG.CHEM., 39, 352-4 (1947). Talbot, F., Ibid., 40, 969 (1948). Taylor, R. F., and Morey, G. H.,Ibid., 40, 432-5 (1948). Thomas, C. A., and Morris, H. E., U. S. Patent 2,285,473 (June 9, 1942). Tischenko, D. V., and Churbakov, A . N., J . Applied Chem. (U.S.S.R.), 19, 243-50 (1946). Turnbull, S.G., Benning, A. F., Feldmann, G. W., Linch, .4.L., McHarness, R. C., and Richards, M . K., IND. ENG.CHEM. 39, 286 (1947). Vaughan, W. E., and Rust, F. F., J. Org. Chem., 5,449 (1940). Ibid., 5, 472 (1940). Ibid., 6, 479 (1941). Vaughan. W. E.. and Rust. 3'. F . U. S. Patents 2,246,082 (May 28, 1941), 2,278,527 (April 7, 1942), 2,284,479 ( M a y 26. 1942). Ibid.,'U. S.'Patent 2,249,922 (July 22, 1941). Ibid., 2,284,482 (May 26, 1942). Ibid., 2,299,441 (Oct. 20, 1943). Vining, W. H., and Cass, 0. W., U. S. Patent 2,440,731 (May 4, 1945). Weinmayor, V., U. S.Patent 2,395,483(April 16,1946). Weiss, F. T., and Sullivan, W. A., U. S. Patent 2,403,200 (July 2, 1946). Wise, P. H.. and Milone, C. R., U. S.Patent 2,342,173 (Feb. 22, 1944).
RECEIVED July 6, 1948. Presented in part before the Division of Petroleum SOCIETY,st. Chemistry a t the 114th Meeting of the AMERICANCHEMICAL Louis. N o .
Hydration and Hydrolysis ms
WILLIAM J. TAPP,
CARBIDE AND C A R B O N CHEMICALS CORPORATION, S O U T H CHARLESTON, W. VA.
T
HE reactions of water with another molecule can be divided into two broad classes, hydration and hydrolysis, and for convenience it may be well t o define the scope of each. For the purposes of the following discussion hydration is meant to implv the reaction of water with any chemical entity such t h a t the product contains the component atoms of both of the reactants. Hydrolysis, conversely, is defined as the reaction of water with any chemical entity to yield two or more products, no one of which contains all of the components of the reactants. These definitions are not new but they are included to avoid any misinterpretation of the basis of cataloging the reactions described below. Thus the reaction of alkylene oxides t o yield glycols has been classed as hydration, but the reaction of noncyclic ethers with water to yield alcohols has been called hydrolysis. Some limit must be set in a discussion of this nature both as to extent and scope. Thus a number of fields which might justifiably be included as enzymatic hydrolyses-water treat-
ment involving hydrolysis of inorganic salts, inversion of sugars, and the hydration of a host of organic compounds on a laboratory scale-are mentioned only in passing. An attempt has been made to present developments of current interest to the industrial chemist and chemical engineer.
HYDRATION OLEFINS
Of the two fields discussed, hydration is more limited in sense of application, as the principal industrial applications lie in two general classes: hydration of olefins, and hydration of acetylenes. Hydration of olefins to yield alcohols was one of the early processes of the aliphatic chemical industry in this country, until now the amount of ethanol made by the hydration of ethylene has begun to approach that produced in the age-old fermentation of starches and sugars. An excellent survey of the current status
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of ethanol production has been made by Beamer (9). Principal improvements reported in the hydration of ethylene have been those in design to improve contact b e t m e n the reactive phases, but in general the catalyst has remained sulfuric acid. Typical of the developments in process design is the process described by Babcock ( 6 ) for the continuous hydrat'ion of ethylene n-ith sulfuric acid in a countercurrent, reactor a t pressures of 500 to 3000 pounds per square inch and above 100 O C. A very thorough survey of the field of catalytic hydration of olefins has been published by Berkman, Morrell, and Egloff (11). Some additional catalysts have been reported. Joshua and others (47) have used phosphoric acid and certain phosphates deposited on activated carbon t o hydrate ethylene and other olefins at 100" to 350" C. and 20 to 100 atmospheres. Tanner (81) has been issued a patent on the use of phosphotungst'ic acid deposit,ed on silica gel for t,he general hydration of olefins. Other Group VI 4 elements in the forin of heteropoly acids are also claimed to be hydration catalysts under the patent. The reaction is carried out at elevated pressures and at temperatures in the range 150' to 325 ' C. in an atmosphere of carbon dioxide, Interesting developments in Germany during World War I1 have been reported by Kammermeyer and Carpenter (49). Although the major portion of these data relate to I. G. Farbenindustrie developments in propylene hydration, mention is made of a patent application for the hydration of ethylene to ethanol in the presence of tungsten oxide activated by zinc oxide, o n specially prepared silica gel as catalyst support. The lower , WOp--were claimed oxides of tungsten-WO, Ts',04, W ~ O l , and to be most effective. The reaction was carried out a t elevated temperatures and pressures. Propylene. As in the hydration of ethylene, most advances in the hydration of propylene are variations of catalysts and equipment design of previously reported processes. Italrura (46) has reported upon the effect of temperature and acid concentration upon yields of isopropanol prepared by the absorption of propylene in sulfuric acid. With 99y0 acid a t 15 C. a yield of 67% alcohol resulted, but with 857, acid little or no alcohol was obtained at 100' C. I n both instances the reaction mixture was under little or no pressure. Propylene at elevated pressure reacted at 110" C. with 527, sulfuric acid t,o yield 247, isopropanol. Eversole and Doughty ( 2 7 ) have been issued a patent upon the production of isopropanol by the hydration of propylene a t 178 O to 375 ' C. and 500 to 3000 pounds per square inch in the presence of either sulfuric or phosphoric acids. The Kammermeyer and Carpenter report (49)deals in detail with a continuous process for the hydration of propylene. The process is based upon relatively small scale experiments but produetion facilities had been designed for its use on a manufacturing scalc. Catalyst for t,he process was tungsten dioxide probably containing some other lower oxides o€ tungsten; tungsten trioxide was claimed to be less efikient. Opt'imuni conditions were obtained by the addit,ion of zinc oxide as a promoter. Catalyst and promoter were impregnated on a specially prepared extruded silica gel. The best cat,alyst reporkd contained 20 to 22% tungsten (calculated as metal) and 5 7 , zinc oxide in terms of final solid catalyst. Propylene and Rater in a mole ratio of 1 to 10 were fed t o the continuous reactor at 230" t o 240" C. and 200 to 250 atmospheres. h conversion of 507, per pass and a yield of 96Yc based on propylene were reported. One wonders a t the planned commercial exploitation of the process in view of the accepted yield of 0.8 kg. of l O O y c isopropanol (as a 207, aqueous solation) per liter of catalyst per day. The lack of corrosion, a critical problem in acid hydration of olefins, and the artificial wartime economic standards niag have been determining factors xhich favored the process despite the rather low- production rate. Catalysts other than tungsten were tried and have been listed in order of decreasing activity: molybdenum oxide, vanadium oxide, and aluminum oxidc and cadmium oxide wycre found to
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function as promoters, but were reported as being inferior to zinc oxide. Reed (65) has patented a process which may be classified in the field of hydration. Olefins were fed to the reaction zone with the simultaneous introduction of halogen, and an oxide of sulfur. tellurium, or selenium. Aqueous sulfuric and phosphoric acids served to catalyze the reaction which was carried out below 100" C. and resulted in a mixture of products. Ethylene was converted t'o ethylene chlorohydrin and ethylene glycol; propylene t o mixture of propylene chlorohydrin, propylene glycol, and glycerol. Burgin, Rearne, and Rust (17) have published data relating to the hydration of 3-chloro-2-methylpropene and l-chloro-2methylpropene to yield 2-chloro-2-methyl propanol. I n the first instance the chloro alcohol was obtained in 63Tc yield by using 80% sulfuric acid a t 5" to 10" C. With the latter isomer essentially no reaction occurred with 807, acid, but a t -10" to 0" C. with 90% sulfuric acid the desired product was isolated in 66yo yield. I n each case unreacted butenyl chlorides were recovered, but partial rearrangements had taken place during the course of the reaction. Butenes. Recent developments reported on hydration of butenes have been limited to isobutylene. Work at I. G. Farbenindustrie and reported as a result of the Technical Surveys (5) involved the hydration of oIefins leading t o t,ertiary alcoliol formation, and principally isobutylene. The optimum cataljkt for the reaction vias 50y0 aqueous ferric sulfate although chromic chloride, cupric chloride, nickel chloride, and ferric bromide as aqueous solutions of 2 to 6O7@salt concentrations were reported. Under presumably optimum condit,ions, 130' C. and 4-hour reaction time, teit-butanol was prepared in 527, yield and 9770 efficiency based on isobutylene. Remiz and Frost (6'7) have published data on the hydration of isobutylene with a catalyst of 10 to 307, sulfuric acid containing 2 to 37, silver sulfate. The process, designed for continuous operation, was reported to yield 2 t o 3 kg. of product per kilogram of l O c l , sulfuric acid arid 37, silver sulfate a t a rcaction temperature of 85' t o 90" C. Variations in acid concentration and reaction temperat.ure were discussed. Katsuno (50) has reported 60 to SOYc yield of tert-butanol by sulfuric acid hydration. Mention should be made of a number of hydration reactions of olefins of somewhat more complex structure than the simple aliphatic olefins. Hepp (39) has been issued a patent on the hydration of cyclopentene and cyclohexene to the corresponding alcohols ; sulfuric acid m-as the catalyst. Hydration accompanied by polymerization t o yield monohydroxydipolycyclopcntadienes with varying degrees of polymerization resulted from the hydration of cyclopentadiene and dicyclopentadiene using sulfuric acid (26). Terpine hydrate has been made in good yields by the hydrat,ion of turpentine with sulfuric and phoPphoric acids (36'); camphene yielded 607, borneol at 50" C. in the presence of sulfonated petroleuni oil as catalyst (69). Camphor production by the hydration of p-cymene over mercuric sulfate in the presence of met,hanol as a mutual solvent was the basis of a recent patent ( 7 3 ) . I-lydroxycitronellal has been produced by the low- temperature hydration of cit'ronellal in the presence of 50% sulfuric acid (67). A recent patent describes the simultaneous hydration and oxidation of terpinolene t o nienthenetriol in the presence of aqueous sodium hydroxide (66). ACETYLENE
The second general field of industrially important hydration reactions is that of acetylene and substituted acotylenes. The reaction of acetylene with water in the presence of various catalysts leads directly t o either of two products-acetaldehyde (or acetic acid) and acetone-although it is liltely that acetaldehyde is an intermediate in the formnt.ion of acetone. KlebanslciI (51) has reported an investigation of the ieaction of acetylene and 20Y0 sulfuric acid containing 1.9 grams of mercuric oxide per 100 grams of Yulfuric acid. The reaction a t 70" to 80" C.
*
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to yield acetaldehyde was promoted by the presence of ferric ions. I n the same publication a report was made concerning the hydration in the presence of either a zinc oxide-vanadium oxide catalyst or a cadmium oxidevanadium oxide catalyst with added ferric oxide. At 400" to 425' C. a yield of 17% acetaldehyde and 5% acetic acid was reported. Pospelova (60) and others have recently described an investigation of acetylene hydration catalysts. Mercuric sulfate-sulfuric acid and organomercury catalysts were compared; the effects of adsorption of mercuric ion and of organomercury compounds on tungsten trioxide were discussed. Phosphate and phosphoric acid catalysts have been used in addition to the mercury salt-sulfuric acid combinations for acetylene reactions. A sintered cadmium dihydrogen phosphate catalyst (3.3)is reported to be an effective hydration agent, as is activated carbon containing phosphoric acid and a small percentage of copper as a promoter (66). Ipatieff and Schaad (46) claim silicophosphoric acid as an effective catalyst for acetaldehyde production. Recently a very thorough discussion was reported (86) upon a mixed catalyst containing phosphoric acid and zinc and cupric acid phosphates supported upon activated carbon. The effects of variation in a number of factors affecting the course of the reaction have been detailed; under optimum conditions, at 350" C. a yield of 88yo with 48y0 conversion was claimed. Zobel (81)has described a hydration catalyst of mixed aluminum, zinc, and tungsten oxides. Two detailed descriptions have been published recently concerning the preparation of acetone from acetylene. The Shawinigan Chemicals, Ltd., process using zinc oxide-ferric oxide catalyst has been discussed by Dyck (36). A detailed presentation has been made by Broun (16)concerning experimental data on acetone production over a basic zinc vanadate catalyst. Variation in factors affecting the reaction have been examined, and under optimum reaction conditions a t 450' C. an acetone yield of 60 to 70y0 has been claimed, The production of oxalicacid by the simultaneous hydration and oxidation of acetylene over sulfuric acid and mercuric salts has been mentioned (34). Nitric oxide was introduced with acetylene in the process. Mita (58) reported a process in which a mixed catalyst containing cuprow chloride, ammonium chloride, and leucine hydrochloride resulte ' in the formation of acetaldehyde and some vinyl chloride. Mercuric salts and sulfuric acid have been used almost exclusively in the hydration of acetylenylcarbinols ( I d , 88) acetylenic ethers (QS),acetylenic esters (64), and substituted acetylenes (18, 19). Schaad and 'Ipatieff (70)have described the use of solid phosphoric acid catalyst with substituted acetylenes. The hydration of alkylene oxides to the corresponding glycol is an old reaction. The few recent developments in this patent field can be mentioned briefly in passing. A few new catalysts have been ~
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COURTESY CARBIDE AND CARBON CHEMICALS CORPORATION
Ether Hydration Units
cited: trichloroacetic acid ('78), oxalic acid (do), iron salts (68) resulting from corrosion in the reaction system, and various amides (24). It is believed that none of these represents any marked advances in the field.
HYDROLYSIS The second general class of reactions of water is hydrolysis, and the groups of compounds that are hydrolyzed on a commercial scale are many. On the basis of tonnage produced and number of consumers, the production of soaps might be classed as of greatest importance. Of all the ester hydrolyses, the manufacture of soap is by far the major important application. Developments in this field represent changes in apparatus design rather than radical changes in reaction conditions, catalysts, or fundamental processes. Two excellent surveys on developments in the field of soap manufacture have been published by Safrin (6,9) and Schwitzer (75). A comprehensive review of developments in soap manufacture cannot be included here. Both acid and base catalysts have been used for hydrolysis reactions in general and much theory and supporting data have accumulated. A thorough summation of theory of acid-base catalysis was published by Schwab ( 7 2 ) . Included are not only ester hydrolyses but also hydrolytic reactions of aliphatic and
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aromatic halides, acetals, anhydrides, nitriles, and Sucrose inversion. Recently ion exchange resins have been reported as being very satisfactory catalysts for thc hydrolysis of esters (79, 82). Because the resins call be removed by filtration thcv are particularly suitable when one of the products is either vcrg high boiling or very viscous. Amberlite In-100is clainied (82) to be more efficient than hydrochloric acid as a hydrolytic agcnt. SILICONES
Most prominent among the recent developments in hydrolysis products are the silicones, and t,he review art,icles describing their uses and applications are too numerous to be cited here. Hyde and Delong (4.Z) described a number of siloxanes derived from phenyl-, phenylethyl-, diphenyl-, dimethyl-, and diphenyldichlorosilanes by hydrolysis in the presence of acid cat,alysts. Dimers, trimers, and high polymers were obtained and characterized. Hydrolysis of mixtures of ethoxyt,rirnethyl- and diethoxydimethylsilane under controlled conditions in the presence of sodium hydroxide was investigated by Hunter and eo-workers (41). I n a very t'horough invcstigation the oil-like products obtained and physical properties have been compared and contrasted with hydrocarbons of comparable properties. A similar investigation upon the controlled hydrolysis of the various nbutoxychlorosilanes both with and without the addition of pyridine as a catalyst has been reported recently (44). Studies on the partial hydrolysis of silicon tetrachloride under the proper conditions indicate the formation of chlorosiloxanes containing two and three silicon atoms ( 7 1 ) . Recent patents on the hydrolysir of silicon esters have been issued; bistrimethylsilicyl oxide is formed by the hydrolysis of ethoxytrimethylsilane in the presence of hydrochloric or sulfuric acids (21) and the oxide is claimed as an intermediate in the preparation of organosilicon polymers. The reaction product of diet,hoxydimethglsilane (55)upon distillation is reported to yield cyclic polymeric silicones. -4novel process has been reported in which the reaction product of silicon tetrachloride with methyl esters of aliphatic acids after being impregnated on fibers is hydrolyzed i n situ ( 7 ) . Thus a water-repellent finish is provided without the liberation of tiny subslances which might deteriorate thc fabric. Krieble and Elliot (53) have studied the stability of the carbonsilicon bond in hexamethyldisiloxane, a dimethyl silicon, and a monomethyl silicon polymer under conditions leading to alkaline hydrolysis. Rates of hydrolysis of orthosilicates under various conditions and with various solvents have been reported (.GO), and Andrianov (4) has discussed mechanisms of hydrolysis of organosilicon compounds and has shown t h a t the degrcc of polymcrization may be related to the mole fraction of water present in the reaction mixture. PHENOL
The hydrolysis of aromatic halides has been limited primarily to the production of phenol. Pat,ents have been issued for the use of calcium hydroxide as catalyst with calcium oxide as a n inhibitor t o reduce the formation of diphenyl ether (3%)and for calcium hydroxide as a catalyst with either calcium chloride or barium chloride as ether inhibitors (22). Calcium phosphate has also been cited as a catalyst for the reaction (64). Vernon and Thompson (84) have investigated the reaction conditions, space velocities, and other factors, and have reported the use of the follom-ing catalysts in phenol synthesis: tin vanadate, cuprous chloride, cupric nitrate, sulfate, and phosphate, and oxides of zinc, nickel, molybdenum, magnesium, and tungsten. The effect,s of alumina, silica, and silicon carbide as catalyst supports were studied. Under optimum reaction conditions a t 510" C. tin vanadate on silica gave phenol in the highest yield and efficiency. Silica gel impregnated with cupric chloride gave excellent' yields a t 450 to 600' C. as reported by Freidlin (SOj, v h o claims silica as the catalyst and cupric ion as an activator.
Vol. 40, No. 9
A very thorough investigation has been made of the hydrolysis of 0- and p-chlorotoluene by Shreve and Marsel (76). Optimum reaction coiidit,ions of time, reactant ratios, and temperatures were determined. Sodium hydroxide a t 350" C. gave 637' yield of cresol from p - chlorotoluene. The astonishing fact was the rcarrangement which occurrcd with either ortho or para isomers t o yield a product t h a t contained ahighproportionof themetaisomer. I n the reaction above, the product Contained 62V0 nz-cresol. Chlorination of tri-, tetra-, or pentachlorophenol in 00 Vc sulfuric acid so t h a t a total of six chlorine atonis arc present in the ring, can be followed by hydrolysis to yield chloranil (2). The reaction of allyl chloride t o yield allyl alcohol in a continuous process has recently been described in great detail by Fairbairn (28). The paper contains an extensive description of the process variables, reaction conditions, and pilot plant data for the manufacturing process. A somewhat earlier paper by brilliams (85),also in great detail, shows the use of ally1 and other chloropropenes as a source of synthetic glycerol. I n both processes sodium and/or calcium hydroxide are the important reagents for t'he hydrolyses. Hatch and Estes (37) have described the hydrolysis of allyl chloride using hydrochloric acid and cuprous chloride as catalysts. The hydrolysis of methallyl chloride in the presence of calcium carbonate 01-sodium hydroxide t o yield isobutyraldehyde has been described (80), and carbonates and hydroxides of copper, cobalt, and zinc have bccn claimed as hydrolysis catalysts for the reaction of mater with allyl or methallyl chloride (62). Acid cat,alysts such as sulfuric, phosphoric, and benzenesulfonic acids on silica and activated carbon have been patented as catalysts for the vapor phase reaction of halopropenes and water (3). The hydrolysis of aromatic subst.ituted aliphatic halides has been described, with dilute sodium carbonate (77) and sodium bica-:bonate ( 1 ) as hydrolytic agents for benzyl type halides. Sodium carbonate, calcium hydroxide, and sodium hydroxide have been used in the preparation of phenyl ethanols (14,35),and for the hydrolysis of 1,3-dichlorobatane ( 1 3 ) t o yield l-chloro-3hydroxybutane. -4cid cat,alysts, such as sulfuric acid, have been used for the hydrolysis of w-trichlorinatcd chlorohydrocarbons l o form chloroaliphatic acids (48),for the preparation of trifluoroacetic acid from I,l,l-trichlorotrifluoroethane(IO) and for the preparation of chlorostearic acid (20). The formation of acids and amides from nitriles has been accomplished by a wide variety of catalysts. Although amide formation is a hydration as defined here, i t is extremely difficult t o make such division a t this point. Sulfuric acid has been uscd at 0 C. for the preparation of 2,2,4-trichlorobutanoic acid (8)and at low t,emperature for the preparation of nicotinamide ($1). Barium hydroxide has been used for the preparation of amino acids as glycine and iV-met h ylglycine from the corresponding aminonitriles (74). A vapor phase reaction for the preparation of acetamide from acetonitrile over a cattalyst composed of silica and alumina has been reported recently (66). Among a number of unclaGficd reactions is the recent process patented by Tollefson (83) for the hydrolysis of diethyl ether t o ethanol. The reaction is carried out at 200 to 250 O C. over acidwashed clay (Super-Filtrol). Price and co-workers have reported upon the hydrolysis products from mustard gas (61, 62) and the nitrogen mustards (63) in the presence of various hydrolytic agents. I n the hydrolysis of alkylsulfongl chlorides with aqueous sodi:im hydroxide, t,ertiary amines were reported t o be effective in improving the reaction (Z3).
LITERATURE CITED (1) Adams, C. E. ( t o Standard 011 Co. of Indiana), U. 8. Patent 2,399,716 ( l f a y 7, 1946). ( 2 ) Alquist, F. N., Groom, L. H., and Haney, 17. H. (to Dow Chemical Co.), U. S. Patent 2,414,008 (Jail. 7, 1947). (3) Anderson, J., Stagei, R . hi., and hIcXllister, S 11. (to Shell Ueveloprncnt C o . ) , U. S. Patent 2,359,459 (Oct. 3, 1944).
September 1948
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
Andrianov, K. A., J . Gen. Chem. (U.S.S.R.), 16, 633-46 (1946). Anon., P B Rept., 66,859, U. S.Dept. Commerce (1947). Babcock, D. F. (to E. I. du Pont de Nemours & Co.), U. S. Patent 2,296,696 (Sept. 22, 1942). Barry, A. J. (to Dow Chemical Co.), U. 5.Patent 2,405,988 (Aug. 20,1946). Bauer, 0. W., and Teter, J. W. (to Sinclair Refining Co.), U. 8. Patent 2,429,791 (Oct. 28, 1947). Beamer, C. M., Chem. Eng. Progress, 1, No. 3 ; Trans. Am. Inst. Chem. Engrs., 43, 92-6 (1947). Benning, A. F., and Park, J. D. (to E . I. du Pont de Nemours & Co.), U. S. Patent 2,396,076 (March 5, 1946). Berkman, S.,Morrell, J. C., and Egloff, G. “Catalysis,” New York, Reinhold Publishing Co., 1940. Blumenfeld. J.. U. S. Patent 2.405.873 (Aun. 13. 1946). Briton, E. C.,’and Coleman, G. H. (to D&v Chemibal Co.), U. S. Patent 2,181,297 (Nov. 28, 1939). Britton, E. C., Coleman, G. H., and Hadler, B. C. (to Dow Chemical Co.), U. S.Patent 2,185,141 (Dee. 26, 1939). Broun, A. S., Kuratova, 0. S.,Mushenko, D. V., and Urinson, R. P., J. Chem. I n d . (U.S.S.R.), 18, No. 1, 24-9 (1941). translation: Tolpin, J. G., Natl. Petroleum News, 37, No. 31, R631-4 (1945). Bruson, H. A. (to Resinous Products and Chemical Co.), U. S. Patent 2,385,788 (Oct. 2, 1945). Bmgin, J., Hearne, G., and Rust, F., IND.ENG.CHEM.,33, 385-8 (1941). Campbell, K. N., and Tomcik, E. J., Proc. Indiana Acad. Sci., 51, 158-60 (1941). Churbakov, A. N., and Ryazantsev, V. N., ! J . Applied Chem. (U.S.S.R.), 13, 1464-9 (1940). Colbeth, I. M. (to Baker Castor Oil Co.), U. 9. Patent 2,270,856 (Jan. 27, 1942). Daudt, W. H. (to Corning Glass Works), U. S.Patent 2,386,441 (Oct. 9, 1945). Dierichs, A. (to General Aniline and Film Corp.), U. 5.Patent 2,217,836 (Oct. 15, 1940). Dillon, T . E. (to E. I. du Pont de Nemours & Co.), U. S. Patent 2,408,300 (Sept. 24, 1946). Distillers Co., Ltd., British Patent 529,476 (Dee. 21, 1940). Dittrich, E. (to Chemical Marketing Co.), U. S. Patent 2,212,693 (Aug. 27, 1940). Dyck, A. W. J., Can. Chem. Process Inds., 30, 34-6 (1946). Eversole, J. F., and Doughty, E. W. (to Carbide and Carbon Chemical Coro.) Canadian Patent 391,794 (Oct. 8. 1940). Fairbairn, A. W., Cheney, H. A., and Cherniavsky, A. J., Chem. Eng. Progress, 1, No. 6 ; Trans. Am. Inst. Chem. Engrs., 43. -, 280-90 -~ (1947). , Ferrero, P., Vandendries, C., and Berbe, F., German Patent 701,463 (Dec. 19,1940). Freidlin, L. Kh., Balandin, A. A., Fridman, G. A,, and Lebedeva, A. I.. Bull. Acad. Sei. (U.S.S.R.), Classe sei. chim., 1945, 375-83. Geigy Colour Co., Ltd., British Patent 675,119 (Feb. 7, 1946). Greibe, J. J. (to Dow Chemical Co.), U. S. Patent 2,275,044 (March 3, 1942). Groombridge, W. H., and Dee, T. P. (to Celanese Corp. of America), U. S. Patent 2,206,226 (July 2, 1940). Gruber, W., Reichsamt Wirtschafts-ausbau Chem. Ber., Priif-Nr. 38 ( P B 52,007) (1940). Hanai, S.,J . Chem. SOC.J a p a n , 62, 1208-15 (1941). Hasselstrom, T.(to G. and A. Laboratories, Inc.), U. S. Patent 2,330,579 (Sept. 28, 1943). Hatch, L. F., and Estes, R. R., J . Am. Chem. Soc., 67, 1730-3 IlO4s. ,- .- -,. Heilbron, I. M., Jones, E. R. H., Smith, P., and Weedon, B. C., J . Chem. Soc., 1946,54-8. Hepp, .. H. J. (to Phillips Petroleum Co.), U. S. Patent 2,414,646 (Jan. 21, 1947). HolzaDfel. L., Kolloid-2.. 100, 380-8 (1942). Hunter, M. J., Warrick, E. L., Hyde, J. F., andCurrie, C. C., J . Am. Chem. S O L , 68, 2284-90 (1946). Hyde, J . F., and DeLong, R. C., Ibid., 63, 1194-6 (1941). I. G. Farbenindustrie A. G., French Patent 849,807 (Dec. 2, 1939). Iler, R. K., IND. ENC.CHEM.,39, 1384-8 (1947). Ipatieff, V. N., and Schaad, R. E . (to Universal Oil Products Co.), U. S.Patent 2,253,034 (Aug. 19, 1940). Itakura, T., J . Chem. SOC.J a p a n , 63, 1400-13 (1942). Joshua, W. P., Stanley, H. M., and Dymock, J . B., U. 5. Patent 2,232,610 (Feb. 18,1941). Joyce, R. M., Jr. (to E. I. du Pont de Nemours & Co.), U. S. Patent 2,398,430 (April 10, 1942). Kammermeyer,‘K., and Carpenter, G . B., F I A T Final Rep. 968 ( P B 78,277), April 2, 1947. Katsuno, M., Bull. Chem. Soc. J a p a n , 18, 211-17 (1943).
1623
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RECEIVED June 5 , 1948.
Installation for Manufacture of Nitroglycerin b y Batch Process (See “Nitration,” page 1627)
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