Oxidation - Industrial & Engineering Chemistry (ACS Publications)

2000

INDUSTRIAL AND ENGINEERING CHEMISTRY

The role of nitrous acid in organic chemistry is presented by Ingold (14). Catalyzed nitration, diazotization, halogenation, etc., are discussed kinetically, including reaction order, rate, and mechanism. By their investigation, Blackall and Hughes ( 3 ) have shown that the formation of nitramines from secondary amines and the formation of alkyl nitrates from alcohols by the action of nitric acid involve attacks by the nitronium ion on the nitrogen or oxygen atom. The oxygen nitration of glycerol and of cellulose was shown indirectly to involve attack on oxygen by the nitronium ion. The rate and order of reactions of the nitration of aromatic compounds are discussed. Bonner, Bowyer, and Williams ( 4 )have investigated the rates of nitration of the trimethylphenylammonium ion in 100 to 82% sulfuric acid solutions. The velocity coefficient for nitration has a maximum value in 90.40% sulfuric acid, and the variation in 90 to 82% sulfuric acid can be correlated with the carbinol acidity function or directly with results for the extent of ionization of 4,4',4"-trinitrotriphenylcarbinol in the same medium range. The correlation suggests that the diminution in the extent of ionization of nitric acid to the nitronium ion is the major factor which causes a 200-fold diminution of the nitration velocity coefficient in this medium range.

Yol. 45, No. 9

LITERATURE CITED (1) Baohman, G. B., Addison, L. RI., et al., J. Org. Chem., 17, 90613,914-27,928-34, 942-54 (1952). (2) Bachman, G. B., and Hewett, J. V. (to Purdue Research Foundation), U. S. Patent 2,597,698 (May 20, 1952). (3) Blackall, E. L., and Hughes, E. D., Nature, 170,972-3 (1952). (4) Bonner, T. G., Bonyer, F., and Williams, G., J . Chem. SOC., 1952,3274-SO. (5) Bryson, A., and Garnett, J. L., Nature, 171, 41 (1953). (6) Bunton, C. A., Halvei, E. A,, et al., J . Chewa. Soc., 1952, 491316,1417-24. (7) Chedin, J., and Tribout, A,, Mhm. services chim. &tat ( P a r i s ) , 36, SO. 1,31-42 (1951). (8) Chem. Eng., 60,No.3,130 (1953). (9) Crater, W.deC., IND. ENG.CHEW,44, 2039-43 (1952). (10) Desseigne, G. (to fitat Francais), French Patents 972,694 and 972,695 (February 1951). (11) Desseigne, G., Mdm. poudres, 32, 117-20 (1950). (12) Dunning, ITr. J., Millard, B., and Nutt, C. W., J . Chem. Soc., 1952,1264-9. (13) Epstein, S., and Winkler, C. A,, Can. J. Chena., 30, 734 (1952). (14) Ingold, C . K., Bull. soc. chim. France, 1952, 667-71. (15) Kobe, K. A , and Mills, J. J., IND. ENG.CHEX, 45, 287 (1953). (16) Kobe, K. A., and Pritchett, P. W., Ibid., 44, 1398-401 (1952). (17) McKay, A. F., Chem. Revs., 51, 301-46 (1952). (18) Phillips, M. A , , Chemistry & Industry, 1952, 714-15. (19) Simkins, R. J. J., and WXliams, G., J. Chem. SOC.,1952, 3086-94. (20) Willson, F. G., Forster, A., and Roberts, E., Brit. Patent 658,978 (Oct. 17, 1951).

OXIDATION BZ

L. F, MAREK

ARTHUR D. LITTLE, INC., CAMBRIDGE, MASS.

During the past year, commercialization of the process for the manufacture of phenol and acetone by breakdown of cumene hydroperoxide has been achieved and further progress has been made toward more widespread use of this process for production of these important organic chemicals. Major commitments for plants have been made and plans for commercialization announced for processes of ammonia synthesis based on partial combustion of natural gas by oxygen obtained From liquid air Fractionation. Little has been reported on the commercial production of acetylene from hydrocarbons by partial combustion. Considerable work has been done relating to mechanism of combustion studies and to the burning of fuels in Diesel and spark ignition engines. More results have been reported concerning the role of oxidation in the deterioration of rubber, elastomers, and surface coatings, and in the degradation of lubricating and similar oils. Use of ozone in commercial synthesis OF organic products has been reported.

EVELOPMENT of processes, on a commercial scale, for the conversion of hydrocarbons to useful organic compounds has received widespread attention in the field of oxidation.

LOW MOLECULAR WEIGHT HYDROCARBONS The direct oxidation of natural gas is being commercially practiced by several companies to produce alcohols, aldehydes. acids, and derivatives (37, 133, 136, 188). Acetic acid and anhydride are major products a t Celanese Corp. of America's new plant a t Pampa, Tex. (Figure 1); other chemicals from the direct oxygen oxidation of n-butane are methanol, acetone, and acetaldehyde. It is claimed that aqueous formaldehyde obtained by the vaporphase partial oxidation of hydrocarbons behaves differently from methanol-derived formaldehyde in reacting rvith acetaldehyde to form pentaerythritol, in that much smaller proportions of the diand polypentaerythritols are formed (160). The mzthod of performing the pentaerythritol reaction is described Acetylene from hydrocarbons continues to be of int-rest and a recently published joint study gives a detailed process description and economic analysis of the Wulff regenerated cracking process ( 9 ) . Other processes have been mentioned ( 6 6 ) .

Slow, noninflammatory oxidation of methane by nitrous oxide results in formation of carbon monoxide, carbon dioxide, and water vapor as main products of a two-stage reaction (161). A reaction mechanism for the process is discussed. Reaction between acetylene and nitrogen dioxide and the catalytic action of nitrogen dioxide on acetylene oxidation have been studied (174). The major product is glyoxal, 32% of the reacted acetylene going to form this product. Further studies are under way in an attempt to gain further insight into the mechanism of the reaction. A noncatalytic, flame process for the synthesis of hydrogen cyanide from methane and ammonia has been claimed to result in satisfactory yields and to avoid the catalyst problems associated with current methods used commercially ( 1 8 s ) . Examples show that ammonia conversions to hydrogen cyanide of up t o 91 % have been obtained. The technique for producing synthesis gas mixtures of hydrogen and carbon monoxide by the incomplete combustion of natural gas with oxygen, which received so much attention a few years ago in connection with modified Fischer-Tropsch syntheses, has again come to the fore and is now ~vellon the way to major industrial importance (43, 137, 166). Plants based on processes developed jointly by Texaco Development Co. and Hydrocarbon Research, Inc., are now in process of erection or design and will furnish synthesis gas for use in the manufacture of ammonia and urea. Companies reported to be proceeding with such plants include W. R. Grace & Co., Spencer Chemical Co., and John Deere Co. The oxygen unit for the W. R. Grace & Co. ammonia-

September 1953

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I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY

and increase the hydrogen t o carbon monoxide ratio (99). The recovery of carbon from the incomplete combustion as a water slurry and subsequent recycle of the slurry to the reaction zone is claimed to regulate temperature as well as increase synthesis gas yields (126). It has been proposed t o use preferential diffusion of hydrogen through a permeable partition to produce synthesis gas fractions respectively richer and poorer in hydrogen than possible directly from incomplete combustion (134). The steam-methane reaction for formation of hydrogen-carbon monoxide mixtures continues to be of interest and importance. Work a t the U. S. Bureau of Mines has extended the temperature range of studies of mechanism (76). I n the range of 1000° to 1100O C., the presence of less than 1% of acetylene added to pure methanol used in the studies more than doubled the rate of disappearance of methane in the reaction. Acetylene is an efficient catalyst for methane decomposition, whereas ethylene is a relatively poor one. Both are formed as intermediate decomposition products. In efforts to eliminate the necessity for producing oxygen to avoid nitrogen dilution in partial combustion processes of hydrogen-carbon monoxide formation from natural gas, considerable effort has been expended in the development of oxidation carriers in the form usually of metal oxides used in fluidized masses. One such mass consists of equal parts by weight of iron oxide and manganese oxide to which from 10 to 40% of magnesia or chromia has been added (118). In the case of copper oxide acting as oxidation carrier, it has been shown that a portion of the hydrocarbon is completely converted to carbon dioxide and water and the remaining hydrocarbon subsequently reacted in the presence of copper with the carbon dioxide and water to form hydrogen and carbon monoxide. This mechanism has been made the basis of a control method (116). It is claimed that saturated hydrocarbons, such as ethane, may be dehydrogenated by heating with carbon dioxide in the presence of an iron oxide catalyst to form a mixture of ethylene and carbon monoxide suitable for conversion to propionic acid by reaction over suitable catalysts (89). Examples show conversions of ethane to ethylene as high as 68.7% from feed mixtures of 1.77 moles carbon dioxide per mole of ethane. Isobutane containing 4.4 mole yodissolved oxygen, heated to 325 ' f 5' C. a t 23,000 pounds per square inch for 20 to 24 hours, results in the formation of products of which 75% are normal

2001

oxidation products and 25% are coupling products (86). The normal oxidation products consist of about 75% tert-butyl alcohol and 25% its degradation products, acetone and methanol; coupling products are octanes. Reaction of cyclopropane with nitric acid or nitrogen dioxide in the vapor phase yields nitrocyclopropane (M).I n the nitration of methane homologs to yield nitroalkanes, two types of homogeneous reactions occur simultaneously, the replacement of hydrogen atoms by nitro groum and the replacement of alkyl radicals by nitro groups.

HIGH MOLECULAR WEIGHT HYDROCARBONS Liquid-phase oxidation of paraffinic oils and waxes continues to receive attention with the objective either of forming oxygenated products of commercial interest or of studying mechanism. Most of the developments in the oxidation to form useful products have to do with details of either reaction or product recovery. Synthetic fatty acids of high molecular weight, ranging up to 40 or more carbon a t o m per molecule, are produced by the air oxidation of microcrystalline paraffin waxes having 34 to 55 carbon atoms per molecule (138). Air oxidation of such microcrystalline wax a t temperatures of 110' to 130' C., in the presence of small percentages of potassium permanganate, may be carried t o essentially complete conversion of hydrocarbons with the formation of essentially monocarboxylic acids. Product separation is accomplished by water washing and distillation. Disadvantages appear to be the length of time required for the batchwise process and the presence of hydroxy or lactone groups in the structure. Attention has recently been directed t o the results of some Soviet research work published in 1950 and 1951 on the oxidation of paraffin wax (64, 1.44). I n this work, the reaction was performed a t temperatures in the range of 200' to 500 ' C., considerably higher than usual in such processes. At the preferred range of 300' to 400 'C. reaction was rapid and the product characterized by the almost complete absence of hydroxy acids, in contrast to products from lower temperature processes. Replacement of paraffin wax with paraffinic distillate containing about 30% wax resulted in a much slower process, even with added catalyst, because of the retarding effect of aromatic acids formed during the reaction. Purified fatty acids from the process included a series

2002


of monocarboxylic of normal structure with 7 to 24 carbon atoms per molecule. A study of the conversion of oils and resins to asphaltenes during the oxidation of petroleum residues was based on a comparison of the behavior of a steam refined reduced crude and a cracked stock (82). Based on the proportions of oxygen evolved as water, it was evident that the primary reactions in both cases involved dehydrogenation. The cracked stock was shown to be capable of polymerization by heat and agitation in the absence of oxygen. Otherwise, the proportion of asphaltenes in both stocks increased with continued blowing a t the expense of oils and resins. I n the oxidation of paraffin wax by the simultaneous action of concentrated sulfuric acid and nitrogen oxides, it has been claimed that the use of sulfuric acid of 80 to 90% concentration gives superior results to those previously found with 96y0 acid (81). Besides monocarboxylic fatty acids, only low percentages of nitroparaffins are formed. Deterioration of lubricating oils has frequently been studied by means of oxidation phenomena. Shell Development Co. has published results of a kinetic study in the range above 220" C., made to explain more completely lubricating oil performance and to extend the range of existing knowledge from the lowest reaction temperature to the point of ignition ( 6 9 ) . Aircraft lubricating oils underwent spontaneous ignition a t 280 O C. in the equipment used. Copper, iron, and lead in both metallic and dissolved form catalyze the reaction. The authors conclude that there is no dearth of reactive components potentially capable of rapid oxidation in an engine to form piston skirt lacquer, ring groove and combustion chamber deposits, and so on. Ovygen absorption studies were made on a series of pure hydrocarbons and compared with similar data from several hydrocarbon mixtures and a composite lubricant (11). With the seven pure hydrocarbons, over a thousandfold difference in oxidation stability was observed in going from the least stable 1-hexadecene through increasingly stable l-methyl-4-isoprop~~lbenzene,cisDecalin, tetraisobutane, hexadecane, and ]-methylnaphthalene, to the most stable phenanthrene. The oxidation stability of hydrocarbon mixtures can seldom be predicted from the characteristics of the component members. The presence of a solid phase, such as glass, affects both the length of induction period and the oxidation rate during the reaction period of the liquid-phase oxidation of mineral oils (110). Despite considerable study, the nature of the phenomenon is believed to be still obscure and to warrant further consideration. Addition of increasing amounts of copper filings, either ordinary or specially reduced, to white mineral oil subjected to oxidation rapidly reduces the induction period to zero; further additions cause a reappearance of the induction period (111). It is believed that the reappearance of the induction period may indicate the breaking of reaction chains, Lithium soaps, classed as pro-oxidants, have been found, by workers a t the Naval Research Laboratory (33,to aid antioxidants incorporated in lubricating compositions. Antioxidants often used are aromatic silicones. A basic study is being made of the oxidation stability of diesters in connection with uses as lubricants for engines, instruments, etc. (131). The oxidation of diesters has been shown to be autocatalytic. It has been shown that a representative diester, bis(2-ethylhexyl) sebacate, can be adequately inhibited against oxidation a t temperatures up to 163O C. Alkaline permanganate oxidation of Colorado oil shale kerogen results in 96 to 99% conversion of organic carbon to oxidation products (152). Products consist of carbon dioxide, oxalic acid, steam-volatile acids, and under 1%of nonvolatile nonoxalic acids. Benzene carboxylic acids arc not found. Catalysts of iron-manganese fluoride used for the dehydrocyclization of straight-chain hydrocarbons are claimed t o be maintained in an active state by the introduction of small pro-

Vol. 45, No. 9

portions of oxygen and hydrogen fluoride into the feed stream of hydrocarbon (97). Examples show the addition of on the order of 5% each of air and hydrogen fluoride to n-heptane for reaction a t 450 O to GOO O C. over a 50-50 iron fluoride-manganese fluoride catalyst. Autothermic cracking of heavy hydrocarbons to form lower molecular weight hydrocarbons, such as olefins, diolefins, and aromatics, is effected by means of internal oxidation with air ( 5 5 ) . It is claimed that by performing this operation in the presence of a fluidized bed of coke it is possible to bring about the deposition and decomposition of the tar fog accompanying such autothermal cracking processes. Organic peroxides, suitable as ignition promoters for Diesel fuels, are readily prepared by air blowing a t temperatures of 115 to 165" C. straight-run petroleum distillates boiling in the range of 80" to 190" C. which are substantially free of unsaturates and aromatics (149). Peroxides are recovered from the oxidized oil by adsorption on silica gel or other adsorbents, and are desorbed from the adsorbent with acetone or other suitable solvent. Processes for the manufacture of hydrogen peroxide have been reviewed and described in recent literature (196). Liquid-phase reactions of nitrogen tetroxide with olefins have been extended to include I-octadecene and lj3-butadiene (246) Addition reactions of the nitrogen tetroxide occur at the double bond positions. The collision efficiency of the reaction between methyl radicals and nitric oxide in a flow system has been investigated by means of radioactive tellurium mirrors ( 6 6 ) . A value of between 0.5 and 0.05 for the collision efficiency of methyl combination is believed compatible with existing data. The combustion behavior of a number of pure hydrocarbons with white fuming nitric acid under conditions comparable with those prevailing in rocket motors has been described in terms of an experimental study (17'8). Polyolefins and acetylenic hydrocarbons react with almost explosive violence and olefins react vigorously, while saturated hydrocarbons, such as n-decane, react slowly when nitric acid exceeding 90% concentration is rapidly added to the hydrocarbon. Vapor-phase nitration of saturated aliphatic hydrocarbons a t elevated temperatures by nitric acid or oxides of nitrogen to form nitro alkanes is claimed to be materially improved by the presence of regulated amounts of oxygen (91). Both increased yields and conversions are claimed when oxygen is present to the extent of from 5 to 40% by volume of the hydrocarbon used. It is claimed that cyclomono-olefins may be reacted with nitrogen tetroxide a t temperatures as high as 300" C. and under pressures of 100 atmospheres without hazard of explosion by performing the process in solution and continuously (63). Examplos show nitration of cyclohexene to form mixtures of 1,2dinitrocyclohexane and nitrito-nitrocyclohexane. The use of sulfur trioxide for the oxidation of methane to formaldehyde is claimed to result in yields based on methane of 807, and on sulfur trioxide of 70% (146). Fixed bed catalysts prepared from the usual oxidation catalysts supported on porous media are used at temperatures in range of 175' to about 450" C. Improvement in the liquid-phase, air oxidation of naphthenic hydrocarbons to hydroperoxides, alcohols, and ketones is claimed to result from operation of a liquid-full reactor ( 6 2 ) . Reactor arrangement is such that reaction is liquid phase and the liquid level is maintained in contact with the top of reactor. Liquid-phase catalytic oxidation of substituted cyclohexanes may be made to yield cyclic acids and ketones by means of the use of aldehyde activated metal catalysts (96). Cobalt is especially useful, but manganese, iron, nickel, and copper may also be used. Solvent mixtures, consisting principally of acetone, produce alkane dicarboxylic acids (181) in the liquid-phase oxidation of liquid cycloalkanes containing four to six carbon atoms Polyvalent heavy metal catalysts are used for the air oxidation.

September 1953

INDUSTRIAL A N D ENGINEERING CHEMISTRY OLEFINS

Ethylene oxide has rapidly become one of the most important organic intermediates being manufactured today. Estimated production was 483,000,000 pounds in 1950, the Defense Production Authority goal for 1955 provides for 969,000,000 pounds capacity, and industry estimates for 1962 call for 1.1 billion pounds. The U. S. Tariff Commission unit sales value in 1951 was 18 cents per pound. Most attention has been directed to methods of manufacture by the direct catalytic oxidation of ethylene; and projected plant capacities (28) show that by 1955 more ethylene oxide will be produced by ethylene oxidation than by the chlorohydrin route (46). The Vulcan Engineering Division of Vulcan Copper and Supply Co. and Atlantic Refining Co. have cooperated in developing a fluid bed catalytic process for the direct oxidation of ethylene to ethylene oxide (32,34,62). The pilot plant demonstrations have attracted considerable attention. The process is based on the use of a special catalyst in a completely captive fluid catalyst bed without regeneration. Boiling Dowtherm is used to remove heat and give temperature control in the reactors. Waste heat boilers are employed to use reaction heat. Vulcan estimates that with ethylene a t 4.5 cents per pound, the economic optimum yield is close to 60% and manufacturing cost, including fixed charges, is about 8 cents per pound. It is claimed that yields can be raised t o 70% if necessary t o offset higher ethylene costs. In late 1952, Vulcan estimated capital investment for a plant producing 40,000,000 pounds of ethylene oxide per year to be about $425,000,000. Various assemblies of equipment have been tried in connection with fluid bed operations of silver catalyzed ethylene oxidation, but few descriptions are to be found in the literature. One form of reactor which has been patented uses a unitary mass of fluidized catalyst in a multizoned reactor designed to provide a reacting zone and a cooling zone ( 172). There is ample evidence that the search for improved catalysts for use in the direct ethylene oxide process has continued both here and abroad. It is claimed that the presence of silica, quartz, or silicate glass in a silver-containing catalyst permits an increase in per pass conversion from 52% with no silica to 83% with silica present in the catalyst, while the yield is maintained a t about 65% (116). If the silica is incorporated in the catalyst in the form of finely divided, fused sodium aluminum silicate, substantially complete per pass conversion can be realized, while yields are maintained a t a level of 60 to 64% (123). The use of spinels as catalyst supports has been claimed to result in superior catalysts for ethylene oxidation. Thus, a zirconium oxide-silica spinel support is claimed to result in a silver catalyst of superior thermal st9bility which is capable of operation in a fluid bed (21). Similarly, a magnesia-alumina spinel offers superior thermal stability (Bb). A support of essentially 10 to 20% barium oxide and 70 to 85% magnesia for a silver catalyst gives a catalyst with superior fluidizing properties ( 2 4 ) . In connection with catalysts prepared with these supports, it is claimed that organic peroxides, such as benzoyl peroxide, acetyl peroxide, urea peroxide, cumene hydroperoxide, and the like, are exceptionally good promoters and result in stable catalysts (20). Magnetite having a spinel structure has been used as a support for silver catalysts (113). Fused beryllium oxide particles offer a surface which is wetted more thoroughly by silver films than are surfaces of silica or alumina. This superior wettability supposedly results in better physical adhesion of silver during the use of the catalyst (93). The difficulty of satisfactorily fluidizing finely divided silver catalysts for ethylene oxidation is well recognized and has received considerable attention. Characteristically, the catalyst does not remain "fluid" and either sinters into a porous mass or degenerates with the silver, depositing on reactor walls or collecting in masses. It is claimed that dilution of a supported-silver catalyst

2003

with substantial proportions of artificial graphite overcomes this difficulty (162). -Various compositions ofsiiver catalysts may be thus used in fluid beds-e.g., silver containing small proportions of rare metals, beryllia-supported silver, etc. The presence of halogens in the catalytic reaction zone in the direct oxidation of ethylene to ethylene oxide has previously been reported to result in suppression of the proportion of oxidation to carbon dioxide. Advantage is taken of this phenomena and the solvent properties of certain organic halogen compounds to obtain a process for the recovery of ethylene oxide by solvent extraction of reaction gases and the recycle of ethylene containing small amounts of halogenated compounds ( 173). Experimental results for the catalytic oxidation of ethylene over a wide range of conditions have been published recently (187). From the results, an empirical kinetic equation was established. The conditions covered by experiments were temperatures of 200 O to 270" C., space velocities of 1200 to 3600 per hour, and feed compositions from 90% ethylene-10% oxygen to 15% ethylene85% oxygen. Yields of ethylene oxide a t constant temperature and space velocity appear to be highest in the region of 30 t o 40'% ethylene concentration in the feed. Conditions for the direct catalytic oxidation of propylene to acrolein have been described, including a catalyst of cuprous oxide deposited on granular silicon carbide, a catalyst temperature of 375" C., feed stream composition of 20% by volume of propylene, 20% b y volume of air, and 60% by volume steam, and apparent contact time of 1 second (68). Catalyst life and activity in this process are both functions of the oxygen partial pressure and of the hydrocarbon to oxygen ratio in the reaction feed mixture. It is claimed that catalyst activity may be maintained a t desired high levels by periodically interrupting or decreasing the flow of oxygen to the catalyst without otherwise changing the operating conditions (67). It has also been stated that the presence of elementary selenium in the reaction zone over a catalyst of copper oxide serves to maintain catalyst activity in the oxidation of propylene or butylenes to form unsaturated aldehydes and ketones (80). This condition is obtained by maintaining a small partial pressure of selenium vapor in the reactor feed mixture. Removal of the carbon monoxide present in the recycle olefin stream in the copper oxide catalyzed air oxidation of propylene to acrolein results in maintenance of catalyst activity a t several times the activity maintained when carbon monoxide is not removed (66). Passage of the scrubbed recycle gas stream over a Hopcalite catalyst results in oxidation of the carbon monoxide to carbon dioxide by residual oxygen present, without significant reaction of the olefin. Recovery and primary purification of the acrolein from the reaction product of this process is effected by quench-scrubbing the reactor effluent with water and with liquid propylene. The composition of the carbonylic compounds in the mixtures obtained from oxidation of propylene is, approximately, acrolein, 90% by weight; acetaldehyde, 6.0%; propionaldehyde, 2.0%; and acetone, 2.0% (47). Oxidation of isobutylene in a similar manner results in carbonylic mixtures approximating methacrolein, 91.6% by weight; acetaldehyde, 2.2%; propionaldehyde, 1.4%; acetone, 3.4%; and acrolein, 1.4%. Studies a t the Stanford Research Institute of the kinetics of the gas-phase reaction of olefins with ozone have shown that reaction is rapid, over-all reactions are quite complicated, and stoichiometry varies with reaction pressures (28). Studies were made with 1-decene, 1-octenc, 1-heptene, 1-hexene, cyclohexene, 1pentene, and propylene. Reaction with ethylene was much slower than with the higher olefins, with pentene and propylene somewhat slower, and with the others practically identical with 1-hexene. A chamber technique employing 10 to 20 atmospheres of olefin and 1 atmosphere of ozone was used. Reaction products from the homogeneous, gas-phase oxidation of ethylene and propylene, under reaction conditions which fill the gap between the high and low pressure areas already reported

I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY

2004

in the literature, have been recently shown to be consistent with previous data (17). Most of the ethylene and propylene which reacts appeals in the product as higher olefins. Copper oxide in finely divided form and in a fluidized bed has been employed as the oxidizing agent for conversion of light and normally gaseous aliphatic hydrocarbons to intermediate oxidation products such as alcohols, aldehydes, ketones, and organic acids, and also for the conversion of aromatic hydrocarbone to maleic and benzoic acids and phthalic anhydride (106). The reduced oxidizing mass is regenerated by oxidation with air in a separate zone.

AROMATIC HYDROCARBONS AND COMPOUNDS The very significant development of the cumene hydroperoxide process for phenol manufacture has continued to receive attention in the technical and patent literature (41, 136, 170). Reviews of the several process modifications, projected plants, and general economics have been published. Two processes for the formation of cumene hydroperoxide have been described (55). I n the Allied Chemical and Dye Corp. process, cumene in the liquid phase is contacted with elemental oxygen a t 100" to 130' C. until not over 5% by weight of the reaction mixture of cumene hydroperoxide is formed. Cumene is then treated with a strong base and oxidized again with elemental oxygen a t about 110' C. until the concentration of hydroperoxide in the reaction products reaches a t least 11%. In the Hercules Powder Co process, cumene is also oxidized in the liquid phase at temperatures of 105' to 135' C., but no catalytic material is added. Excess oxygen is used and steam is introduced into the gas space above the reaction mixture to reduce explosion hazard (6). ,4 general description of the B.A.-Shawinigan, Ltd., p l m t in Montreal, Canada, for the manufacture of phenol and acetone via cumenc hydroperoxide, gives the annual capacity as 13,000,000 pounds phenol, 8,000,000 pounds acetone, and 1,000,000 pounds a-methylstyrene (27). The use of alkaline materials in conjunction with cumene oxidation to hydroperoxide has been claimed to improve various aspects of the process. Thus, the use of a suspension of solid calcium carbonate in the liquid cumene being oxidized is said to reduce by-product formation (108). Treatment of partially oxidized (less than 570) cumene with a strong base, such as aqueous potassium hydroxide, and continued oxidation of the washed cumene results in accelerated oxidation (105). Pretreatment of cumene with aqueous solutions of strong hases before any oxidation eliminates the irregularities in induction periods obtained from commercial lots of cumene (104). Naphthene hydroperoxides may be precipitated from hydrocarbon solution as the alkali metal salts, but the process is not useful in practice since tars and other contaminants are carried down also (98). Naphthenes may be oxidized to hydroperoxides a t temperatures of 135'to 165 C. by maintaining pressures in the range 150 to 4000 pounds per square inch. Organic peroxides, suitable for use as promoters of polymerization reactions, are formed by the reaction of an organic hydroperoxide-e g., tertbutyl hydroperoxide-with a 2,4,6-trialkyl phenol a t temperatures of 60" to 100' C.(16). The phthalic anhydride economic picture has continued to expand as new uses and larger volumes for old uses come into existence (169). The 1952 production volume is estimated a t over 250,000,000 pounds, with eight companies participating. Important developments in petroleum reforming and in the processes for the separation of xylene isomers are making available these new raw materials to the petrochemicals industry (167). Three isomeric phthalic acids can be produced, phthalic acid and anhydride, terephthalic acid, and isophthalic acid. It has been found that phthalic anhydride can be produced in high yield by the oxidation with air over vanadium pentoxide catalysts of 0,3,4bicyclononane and 0,3,4-bicyclononadiene (180,188). At reactor temperatures of 360' C. weight yields of phthalic anhydride O

Vol. 45, No. 9

of about 75% are obtained, the unsaturated hydrocarbon giving the higher yields. Substantial amounts of these hydrocarbons have been found in an unsaturated stock obtained from high temperature cracking operations. Recently announced commercial production of dimethyl isophthalate by Hercules Powder Co. is based on the oxidation of a commercial xylene isomer (56). The material is expected to find use in plastics, plasticizers, protective coatings, and laminating resins. Toluic acids, from the air oxidation of mixed xylenes, are oxidized to phthalic acids by a process in which a mixture of the toluic acid isomers, elemental sulfur, and aqueous sodium hydroxide is heated to a temperature of 600' F. for 1.5 hours in a pressure bomb (177'). An example shows conversion of 87% of toluic acids to phthalic acids, giving a weight yield of 115.2% of phthalic acids. Flow charts for the commercial process of oxidizing naphthalene to phthalic anhydride have been published (89). Because of the problems involved in removal of reaction heat a t controlled reaction temperatures in naphthalene oxidation, considerable effort has been expended in attempts to adapt the fluidized catalyst bed technique to the process. One modification claims the use of a technique whereby the catalyst, a t a critically controlled temperature, is carried in suspension concurrently with a stream of reactant vapor through a reaction zone for a short reaction period and is then suddenly separated from reaction gases, stripped clean, reactivated, and recycled (164). An indirect method for the conversion of p-xylene to terephthalic acid eliminates the use of permanganate, chromic acid, or other direct chemical oxidation (5.4). The process involves the formation of polyalkyl aromatic chlorides in which a chlorine atom is attached to a primary alkyl carbon atom and the conversion of such chlorides to carboxylic acids by reactions involving oxidation with aqueous caustic alkali. Maleic anhydride has increased rapidly in commercial importance, production rising from 24,000,000 pounds in 1951 to an estimated 40,000,000 pounds for 1953 (44). Major uses, in order of decreasing importance, are alkyd coating resins, polyester casting resins, drying oils, agricultural chemicals, plasticizers, and a variety of smaller uses, including pharmaceuticals, wetting agents, and adhesives. The construction of a large, $4,500,000 plant for the oxidation of benzene to maleic anhydride has recently been announced (3'9). Operation is expected for late 1953 or early 1954. Ethylnaphthalene is oxidized to a mixture of methylnaphthylcarbinol and methyl naphthyl ketone by means of air in the presence of manganous naphthenate as a dissolved catalyst (101). It is claimed that benzaldehyde and benzoic acid may be obtained by the catalytic reaction of hydrogen and carbon monoxide with benzene (18). Cobalt supported on kieselguhr is used as a catalyst. The uncatalyzed oxidation of benzaldehyde in benzene solution has been studied in connection with studies of the mechanism of hydrocarbon oxidation (150). The rate of oxidation is a t its maximum value a t the beginning of the reaction and thereafter falls quite rapidly. A method has been described for the oxidation of toluene to benzaldehyde and benzoic acid, whereby a mixture of toluene vapor and air is passed through a high tension, high frequency electric discharge at reduced pressures (63). Nitric acid, nitrous acid, and oxides of nitrogen higher than nitric oxide are claimed for the oxidation of hydronaphthoquinone compounds to naphthoquinone compounds (61). Treatment of certain alkyl aromatic hydrocarbons and nuclearly chlorinated alkyl aromatic hydrocarbons with air in the presence of magnesium or aluminum metal catalyst results in the removal of hydrogen from the aromatic compounds and the formation of an aromatic hydrocarbon of higher molecular weight, including a diary1 alkane and a di(chloroary1) alkane (148).

September 1953

INDUSTRIAL A N D E N G I N E E R I N G C H E M I S T R Y ORGANIC COMPOUNDS

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Brief deaariptions have been published of the new process of Reichhold Chemicals, Inc., for the production of formaldehyde from methanol t o be employed in a 24,000,000 pound per year formaldehyde plant in Seattle, Wash. (40, 43). The new process is stated to give yields of better than 95% relative to yields of 85 to 90% usually obtained from methanol oxidation. A single converter 5 feet in diameter has the equivalent throughput of from 20 to 50 of the smaller converters used in the old processes. Details are not available. The presence of from 5 t o 100 parts, preferably 30 parts, of sulfur per million parts of alcohol is claimed to suppress the formation of by-products in the oxidation, by usual means, of alcohols to aldehydes (141). A variety of organic sulfur compounds may be used with the alcohol-for example, with methanol which is to be oxidized to formaldehyde over a silver gage catalyst. The history of the presently used method for the manufacture of hydroquinone in the United States has recently been reviewed with an appraisal of uses and future prospects (165). The method described consists of the oxidation of aniline to quinone by means of an excess of manganese dioxide and sulfuric acid, steam distillation to separate quinone, and immediate hydrogenation to hydroquinone by a suspension of iron dust in water. Selenium dioxide is used for the oxidation of an N-(2-ketoalkyl)p-aminobenzoate compound to the corresponding N-(2,3dioxyalky1)-p-aminobenzoate compound (189). The method used is to mix an excess of selenium dioxide with the 2-keto alkyl compound and t o heat the mixture in a suitable inert solvent, such as acetic acid or toluene, to 80" to 150" C. Liquid-phase catalytic air oxidation of isobutyraldoxan, obtained by alkali catalyzed condensation of isobutyraldehyde, results in the formation of the hydroxy octanoic acid, 2,2,4-trimethyl-3-01-1-pentanoic acid (60). A diluent, such as isobutyl alcohol, is preferred and catalysts such as manganese acetate have been found suitable a t reaction temperatures below 60 C. Long-chain dibasic acids are produced in one step by treating under redox conditions a compound having a cyclic structure containing from four to ten carbon atoms in the primary ring and having a peroxide grouping attached directly t o one of the carbon atoms of the structure (163). For example, the peroxide compound derived from the reaction of cyclopentanone and hydrogen peroxide is treated under redox conditions t o produce sebacic acid in one step. By fusing an alkali metal hydroxide with a saturated munohydroxy monocarboxylic acid or its alkali metal salt the hydroxyl group of which is linked to a nonterminal, secondary carbon atom, it is claimed (127) that an improved flexible procedure for preparing dicarboxylic acids results. The hydroxy acid is cleaved a t the carbon atom linked to the hydroxyl group. The use of ozone for the oxidation of oleic acid to azelaic plus pelargonic acids in a new multimillion dollar plant of Emery Industries has been described (SI). Ozone is produced from oxygen in ozonizers designed and manufactured by Welsbach Corp. The performance of this plant is being watched with interest. Reaction of ethylene with saturated aliphatic carboxylic acids containing from one to five carbon atoms per molecule is claimed to occur under controllable conditions in the presence of peroxide activators to produce acids of higher molecular weight (7). Activators such as tert-butyl hydroperoxide and benzoyl peroxide are active a t 50" to 150' C., and materials like cumene hydroperoxide and di-tert-butyl peroxide are active at 125" to 250' C. The higher boiling fractions of synthetic organic products obtained by the Oxo synthesis reactions and containing acetals, ethers, alcohols, and esters may be oxidized with molecular oxygen in the presence of metallic soap catalysts to produce useful alcohols and acids (138). Oxo alcohols, themselves, may be jpO

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proved in color and odor by treatment with air and caustic soda washing (90). A method for the formation of relatively high molecular weight fatty acids and derivatives containing an odd number of carbon atoms is based on the selective oxidation of an olefin to form a saturated dihydroxy compound, followed by further oxidation to cause cleavage between the contiguous carbons of the diglycol (78). Hydrogen peroxide in glacial acetic acid solution is described as the oxidizing agent. Glycol esters may be formed by the reaction of an aldehyde, an unsaturated organic compound, and oxygen (89). Thus, reaction of equimolar proportions of acetaldehyde, propylene, and oxygen results in the formation of propylene glycol 0-acetate, and with larger proportions of acetaldehyde in the formation of propylene glycol diacetate. Oxidation catalysts, such as cobalt. acetate, ferric oxide, vanadium oxide, or platinum oxide, are used, ai, temperatures in the range of -20' to + l o " C. and in t h e presence of ultraviolet light. Research work over a period of years on the oxidation of acef aldehyde to acetic anhydride has led to the formulation of a reaction mechanism different from that generally assumed and which calls for part of the oxidation of acetaldehyde t o proceed directly to acetic anhydride ( 6 7 ) . Based on this reaction theory, the oxidation process has been modified to give materially higher yields of acetic anhydride, an example showing a 65% yield based on acetaldehyde converted. Improvement in the process for oxidizing acetaldehyde to glyoxal with nitric acid is claimed to result from the maintenance of suitably high concentrations of nitrous acid in the reaction mixture (114). The method described involves recycle nitric and nitrous acids, plus the recovery of unreacted aldehyde by cold water scrubbing of reaction gases. Continuation of previous work on the oxidation of synthetic drying oil films has resulted in the publication of data on phthalic alkyds modified with several unsaturated fatty acids (46). Previous work has described the oxidation of unsaturated fatty acid esters of pentaerythritol, glycerol, and dipentaerythritol. Graphs are presented of the film condition, peroxide accumulation, and change in ultraviolet light spectral absorption-all versus oxygen absorption. A new process for the low temperature production of oxidized oil gels has been described as combining some of the merits of both the scrim and the mechanical processes (184). The new process uses a randomly packed column in which there is a constantly flowing thin film of oil passing down, countercurrent to a stream of heated air. Oxidation of rubber continues to be of interest in connection with studies of age deterioration. Several papers were presented a t the Division of Rubber Chemistry of the AMERICAN CHEMICAL SOCIETY meeting in Buffalo, N. Y . (166). In the case of amine inhibited vulcanizates of natural rubber and GR-S, the rate of oxygen absorption in the constant-rate stage is a function of the square root of the partial pressure of oxygen in the aging atmosphere, indicating that amine-type antioxidants may function by the promotion of peroxide decomposition to stable products rather than to chain-initiating free radicals (164). The over-all rate of deterioration of physical properties increases with oxygen concentration, as would be expected from increased rate of oxygen absorption. In a continuation of the Case Institute of Technology studies of the oxidation of olefins structurally related t o GR-SI one of the possible repeating units of GR-S, 5-phenyl-a-pentene, has been studied (128). The rate of oxygen absorption by this olefin was much higher than thdt of GR-S. Hydroperoxide, carbonyl, ester, epoxide, acid, water, and carbon dioxide formation are compared. It has been observed ( 3 ) that the rate of oxidation of natural rubber vulcanizates increases directly as the surface area (square

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meters per gram) of carbon black increases from Thermax (19 square meters per gram) to Voltex (200 square meters per gram). An attempt is made to relate the observed effects to abrasion resistance, etc. The use of an isotropic technique for the study of rubber oxidation has been described (109). A water bomb has been used for studying the oxidation of elastomers (79). Ozone testing techniques have been described in a summary of latest developments in the field of synthetic elastomers ( 7 3 ) . I n connection with research on rubber, the oxidation initiation efficiencies of azobis(isobutyronitrile), benzoyl peroxide, and cyclohexenyl hydroperoxide have been evaluated in certain olefinic oxidations. In the case of the azo compound, it was indicated that primarily formed radicals initiate oxidation both by removing an a-methylenic hydrogen and by combining a t a double bond. It has been shown that the oxidation reactions of unvulcanized cold rubber and natural rubber films are inhibited by carbon black. Further work has shown that the piofound effect of carbon black on polymer oxidation reactions is influenced by the type of polymer and the type of oxidizing treatment and by the chemistry of the carbon surface (119). A mechanism for the oxidation of rubber which includes a probable mechanism of antioxidant action has been developed in which the antioxidant is considered capable of functioning in more than one way (166). Various anomalous observations are explained by the proposed mechanism. Various oxidizing media have been studied for the oxidation of bituminous coal to organic acids. I n this process, nitric acid seems unique in giving much higher product yields than other acid media-e.g., acid permanganate (168). The presence of oxygen promotes the nitric acid reaction and studies have been undertaken to determine effects of acid concentration temperature, time, and oxygen pressure on the reaction. Comparison of the results with those obtained in the alkali-oxygen process fail to show over-all advantages for the nitric acid process.

C O M B U S T I O N AND M E C H A N I S M STUDIES A broad survey of the phenomena associated nith the inflammability ranges in air, a t atmospheric temperatures and pressures, of some olefins, olefin oxides, ethers, and aldehydes has been initiated (18). The open tube method with inflammability ranges centered upon the stoichiometric mixture of combustible with air is being used. Results are shown in tabular form. Ethers and aldehydes show three ranges of inflammability, in order of increasing proportion-normal flames, nonIuminous a t lower limit, luminous a t upper limit, blue and two-stage flames, and cool flames. The influence of reduced pressures and elevated temperatures upon the range of inflammability of propane, ethylene, ethylene oxide, and dimethyl ether has been examined in closed tube experiments (19). Temperature has little effect either upon the lower limit, or upon the minimum pressure for flame propagation. This work shows that there is a close connection between the pressure limit and the relative pressure increase from burning upon inflammation near the limit. DIESEL FUELS

Substances such as alkyl thionitrites, nitrites, nitrates, peroxides, and nitro compounds improve the cetane number of Diesel fuels when added to the fuel. It has been found that, with the exception of tert-butyl hydroperoxide and 2-nitropropane, these additives are more effective when added in the vapor phase to the intake air of an engine than when added to the fuel (7'7). The effect of additive upon the cetane number of the fuel is related to the chemical nature of the fuel, and is greatest in the case of paraffinic fuels and least in the case of naphthenic fuels. A different mechanism appears to be concerned with the effect of additives in cetane number improvement and cold starting per-

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formance, on the basis of certain observed anomalies. A study of preflame reactions occurring in the Diesel engine with selected fuels, with and without added ignition accelerators, has been made to explore this point (76). As might be expected, preflame reactions arc related to the chemical nature of the fuel. Hydrocarbon oxidation under cold-starting conditions in a Diesel engine is characterized by the foimation of aldehydes, the extent of mhich reaction may determine the cold-starting qualities of the fuel. Delay period, however, seems dependent upon the extent of peroxide formation, determined by the fuel type and the nature of the additive Various catalysts of the auto-oxidation of saturated hydrocarbons in the liquid phase have been investigated to determine the influence of the metal in the organometallic compounds, the influence of ths organic part in organometallic compounds, and the catalytic influence of radical forming compounds (190) Organometallic compounds of copper, tin, lead, chromium, molybdenum, and similar bivalent metals dissolved in neutral coal tar oils have been claimed as additives to liquid hydrocarbon fuels to improve combustion ( I S ) . Compounds are of the type formed by the reaction of the metals with P-diltetones. dialdehydes, keto esters, and other substances having at least two double-bonded oxygen atoms attached to carbon atoms separated by a methylene or substituted msthylene group. Test data on five test Diesel fuels indicate that for fuels of essentially the same composition and volatility, the one with the highest cetane number may be expected to start a t a somewhat lower temperature than the lower cetane number fuel. A gain of possibly 15' F. may be obtained through fuel selection (193). Addition of cetane number improvers may 01 may not be as effective as the same natural cetane number. From observations it appears that tht. limit of effectiveness of presently available starting fluids is between -25' and -30" F. Engine starts a t lower temperatures are possible by warming starting fluid. At these low temperatures, vdrious other factors pertaining to engine equipment or condition may make starting difficult. The ignition quality of Diesel fuels may be evaluated with very small fuel samples by use of a modified Jentzsch ignition apparatus (100). Various Diesel fuel blends having cetane numbers from 29 to 110 were tested in two forms of this apparatus. Ignition characteristics of a large number of fuel types have been determined on the basis of the minimum spark ignition energies required a t 1 atmosphere and stoichiometric air-fuel mixtures (8.9). From the results a series of general rules were evolved; the application of these rules is claimed to permit prediction of ignition energy for almost any organic molecule. F L A M E VELOCITIES

The maximum burning vrlocities for 36 hj-drocarbon-air mixtures as predicated by the semiempirical thermal equation of Semenov have been compared with National Advisory Committee for Aeronautics experimental velocities and with those predicted b y the semiempirical Tanford and Pease diffusional equation (186). I n general, it was found that the diffusional equation predicts the burning velocity of the room temperature mixtures more closely than does the thermal equation. The thermal equation is more sensitive to a given percentage change in reaction rate constant than the diffusional equation. The Semenov thermal equation, however, closely predicts the burning velocities of ethylene and acetylene relative to propane when the newer and lower activation energies for the combustion reaction are used (186). Flame velocities for 25 fuels have been determined in order to evaluate the effects of burner variables, hydrocarbon structure, and chain length (2). Methods used were the angle method, requiring measuremellt of the slope angle of an element of the cone a t various burner radii, and the total area method. Agreement of results from the two methods was good. Burning veloci-

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ties for propylene-air and propane-air mixtures have been measured by the burner method using Schlieren photography and by the soap bubble method using direct photography (84). The results are compared with those obtained by other workers using various procedures. Details of the structure of Bunsen burner flames and the evaluation of flame speed a t burner flame tip have been discussed (117). The study indicates that there is appreciable ram of the central lamina of the Bunsen burner stream and that the accompanying pressure rise is much greater than the pressure build-up in the burner tube. T o account for certain anomalous results in the experimental phenomena observed in hydrocarbon flames, it has been postulated that formation of highly unsaturated chain polymers occurs and is followed by subsequent rapid breakdown to active fragments and the oxidation of these fragments (176). Among the anomalies explained are the data on carbon formation, the differences between premixed and diffusion flames, and the abnormal spectroscopic temperatures in the reaction zone of certain free radicals. Various hydrocarbons have been mixed, individually, with a mixture of acetaldehyde and air undergoing oxidation a t 150" to 250' C. t o determine the inhibiting action (169). I n general, the inhibiting effect increased with hydrocarbon chain length, with branching, and with unsaturation of the hydrocarbon. The crossing of reaction chains leads to inhibition. Reaction of hydrogen and bromine has been used in studies ( 4 9 )of flame propagation mechanism. Although recent developments in the theory of flamw have emphasized that flame propagation may be a function of diffusion and reaction of active chemical particles as well as of heat flow, there is still uncertainty as t o how these relations may be used in calculating or predicting flame properties. The experimental work was on the measurement of burning velocities and calculations were applied t o the mechanism of flame propagation. LOW TEMPERATURE OXIDATION

The static method of slow thermal oxidation of cyclopropane a t 380" to 430" C. and reactant partial pressures between 50 and 400 mm. mainly leads t o the formation of carbon monoxide and water with small amounts of carbon dioxide and formaldehyde (121). Experimental results from the low temperature oxidation of n-heptane accord with the concept of a slow branching reaction occurring via peroxides (71). Two peaks occur in the peroxide versus temperature curve for n-heptane oxidation, the first involves chain branching by oxygen attack on a tertiary C H of the hydroperoxide, and the second involves attack on a secondary CH. Studies have been made on the low temperature oxidation of methylcyelohexane in the vapor phase, using a continuous flow system (172). The predominance of straight-chain aldehydes in the oxidation products and the nature of the ketones found suggest that ring cleavage occurs a t an early stage of the oxidation process. Comparison with results of liquid-phase oxidation suggests that oxidative degradation is more severe in the vaporphase condition, The nature of the products indicates initial oxygen attack a t the tertiary carbon atom. FUEL PERFORMANCE

Experimental equipment was used to produce and study detonative combustion of gaseous inflammable mixtures precipitated in a shock tube by means of shock waves (129). Detonation velocities associated with shock waves were measured for oxygen mixtures with methane, ethane, propane, butane, hexane, hydrogen, diethyl ether, and acetylene. Experiments with diethyl ether and acetaldehyde as engine fuels have been performed under conditions of compression ignition (107). Information is given regarding fuel ratios, rela-

2007

tion of optimum compression ratio to mixture composition, power output, optimum ignition timing, and the nature of piston deposits. Indications are given that autoignition obtained by compression is a nuclear effect. I n further experiments to verify the validity of King's nuclei theory for detonation, methanol, acetaldehyde, and ether have been compared as fuels for the Cooperative Fuel Research ( C F R ) engine (106). Methanol cannot decompose in the engine t o the degree needed for nuclei formation and does not undergo autoignition. On the other hand, acetaldehyde and ether decompose easily and autoignition occurs at relatively low compression ratios. It is possible t o operate a standard CFR knock test engine without spark ignition with pentane, hexane, and heptane as fuels, provided the compression ratio is adjusted to maintain a particular standard of knock intensity (108). It is possible to operate the engine by compression ignition over an extremely wide range of fuel-air ratios, and many important ignition characteristics may be studied. The current theoretical concepts of steady-state flame propagation have been comprehensively received (70). The exhaust flames from a number of aero engines have been characterized as consisting of two components-the red component due to incandescent carbon particles in the exhaust and the blue component bordering the red cone and arising from the ignition of hydrogen and carbon monoxide present in the exhaust gases a t rich mixture engine operation ( 6 ) . The effect of various inhibitors, including hydrocarbons, on this blue component is discussed. Results of tests made to determine the relationship between quality of atomization of liquid fuel and stability of combustion have been published (4). Kerosine was used as the fuel sprayed from an air blast atomizer. I n connection with work toward formulation of lubricants of reduced flammability, the effects of structure, metal catalysts, and additives on the spontaneous ignition of organic compounds have been studied ('74). Over 40 compounds were studied, including straight-chain paraffins, a-olefins, primary alcohols, and symmetr rical ethers. A close parallel was observed between the spontaneous ignition temperature and antiknock performance in spark ignition engines. The effects of antiknock dopes and othei fuel additives, including tetraethyllead, methyl aniline, di-tert-butyl peroxide, acetaldehyde, and diethyl disulfide, on the cool flame and autoignition limits of n-heptane have been the subject of detailed investigation (126). Observations included: (1) tetraethyllead produces a broadening of the range of conditions for cool flame existence, (2) methyl aniline markedly retards the precool flame reactions, (3) di-tert-butyl peroxide greatly accelerates cool flame reactions, and (4)acetaldehyde is not a primary cause of knock with n-heptane. New inhibiting effects due to mercury atoms and molecular hydrogen during the initial stages of the oxidation of n-hexane in the range 260' to 290" C. have been reported (168). The observed effect is related t o combustion mechltnism in the aecompanying discussion. The ignition Characteristics of methane under high pressure have been re-examined (16)in connection with studies on knoeking in internal combustion engines. Ignition delays varied from 30 seconds at 17 atmospheres t o 90 seconds a t 45 atmospheres, the highest pressure used. Formaldehyde in large amounts was detected in the exhaust gases if the gas was exhausted during the delay period before ignition. The Research Laboratories Division of General Motors Corp. has produced flame photographs of three different engines running under a number of different conditions-afterrunning, autoignition, preignition, and knocking (191). Various interesting deductions are drawn from these results.

2008


MISCELLANEOUS

An accelerated laboratory test has been developed for determining fuel oil storage stability based on air oxidation ( 1 4 7 ) . This test can be used t o predict drum storage, to evaluate commercial oils, and to evaluate inhibitors. The mercury photosensitized oxidation of ethane a t 25 C. gives ethyl hydroperoxide as the main product, in agreement with the proposed peroxide mechanism of oxidation (83). Methane gives a product which is predominantly methyl hydroperoxide. Tests of fluorinated hydrocarbons as fire extinguishers show that those materials also containing bromine are superior to the nonfluorinated compounds now usedandaresuperior to fluorinated compounds containing chlorine (48). The fluorinated hydrocarbons show higher extinction efficiency and lower toxicity than the conventional methyl bromide and carbon tetrachloride. Materials of the type of @-alkylmercapto ketones are effective antioxidants for such diverse substances as lard, gasoline, styrene, and paraffin wax (176). Studies have been reported on the effect of various structural features of such materials on their effectiveness as antioxidants. The equation for predicting net heating values from the anilinegravity constant of petroleum hydrocarbons can be used for aviation fuels with a precision comparable to that of a single careful calorimeter measurement (72). The equation for predicting net heating values from aniline gravity or characterization factor and gravity can be used for all petroleum products, for which aniline points or ASTM distillations are possible, with sufficient accuracy for most engineering purposes. When burning acidic fuels such as acid sludges, acid tars, and other high sulfur refinery by-products corrosion is lessened by preheating the air used for combustion to over 300" F. and by handling the fuels in equipment made from suitable materials of construction (14%). T o speed up the oxidation testing of inhibited turbine oils, a rotary bomb oxidation test has been developed and described (179). This test is claimed to provide useful information, usually within a working day-much more rapidly than the ASTM Method D-943. O

SOLID CARBONACEOUS SUBSTANCES A process has been developed to gasify solid carbonaceous materials such as coal or coke breeze by means of such metal oxide oxidation carriers (60). A fluidized bed procedure is proposed with zones for oxidizing the metal or lower oxide with air and for reacting the oxidation carrier with carbonaceous matter. Steam may be added or used separately to introduce hydrogen when wanted in synthesis gas mixtures. The experimental work of the U. S. Bureau of Mines on the gasification of pulverized coal with oxygen and steam in a Vortex reactor has been described in various articles and was summarized in 1952 (68). A review of some of the aspects of the gasification of coal in fluidized beds has been published (96). Kinetics of the combustion of carbon has been studied with carbon cylinders placed in high temperature, high velocity air streams (112). Data obtained indicate that the reaction rate should change from diffusion controlled to chemically controlled as the air velocity is increased to some limiting value. At high air velocities the reaction rate approaches that predicted on the basis of the Arrhenius equation. I n the removal of carbon deposits from petroleum cracking catalysts by combustion with air, i t is claimed that the oxidation may be materially limited to the formation of carbon monoxide by introducing into the combustion air stream small propoi tions of chlorine plus a chloride of silicon, zirconium, titanium, or aluminum (87). The purpose of such limitation is to reduce the heat release and attendant temperature rise of the catalyst, thereb y reducing the likelihood of damage.

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The oxidation of carbon black b y air in a closed system was studied a t 367" C. in the presence of ten different potassium salts and the chlorides of six different metals (139). Basicity of the catalyst seems important, since potassium carbonate and orthophosphate are very active, whereas potassium metaphosphate shows almost no activity. The oxidation of graphite, Nuchar, and sugar charcoal by air was studied in the presence of different catalysts. Apparent activation energies of the uncatalyzed and potassium carbonate catalyzed oxidation were determined (1.40). The oxidation of industrial diamond, bort, has been studied a t various temperatures and in proximity of certain other substances (194). Oxidation of bort is markedly decreased in the presence of certain substances such as tungsten carbide, tungsten, cobalt, and graphite. Bort larger than -10 14 mesh shows virtually no oxidation or loss when heated a t 500" C. for periods up to 3 hours.

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MISCELLANEOUS

A review of the chemistry of the isotopes of oxygen has been published (61). I n order to find a more economical process than distillation or thermal diffusion for the concentration of oxygen-18, a chemical exchange method has been developed (14). Carbon dioxide gas is fed to the bottom of a packed tower, countercurrent to water reflux fed to the top of the column. The stream of carbon dioxide from the top of the column is enriched with respect to heavy oxygen and is reduced with hydrogen over a catalyst to methane and water. The water is condensed and returned t o the column as reflux a t the top. Water withdrawn from the bottom of the column is depleted with respect to heavy oxygen and is discarded. Ammonia in the streams increases the carbon dioxide solubility and results in higher exchange. Results are reported in terms of separation factor or relative volatility and height of column packing equivalent to an equilibrium stage. The effect of different variables on the production of ozone during the electrolysis of sulfuric acid, including current density, acid concentration, temperature, and nature of the diaphragm, has been studied (160). At low temperatures, below 0" C., current efficiencies of u p to about 32% were realized, with energy yields of up to 10.8 grams per kw.-hr. The principles and applications of oxygen recorders have been described (148). The discussion includes techniques available for measuring combustion efficiency, the principles of various commercial analyzers, and sampling systems. Analysis of small amounts of oxygen dissolved in hydrocarbon liquids is frequently of considerable importance. A method has been developed which is based on stripping the dissolved oxygen into a stream of pure nitrogen, followed by analysis of the gaseous oxygen b y an improved version of the MacHattie-Maconachie method of reaction with copper (16). Reliable determinations of oxygen in gases were obtained in a concentration range of 0.003 to 2% with gas samples of 150 ml. The use of heavy oxygen in the analytical determination of oxygen in organic compounds has been described (88). Semimicrodetermination methods used a t the U. S. Bureau of Mines for oxygen in organic compounds have been described (94). These methods were used in connection with studies of products obtained in the liquid fuels development program. A number of techniques have been advocated and used for the combustion of noxious odors in gas streams, organic fumes, and other waste products. Thus, oxidation with ozone, when preceded by proper pretreatment, appears to provide an economical solution to the destruction of phenols in a wide variety of industrial wastes (13.4). The optimum pH for a particular coke oven waste lies near p H 11.8. Pure phenols undergo oxidation by ozone over a wide p H range. Combustion of odors in stack gases at refineries, from paint drying ovens, and so on, has been claimed to result in the effective elimination of nuisances and, in some instances, recovery of by-product heat by the Oxy-Catalyst, Inc.,

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unit developed b y Houdry (58, 120). The msthod uses an alumina supported platinum oxidation catalyst. Another technique makes use of platinum coated alloy metal ribbon bundles as the catalyst (167). Air blowing of sulfite paper mill liquors in towers has been adapted b y the Weyerhaeuser Timber Co. mill in Springfield, Ore. (30). The process developed in England in 1936 for the decomposition of organic sulfur compounds in cool gas by oxidation over a nickel subsulfide catalyst at temperatures of 220 O to 370' C. has been described recently (86). Thiophene is not decomposed and most of the residual sulfur in the gas after suitable scrubbing consists of thiophene. The controlled oxidation of anhydrous ammonia to nitrogen and water for the production of neutral atmospheres has been described (166). Platinum and/or rhodium catalysts are used with ammonia preheat temperatures of 500 O C . Polyhydric phenols act as promoters for the oxidation b y air of acidic sulfur compounds, such as mercaptans, contained in petroleum products (10). Of the compounds tested as promoters, 3isopropoxycatechol was found to be most effective. It is claimed that 80 to 83% yields of chlorine dioxide may be obtained from the decomposition reaction of acidified chlorate solutions by the improvement of recycling to a reaction column the spent solution from the process (185). Such recycle permits control of concentrations while maintaining proper reaction proportions of reagents. In the production of chlorine b y the oxidation of hydrogen chloride, i t has long been known that copper catalysts are effective inkromoting the reaction. One difficulty in the use of fixed bed catalysts of this type has been the rapid catalyst deterbration by vaporization loss of copper. It has been proposed to overcome this difficulty b y means of an arrangement of apparatus in which catalyst circulates and functions as a fluidized bed in the reaction zone (8). Hydrogen peroxide is finding increasing use in the bleaching of paper pulp ( I ) , and has now become the most commonly used bleaching agent in the textile industry (162).

LITERATURE CITED (1) Aitken, K. G., C a n . Chem. Processing, 37, No. 2, 42-4 (1953). (2) Albright, R. E., Heath, D. P., and Thena, R. H., IND.ENG. CHEM.,44, 2490-6 (1952). (3) Amerongen, G. 3. van, Ibid., 45,377-9 (1953). (4) Anson, D., Fuel, 32, 39-51 (1953). (5) Armstrong, G. P., and Turck, K. H. W. (to Hercules Powder Co.), U. S. Patent 2,619,510 (Nov. 25, 1952). (6) Baldwin, R. R., Fuel, 31,312-40 (1952). (7) Banes, F. W., Fitz Gerald, W. P., and Nelson, J. F. (to Standard Oil Development Co.), U. 5. Patent 2,585,723 (Feb. 12, 1952). (8) Belschetz, Arnold (to M. W. Kellogg Co.), U. S. Patent 2,602,. 021 (July 1, 1952). (9) Bogart, M. J. P., Schiller, G. R., and Coberly, C. J., Petroleum Processing, 8,377-82 (1953). (10) Bond, D. C. (to The Pure Oil Co.), U. 5. Patent 2,600,465 (June 17, 1952). (11) Booser, E. R., and Fenske, M. R., IND. ENG.CHEM.,44,1850-6 (1952). (12) Bordenca, C. (to Sloss-Sheffield Steel & Iron Co.), U. 8. Patent 2,619,506 (Nov. 25, 1952). (13) Bottoms, R. R. (to National Cylinder Gas Co.), Ibid., 2,591,503 (April 1, 1952). (14) Boyd, W. T., and White, R. R., IND. ENG.CREM.,44, 2202-7 (1952). (15) Broatch, J. D., and Egerton, A. C., Fuel, 31,494-6 (1952). (16) Brooks, F. R., Dimbat, M., Treseder, R. C., and Lykken, L., Anal. Chem., 24, 520-4 (1952). (17) Burgoyne, J. H., and Cox, R. A., J . Chem. SOC., 1953, 876-83. - . _. (18) Burgoyne, J. H., and Neale, R. F., Fuel, 32,5-15 (1953). (19) Ibid., pp. 17-27. (20) Burt, William E. (to Ethyl Corp.), U. S. Patent 2,593,098 (April 15, 1952). (21) Burt, W. E,, Burt, J. T., and Ligett, W. B. (to Ethyl Corp.), Ibid., 2,593,097 (April 15, 1952).

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(22) Cadle, R. D., and Schadt, Conrad, J . Am. Chem. Soc., 74, 6002-4 (1952). (23) Calcote, H. F., Gregory, C. A., Jr., Barnett, C. M., and Gilmer, R. B., IND. ENG.CREM..44, 2656-62 (1952). (24) Calingaert, Geo. (to Ethyl Corp.), U. S. Patent 2,593,099 (April 15, 1952). (25) Ibid., 2,593,100 (April 15, 1952). (26) Campbell, T. W., and Coppinger, G. M., (to the United States of America), Ibid., 2,610,972 (Sept. 16, 1952). (27) Can. Chem. Processing, 37, No. 5, 50-2 (1953). (28) Chem. Age, pp. 593-5 (Nov. 1, 1952). (29) Chem. Eng., 59, No. 9, 208-11 (1952). (30) Ibid., pp. 232-5. (31) Ibid.. DD. 246-8. (32) Ibid.; N o . 11, p. 114; 60, No. 2, 134-8 (1953). (33) Ibid., p. 104. (34) Chem. Eng. News,30,4746 (1952). (35) Ibid., 31,400 (1953). (36) Ibid., p. 434. (37) Ibid.. D. 2072-3. (38) Chementator, Chem. Eng., 59, N o . 11, 108-12 (1952). (39) Ibid., 60, 102 (1953). (40) Ibid., pp. 104-8. (41) Chem. W e e k , p. 34 (Dee. 13, 1952). (42) Ibid., p. 5 (Jan. 31, 1953); p. 60 (April 11, 1953). (43) Ibid., pp. 67-8 (Feb. 28, 1953). (44) Ibid., pp. 70-2 (April 11,1953). (45) Ibid., p. 46-8 (May 23, 1953). (46) Chipault, J. R., Nickell, E. C., and Lundberg, W. O., Oficial Dig. Federation P a i n t & Varnish Production Clubs, 328, 319-28 (May 1952). (47) Cole, R. M., Dunn, C. L., and Pierotti, G. J. (to Shell Development Co.), U. s. Patents 2,606,932 and 2,606,933 (Bug. 12, 1952). (48) Coleman, E. H., Fuel, 31,445-7 (1952). (49) Cooley, S. D., and Anderson, R. C., IND.ENG. CHEM.,44, 1402-6 (1952). (50) Cooper, L. E., and Lacey, R. N. (to British Industrial Solvents, Ltd.), U. S. Patent 2,623,068 (Dec. 23, 1952).

(51) Coover, H. W., and Dickey, J. B. (to Eastman Kodak Co.), Ibid., 2,585,229 (Feb. 12, 1952). (52) Corrigan, T. E., Petroleum Refiner, 32, No. 2, 87-90 (1953). (53) Cotton, W. J., U. S. Patent 2,595,227 (May 6, 1952). (54) Darragh, J. L., and Miller, R. J., (to CaliforniaResearch Corp.), Ibid., 2,610,211 (Sept. 9, 1952). (55) Deansly, R. M. (to Universal Oil Products Co.), U. S. Patent 2.587.703 (March 4. 1952). (56) Detling; K. D., and Guinn, V. P. (to Shell Development Co.), U. S. Patent 2,620,358 (Dee. 2, 1952). (57) Detling, K. D., and Skei, Thurston (to Shell Development Co.). Ibid., 2,608,585 (Aug. 26, 1952) (58) Ibid., 2,614,125 (Oct. 14, 1952). (59) Diamond, H., Kennedy, H. C., and Larson, R. G., IND.'ENG. CHEM.,44, 183443 (1952). (60) Dickinson, N. L. (to The M. W. Kellogg Co.), U. S. Patent 2,602,809 (July 8, 1952). (61) Dole, Malcolm, Chem. Revs., 51,263-301 (1952). (62) Dougherty, C. F., Jr., and Chapman, C. C. (to Phillips Petroleum Co.), U. 9. Patent 2,615,921 (Oct. 28, 1952). (63) Doumani, T. F., Coe, C. S., and Attane, E. C., Jr. (to Union Oil Co. of Calif.), Ibid., 2,621,205 (Dee. 9, 1952). (64) Drabkin, A. E., and Soloveichik, Z. V., J . A p p l . Chem. (U.S.S.R.), 23, 1405-8 (1950); 24, 549-56 (1951). English trans., Consultants Bureau, New York, N. Y . (65) Durham, R. W., and Steacie, E. W. R., J . Chem. Phus., 20, 682-5 (1952). (66) Egloff, G., Oil GUSJ.,51, NO,49,124-35 (1953). (67) Elce, Alec, Stanley, H. M., and Turck, K. H. W., (to The Distillers Co., Ltd.), U. S. Patent 2,622,098 (Dee. 16, 1952). (68) Elliott, M. A., Perry, H., Jonakin, J., Corey, R. C., and Khullen, M. L., IND. ENG.CHEM.,44,1074-82 (1952). (69) Erkko, E. 0. (to Hercules Powder Co.), U. S. Patent 2,604,495 (July 22, 1952). (70) Evans, M. W., Chem. Revs., 51, 363430 (1952). (71) Fallah, A., Long, R., and Garner, F. H., Fuel, 31,403-8 (1952). (721 . . Pein. R. S.. Wilson. H. I.. and Sherman. Jack. IND.ENG. CHEM.,45, 610-14'(1953). (73) Fisher, H. L.. I n d i a Rubber World. 127, No. 5, 1953. (74) Frank, C. E., and Blackham, A. U., IND.ENG. CHEM.,44, 862-7 (1952). (75) Gardon, A. C., Ibid., 44, 1857-9 (1952). (76) Garner, F. H., Malpas, W. E., Morton, Frank, Reid, W. D., and Wright, E. P., J. Inst. Petroleum, 38, 312-29 (1952). (77) Garner, F. H., Morton, Frank, Nissan, A. H., and Wright, E. P., Ibid., 38, 301-12 (1952).

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(78) Gebhart, A. L., and Ross, John (to Colgate-Palmolive-Peet C o . ) . U. S. 2.585.129 (Feb. 12. 1952). (79) Gillman, H. H., and Haines, 'W. il.,Jr., Rubber A g e , 71, SO.6 , 767-71 (1952). (80) Goodings, E. P., and Hadley, D. J. (to Distillers Co., Ltd.), C. S.Patent 2,593,437 (April 22, 1952). . 181) Gottschall, W., Kolling, H., and Hagemann, 9. (to Ruhrschemie Aktiengesellschaft, Oberhauien-Holton, Germany), Ibid..2.602.812 (Julv . - 8. 1952). ( 8 2 ) Graham, W., Cudmore, J. G., and Heyding, R. D.. J. - , Can. Technol., 30, 143-52 (1952). (83) Gray, J. A,, J . Chem. Soc., 1952, 31150-4. (84) Gray, K. L., Linnett, J. W., and MelIish, C. E., T r a n s . F a m d a y Sbc., 48, 1155-63 (1952). (85) Griffieth, R.H., IND.ENG. C H E M . , 1011-14 ~~, (1952). (86) Grosae, A. V., J . Am. Chem. Soc., 75, 1261 (1953). (87) Grosse, A. V., G. S. Patent 2,600,360 (June 10, 1952). D., A n a l . Chem., 24, 584-5 (88) Grosse, A. V.,and Kirshenbaum, -4. (1952). (89) Hackmann, J. T. (to Shell Developinent Co.), U. S. Patent 2,600,054 (June 10, 1952). (90) Hale, C. H. and Starr, C. E., Jr. (to Standard Oil Development Co.), Ibid., 2,595,785and 2,596,786 (May 6, 1952). (91) Hass, H. B., and Alexander, L. G. (to Purdue Research Foundar tion), U. S. Patent 2,609,401 (Sept. 2, 1952). (92) Hass, H. B., and Shechter, H., J . Am. Chem. Soc., 75, 1382-4 (1953). (93) Heider, R. L. (to Monsanto Chemical Co.), G. S. Patent 2,606,160 (Aug. 5, 1952). (94) Hinkel, R . D., and Raymond, R., A n a l . Chem., 25, 470-9 (1953). (95) Holroyd, R. H., Chemistry and I n d u s t r y , 1952, 439-40. (96) Hull, D. C. (to Eastman Kodak Co.), U. S. Patent 2,588,388 (March 11, 1952). (97) Hurley, F. R. (to Monsanto Chemical Co.), Ibid., 2,598,642 (May 27, 1952). (98) Hutchinson, W. R.1. (to Phillips Petroleum Co.), Ibid., 2,618,662 (Nov. 18, 1952). (99) Jacolev, Leon, and Gaucher, L. P. (to The Texas Co.), Ibid., 2,606,826 (Aug. 12, 1952). (100) Johnson, J. E., Crellin, J. W., and Carhart, H. W., IXD.ENG. CHEM.,44, 1612-18 (1952). a (101) Johnson, R. (to Koppers Co., Ino.), U. S. Patent 2,595,265 (May 6,1952). (102) Joris, G. G. (to Allied Chemical 6: Dye Corp.), U. S. Patent 2.613.227 (Oct. 7, 1952). (103) Ibid., 2,619,509 (Nov. 25, 1952). (104) Ibid., 2,621,213 (Dec. 9, 1952). (105) Keith, P. C. (to M. W. Kellogg Co ), Ibzd., 2,616,898 (Sov. 4, 1952). (106) King, R. O., and Allan, A. B., Can. J . Technol., 30, 44-60 (1952). (107) King, R. O., Durand, E. J., Allan, A. B., and Hansen, E. J. T., Zbid., 30, 29-43 (1952). (108) King, R. O., et al., Zbid., 30, 222-57 (1952). (109) Kirshenbaum, A. D., Streng, A. G., and Nellen, A. H., Rubber Age, 72, NO. 5, 625-30 (1953). (110) Kreulen, D. J. W., J . I n s t . Petroleum, 38,445-8 (1952). (111) Ibid., pp. 449-57. (112) Kuchta, J. iM., Kant, A,, and Damon, G. H., IND.EKG.C H m r . , 44, 1559-63 (1952). (113) Lamb, F. W. (to Ethyl Corp.), C. S. Patent 2,593,156 (April 15, 1952). (114) Lehmann, R. L., and Lintner, J. (to Bozel-Maletra Soc. Ind. de Produits Chem., Paris), Ibid., 2,599,335 (June 3, 1952). (11.5) Levy, Norman ( t o Imperial Chemical Industries, Ltd.), Ibid., 2,585,478and 2,585,479 (Feb. 12, 1952). (116) Lewis, W. K., and Gilliland, E. R. (to Standard Oil Development Co.), I b i d . , 2,603,608 (July 15, 1952). (117) Lichty, L. C., IND. ENG.CHEM.,44, 1396-8 (1952). (118) Lynch, C. S., and Corner, E. S. (to Standard Oil Development Co.), U. S. Patent2,588,260 (RIarch4, 1952). (119) Lyon, F., Burgess, K. A., and Sweltzer, C. W., piesented before the Division of Rubber Chemistry, AM. CHEM. SOC., Boston, Mass., May 27-29, 1953. (120) bIcCabe, L. C., IND. ENG.CHEM.,45,109A-112A (March 1953). (121) McEwan, A. C., and Tipper, C. F. H., Nature, 170, 462 (1952). (122) McKmnis, A. C. (to Union Oil Co. of Calif.), U. S. Patent 2,596,421 (May 13, 1952). 1123) -Mawer. F. C. (to Imaerial Chemical Industries, Ltd.), Ibid., 2,585,483 (Feb. 12, i952). (124) Mayland, B. J. (to Phillips Petroleum Co.), I b i d . , 2,609,382 (Sept. 2,1952). (125) Ibid., 2,618,543 (A-ov. 18, 1952). (126) AMelby,A. O., J . I n s t . Petroleum, 38, 965-73 (1953).

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Vol. 45, No. 9

(127) Mikeska, L. -1.(to Standard Oil Development Co.), U. S. Patent 2,614,122 (Oct. 14, 1952). (128) MitcheI, G. R., and Shelton. J. R., IND.ENG. CHEM?., 45, 386-92 (1953). (129) Morrison, R. B., Univ. Michigan, Dissertation Abstr., 12, No. 4. 456 (1952). (130) Mulcahy, M. F. R:,and Watt, I. C., Proc. Roy. Soc. (London), A216,lO-29,30-44 (1953). (131) Murphy, C. h4., and Ravner, H., IND.ENG.CHEaf., 44,1607-12 (1952). (132) Nelson, J. W.(to Sinclair Refining Co.), U. S. Patent 2,610,974 (Sept. 16, 1952). (133) hTeuhaus, Max, and Sommer, N. B., Petroleum Processing, 7, 641-6 (1952). (134) Niegowski, 9. J., IND. EXG.CHEM.,45, 632-4 (1953). (135) Nieuwenhuis, H. K., Chem. W e e k , p. 30-9 (May 2, 1953). (136) Oil Gas J., 51, No. 29, 159 (1952). (137) Oil Gas J., 52, No. 3, 246 (1953). (138) Owen, J. J., and Fasce, E. V. (to Standard Oil Development '20.).U. S.Patent 2.594.341 (ilaril29. 1952). (139) Patai,'S., Hoffmann, E., and Raibenback, L.', J . A p p l . Chem., 2,306-10 (1952). (140) I b i d . , pp. 311-14. (141) Payne, W.A , , and Vail, W. E. (to E. I. du Pont de Nemours & Co.), U. S.Patent 2,618,660 (Xov. 18, 1952). (142) Petroleum Processing, 7, 806-7 (1952). (143) Pines, H., Kvetinskas, B., Ipatieff, V. N. (to Universal Oil Products Co.), U. S.Patent 2,614,130 (Oot. 14, 1952). (144) Plisev, A. K., and Bykovets, A. I., J . A p p l . Chem. (U.S.S.R.), 23, 1357-9 (1950). English trans., Consultants Bureau, New York, N. Y . (145) Porter, C. R., and Wood, B., J . I n s t . Petroleum, 38, 877-81 (1952). (146) Reeder, W.H., I11 (to Clark Bros. Co.), U. S. Patent 2,590,124 (March 25, 1952). (147) Rescorla, A. R., Gromwell, J. H., and Milsom, D., A n a l . Chem., 24, 1959-64 (1952). (148) Riggs, 0. W., Instruments, 26,248-51, 280-8 (1953). (149) Robertson, -4.E., and Jones, A. R. (to Standard Oil Development Co.), U. 9. Patent 2,605,290 (July 29, 1952). (150) Robeson, M. O., and Blundell, S.A., Jr. (to Celanese Corp. of ilmerica),I b i d . , 2,612,525 (Sept. 30, 1952). (151) Robinson, P. L., and Smith, E. J., J . Chem. Soc., 1952, 3895-904. (152) Robinson, W. E.. Heads. H. H.. and Hubbard. A . B.. IND. ENG.CHEM.,45, 788-91 (1953). (153) Roedel, M. J. (to E. I. du Pont de Nemours & Co.), U. S. Patent 2,601,223 (June 24, 1952). (154) Rollman, 11'. F. (to Standard Oil Development C o . ) , Ibid., 2,604,479 (July 22, 1952). (155) Rosenblatt, E. F., and Cohn, J. G. (to Baker & Co., Inc.), Ibid., 2,601,221 (June 17, 1952). (156) Rubber A g e , 72, S o . 1 (1952). (157) Ruff, R. J., I n d . Gas ( U . S.),30, March 1953. (158) Savich, T. R , and Howard, H. C., IND.ENG.CHEM.,44, 1409-11 (1952). (159) Sayre, J. E., Chem. E n g . S e w s , 30,5138-42 (1952). (160) Seader, J. D., and Tobias, C. W., IND. ENG.CHEM.,44, 2207-11 (1952). (161) Sears, G. W., Jr. (to E. I. du Pont de Nemours & C o . ) , U. S. Patents 2,615,899, and 2,615,900 (Oct. 28, 1952). (162) Secord, R. A., Am. Duestuff Reptr., 41, No. 19, 581-4 (1952). (163) Shearon, W. H., Jr., Davy, L. G., and \'on Bramer, H., IXD. EKG.CHEX,44, 1730-5 (1952). (164) Shelton, J. R., and Cox, W.L., Ibid., 45,392-401 (1953). (165) Shelton, J. R., and Cox, W. L., presented before the Division of Rubber Chemistrv. i i ~ CHEV. . SOC.. Boston. Mass.. May 27-29, 1953. (166) Sherwood, P. W., Petroleum Processing, 8, 1633-8 (1952). (167) Sherwood. P. W., Petroleum ReJiner. 32, KO,3, 113-17 (1953). (168) Small, N. J. H., and Ubbelohde, A . R., J . Chem. Soc., 1952. 4619-28. (169) Ibid., 1953, 637-426. (170) Stormont, D. H., Oil Gas J . , 51, No. 40, 106-7, 128 (1953). (171) Sullivan, F. W., Jr., U. S.Patent 2,600,444 (June 17, 1952). (172) Temple, R. G., Long, R., and Garner, F. H., Fuel, 32, 117-19 (1952). (173) Thomas, C. J. (to Phillips Petroleum Co.), U. S. Patent 2,622,088 (Dee. 16, 1952). (174) Thomas, J. H., T r a n s . Faraday Soc., 48, 1142-9 (1952). (175) Thomas, N., J. Chem. Pkys., 20,899-904 (1952). (176) ENG. . , ThomDson. R. B.. Chenicek. J. A., and Symon, Ted, IND. C H ~ M44, . , 1659-62 (1952). (177) Toland. W. G., Jr. (to California Research Corp.), U. S.Patent 2,587,666 (March 4, 1952). I

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September 1953

(178) Trent, C. H., and Zucrow, M. J., IND.ENG.CHEM.,44,2668-73 (1952). (179) Von Fuchs, G. H., Claridge, E. L., and Zuidema, H. H., Am. Soc. Testing Materials, Bull. 186, pp. 43-6 (December 1952). (180) Wadsworth, F. T. (to Pan-American Refining Corp.), U. S. Paten’12,586,128 (Feb. 19, 1952). (181) Ibid., 2,589,648 (March 18, 1952). (182) , . Wadsworth. F. T.. and Smith. F. J.. IND. ENG.CHEM..45. 217-21 (i953). ’ (183) Wagner, E. (to Deutsohe Gold-u-Silber Scheideanstalt Y. Roessler), U. S. Patent 2,605,168 (July 29, 1952). (184) Walker, F. T., and Mackay, T., J. A p p l . Chem., 2, 344-52 (1952). I

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(185) Walker, P. L., Jr., and Wright, C. C., J . Am. Chem. Soc., 74, 3769-71 (1952). (186) Ibid., 75,750-1 (1953). (187) Wan, Shen-Wu, IND.ENG.CHEM., 45,234-8 (1953). (188) Weber, Geo., Oil Gas J., 51, No. 29, 118-19 (1952). (189) Weisblat, D. I., and Magerlein, B. J. (to The Upjohn Co.), U. 5.Patent 2,615,040 (Oot. 21, 1952). (190) Wibant, J. P., and Strang, A., Koninkl. Ned. A k a d . Wetenschap., Proc., Ser. B,55, 207-18 (1952). (191) Withrow, L. L., and Bowditch, F. W., S.A.E. Quart. Trans., 6 , 724-52 (1952). (192) Wood, W. S., Chemistry &Industry, 1953,2-6. (193) Young, H. D., Petroleum Engr., 25, C-10-20 (1953). (194) Young, R. S., and Benfield, D. A,, J . A p p l . Chem., 2, 320-53 (1952).

POLYMERIZATION mg

CHARLES C. WINDING and HERBERT F. WIEGANDT CORNELL UNIVERSITY, ITHACA, N. Y.

The number of 1959 publications dealing with polymerization” was approximately the same as For the previous year. The polymeric soil conditioners received much attention, but other less-publicized developments may b e even more important. N e w catalysts end continuous processes For synthetic rubber indicated that marked changes are certain to occur in this field. The disposal of the government rubber plants moved one more step toward reality. The newer fibers began to reach the ultimate consumer in relatively large quantities and brought to light many new problems. The epoxy resins gained a foothold among the coating and adhesive resins. Behind the more sDectacular developments was a remarkable increase in Droduction capacity For polyethylene, the vinyls, and nylons.

T

HE number of publications dealing with various phases of the unit process of polymerization appears to be leveling off. The previous review of this series (533) for 1951 covered 585 references; 557 are cited for 1952. However, predictions of present and future production of polymeric materials indicate that plastics, rubbers, fibers, coating materials, and adhesives are all still growing at a remarkable rate and will continue to do so. Without doubt the most publicized development in the field of of polymers in 1952 was the public announcement of soil conditioners and the race to get them into the hands of the consumer. The resulting controversy over their effectiveness probably will not be settled for years to come. The rubbers also received considerable attention both because of the imminent disposal of government plants and the announcement of new catalysts and processes. The new fibers reached the more or less confused consumer bringing new problems but little or no reduction in proposed new plants and expansion of existing capacity. The few new polymers that emerged from pilot plants appeared to be headed for specialty uses rather than competition with existing materials. Behind the more spectacular developments was a remarkable increase in production capacity for polyethylene, the vinyls, and nylons. This review attempts to cover 1952 material directly related to the unit process of polymerization, including general theoretical aspects, reaction mechanisms and kinetics, effect of all types of addition agents on reactions, monomeric reactants and resulting polymers, reaction conditions, complete processes, apparatus, and descriptions of existing plants. It does not include publications dealing exclusively with production statistics, uses, applications, structure, properties, or modifications of high polymers. However, many of the references cited may be devoted in part to such subject matter. Eight general reviews (220, 346-347, 978, 288,473, 514) other than the preceding one of this series, appeared during 1952.

CATALYSTS, ACTIVATORS, MODIFIERS, AND INHIBITORS

In the petroleum industry, catalYsts and reaction conditions are selected to produce low molecular weight polymers; usually dimers, trimers, and tetramers. Anderson (18) used alumina-silica isomerization catalysts followed by aluminum chloride polymerization catalysts to produce lubricating oils from olefinic FischerTropsch fractions. Bailey (43) polymerized olefins using silica gel impregnated with nickel and aluminum oxides. Boron trifluoride was employed to polymerize propylene (101 ) and, in an ether complex, to form polyisobutylene (473). Phosphorus pentoxide catalysts were investigated by Kolfenbach and Small ($86)and Meerbott (352). Ortho phosphoric acid was also suggested (98, 270, 876) for olefinic polymerizations. Krug (296) polymerized monoijlefins in the presence of boron phosphate. I n the formation of high polymers by addition polymerization, most catalysts actually initiate the reaction by free-radical or ionic mechanisms rather than by true catalytic action, but many authors do not distinguish between catalysis and initiation. It is beyond the scope of this review to attempt to make such distinctions and the words “catalyst” and “initiator” will be used synonymously. Per compounds, azo compounds, and Grignard reagents initiate polymerizations by forming free radicals which react with, and activate, monomers. Three general reviews (856, 346, 400) of this type of initiation were published. Adman and Wagner (26) conducted experiments to investigate the degree of conversion and molecular weight as a function of type and concentration of initiators. Sengupta and Palit (443) compared induction times and reaction rates at different temperatures for persulfate and peroxide catalysts. Cooper (124, 186) studied the effect of peroxide structures on the rate of the initiation reaction. The following peroxide catalysts were proposed: a,a’-dialkylarylmethyl hydroperoxides (607), phthaloyl peroxide (511), acrylyl and cyclic succinyl peroxides (376), peroxides of vinylcyclopentene (68), p-hydroxydialkyl peroxides (63),pinacolone peroxide (376), and alkyltetrahydronaphthalene hydroperoxide (411). Reynolds, Wicklatz, and Kennedy (413) speeded up GR-S

Oxidation - Industrial & Engineering Chemistry (ACS Publications)

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