un II/GC [Unit Processes Review
Hydration
and Hydrolysis
by David W. McDonald and William F. Hamner, Monsanto Chemical Co., Texas City, Tex.
b Hydrolysis of organosilicones gives improved lubricants and rubbers for application under extreme conditions
b b
N e w phenol processes compete with established hydrolytic routes
Nitrile silicone rubbers offer high solvent resistivity for specialty uses
b Synthetic glycerol production now equals by-product manufacture and is still growing
ALTHOUGH outstanding advancements in this well-established field were relatively few in the past two years, important developments continue to be reported. I n general the references cited here have been selected for industrial significance. No attempt has been made to cover processes in which hydrolysis is a minor step or to report the many fundamental studies on the kinetics of hydrolysis of a wide variety of compounds. Activity in the field of olefin hydration appears to have declined. Most of the reports are concerned u,ith purification techniques, although a few new catalyst systems have been described. Hydrolysis reactions play an important role in the petrochemical industry, and capacity increases for materials such as ethylene oxide, glycol, and glycerol continue to be announced. A new producer, Olin Mathieson, will enter the synthetic glycerol field in early 1961. Phenol is another basic chemical that has continued to grow. Production of phenol jumped from about 520 million pounds in 1958 to around 675 million pounds in 1959. Current capacity is approximately 725 million pounds, but expansions by several producers are expected to result in a capacity of about 850 million pounds by mid-1961. The conventional sulfonation and chlorination processes involving hydrolysis reactions continue to be expanded, along with the newer but well-established cumene route. I n addition, a relatively new process based on benzoic acid will apparently be used in a new plant by Dow Chemical; this may be a real challenge to the older processes as benzoic acid is derived from toluene instead of the more costly benzene on which the older processes are based.
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.4lthough still small in total poundage compared with these petrochemicals, the organic silicon compounds form the basis of a strong and growing industry. Work is continuing on the synthesis of improved silicone oils for high temperature, high pressure lubricants. Of particular significance in the silicone field is the development of the nitrile silicone rubbers. These materials have excellent oil and solvent resistance, in addition to the high thermal stability characteristic of organic silicon compounds. Kitrile and amide hydrolysis continues to be an active field. Hydrolysis of acrylonitrile telomers to acrylamide or acrylic acid derivatives is an interesting application. A synthetic route to monosodium glutamate via hydrolysis of an acrylonitrile derivative is another development of note, while refinements on syntheses of amino acids, such as alanine and lysine, by nitrile or hydantoin hydrolyses are still being reported.
Hydration
As in the previous review (September 1958), hydration processes are described under the general headings of direct and indirect processes. I n the direct hydration field a few new catalyst systems have been reported, while references on indirect processes continue to emphasize methods of improving the economics of these processes. Direct Hydration. The use of silicophosphoric acid, H2Si(P04)2,or its salts is claimed to give higher conversions per pass in the direct hydration of C&4 olefins (12A). For example, catalysts containing either iron or aluminum salts of silicophosphoric acid were reported to give 60 to 80% higher conversions of
INDUSTRIAL AND ENGINEERING CHEMISTRY
ethylene to ethyl alcohol than the standard phosphoric acid-on-Celite catalyst. The direct hydration of propylene in the presence of either permanganates, aluminates, or silicates of merals of the iron transition group (Group V I I I ) , Group IB, or Group IIB has been patented (7 7A). Another process employing acidic ion exchange resins modified with eirher Group IB, 11, VI, or VI11 metals has been patented ( 6 A ) . These modified resins are said to have high capacity and to give good yields of either alcohols or ethers. They are readily prepared by treating a conventional strong acid resin with a solution of a metal salt, such as copper(I1) chloride or nickel(I1) chloride, to exchange part of the hydrogen ions in the resin with the metal ion. A two-stage catalyst system utilizing an inorganic hydration catalyst, such as silica-alumina cracking catalyst, ahead of an acid ion exchange resin catalyst is claimed to be more effective than the resin alone because the inorganic catalyst removes impurities such as allene, methylacetylene, and diolefins ( 3 A ) . The latter impurities tend to polymerize on the surface of hydration catalysts and can be removed from silica-alumina cracking catalysts or similar materials by high-temperature regeneration techniques. Purification systems connected with hydration processes continue to be of commercial interest. In the hydration of propylene to isopropyl alcohol, a clean separation of unreacted propylene and the alcohol has proved to be difficult. A distillation process to accomplish the propylene-alcohol separation has been patented ( 7 A ) . An acid extraction process to remove other hydrocarbons
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and sulfur compounds from n-butylene prior to hydration of the olefin has been reported ( Q A ) . Indirect Hydration. The use of a halogenated polycarboxylic acid as an indirect hydration catalyst instead of either sulfuric acid or aromatic sulfonic acids has been described by Friedman and Morritz (ZA). Acids such as dichloromalonic acid and tetrafluorosuccinic acid, which have all a-hydrogen atoms substituted by either chlorine or fluorine, are claimed. The conventional sulfuric acid process, in which an alkyl aryl sulfonate is added to the acid extract used to absorb the olefin, has been modified to improve the absorption capacity of the system ( 7 3 A ) . Numerous modifications of purification systems for the indirect process continue to appear in the patent literature. A process involving a preliminary topping step to remove diethyl ether, followed by a water-extractive distillation system to purify ethyl alcohol, has been described by Catterall and Fuqua (7A). A similar extractive distillation purification system for ethyl alcohol has been patented by Hawkins and Miller (44). Another patent claims that periodic flushing of the acid extract stripper column and reboiler with product ethyl alcohol in the conventional ethylene hydration process will remove carbonaceous materials which tend to foul the equipment ( 7 4 4 ) . I n a propylene hydration process, unreacted propane in the feed is preheated, then introduced into the hydrolyzer where the hot gas supplies a portion of the heat required to concentrate the dilute sulfuric acid and release the isopropyl alcohol ( 5 A ) . A similar principle is employed in a process for diisopropyl ether, in which the acid extract is stripped under pressure with preheated propylene (70A). T h e removal of odorous impurities from isopropyl alcohol by contact with diatomaceous earth and high surface-area iron metal has been described (8A).
a by-product from soap manufacture, with the total from both estimated at 270 million pounds for 1960. While there is a continuing decrease in supply of natural glycerol from soap manufacture (as a result of synthetic detergents), there is an increase from the manufacture of fatty acids so that the over-all supply of natural glycerol is expected to remain steady. Synthetic production will continue to grow as the glycerol market grows. Dow and Shell are currently the only producers of the synthetic material, but they will be joined by Olin Mathieson who is building a 35 million pound per year plant at Doe Run, Ky. A patent (8B) issued to Thomas describes an improved process for the manufacture of glycerol by hydrolysQ of a n aqueous solution of the dichlorohydrin isomers. The crude product from the chlorohydrination of allyl chloride is fed to an enrichment still where the dichlorohydrins are concentrated overhead as a n azeotrope, and the impurities with the remaining dichlorohydrin are taken off at the bottom. The bottoms are treated with caustic to convert the dichlorohydrin to epichlorohydrin which is stripped off, combined with the overhead, and sent to the hydrolyzer to produce glycerol. Fewer impurities and salts are present, so that recovery of glycerol is greatly simplified. A process for obtaining U.S.P. grade glycerol from hydrolysis of chlorohydrin mixtures has been described by Cofer
Unit Processes Review
(3B). The method involves a two-phase separation by adjusting the water content of the chlorohydrins to concentrate the undesirable high boilers. The chlorohydrins are recovered from this phase by extraction. The use of a series of reaction zones to control the alkalinity and formation of undesirable high boilers has been described (ZB),and reduced consumption of base is claimed. A process for preparing monoalkylene glycols from the corresponding C Z to CS alkylene oxide has been patented (7B). A novel method for the preparation of glycols from conjugated aliphatic diolefins involves reaction of the diolefins with sodium in dispersed form to obtain the metal derivatives of dimerized dienes, which are then reacted with an epoxide, followed by hydrolysis to the corresponding glycol (6B). Aliphatic polycarboxylic acids have been prepared by a single stage combined hydrolysis and oxidation of ozonides of cyclic olefins (5B). The hydrolysis of primary and secondary monochlorides of diisobutylene to primary alcohols has been disclosed by Chambers and Foster (7B). The preparation of 2-menthene1-01 from a-terpinene has been accomplished by hydrolysis of the aterpinene monohydrochloride (9B). Michalek has prepared 2,5-dichlorostyrene from 2,5-dichloro-a-bromoethylbenzene by hydrolysis to the 2,5-dichlorophenyl methyl carbinol and subsequent dehydration (4B).
MILLIONS OF POUNDS
-.-
Total Glycerol Production
260
250
Hydrolysis of Oxides and Halides Ethylene oxide capacity in the U.S. has grown to over 1.5 billion pounds per year. Most of the new facilities employ the direct oxidation process in preference to the chlorohydrin route. The hydrolysis to ethylene glycol is a major outlet for ethylene oxide, and antifreeze use alone is expected to climb from 900 million pounds in 1960 to over 1 billion pounds per year by 1965. New automobile engine designs are expected to have some impact on the ethylene glycol market by that time, and so new uses for this material must be found. Synthetic glycerol production has now reached a level equal to that produced as
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Hydrolysis--Phenols iMost of the work now being reported on the preparation of phenols by hydrolysis reactions concerns substituted phenols rather than phenol itself. However, there have been some interesting developments on new processes for phenol which promise stiff competition for the traditional hydrolysis-type processes-i.e., the sulfonation or chlorination processes. For example, Dow has patented a process in which benzoic acid is oxidized and decarboxylated to form phenol ( I C ) . The reaction is carried out in the presence of a catalysL such as copper(I1) oxide and in the presence of steam, which serves two purposes-removal of phenol from the catalyst and hydrolysis of phenyl benzoate, a byproduct, to phenol and benzoic acid. Trade sources report that DOWplans to build a new phenol plant at Kalama, Wash., based on the benzoic acid process. Because benzoic acid is readily produced from toluene, this process offers raw material cost advantages over processes based on the more expensive benzene. Another new phenol process, recently announced by Scientific Design Co., is claimed to permit the direct oxidation of benzene to phenol without the customary production of by-products. O n the other hand, Hooker Chemical has announced plans to build a phenol plant by a modified chlorination (RaschigDurez) process, indicating that hydrolysis-type processes will continue to be used where raw material economics are favorable. This is further supported by reports That both Monsanto and Reichhold are expanding their plants, which employ the sulfonation process, and that Union Carbide is increasing the capacity of its chlorination process plant at Marietta, Ohio. Preparation of phenolic compounds by heating aromatic sulfur compounds such as sulfonic acids or sulfones with a copper(I1) salt in the presence of water has been patented (7C). This process is similar in some respects to the Do\\, benzoic acid process described above. Another interesting process involves the conversion of ethers such as diphenyl ether to the corresponding phenol by treatment with sodium metal and hydrogen in an inert solvent (GC). Alkaline hydrolysis of p-bromofluorobenzene to the salt of p-fluorophenol is described in a recent patent ( 5 C ) . This patent claims that addition of a small amount of cobalt naphthenate reduces the severity of the reaction conditions required and decreases the formation of by-product phenol. Another patent (8C) describes a process for producing m-chlorophenol by selective sulfonation of m-dichlorobenzene in the presence of p dichlorobenzene and conversion of the
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rn-dichlorobenzenesulfonic acid to the phenol by alkaline hydrolysis. This process is attractive because it provides a way of separating the dichlorobenzene isomers, yielding the para-isomer, which has a higher value than the mixture, plus the m-chlorophenol which is also a desirable product. I n a similar process, rn-dichlorobenzene in admixture with the para-isomer is preferentially sulfonated to form mdichlorobenzenesulfonic acid, which is converted to resorcinol by treatment with aqueous caustic at 100' to 300' C. rather than by caustic fusion (4C). Another process for resorcinol involves the sulfonation of benzene with stabilized y-sulfur trioxide dissolved in sulfuric acid to yield m-benzenedisulfonic acid which is converted to resorcinol by the caustic fusion process (2C). A process, reported by Hcllcr ( 3 C ) , involves sulfonation of crude naphthalene at elevated temperatures. then dilution with water to givc a pure naphthalene phase plus an aqueous phase of naphthalenesulfonic acid which is partially converted to additional naphthalene by treatment w-ith steam. T h e remaining naphthalenesulfonic acid is then hydrolyzed to 2-naphthol by the usual caustic fusion process.
Hydrolysis of Organic Silicon Compounds The silicone industry continues to grow with a n estimated demand now well over 1 5 million pounds per year. Classified into general types-resins, rubbers, and oils-the silicones offer a broad spectrum of uses. Commercial applications are generally in areas requiring greater thermal stability than conventional organic materials. These polymeric materials are prepared by hydrolysis of the corresponding monomeric silane. T h e hydrolysis of silanes containing one silicon-bonded hydrolyzable group produces oils; silanes containing two such groups give rubbers; and those containing three yield resins. Cohydrolysis of mixtures yields intermediate-type materials. A method has been patented by Prober ( 2 7 0 ) for replacing a hydrolyzable group with a hydrocarbon radical, thus providing a means of varying the product obtainable from a starting material containing three hydrolyzable groups. H e has accomplished this by reacting a cyanoalkylsilane with a Grignard reagent in the presence of a tertiary amine. Of growing importance is the recent development of nitrile silicone rubber. This material has superior oil and solvent resistance, excellent high- and low-temperature properties, and easy processability. T h e preparation of nitrile-con-
INDUSTRIAL AND ENGINEERING CHEMISTRY
taining silanes and the hydrolysis to the corresponding polysiloxanes have been disclosed by Sommer (250). Greater strength is found for the materials where the cyanide radical is in a nonterminal position. T h e cyanoalkylsilanes are prepared from olefinic nitriles such as acrylonitrile, methacrylonitrile, and crotononitrile by heating with a silane containing at least one silicon-bonded hydrolyzable group, usually in the presence of a catalyst. The following catalysts have been used: platinum on charcoal (250):amides ( 2 2 0 ) , diarylamines (7201, phosphorus halides ( 7 5 0 ) , dialkylcyanamides ( 7 7 0 ) , phosphonates ( 7 3 0 ) , hydrocarbyl-substituted phosphine ( 7 4 0 ) , hindered phenols ( 7 6 D ) , and hydrocarbyl-substituted amines (780). A continuous process for the hydrolysis of organosilanes to produce monomeric or slightly condensed silanols of low molecular weight has been patented by Gordon (80). These materials are very reactive and are used as intermediates for silicone modified products. Work is continuing on the improvement of silicone oils for lubricants. Improved lubricity is obtained if the oil contains a halogen-substituted aromatic side chain. The bis(chloropheny1)tetramethyldisiloxanes, prepared by Gainer and Lewis (GD),are claimed to offer good lubrication properties. Phosphorus-containing derivatives of polysiloxanes have been prcpared; they- are claimed to be particularly useful as lubricating fluids under kinetic boundary conditions ( 7 0 ) . Patents describe halogenated siloxanes derived from mono- and divinylsilanes containing either a halogenated cyclobutyl: a trifluoropropj-I, a trifluorotolyl, or a hexafluoroisohexyl group on the silicon. Various copolymers are possible by cohydrolyzing the above siloxanes xvith other siloxanes (230,240). Compounds containing the trifluoromethyl group are claimed by Tarrant and Dyckes ( 2 7 0 ) , and fluorine-containing chlorosiloxanes have been described by Brown ( 3 0 ) . Hydrolysis of the chlorosilanes results in the corresponding fluoroalkylsilane diol ( 7 I D ) , Other hydroxy-containing siloxane fluids have been reported by Wehrly (280)> and a process for making diphenylsilane diol by hydrolysis of diphenyldichlorosilane has been patented
(260). Silicone compounds containing various functional groups continue to be developed. Ether linkages in the side chain ( 9 D ) and connecting silicon atoms (700)have been reported. Other functional groups include acryloxy (ZOD), aminopropyl (7QD), and phenyl and methyl (50). Bailey and others have prepared novel cyclic siloxane
a n y &
Unit Processes Review
to be reported (4E, SE, 72E, 74E-76E). However, a synthetic
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route to monosodium glutamate via the hydrolysis of or-aminoglutaronitrile, a derivative of acrylonitrile, has been disclosed ( I E ) . Reportedly, a large plant employing this process will be built in Japan. Reduction of nitriles to aldimines by means of a dialkylaluminum hydride and hydrolysis of the aldimines to the corresponding aldehydes has been reported (7E). Examples of nitriles which may be converted to aldehydes by this procedure are benzonitrile and vitamin A nitrile. Preparation of soaps of wax acids by hydrolysis of long chain aliphatic nitro compounds has been patented (8E). T h e nitrated paraffins are treated with a mineral acid at 110' to 140' C., then with chromic acid solution to remove resins, and finally with a base such as potassium hydroxide to yield the desired soap.
Hydrolysis of Esters and Carbohydrates Sample o f ordinary silicone rubber (right) swells and curls when placed in a dish o f iet engine fuel. Nitrile silicone rubber (left) is unaffected. in the manufacturing process for nitrile silicone rubber, highly pure nitrile monomer is hydrolyzed and then polymerized. Resulting polymer is processed b y conventional techniques
polymers by cohydrolysis (7D, 2 0 ) . Clark has used cohydrolysis to prepare novel siloxanes containing silicon-bonded hydrogen atoms (40).
Hydrolysis of Nitrogen Compounds As noted in the previous review, the preparation of amino acids by hydrolysis of either nitriles or hydantoins is continuing to develop as a major application of hydrolysis reactions. A modification of the well-known synthesis of /3-alanine from a reaction product of acrylonitrile and ammonia has been reported. In this process, formaldehyde, acrylonitrile, and ammonia are allowed to react at atmospheric pressure to form a new compound, 0-methyleneaminopropionitrile, which may be readily hydrolyzed in acid solution to form /?-alanine hydrochloride (70E). Another route to /?-alanine, in which ethylene cyanohydrin is treated with an alkaline catalyst and the resulting polymeric product is hydrolyzed with a mineral acid to p-alanine, has been patented (9E). The synthesis of lysine by hydrolysis of 4-aminobutylhydantoin is another well-known hydrolysis reaction. Pollack has patented a modification of the process for the 4-halobutylhydantoin, which is a key intermediate in the lysine process (7323). Use of ion exchange
resins to separate the amine-type impurities from lysine made by this process has been described in two patents (SE,
77E). Hydrolysis of acrylonitrile telomers to the corresponding telomers of either acrylamide or acrylic acid has been described by Burland and Roth (ZE). For hydrolysis to the amide stage, 1 mole of acid and 1 mole of water per mole of telomer were used, while hydrolysis to the acrylic acid stage usually required 1 mole of base and 2 moles of water per mole of telomer. A novel process has been disclosed (3E) in which an unsaturated CG-CLs nitrile is oxidized in alkaline permanganate solution to yield a Cq cyano acid which is then hydrolyzed to succinic acid. Hydrolysis of nylon wastes to recover the contained difunctional acids and amines has been described (77E). The alkaline hydrolysis is carried out in the presence of an aliphatic alcohol of at least three carbon atoms; the dibasic acid salt accumulates in the aqueous phase, while the diamine collects in a supernatant alcoholic phase from which it is recovered by distillation. Modifications of the process for recovery of monosodium glutamate from hydrolysis of waste sugar beet liquor
Manufacture of tall oil by hydrolysis of rosin and fatty acid soaps from kraftprocess black liquor is carried out in 50 to 60 commercial units in the United States, mostly in batch-process systems. However, a growing number of companies are using continuous processes which offer lower costs and improved tall oil quality. An excellent description of the continuous process used at St. Mary's Kraft Corp. plant in Georgia has been published ( I F ) . An improved process for the hydrolysis of fats and oils is described in a patent issued to Schlenker ( 5 F ) . This patent describes an autoclave containing cooling coils in the vapor space which are used to cool the reaction mixture rapidly by cooling the vapor. Preparation of furfural by acid hydrolysis of pentosan-containing materials such as corn cobs, oat hulls, or wood chips is another well-known commercial operation. A patent claims that presteaming the pentosan raw material prior to the conventional digestion process results in higher yields of furfural and more efficient utilization of the digester ( 7 F ) . The presteaming treatment results in a substantial increase in bulk density of the raw material, allowing a greater amount of it to be charged to the digester with a proportionate increase in furfural produced per charge. Hydrolysis of hardwood waste liquors, under special time-temperature conditions which give good yields of furfural yet avoid its destruction, has been reported ( 3 F ) . Another patent describes a continuous process for furfural by hydrolysis of a pentosan-containing material in which the reaction product from the digester is passed into a n expansion VOL. 52, NO. 1 1
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Unit Processes Review
vessel a t reduced pressure causing furfural and steam to be flashed from the reaction mass into a furfural distillation column ( 6 F ) . This is claimed to give a furfural-steam mixture of relatively high furfural content resulting in economies in the distillation step. A process has been patented by Leonard for making levulinic acid by acid hydrolysis of spent pine wood from which rosin has been removed by solvent extraction (ZF). T h e spent wood, preferably in finely divided form, is treated with excess dilute sulfuric acid a t 140' to 210' C., then cooled, and filtered to remove tars using the lignins present as a filter aid; the filtrate is extracted with a solvent to recover the levulinic acid. Recovery of acetic acid from waste liquor from wood pulping operations has been described (4F). A key step in the process is the countercurrent scrubbing of acetic acid-water vapors from the evaporators with fresh 100% sulfuric acid, resulting in absorption of the water by the mineral acid.
literature Cited Hydration (IA) Catterall, W. E., Fuqua, M. C. to Esso Research and Engineering Co.), .S. Patent 2,836,545 (May 27, 1958). (2A) Friedman, B. S., Morritz, F. L. (to Sinclair Refining Co.), Zbid., 2,830,091 (April 8, 1958). (3A) Zbid.,2,845,463 (July 29, 1958). (4A) Hawkins, J. J., Miller, F. D. (to National Petrochemicals Corp.), Zbid., 2,865,818 (Dec. 23, 1958). (5A) Hennig, H. (to The Pure Oil Co.), Zbid.,2,868,848 (Jan, 13, 1959). (6A) Langer, A. W. (to Esso Research and Engineering Co.), Zbid.,2,891,999 (June 23, 1959). (7A) Leyy, N., Thomson, R. C. (to Imperial Chemical Industries, Ltd.), Ibid.,2,834,816 (May 13, 1958). (8A) Mackinder, R., Kenzie, R. G., Tiso, P. (to Shell Development Co.), Ibid.,2,857,436 (Oct. 21, 1958). (9A) Peters, T. J., Gathman, A. (to Esso Research and Engineering Go.), Zbid., 2,918,499 (Dec. 22, 1959). (10A) Scheeline, A. W., Hubbard, A. Mi., Hakala, T. H. (to Esso Research and Engineering Co.), Zbid., 2,825,746 (March 4, 1958). (11A) Teter, J. W.,Gring, J. L., others (to Sinclair Refining Co.), Zbid., 2,830,090 (April 8, 1958). (12A) Wegner, C. (to Farbenfabriken Bayer A.-G.), Zbid.,2,876,266 (March 3, 1959). (13A) Wilson, S. W. (to Esso Research and Engineering Co.), Zbid., 2,859,237 (Nov. 4, 1958). (14A) Wilson, S. W., Silver, W. H. (to Esso Research and Engineering Co.), Zbid.,2,872,491 (Feb. 3, 1959).
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(5B) Niebling, K. F. J., Rumscheidt, G. E. (to Shell Development Co.), Zbid., 2,848,490 (Aug. 19, 1958). (6B) Nobis, J. F., Allgeier, E. A. (to National Distillers and Chemical Corp.), Zbid.,2,850,538 (Sept. 2, 1958). (7B) Parker, A. S. (to Gulf Oil Corp.), Zbid.,2,839,588 (June 17, 1958). (8BI Thomas. R. M. (to Olin Mathieson Chemical Corp.), Zbid., 2,858,345 (Oct. 28, 1958). (9B) Webb, R. L. (to the Glidden Co.), Zbid.,2,868,845 (Jan. 13, 1959). I
Hydrolysis-Phenols (IC) Barnard, R . D., Meyer, R. H. (to The Dow Chemical Co.), U.S. Patent 2,852,567 (Sept. 16, 1958). (2C) Cake, W. R. (to Heyden Newport Chemical Corp.), Ibid.,2,856,437 (Oct. 14, 1958). (3C) Heller, A. N. (to Allied Chcmical Corp.), Zbid.,2,884,463 (April 28, 1959). (4C) Kamlet, J. (to The Goodyear Tire and Rubber Co.), Zbid.,2,835,708 (May 20, 1958). (5C) Kuehlewind, W. E., Jr. (to Olin Mathieson Chemical Corp.), Zbid., 2,934,569 (April 26, 1960). (6C) Muller, K., Delfs, D. (to Farbenfabriken Bayer A.-G.), Zbid., 2,862,035 (Nov. 25, 1958). (7C) Stevens, D., Harris, G. H. (to The Dow Chemical Co.), ZCid., 2,831,895 (April 22, 1958). (8C) Stoesser, W. C., Gentry, W. M. (to The Dow Chemical Co.), Zbid., 2,835,707 (May 20, 1958). Hydrolysis of Organic Silicon Compounds (ID) Bailey, D. L., Black, W. T . (to Union Carbide Corp.), U.S. Patent 2,849,473 (August 26, 1958). (2D) Bailey, D. L., York, E. R. (to Uniolt Carbide Corp.), Zbid., 2,905,703 (Sept. 22, 1959). (3D) Brown, P. L. (to Dow Corning Corp.), Zbid.,2,911,427 (Nov. 3, 1959). (4D) Clark, H. A. (to Dow Corning Corp.), Zbid., 2,877,255, 2,877,256 (March 10, 1959). (5D) Fletcher, H. J., Constan, G. L. (to Daw Corning Corp)., Ibid.,2,890,234 (June 9,1959). (6D) Gainer, G. C., Lewis, D. W. (to Westinghouse Electric Corp.), Zbid., 2,891,981 (June 23, 1959). (7D) Garden, W. D., Thompson, J. M. C. (to Imperial Chemical Industries, Ltd.), Zbid.,2,889,349 (June 2, 1959). (8D) Gordon, T. H. (to Allied Chemical and Dye Corp)., Zbid., 2,832,794 (April
Hydrolysis of Oxides a n d Halides (IB) Chambers, R. R., Foster, R . L. (to Sinclair Refining Co.), U.S. Patent 2,885,445 (May 5, 1959). (2B) Cofer, K. B. (to Shell Development Co.), Zbid.,2,838,574 (June 10, 1958). (3B) Zbid.,2,873,298 (Feb. 10, 1959). (4B) MichaIek, J. C., Zbid.,2,916,523 (Dec. 8, 1959).
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INDUSTRIAL AND ENGINEERING CHEMISTRY
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(21D) Prober, M. (to General Electric Co.), Zbid.,2,913,472 (Nov. 17, 1959). (22D) Saam, J. E. (to Dow Corning Corp.), Zbid.,2,860,153 (Nov. 11, 1958). (23D) Smith, D. D. (to Dow Corning Corp.), Zbrd.: 2,884,433 (April 28, 1959). (24D) Zbid.,2,884,434 (April 28, 1959). (25D) Sommer, L. H. (to Dow Corning Corp.), Zbid., 2,906,767 (Sept. 29, 1959). (26D) Spector, M. L., Strong, R. P. to General Electric Co)., Zbid.,2,899,453 4ug. 11, 1959). (27D) Tarrant, P., Dyckes, G. W. (to Dow Corning Corp.), Zbz'd.,2,934,549 (.4pril 26, 1960). (28D) Wehrly, J. R. (to Dow Corning Corp.), Zbid.,2,853,897 (Dec. 9, 1958). Hydrolysis of Nitrogen Compounds (1E) Ajinomoto Co., Ger. Patent Appl. DAS 1,050,342 (1959). (2E) Burland, P. D., Roth, R. G. (to Monsanto Chemical Co.), U.S. Patent 2,868,837 (Jan. 13, 1959). (3E) Crosby, G. W., Braunwarth, J. B. (to The Pure Oil Co.), Ibid., 2,862,028 (Nov. 25, 1958). (4E) Hoglan, F. A. (to International Minerals and Chemicals Corp.), Zbid., 2,842,592 (July 8, 1958). 5E) Ibid., 2,909,564 (Oct. 20, 1959). I6E) H ouse, N. L., Schmidt, W. R., others (to E. I. du Pont de Nemours 6r Co.), Zbid.,2,894,026 (July 7, 1959). (7E) Huisman, H. O., Smit, A. (to North American Phillips Co.), ?bid., 2,904,594 (Sept. 15, 1959). (8E) Kaupp, J., Zinnert, F. (to Farbwerke Hoechst), Ibid., 2,908,697 (Oct. 13, 1959). (9E) Kleinschmidt, R. F., Mahan, J. E., Pitts, S. H. (to Phillips Petroleum Co)., Ibid.,2,831,890 (April 22, 1958). (10E) Knox, L. H., Bernotsky, G. .4. (to Nopco Chemical Co)., Zbid., 2,935,524 (May 3, 1960). (11E) Miller, B. M. (to E. I. du Pont de Nemours & Co.), Zbid.,2,840,606 (June 24, 1958). (12E) Ogawa, T.; Komori, I.. Kawaoka, J. (to .4jinomoto Co.), Zbid.? 2,905,710 (Sept. 22, 1959). (13E) Pollack, M. A., Ibid., 2,870,201 (Jan. 20,,1959). (14E) Purvis, J. L., Vassel, B. (to International iMinerals and Chemical Corp.), Zbid.,2,834,805 (May 13, 1958). (15E) Shafer, R. W., Heegaard, E. V. to International Minerals and Chemical orp.), ?bid.,2,829,161 (April 1, 1958). (16E) Shelton, J. L. (to International Minerals and Chemical Corp.) Zbid., 2,842,591 (July 8, 1958). (17E) Sutor, W. L., Zbid., 2,894,027 (July, 7, 1959).
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Hydrolysis of Esters and Carbohydrates (1F) Chem. Eng. 60, No. 5, 84-6 (1959). (2F) Leonard, R. H. (to Heyden Newport Chemical Corp.), U.S. Patent 2,840,605 (June 24, 1958). (3F) Morse, E. E., Hearn, W. L. (to Brown Co.), Zbid., 2,845,441 (July 29, 1958). (4F) Othmer, D. F., Zbid.,2,867,655 (Jan. 6, 1959). (5F) Schlenker, E., Zbid.,2,831,006 (April 15, 1958). (6F) Skogh, C. G. C., Savo, G. E., Zbid., 2,862,008 (Nov. 25, 1958). (7F) Wamsley, H. C., Wells, P. A., Jr. (to The Quaker Oats Co.), Zbid., 2,884,428 (April 28, 1959).
