September 1954
INDUSTRIAL AND ENGINEERING CHEMISTRY
not part of the rate determining step in aromatic nitration and extend it to more highly acid nitrating conditions.
LITERATURE CITED (1) Bachman, G. B., Atwood, M. T., and associates, J . Org. Chem., 19.312-23 (1954). (2) Bachmann, W. E. (to IJnited States of America), U. 5. Patent 2,656,355 (Oct. 20, 1953). (3) Baryshnikova, A. N., and Titov, A. I., Dokladu Akad. Nauk S.S.S.R., 91, NO.5, 1099-1102 (1953). (4) Bonner, T. G., Bowyer, F., and Williams, G., J. Chem. SOC., 1953,2650-2. (5) Cherubin, G., Bull. SOC. chim. France, 1954,192-5. ( 6 ) Crater, W. deC., IND.ENG.CHEY.,45, 1928-2000 (1953). (7) Desseigne, G. (to Etat Francais, Ministre de la Defense Nationale), U. S. Patent 2,629,739 (Feb. 24, 1953). (8) Dijkenna, J. H. (LO AlS Norduco, Oslo, Norway, a Norwegian Co.), Ibid., 2,612,523 (Sept. 30, 1952). (9) Doumani, T. F., Coe, C. S., and Attane, Jr., E. C. (to Union Oil Co. of Calif.), Ibid. 2,621,205 (Dec. 9, 1952). (10) Franz, A. O., and Keplinger, 0. C., Jr. (to Olin Industries, Inc.), Canadian Patent 497,792 (Nov. 17, 1953). (11) Gillespie, R. J., and Norton, D. G., J . Ckem. SOC.,1953, 971-9. (12) Hass, H. B., and Schechter, H., J . Am. Chem. SOC.,75, 1382-4 (1953).
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(13) Honeyman, J., and Morgan, J. W. W., Chemistry & Industry, 1953,1035. (14) Kirkwood, M. W., and Wright, G. F., J . Org. Chem., 18, 629-42 (1953). (15) Klassen, H. J., and Humphrys, J. M., Chem. Eng. Prop., 49, 641-6 (1953). (16) Kumbler, W. D., and Sah, P. P. T., J . Org. Chem., 18, 669-75 (1953). 75, 3689(17) Lauer, W. M., and Noland, W. E., J. Am. Chem. SOC., 92 (1953). (18) Marcus, F. A., and Winkler, C. A., Can. J . Chem., 31, 602-14 (1953). (19) Marshall, W. H., Jr. (to The M. W. Kellogg Co.), U. 5. Patent 2,654,658 (Oct. 6, 1953). (20) Ibid., 2,654,788 (October 6 , 1953). (21) Melander, L., Nature, 163, 599 (1949); Arkiv Kemi, 2, 211 (1950). (22) Nichols, P. L., Jr., Magnusson, A. B., and Ingham, tJ. D., J. Am. Chem. Soc., 75,4255-8 (1953). (23) Nitroglycerin Aktiebolag, British Patent 698,138 (Nov. 7, 1953). (24) Price, C. C., and Sears, C. A., J . Am. Chem. SOC.,75, 3276-7 (1953). (25) Ramsey, W. C. (to Olin Industries, Inc.), U. S. Patent 2,649,441 (Aug. 18, 1953). (26) Williams, G., and Simkins, R. J. J., J. Chem. SOC.,1953, 1386-92,
OXlDATl L. F. MAREK ARTHUR D. LITTLE, INC., CAMBRIDGE, MASS.
The incomplete combustion of natural gas with oxygen, obtained b y Fractionation of liquid air, for manufacture of synthesis gas has received considerable commercial attention. Direct oxidation of both paraffinic and olefinic hydrocarbons received experimental attention and some commercial expansion. The production of phenol and acetone b y the acid cleavage OF cumene hydroperoxide received prominent attention in all aspects OF the literature. Further interest has been attracted to the oxidation of xylene isomers to dicarboxylic acids as commercialization plans have been announced. Considerable inFormation was published on other aspects of oxidation and combustion processes OF a vafiety of organic substances.
0
XIDATION continues to be the most promising of the major process reactions used industrially for conversion of hydrocarbons to useful organic products (69).
ALlPHATlCS NATURAL GAS
Great interest has attached to the use of oxygen for the incomplete combustion of methane (natural gas) for the preparation of synthesis gas in the manufacture of ammonia. A description of the Texaco Development Company’s process to be used by a t least four new ammonia plants has been presented by one of the plant owners (81). Advantages of the new process are .projected lower production costs and production of tonnage oxygen and nitrogen that fit the ammonia process. Availability of low cost tonnage oxygen will probably open up other uses to owners of such plants. Estimates are that operating costs are lower by 6% relative to the older process based on steam reforming. The process is noncatalytic (46,118). Descriptions of the process of incomplete combustion of methane with oxygen to be used by Spencer Chemical Co. in the new synthetic ammonia plant a t Vicksburg, Miss., have appeared (88, 36). The oxygen plant handles 1000 tons of air per day. This plant is now using natural gas but can be adapted to use of liquid petroleum as source of heat and hydrogen.
Process descriptions and some economics of the air partial combustion of natural gas for synthesis gas manufacture have been published (98). This process is in the developmental stage. Some 50 t o 60% of the aeration needed for complete combustion is used, and a catalyst is required since temperatures are not sufficientlyhigh, as is the case with oxygen. Either low pressure of 45 or high pressure of 350 pounds per square inch may be used. Comparative costs are shown for low and high pressure partial combustion and for low and high pressure reforming, based on 22 cents per thousand cubic feet of natural gas. The plant of the Carthage Hydrocol enterprise a t Brownsvilie, Tex., for the modified Fischer-Tropsch synthesis from hydrogen and carbon monoxide was designed to produce the synthesis gas by the oxygen partial combustion of natural gas. This entire project of major significance has recently received renewed attention because of a projected change in ownership from a group of parties to Standard Oil and Gas Co. (10%’). Many technical difficulties have plagued this project but are believed now to be either eliminated or capable of becoming so. I t s renewed operation will be watched with considerable interest from both technical and economic points of view. Some aspects of the processes and reactions involved in production of petrochemicals from air and methane have been discussed (70). The influence of structure on the oxidation of aliphatic hydrocarbons has been reported (13%’). I n low temperature oxidation of hydrocarbons, the primary steps involved rupture of C-H rather than C-C bonds. Normally, practically all the initial oxidation products of a hydrocarbon react with oxygen much more readily than the parent hydrocarbon, so that the influence
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INDUSTRIAL AND ENGINEERING CHEMISTRY
of structure is most probably related to the very early stages of attack on the hydrocarbon molecule. Petroleum companies continue to develop modifications of processes for the conversion of methane to synthesis gas mixtures and to patent them. Thus, the use of metal oxides as oxidizing agents capable of being regenerated wit'h air continues t o receive attention. One niodificat'ion calls for introduction of a gaseous oxidizing agent to the fluidized reaction zone of iron oxide and methane to secure maximum conversion (92). Another modification provides for recycle of unreacted synthesis gas to the oxidation process (236). The most act,ive metal oxides, such as those of iron and manganese tend to agglomerate during the reaction procPSS, and it has been proposed continuously to remove the "seed" agglomerates by a process of size classification in the fluid bed reactor ( 7 2 ) . Direct, oxidation of propane and/or butane to Oxygenated organic chemical products has received further commercial att,ention. The plant of Warren Petroleum Co. a t Houston, Tex., for oxidat'ion of propane or butane vith oxygen is scheduled to have a capacit,y for 2,000,000 pounds of formaldehyde, 4,000,000 pounds of methanol, and 2,500,000 pounds of pentaerythritol ( 1 9 ) . This process has been previously described here. The neTv plant of Celanese Corp. at Pampa, Tex., was recently dedicated (58, 108). This plant employs direct oxygen oxidation of propane-butane for manufacture of acetic acid, vinyl acetate, and acetic anhydride. This Celanese plant, has a capacity designed for 1,800,000pounds of glacial acetic acid per week by the relative lom- temperature, high residence t,inie, catalj butane with air (103, 137). \Then oxygen is present a t less than 10% in niisturee with n-butane at, reaction t,emperatures of 450' t o 550 C. in flow-type reactions, the action of oxygen is predominantly as a dehydrogenation agent ( 4 ) . At, lorn concentrat,ions, below 8%, no oxygenated products appear and only hydrocarbons and r!-ater are detect able. The possible production of hydrogen peroxide by partial oxidation of propane has received study for a number of years. Results of some of this work has recently been published (117). Conditions chosen to study the reaction and appraise the industrial value were: inlet gas temperature 350" to 475" C.; propane/oxggen ratio 5.6 to 12.3; and reaction times oE 3.2 to 11.8seconds. The key reaction seems t o be between oxygen and the propyl radical to give either oxygenated organic products or propylene plus perhydroxy radical. The perhydroxy radical in turn reacts with propane to hydrogen peroxide plus a free radical. I n the process hydrogen peroxide disappears by decomposition at reactor surfaces to mat,er and oxygen and tends to react with the aldehydes present to form organic peroxides. Substantial proportions of aldehydes always form under condit'ions leading to hpdrogen peroxide formation ( 1 1 6 ) . The hydrogen peroxide \vas found to be most satisfactorily recovered by precipitation as calcium peroxide and subsequent regeneration. I n a discussion of the commercial nonelectrolytic hydrogen peroxide race, it is point,ed out that Du Pont is in the lead timevise with an operating plant a t llemphis (39). Buffalo Electrochemical Co., using the electrolyt,ic process, iy reportedly waving rapidly t,omwd a nonelectrolytic process. Mathieson Chemical Co. may be interested also. The Solvay Process Division of Allied Chemical & Dye Co. is reported to have developed a new, nonelectrolytic pr0ces.i for hydrogen peroxide and has started engineering a plant (48). Process and raw materials have not been ident'ified. In the course of studies of the methane-oxidation in borosilicate glass vessels a t 440' t o 5 2 0 3 C., it has been observed that a relationship exists between the measured rate of pressure change in static experiments and the "peroxide" content (9Sj. ; iwide range of conditions was used t o study the behavior of rich et,hane-oxygen mixtures in a f l o ~system a t atmospheric
Vol. 46, No. 9
pressure and temperatures above 400"C.(65). -4gaseous product rich in ethylene mas obtained. T h e mechanism proposed provides an explanat,ion of the close connect,iou between oxidation and cracking. Revie$% of the use of oxygen in the petrochemical industry have been presented from the standpoint of commercial partial combustion processes ( 1 2 7 ) . By using a bismuth compound as catalyst for the air oxidation of the lower aliphatic hydrocarbons, it is claimed that formic acid format'ion is minimized without affecting yields of desirable oxygenated products (97). Such liquid phase oxidation of liquefied petroleum gas (LPG) hydrocarbon? is performed a t 135" t o 232" C. and 200 to 2000 pounds per square inch pressure. The action of chromyl chloride on a series of ten saturated hydrocarbons has been st,udied (75). This oxidizing agent has previously been reported to form complexes with pentane, hexane, heptane, cyclohexane, and methylcyclohexane. All types of hydrocarbons form solid complexes with chromyl chloride, the reaction being much faster 1Tith those having a tert'iary hydrogen atom. S o glycols are found among the hydrolysis products but products could be accounted for by the oxidative fission of a glycol or by rearrangement. An exploratory study has been reported of the ~10'soxidation with nitrous oxide of paraffin hydrocarbons from propane t o n-nonane (2531. Reactions are chain reactions involving alli:;I radicals, inhibit'ed by nitric oxide and r e a d o n products, Oxidation of petroleum !Tax with air using zinc stearate and colloidal manganese dioxide catalysts at' 275' F. produces acidi suitable for manufacture of grease bases ( 8 2 ) . Sodium and lithium greases offer the most promise. Lit'hium base grease from :t mixture of 75% oxidized wax plus 25% hydrogenated tallox fatty acids is an excellent multipurpose lubricant. Introduction of minor concentrations of organic peroxides in petroleum paraffin wax prior to oxidation with air reduces t,hc time necessary to reach the desired stage of oxidation JI-itb rcsultant better product color (94). It is claimed that the carboxy acids obtained by the controlled oxidation of microcrystalline paraffin mas are useful in the prcvention of corrosion of iron and steel equipment in drilling oil viells (100). Small concentrat'ions of the oxidized wax are usrd in t8heaqueous drilling fluids. OLEFINS
The direct oxidation of ethylene to ethylene oxide coiit.inucs to receive attention and comparative analyscs oi the direct oxidation in both fixed bed and fluid bed processes relative t o thr chlorhydrin have been published (9, 8 7 ) . The scient,ific design process using a fised bed catalyst, proved in a French plant and being installed in a domestic plant, is claimed to at'tain yields oi 5: to 65% in practice (39,107). The ncivly promoted Shell Oil Go. process for direct oxidation of ethylene is analyzed to show an unamortized manufacturing cost of i . 4 cents per pound of ethylene oxide and 5.9 cenk per pound of ethylene glycol (209). Data are furnished on plants, owners. and chemical uses. The silver catalyst cost, contributcs as much as 0.38 to 0.40 cents per pound of ethylene oxide (49). Data obtained from t,ests made with a fluidized bed reactor w e ~ c used as the basis of design for a commercial plant of 40,000,000 pounds annual capacity. Based on a selling price of 15.5 cents per pound of ethylene oxide, net income mas estimated a t 15.6% of capital invest.ment (7.5). Kinetics of ethylene oxidation to ethylene oxide over silver catalysts show that catalyst activity is dependent upon condit'ions of previous treatment because of the slow establishment of equilibrium a t the catalyst surface (106), The kinetic data indicate that both ethylene oxide and carbon dioxide formation involve interaction of single gaseous ethylene molecules Kith single oxygen atoms. An approach to the use of ethylene in gaseous mixt,ures Kith
September 1954
INDUSTRIAL AND ENGINEERING CHEMISTRY
other hydrocarboris is based on the absorption of the olefin in a solution of a metallic salt t o form a coordination compound. This coordination compound is then oxidized with gaseous oxygen to form the olefin oxide and an oxidized form of the metallic salt (131). Acidification of the oxidized salt regenerates it for recycle to the process. Typical salts are chlorides of copper, zinc, silver, aluminum, and mercury. During the 30-minute induction period in the oxidation of propylene a t low temperatures of 290" C., small amounts of formaldehyde, higher aldehydes, and peroxides are produced (98). Thereafter, reaction proceeds with increasing speed, and the concentrations of aldehydes and peroxides rise to a maximum. Tellurium dioxide is a useful catalyst for the halogen promoted oxidation of methyl and methylene groups to carbonyl groups a t 600" t o 800" F. (6). Thus, oxidation of a refinery gas reaction containing 52y0 propylene a t 750" F. results in conversion of 12.6% of the propylene to acrolein. Isobutylene goes to methacrolein, and toluene to benzaldehyde. It has been claimed that by use of catalysts consisting of copper deposited on silica gel, it is feasible t o oxidize propylene with molecular oxygen to acrolein and other olefins to other unsaturated aldehydes (52). At reaction temperatures of about 300" C. and conversion of about 5Oy0 a selectivity to acrolein of about 40% is reported for air to propylene mixtures of 90: 10. It is claimed that activity of copper oxide catalysts used in oxidation react,ions may be maintained a t a high level for longer periods of use if the operating conditions, temperature, pressure, or composition of mixture are varied during the operation (55). Direct air oxidation of isobutylene to isobutylene glycol is claimed for a process in which air is contacted with the olefin in presence of a liquid medium consisting of water and benzene and some produck from previous oxidation and small amounts of pot,assium dichromate (120). Yields of the order 60% are claimed. A method of manufacturing an unsaturated or-ketone having a t,erminal methylene group comprises forming a mercuric complex by contacting a 1-olefin with an aqueous solution or dispersion of an oxidizing agent in a first reaction stage and thermally decomposing the complex in a second reaction stage to form the ketone (139). For example, 1-butene is thus converted to methyl vinyl lcet'one. When olefins are reacted with 1 to 2 volumes of nitrous oxide a t temperatures between 200" and 350' C. and high pressures, generally in the range 100 to 200 atmospheres, oxidation is claimed to be the main reaction, with nitrogen appearing as the by-product (12). The process results in formation of aldehydes from olefins with a terminal double bond and ketones from other olefins. Thus, from 36 parts of cyclohexene a liquid product containing 26 parts cyclohexanone and 14 parts unchanged cyclohexene is obtained. Propylene gives propionaldehyde.
AROMATICS Very prominent in the trade, technical, and patent literature during the year has been the production of phenol and acetone via the cumene hydroperoxide route. Process developments leading to the commercialization of this general process have been mentioned in previous reviews here. About the middle of 1953, announcements appeared concerning the Montreal, Can., plant of I3.A.-Shawinigan, Ltd., having come into production. This plant is the first to make use of the petrochemical process based on isopropylbenzene developed by Hercules Powder Co. and Distillers Co., Ltd., for manufacture of phenol plus acetone. By-products are a-methyl-styrene, acetophenone, and mesityl oxide ($0, 31, 38, 67, 101). .\bout the middle of March 1954, the Standard Oil Co. of California announced the first successful production of phenol directly from 100% petroleum sources in a new plant a t Richmond, Calif., operating under license from Hercules Powder Co.
1865
Cumene obtained from the phosphoric acid catalyzed liquid-phase alkylation of propylene and benzene is oxidized directly to cumene hydroperoxide, and this in turn is subjected to acid cleavage t o produce mainly phenol plus acetone. The over-all phenol yield is about SO%, and total product ratio is as follows (35,110):
Per Cent 57 (35,000,000 lb /yr.) 34 (20,000.000 lb / y r . ) 6 3
Phenol Acetone or-Methylstyrene Acetophenone
Other companies have been active in plant construction for phenol manufacture by the same or related processes. These include Hercules Powder Co. and Barrett Division of Allied Chemical & Dye Corp whose plant a t Frankford, P a , is to have a caparity of 24,000,000 pounds of phenol per year. Descriptions of the cumene hydroperoxide process, comparisons with other phenol processes, and tabulations of plant capacities have been published (15,59, 115, 126). The phenol supply-demand relationship and the relation of the cumene-derived phenol production to established processes in older plants has been analyzed ( A d ) . The acid-catalyzed decomposition of cumene hydroperoxide in a homogeneous medium, 50% aqueous acetic acid, a t 60" C , gives a yield of 92% phenol and 81% acetone (1dZ). The activation energy for the decomposition was computed to be 21 3 kcal per mole. Addition of an electropositive group t o the paraposition, as in nitrocumene hydroperoxide, decreases the activation energy of reduction by iron (104). Much of the research and development work leading t o the achievement of a successful commercial project for manufacture of phenol via cumene hydroperoxide has been done in commercial laboratories, and information concerning the methods is now contained largely in the patent literature. Some examples seem north citing. It is claimed, for instance, that the use of copper catalyst compounds dissolved in the isopropylbenzene while reducing the induction period of the air oxidation tend to increase the proportion of undesired reactions. B y performing the oxidation in a may which brings air or oxygen-containing gas into intimate contact with the hydrocarbon a t 70" to 150" C. in the absence of heavy metal catalysts and introducing fresh feed continuously as oxidation proceeds, the induction period is eliminated and a satisfactory rate of reaction maintained. Efficiency of perexide formation based on percentage of oxygen consumed is in the 90% range (6). Alternatively, the process may be prosecuted by adding a portion of previously oxidized cumene containing on the order of 30% of hydroperoxide to a batch of cumene and aqueous solution of an alkali, like caustic soda (14). That impurities present in the commercial cumene used in this process of phenol production may adversely affect the induction period of the ovidation process has led to improvements intended to remove them. Thus, contacting the commercial cumene with activated alumina is claimed to minimize the usual induction period of the oxidation (79). Another purifying treatment claimed to improve the oxidation process is that of treating the cumene with repeated sulfuric acid washes as one step and then contacting with metallic sodium as a second step (121). The transition metals-iron, cobalt, nickel, copper, lanthanum, lead, thallium, cerium, and manganese-are oxidation catalyst8 and have been claimed for promotion of the cumene to hydroperoxide oxidation (11). It is claimed that various nonoxidizing acids may be used for the acid-catalyzed decomposition of the cumene hydroperoxide t o phenol and acetone. Although dilute sulfuric acid is apparently preferred, other suitable acids mentioned are phosphoric, hydrochloric, acetic, p-toluenesulfonic, and similar aryl sulfonic acids (3). The several coproducts of the cumene hydroperoxide decomposition, acetophenone and methylstyrene espe~
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INDUSTRIAL AND ENGINEERING CHEMISTRY
cially, cause trouble in recovery of pure phenol from the product mixture. One method claimed to be successful is that of extracting the phenol with water a t 50" t o 100' C. and subsequently recovering the phenol from the water extract ( 7 ) . Conversion of a-methvlstyrene and a-a-dimethylbenzyl alcohol t o phenol by reaction with peroxides and decomposition has been claimed (118). Both tert-butyl hydroperoxide and hydrogen peroxide are claimed to be effective. Phenol is also claimed t o resolt from the decomposition of a-methylbenzyl hydroperoxide obtained from the tert-butyl hydropeloxide initiated oxidation of styrene. Oxidation of styrene is claimed to occur to the hydroperoxide with oxygen a t 70" to 90" C. in presence of lert-butyl hydroperoxide initiator (51). This general peroxidation-cleavage process for conversion of hydrocarbons to mono- and polyhydric phenols is to be used by Hercules Ponder Co. in manufacture of p-cresol, resorcinol, hydroquinone, and acetone in several plants (SO). Since the initial utilization of o-xylene for phthalic anhydride manufacture several years ago by Standard Oil Co. of California, both p- and m-xylenes have become significant raw materials for oxidation processes (44). Conventional method of oxidation of p-xylene to terephthalic acid is b y means of nitric acid and has previously been described in the technical and patent literature A new approach has been introduced recently which permits the use of catalyzed air oxidation of p-xylene and results in production of dimethyl terephthalate, intermediate for polyester manufacture. The Hercules Powder Co. process employs a four-stage process: air oxidation of p-xylene to toluic acid using oil-soluble catalysts of cobalt or manganese, esterification with methanol to methyl p-toluate, a second air oxidation monomethyl terephthalate, and a final esterification with methanol to dimethyl terephthalate (DBIT). A plant to have an annual capacity for 12,000,000 pounds of D M T is t o be brought into production by Hercules about May 1955 (2,27 1%). The availability of m-xylene, partly as a result of the commeicia1 interest in o- and p-xylene has led to the expenditure of many man hours of effort toward its utilization in inanufaeture of isophthalic acid as a replacement for phthalic anhydride and for uses of its own. It is said that the process for D M T is suitable also for manufacture of dimethyl isophthalate. Engineering studies for a 15,000,000-pound-per-year isophthalic acid plant t o come into production mid-1955 are reported under way (46). Oronite Chemical Co. expects to ship the product t o the East Coast via water freight. A review has been published of the four general processes for phtha,lie anhydride manufacture: vanadium pentoxide catalysts in fixed bed; German catalyst in fixed bed; and the same t x o catalyst types in fluidized catalyst beds (11.4). Statistics of production partly from the President's Materials Policy Commission have also been compared from the point of view of predicting future prospects. Estimated capacity a t the end of 1954 is €or a total of 315,000,000 pounds per year in 12 plants (40, 141). It is expected that the price of isophthalic acid from the new plants will be about 25 cents per pound compared with about 22 cents per pound for phthalic anhydride. Phthalic anhydride yields greater than the equivalent of the naphthalene content of coal tar oils may be obtained by use of the German-type of V2O,-K2SO4-SiOzcatalyst ( 123). The heat release during oxidation is considerably more than with naphthalene, and control of heat removal is the most important problem in use of the raw material. Among the oxidation processes practiced commercially on a substantial scale, the oxidation of benzene to maleic anhydride continues t o receive attention in the literature (43). A production volume of 24,000,000 pounds was reached in 1951. and 1953 production is estimated between 30,000,000 and 40,000,000 pounds Raw materials for maleic anhydride may be benzene, ayclohexane, cyclohexene, toluene, butadiene, cyclopentadiene,
Vol. 46,No. 9
and others. The plant of Reichhold Chemicals has recently been described (18). Among new developments is the use of dibutyl phthalate as a solvent t o dissolve maleic anhydride (or phthalic anhydride) vapors from the oxidation reactors ( 2 3 ) . The United States product'ion average for fumaric acid during 1951 t o 1953 has been a t about 5,000,000 pounds per year with a rising trend toward an expected G,500,000 for 1954 (47). New capacihy in 1954 is expected t o add 10,000,000 pounds of maleic anhydride and 1,000,000 pounds of fumaric acid. Ammoniation of the inside surfaces of the steel reactor vessels used in oxidation of benzene to maleic anhydride has been claimed to improve the yield (53). I n the oxidation of but'enes or butadiene to maleic anhydride, it has been found that catalysts containing oxides of p:iosp!iorus and molybdenum in combination a t 250' to 400 ' C. result in yields higher than those obtained from use of vanadium pent'oxide catalyst (76). I n oxidizing benzene to maleic anhydride, catalyst carriers of highly siliceous nature are claimed (64). Precipitated oxide catalysts comprising molybdenum oxide combined with a basic metal oxide from the cobalt and nickel group are claimed to be particularly advantageous in oxidations of hydrocarbons in vapor phase such as the oxidation of butane t o maleic acid (68). The obvious advantages of a direct process for oxidation of benzene to phenol continue t o lure experimenters into investiqations of the possibilities. A summary of the results of previous investigations has been presented in connection with publication of results from a new exploration of the reaction (60). Direct oxidation of benzene to phenol in the presence of an electric discharge a t G to 12 mm. of mercury and 3000 to 4000 volts gave a conversion rat,e of 10 to 12.5 mole % phenol per pass. I n the range of 100" to 340' C.; temperature seemed to be unimportant. Economic prospects cannot be appraised on the basis of these results, and the authors expect that substantial improvements can be made in results by modifications in equipment. Oxidation of tetramethylbenzenes of petroleum origin to aryl tetracarboxylic acids has been described (95). Vapor phase oxidation with air over vanadium or molybdenum catalysts is claimcd. A brief description of Dow Chemical Co. plans for manufacture of styrene oxide in a Texas plant, probably via styrene to styrene chlorohydrin to styrene oxide has been given ( 4 1 ) . The product is expected to find use in making styrene glycol for making modified alkyd resins, for polymerization with vinyl halides, vinylidene halides, and other monomers. Alkylated anthraquinones are useful as intermediat'es in a nonelectrolytic process for manufacture of hydrogen peroxide. A cyclic process of oxidation and hydrogenation over catalysk of nickel, palladium, and like composition, results in formation of dilute aqueous hydrogen peroxide formation (15.4). Nitric acid oxidation has been used commercially in the oxidation of alkylbenzenes, like the xylenes, to form useful products. It is claimed that nitric acid oxidation of alkylnaphthalenes can be used for production of 2,B-naphthalic acid, useful in manufacture of polyester type resins (136). Using lead oxide as catalyst, 01- and p-isopropylnaphthalenes may be oxidized to corresponding hydroperoxides with molecular oxygen (80). I n the reaction of nitrogen dioxide with benzene a sharp acceleration in reaction has been observed when t'he mixture was sat'urated with oxygen (158). Heterocyclic aromatic nitrogen compounds having an oxidizable organic group attached t o the heterocyclic aromatic nucleus may be catalytically oxidized to pyridinecarboxylic acid (111). Thus, quinoline or 3-picoline may be oxidized t o nicotinic acid by means of nitrogen tetroxide in a sulfuric acid medium using selenium dioxide a9 a catalytic material. The process used by Du Pont a t its Memphis, Tenn., plant for the nonelectrolytic production of hydrogen peroxide is based on a modification of the I. G. Farbenindustrie process of World War
September 1954
INDUSTRIAL AND ENGINEERING CHEMISTRY
I1 (g2). A mixture of alkylated anthraquinones and tetrahydro derivatives is dissolved in a solvent mixture of primary and secondary nonyl alcohols with methyl- or dimethylnaphthalene. In the presence of activated alumina the anthraquinone mixture is reduced, and the hydrogenated derivatives are separated by filtration. Oxygen is blown through a t 30' to 60" C. to form hydrogen peroxide and regenerate the original anthraquinones. The hydrogen peroxide is extracted with water, and the anthraquinones are recycled. Buffalo Electrochemical Co. is reported to be pilot planting a similar process. ORGANIC COMPOUNDS
3,
Acid anhydrides, such as acetic anhydride, may be obtained by passing a gas containing molecular oxygen and an aldehyde into a liquid bath in which are dissolved the acid corresponding to the aldehyde, soluble metal salt catalysts, and an inert solvent such as a high boiling ester (113). Catalysts of cobalt, nickel, copper, or vanadium salts are used. An example shows a yield of acetic anhydride corresponding to 75% of the oxidized acetaldehyde. A review of formaldehyde manufacture including a brief historical review, producers, U. s. production, and use statistics and comments on processes has been presented recently (1). Formaldehyde is expected t o resume its steady upward growth in 1955 and to continue to be obtained basically from methanol oxidation. Production of 37% formaldehyde in 1953 is estimated a t 1.2 billion pounds, and projections for 1955 are between 1.67 and 1.8 billion pounds. The thermodynamias of the formation of formaldehyde from methanol has been reported (78). Of the estimated 1.2 billion pounds of 37% formaldehyde produced by the United States manufacturers in 1953 an estimated one quarter was obtained by oxidation processes using natural gas and LPG as raw material. Considerable publicity has attended the Joint Conference on Oxidation Processes in Amsterdam, Holland, May 6-8, 1954 (17, 37). This program was held by the Institute of Chemical Engineers and the Chemical Engineering group of the Society of Chemical Industry with the Royal Institute of Engineers of Netherlands, Royal Netherland Chemical Society, and Royal Tropical Institute. The program included papers on oxidation with vanadium catalysts, fatty acids by oxidation of hydrocarbons with oxygen, kinetics of liquid phase oxidation, preparation of cumene hydroperoxide, and many others. The papers are to be published in Chemical Engineering Science. A development of the Eastern Regional Research Laboratory for the oxidation of fatty oils by means of peracetic acid is to be commercialized a t an annual volume of about 5,000,000 pounds (91 ). The products are epoxidized, hydroxylated, and acetylated and are expected t o find use in vinyl plasticizers, greases, and other products. A review of the current research and progress on the catalytic autoxidation of monoethenoid fatty acids and esters shows that (1) the formation and nature of hydroperoxides is known; (2) their decomposition or transition has been substantiated; (3) the formation of ketonic derivatives, epoxides, and hydroxylated derivatives is now established; and (4) the ultimate formation of dimers through oxygen-linked monomers seems likely on present evidence (130). Air oxidation of unsaturated fatty acids may be used to prepare peroxides thereof provided the naturally occurring inhibitors are first removed (89). Oxygen or ozone oxidation of certain monomeric esters, such as diethylene glycol dimethacrylate, polyethylene glycol dimethacrylate, and diglycerol diacrylate, does not affect the polymerization properties but does result in formation of new polymer products having useful properties (IS). The products are, for instance, useful in sealing or bonding a variety of materials t o give water-resistant and substantially heat-resistant seals.
1867
A new synthesis for the convenient and economical preparation of oxides, peroxides, and peroxyhydrates of the alkali and alkaline earth metals was recently reported to a symposium sponsored by the Office of Ordnance Research by G. L. Cunningham (3%). The process uses easily oxidizable organic compounds such as hydraeobenzene as intermediates. The azobenzene formed by oxidation is reduced with an amalgam of the alkali metal desired in the final product. For example, oxygen bubbled through a reaction mixture, using benzene and methanol solution, forms hydrogen peroxide with the hydrazobenzene which then interacts with the alkali metal alcoholate to form the diperoxyhydrate in 90% yield. This product can be used as a bleaching agent, as a source of high strength hydrogen peroxide, or to make superoxides for military purposes. The spotlight of attention has recently been focused on the use of bacterial oxidations (2.4, 33). For example the Sun Oil Co., Ltd., a t its Sarnia, Ontario, refinery is using bacterial oxidation to remove phenol and other organic wastes from refinery waste water. A 6- to 8-hour treatment is employed using an eductor system to circulate and aerate the water. The technique and information on results have been reported t o the International Joint Commission on Water Pollution. The same reaction appears to be rate controlling in the oxidation of natural rubber and GR-S stocks a t all temperatures in the range of 50" to 110' C. in the accelerated age testing of rubber (1a4). The aging characteristics of a rubber stock cannot be well predicted by use of the accelerated test a t only one temperature. It is possible to use short-term oxygen absorption measurements a t three temperatures to establish relationships and t o extrapolate to lower temperatures for aging predictions. Based on further experimental studies a t Case Institute, a mechanism has been postulated t o indicate that rubber antioxidants may function in a t least four ways-some beneficial and some harmful (185). Various anomalous observations such as optimum antioxidants concentration, catalysis of light activated oxidation, differences between phenol and amines, and the role of carbon black are plausibly explained by the mechanism postulated. The effect o€ carbon black on the autocatalytic stage of oxidation of unvulcanized rubber is shown t o be specific for the type of carbon black, the reaction conditions, and the nature of the polymer (90). Carbon black is an efficient antioxidant for cold rubber when the rubber is heated in air or oxygen. Effectiveness increases as the volatile content of the carbon black increases. Initiation of oxidation of polyisobutylene occurs with the cleavage of the molecular chains which are in the high molecular weight fractions. I n butyl rubber, initiation of oxidation depends as much on rupture of C-C bonds as on the oxidation of the double bonds (86). The thermal oxidation of polyethylene follows the pattern of the lower homologs, the paraffin waxes, and oils (8). Work a t the Bell Telephone Laboratories shows that oxidation of polyethylene is an auto-catalytic, free-radical chain reaction subject to inhibition by typical antioxidants. Photooxidation of polyethylene is more rapid than that of the lower saturated aliphatic hydrocarbons, and antioxidants are of little help in protecting against exposure to light. Opaque pigments are of major help in stabilizing against photooxidation, especially finely divided carbon black. Properly compounded polyethylene can be made to last for many years in outdoor exposure. Studies of the reinforcement of butyl rubber with carbon black show the specific action of surface oxygen on the black (14%). Modification of the carbon black surface by heat treatment changes the vulcanieate structure as a function of oxygen on the surface of the black.
GASIFICATION OF CARBON A study of the reaction between wood charcoal and steam mixed with carbon monoxide, carbon dioxide, hydrogen, and ar-
1868
INDUSTRIAL AND ENGINEERING CHEMISTRY
gon has shown that' good reaction rat'es are obtainable a t temperatures as low as 1200' F. (88). Carbon gasification rates a t the lox temperatures weYe greater than expected from extrapolation of data obtained a t higher temperatures, indicating that it is possible to make hydrogen and carbon dioxide the main products. This may have commercial significance in the manufacture of hydrogen. Experimental data on the kinetics of carbon gasification with steam, based on a study of the mechanism of interaction of lorn temperature char and steam-hydrogen mistures a t 1600" F. have been published previously. Recently, an empirical correlation has been offered (65). I n t'his correlation a microscopic aspect, postulating a mobile surface oxygen complex has bee11 pwented to help classify reaction characteristics. D u Pont is conduct'ing a large scale test of a ne17 synt'hesis gas process based on steam-oxygen combustion of pulverized coal ( $ 5 ) . The process is the result of the combined efforts of D u Pont, Babcock & Wilcox, and Bureau of Mines engineers. The oxygen ratio varies with the coal used and is in the range 8 to 10 cubic feet per pound of coal. Ash is slagged for removal. An example of the gas composition shows: hydrogen 40%, carbon monoxide 40%, carbon dioxide 15%, inerts 4%, and methane under 1%. Other processes for the method of gasification of coal have been developed. Claims have been made to methods t'hat, permit production of synthesis gas from caking coal having a composition of: hydrogen 48+y0, carbon monoxide 48+%, other gases 3.770 (56). The fluid bed technique has been described for the gasification of solid carbonaceous matt'er by means of steam-oxygen reaction (6'4). The technique used is t'o have countercurrent interaction between solids and gases such that the fresh solids feed is dried and preheated by the hot product gases in one zone prior to reaching the hot reaction zone. In order that a large number of reaction zones need not be provided to prevent carbon loss in the final solids discharge, specially arranged reaction zones have been devised. One of these interposes a zone wherein the finely powdered coal is suspended in t'he &earn-oxygen reagent gas (71).
COMBUSTION REACTIONS New data on automot'ive combustion obtained at' the Kational Bureau of Standards are providing information of value relative to the chemical processes occurring during the combust,ion cycle of automotive engines (99). Lorn temperature mechanism of hydrocarbon fuel combustion is believed t o be more significant in the spontaneous ignition of fuels in engine operation ( 7 7 ) . Studies h a w been made a t Kava1 Research Laboratory to secure further information of the relationship between fuel composition and ignition behavior. Results obtained from the vapor phase oxidation of iso-octane, n-hept,ane, 2,2,5-trimethylhexane, and isobutane a t 350" to 550' C. led to several conclusions regarding the spontaneous ignition of hydrocarbons (60). Hydroperoxide can be obtained as a major product a t the lower temperatures of reaction, carbonyl compounds became predominant a t higher temperatures, and a t still higher temperatures, hydrogen peroxide and olefins are the most important recoverable products. The preflame oxidation reactions of n-heptane, iso-octane, diisobutylene, and benzene were studied by following the concentrations of intermediate products formed in a motored engine (106). %-Heptane formed large amounts of osidat,ion products, higher aldehydes and ketones, unsaturates, hydrogen peroxide, and formaldehyde prior t'o autoignition, whereas iso-octane formed only limited amounts. Two classes of chemical reactions that can precede knock in engines have been shown by another investigation (140). One class of precombustion reactions is characterized by the athermal formation of preknock compounds. The second class of reac-
Vol. 46, No. 9
tions, occurring a t higher temperature, are accompanied by railiat'ion and evolution of heat. This class of reactions does not increase the knocking tendency of a fuel-air mixture. I n an effort to obtain more information on the mechanism of the low temperature oxidat'ion of hydrocarbons, a detailed examination has been made of the cool flame oxidation of propane (84). Experiments were also made on the cool flame oxidation of propionaldehyde. 111 the cool flame oxidation of propane, aldehydes occurred in the product in the ratio of 1 part propionaldehyde, 20 parts acetaldehyde, and 60 parts formaldehyde. I-Iydrogen peroxide was t,he only peroxide detect'ed. Straight chain paraffins exhibit' better flame stabilit,y than do branched chain isomers ( 8 3 ) . This is in agreement with the greater ease of osidat'ion of the st'raight chain hydrocarbons. Stability limitmaof all fuels are wider under nonhomogeneous mixing conditions in t'hc equipment used here.
MISCELLANEOUS PRODUCTS AND PROCESSES Tonnage oxygen is becoming more arid more a basic raw material in the chemical process industry. A review of the techniques employed in air liquefaction and rectification, heat exchange and removal of impurities, and design of "package units" has been published (129). A diagrammatic description of the process used for liquid air manufact,ure and rectification to commercial oxygen and nitrogen has been published by Air Products Co. ( 6 2 ) . International Kickel Company's new 300-ton-per-day 95% oxygen plant at Copper Cliff, Ontario, is called "Oxyton" ( 1 6 , 34). Oxygen produced in the plant, is used for flash roasting copper sulfide concentrate. Application of the fluid bed technique has been claimed t>o facilitat,e the production of oxygen by dissociation of met,allic. oxides previously made by contacting air with readily oxidizable met,als and metal oxides ( 9 1 ) . This type of reaction received considerable attention during the recent war as a possihle means for producing oxygen for breathing on aircraft. A six-part' review of the chemistry of bleaching and oxidizing agents has been published ( 7 4 ) . Oxidation potent,ials and react,ions of special bleaching oxidants are given, including ozone, hydrogen peroxide, and halogen-oxygen compounds. .4 survey of the new processes, new uses, operations, and costs of chlorine dioxide has been published from the Solvay Process Division of Allied Chemical & Dye Corp. (119). Automatic production processes based on oxidation potential are being used by Mathieson Chemical Co. in one bat'ch and t x o continuous versions ( 2 6 ) . One of these is to be used in t'he hypochlorite reaction vAth ammonia in the company's new plant for hydrazine manufacture. It has been proposed to increase recovery of crude oil from underground reservoirs by a method of pwtinl underground conibustion (86). Magnolia Oil Company's experiments have shown that reservoir oil can be ignited and will continue to burn in the form of a slowly advancing high temperature front as long as the necessary air flow is maintained for combustion. Laborstory experiments have shown oil recoveries of 60% and sometimes as high as 90%. Much work necds to be done before large scale commercial application is attempted. It has been shown that the products of oxidat'ion of lubricating oils partly deposit as a lacquer film on hot parts of an engine and partly remain in the oil where they act to prevent sludge deposition and reduce piston ring st'icking (10). Under certain conditions-as when contacted with hot' met,alsurface lubricating oils may inflame, a possibility in the initiation of fires in aircraft. The effects of molecular structure, additives, and metal surfaces on the spontaneous ignition temperatures of lubricating oils have been determined ( 6 1 ) . The effect of tetrnethgllead was found to be outstanding, even at quite low concentrations, in raising the temperature required for spontaneous ignition to occur.
September 1954
INDUSTRIAL AND ENGINEERING CHEMISTRY
The smog periods in the Los Angeles area are chemically characterized by a pronounced oxidizing effect, of the order 0.6 p.p.m. by volume, calculated as hydrogen peroxide and measured iodimetrically (66). It has been shown that this oxidizing effect of smog is due to the combined action of nitrogen oxides, peroxides, and ozone, counteracted by the reducing action of sulfur dioxide present in concentrations of 0.1 t o 0.2 p.p,m. The presence of peroxides is explained by the photochemical oxidation of large amounts of hydrocarbons released to the atmosphere catalyzed by the presence of nitrogen oxides. Ozone reaches concentrations as high as 0.3 p.p.m. relative t o a normal atmospheric concentration of 0.02 to 0.03 p.p.m., and is difficult to account for. Observations indicate some association with photochemical dissociation of nitrogen oxides. Oxidation of ammonia in the nitric acid manufacturing process has been examined from a thermodynamic standpoint in consideration of what new compounds may be derived from ammonia (67). Nitrous oxide (NIO) can be produced from ammonia oxidation provided a satisfactory catalyst can be found.
LITERATURE CITED Aalto, T. R., Chem. Eng. IVews, 32, Xo. 14, 1398-1401 (1954). Albert, A. A., and Kneisley, J. W., 124th Meeting, ACS, Chicago, Sept. 6-11, 1953. Aller, B. V., and associates (to Hercules Powder Co.), U. S. Patents 2,628,983 and 2,628,984 (Feb. 17, 1953). Appleby, W. G., and associates, J . Am. Chem. Soc., 75, 1809-14 (1953). Armstrong, G. P., and associates (to Hercules Powder Co.), U. S. Patents 2,632,772 and 2,632,772 (March 24, 1953). Augustine, F. B. (to Socony-Vacuum Oil Co.), Ibid., 2,643,269 (June 23, 1953). Bewley, T., and Wilkins, F. J. (to Hercules Powder Co.), Ibid., 2,663,743 (Dee. 22, 1953). Biggs, B. S . , and Hawkins, W.I,., Modern Plastics, 31, KO.1, 121-6 (1953). Borrows, E. T., and Caplin, D. A., Chemistry & I n d u s t r y , 1953, pp. S32-7 (Aug. 10, 1953). Brook, J. H. T., and associates, J . Inst. Petroleum, 39, 454-62 (1953). Bruning, E., and associates (to Farbenfabriken Bayer), U. 9. Patent 2,655,545 (Oct. 13, 1953). Buckley, G. D. (to Imperial Chemical Industries, Ltd.), Ibid., 2,636,898 (April 28, 1953). Burnett. R. E.. and Nordlander, B. W'. (to General Electric Co.), Ibid., 2,628,178 (Feb. 10, 1953) Calhoun, G. &I., and Reese, J. E. (to Hercules Powder C o ) , Ibid., 2,663,740 (Dee. 22, 1953). Can. Chem. Processing, 37, No. 8 , 26 (1953). Chem. Age (London),LPX, 577 (March 6, 1954). Ibid., p. 676 (hlarch 20, 1954). Chem. Eng., 60, KO,7, 238-41 (1953). Ibid., KO.8, p. 110. Ibad., p. 114. Ibid., pp. 118-22. Ib'ld.. NO. 10. DD. 108-12. Ibid., KO.12, b: 114. Ibzd., 61, No. 2, p. 120 (1954). Ibzd., NO. 3, pp. 114-16. Ibid., pp. 128-30. Ibid., KO.4, p. 106. Ibid., p. 126. Chem. Eng. News, 31, No. 19, 1984 (1953). Ibid., No. 22, p. 2259. Ibid., p. 2298. Ibid., No. 39, pp. 4012-14. Ibid., No. 2, 138 (1954). Ibid., No. 6, p. 476. Ibid., KO.12, p. 1114. Chem. Eng. Progr., 50, No. 3, 46 (1954). Chemistry & Industry, 1954, p. 271 (March 6, 1954). Chem. Week, 72, 34-37 (June 13, 1953). Ibid., 73, p. 80-84 ( A 4 ~ g15, . 1953). Ibid., p. 28 (Oct. 24, 1958); pp. 76-79 (Nov. 21, 1953). Ibid., p. 34 (Nov. 7, 1953). Ibid., pp. 64-6 (NOT,. 7, 1953). Ibid., pp. 1319-22 (Dec. 26, 1953). Ibid., 74, pp. 64-5 (Jan. 30, 1954). Ibid., pp. 60-64 (Feb. 20, 1954); 71, 28-30 (Aug. 30, 1952) Ibid., p. 18 (April 15, 1954). Ibid., pp. 94-6 (April 24, 1954).
1869
1451 Ibid.. n. 52 ( l l a v 15 193%) (49) Ibzd , pp 46-54 ?May 23, 1954) G , (50) Chu, Ju Chin, Ai, H. C., and Othmer, D F , ITB E ~ CHFV 45, 1266-72 (1953). (51) Conner, J. C., Jr. (toHercules Powder), G. S.Patent 2,661.375 (Dec. 1, 1953). (52) Connolly, G. C., and Cottle, D. L. (to Standard Oil Development Co.), Ibid., 2,627,527 (Feb. 3, 1953). (53) Darby, J. R. (to Monsanto Chemical Co.), Ibad., 2,624,744 (Jan. 6, 1953). (54) Ibid., 2,625,554 (Jan. 13, 1953). (55) Detling, K. D., and Skei, T. (to Shell Development Co ) , Ibid , 2,659,758 (Nov. 17, 1953). (56) Dickinson, N. L. (to iC1. Mr. Kellogg Co.), Ibid., 2,662,007 (Dee. 8, 1953). (67) Enos. H. I., Jr., and Kixon, J. R.. Jr., 124th Rleetina. - ACS. Chicago, Sept. 6-11, 1953. Farrar, G. L., Oil Gas J . , 52, 119 -122 (dug. 10, 1953). Foster, Arch L., Petroleum Engr., 25, No. 12, C3-C4 (1953). ENG.CHI;M.,46,212-7 Frank, C. E., and Blackham, A. U., IND. (1954). Frank, C. E., Blackham, A. C . , and Smarts, D. E., I b i d . , 45, 1753-9 (1953). Goalwin, D. S., Petroleum. ReJiner, 32, KO.9, 176 (1953) Goring, G. E., Curran, G. P., and associates, IND. ENG.CHEM., 45,2586 -91 (1953). Gornowski, E. J., and Nelson, K. J. (to Standard Oil Development Co.), U. S. Patent 2,633,416 (IMarch 31, 1953). Gray, J. A., J . Chem. Soc., 1953, pp. 741-50. Haagen-Smit, A. J., and associates, IND. ENG.CHEx, 45, 20869 (1953). Harrison, R. H., and Kobe, K. A., Chem. Eng. Progr., 49, KO, 7, 349-53 (1953). Hartig, M. J. P. (to E. I. du Font de Nemours), C. S. Patent 2,625,519 (Jan. 13, 1953). Hatch, L. F., Petroleum Rejiner, 32, No. 9, 123-5 (1953). I b i d . DU.170-5. Hernk&y.?r, C. E. (to Standard Oil Development Co.), U. S. Patent 2,644,745 (July 7, 1953). Herbst, W. A., Ibid., 2,631,933 (Xarch 17, 1953). Hobbs, C. C., Jr., and Houston, Bruce, J . Am. Chela. Soc., 76. 1254-7 (1954). Holst, Gustav, Cham. Rem., 54, KO.1, 169-94 (1954). Jacknin, B., Birgznia Polytech. Inst., 13, KO 4, 327-8 (1953). Jacobs, D. I. H.. and associates (to Distillers Co., Ltd.), U. S. Patent 2,649,477 (Aug. 18, 1953). Johnson, J. E., Crellin, J. W.,and Carhart, H. W.,IND.ENG. CHEM.,45, 1749-53 (1953). Jones, Elwyn, and Fowlie, G. G., J . S p p l . Chem. (London),3, 206-13 (1953). Joris. G. G. (to Allied Chemical & Dye C o w . , ) U. S. Patent 2,629,744 (Feb. 24, 1953). Joris, Q. G., and Griffin. SV. D., Ibid., 2,656,394 (Oct. 20, 1953). Kelly, J. C., and Cain, J. H., 124th RIeeting, ACS, Chicago, Sept. 6-11 (1953). Kirk, J. C., and Nelson, E. W., Oil Gas J.,52, KO.37,97-8 (1954). Kirtley, J. G., and Lewis, d., Fuel, 33, 5-19 (1954). Knox. J. H., and Noriish, R. G . W., Proc. B o g . Soc., 221A, 15170 (1954). Kuhn, C. S., and Koch, R. L., Oil Gas J., 52, 92-6, 113-14 (ilug. 10, 1953). Kurminsky, A. S., and Khitrova, S . G., J . Gen. Chem. (C'SSR), 22, 1549-55 (1952) (Eng. Transl., Consultants Bureau), Landau, Ralph, Petroleum Refiner, 32, No. 9, 146-51 (1953). Lewis, W. K., Gilliland, E. R., and Hipkin, H., TND. ENG. CHEM.,45, 1697-1703 (1953). Lundberg, W.0. (to Regents of Univ. of lfinn.), U. S. Patent 2,636,890 (April 28, 1953). Lyon, F., and associates, IXD.E x . CHEW,46, 596-600 (1954). Martin, H. Z. (to Standard Oil Development Co.), U. S. Patent 2.642.340 (June 16. 1953). Mayland, B.' J. (to Phillips Petroleuni Co.), Ibid., 2,628,161 (Feb. 10, 1953). Mayland, B. J . , and associates, Chem. Eng. Progr. 50, No. 4, 177-81 (1954). Merley, 8.R., and Kofoet, A. (to Cities Service Research and (Jan. 20. 1953). Develonment Co.). U. S.Patent 2.626.277 . . Miller, R: J. (to California Research Corp.), Ibid., 2,625,555 (Jan. 13, 1953). Minkoff, G. J., and Salooia, K. C., Fuel, 32, 516-17 (1953). Morgan, C. S., Jr., and Robertson, N. C. (to Celanese Corp ) , U. S. Patent 2.689.746 (Nov. 17 1953). Mulcahy, M. F. R., and Ridge, A I . J., Trans. Faradau Soc., 49, 906-16, 1297-1312 (1953). Natl. Bur. Standards (Supt. Documents, Washington 25, D. C.), Tech. Kews Bull., 37, 113-15 (1953). I
,
I
1870
INDUSTRIAL AND ENGINEERING CHEMISTRY
(100) Nelson, J. W. (to Sinclrtir Oil and Gas Co.), U. S.Patent 2,640,-
(101) (102) (103) (104) (105)
(106) (107)
(108) (109) (110) (111) (112) (113) (114) (115) (116) (117) .
I
(118)
(119) (120)
(121)
809 (June 2, 1953). Oil Gas J., 52, 136-137 (Sept. 14, 1953). Ibid., p. 66 (Nov. 9, 1953); p. 52 (Nov. 23, 1953). Ibid., pp. 174-8 (Jan. 25, 1954). Orr, R. J., and Williams, H. Laverne, J . P h y s . Chem., 57, 92531 (1953). Orzechomski, A,, and AlacCormack, Can. J . Chem., 32, 388-451 (1984). Pahnke, A. J., and associates, 124th Meeting, AC8, Chicago, Sept. 6-11,1953. Pctrolezrm Processing, 8 , 971 (July 1953). Petyoleum Refi72er, 32, No. 6, 133-4 (1953). Ibid., KO.9, 154-8. Ibid., 33, 3-0,4, p. 184. Porter, F., Bumpus, AI., and Cosby, J. N. (to illlied Chem. & Dye Corp.). U. S.Patent 2,513,251 (June 27, 1950). Reidel, J. C., Oil Gas J . , 6G68 (Oct. 28, 1953). Rigon, Lino (to Les Usines de Melle), U. S.Patent 2,658,914 ( S o v . 10, 1953). Ruthruff, R. F., Petioleurn Refiner, 32,113-14 (1953); 33,1557 (1954). Salt, F. E., Chemistiy & I n d u s i i y , 1953, S-46-9 (.lug. 10, 1953). Satterfield, C. N., and Case, L. C.. IKD.ESG. C m x , 46, 9981001 (1954). Satterfield, C. N.. Wilson, R. E., and associates, Ibid., 46, 100110 (1954). Saunders, R. H. (to Hercules Powdcr Co.), U. S.Patent 2,644,014 (June 30, 1953). Schuber, John, and Kraske, W.4 . , Chem. Eng., 60, KO.9,205-7 (1953). Schweiteer, C. E. (to E. I. du Pont de Neniouis h Co.), U. S. Patent 2,644,837 (July 7 , 1953). Seubold, F. H. (to Shell Development Co.), Ibid., 2,633,476 (March 31, 1953).
Vol. 46, No. 9
(122) Seubold, F. H., Jr., and S’aughan, W. E., J . A m . Ci~e7n.Soc., 75, 3790-2 (1953). (123) Shelmerdine, J., and associates, J . A p p l . Chena., 3, 513-21 (November 1953). (124) Shelton, J. R., and Cox, W.R., IKD.ENG.CHCM.,46, 818-23 (1954). (125) Shelton, J. R., Kherley, F. J., and Cox, IT.L., I b i d . , 4.5, 2080-8 (1953). (128) Sherwood, P. W., Petroleum Pwcessing, 8 , 1348-54, 1543-5, 1722-8 (1953). (127) Sherwood, P. W..Petroleum Refiner, 32, 90-4, 1.41-4 (1953). (128) Ibid.. No. 4. 155-8 11953). (:29j Ibis., 32, KO. 12, 93-7 ii953); 33, NO. 1, 129-33; 33, NO. 2 117-22 (1954) (130) Skellon, J. H., Chemzstru & I m i u s f i u , 1953, p. 1027-9 (Oct 3, 1953). (131) Skclly, J. F. (to hI. W,Rcllogg Co.), U. S. Patent 2,649,463 (Aug. 18, 1953). (132) Small, S . J. H., and Ubbelohde, .i.12., J . A p p l . Chem., 3, 193-8 (1953). (133) Smith, E. J., J . Chem. SOC.,1953, pp. 1271-5. (134) Sprauer, J. W. (to E. I. du Pont de Kernours & Co.) U. 6 . Patent 2,657,980 (Nov. 3, 1953). (135) Symonds, F.L. (to Standard Oil Co. of Indiana), Ibid., 2,631,094 (March 10, 1953). (136) Tabel, G. E. (to E. I. d u Pont de Semours & Co.) [bid.. 2,644 $4 1. (137) Thornton, D. P., Petroleum Processing, 8, S o . 7 , 10414 (1953). (138) Titov, A. I., J. Gen. Chem. ( U S S R ) , 22, 1373-5 (1952). (139) Toland, W.G. (to California Research Corp.), U. S. Patent 2,623,073 (Dee. 23, 1952). (140) Waloutt, C., and associates, 124th Meeting, hCS, Chicago, Sept. G-11, 1953. (141) Weiss, J. AI., Chem. Eng. News, 32, KO. 18, 1820 (1954). (142) Zapp, R. L., and Gessler, A. M., Rubber A g e , 74, No. 2, 243-51 (1953).
HERBERT F. WIEGANDT and RAYMOND G. THORPE SCHOOL OF CHEMICAL AND METALLURGICAL ENSINEERING, CORNELL UNIVERSITY, ITHACA, N . Y.
The number of 1953 publications dealing with polymerizations is approximately 15% fewer than for the previous year. Increased polyethylene production i s alleviating the scarcity of this product. The use of resins in the manufacture of structural items, such as chemical process equipment, as well as the much publicized plastic automobile body, may be another transition in the growth of the industry. Continued interest in synthetic fiber development is indicated b y the large number of formulations For this purpose.
HE most talked about development in 1953 relating to products of polymerization is the fibrous glass reinforced polyester automobile body. Public enthusiasm has continued t o expand, despite the controversy over mass production economies as compared with steel. Advances in the technique of vacuum forming are contributing to the expanding use of thermoplastics for signs and displays. High impact polystyrene is being received favorably, and a rapidly increasing portion of the styrene resins is of this type. Rigid polyvinyl chloride, reinforced polyesters, and others are receiving attention in the chemical industry for use as corrosion-resistant pipe and other structural items. Polyethylene output increased sharply as the first of a series of large units went into operation. The predictions are that plastics, rubbers, and coating materials industries will continue to grow a t a rapid rate. A few fibers faced the slump of the textile industry and also had some production difficulties of their own. Vinyl cyanide polymers and isocyanate polymers show signs of interesting developments. The number of publications dealing with the unit process of polymerization has decreased somewhat. The previous review of this series (W5A) for 1952 covered 557 references; 466 are cited
for 1953. This review cover? 1053 material directly related to the unit process of polymerization, including general theory, reaction mechanism and kinetics, effect of all types of addition reagents on reactions, reaction conditions, processes, apparatus, and existing plants. It does not include publications dealing exclusively with production statistics, uses, applications, structural properties, or modifications of high polymers. Many of the references cited, however, are in part devoted to such subject matter. The development of polyethylene manufacture wab reviewed by Raine (19A). Lever ( I 2 A ) reviewed ethenic copolymerization and Langlois ( Z I A ) considered the various olefin polymerizations with acidic catalysts. Allyl resins were covered by Lynn ( I 3 A ) . Jacini (8A ) wrote about the copolymerization reactions between olefins and drying oils. Ionic polymerization studies leading t o butyl rubber n-eI e reviem-ecl by ;Idams and Buckler (Id). Cooper ( b A ) , Landler (10.4 ), and Fisher ( 6 A ) discussed developments and process variables for synthetic elastomers. Parker ( 1 6 A ) considered emulsion polymerization. Cooper ( 4 A )reviewed the action of various polymerization catalysts and initiators. Polycondensation reactions, including kinetics, mechanism, and structure, were covered by Champetier (SA), Korshak (OA), and Powers (17A). Goldstein ( 7 A ) reviewed melamine resins. T h e chemistry and polymerization mechanics of polyesters were
