INDUSTRIAL AND ENGINEERING CHEMISTRY
1974
(21) Ibid., 2,486,485 (Nov. 1 , 1949). (22) hfcBee, E. T., and Newcomer, J. S. (to U. S. A., represented by Atomic Energy Commission), U. S. Patent 2,506,428 (May 2, 1950). (23) iMcRae, J. A., Bannard, R. A. B., and Ross, R. B., Can. J. Research, 28B, 73-82 (1950). :24) Malinovskii, M. S., J. Gen. Chem. (U.S.S.R.), 19, 130-3 (1949). (25) hlavity, J. M. (to Universal Oil Products Co.), U. S. Patent 2,517,692 (Aug. 8, 1950). (26) Murai, H., J . Agr. Chem. SOC.J a p a n , 23, 35-7 (1949). (27) Norris, J. F., and Sturgis, €3. M., J . Am. Chem. SOC.,61, 1413-17 (1939). (28) Oda, R., and Ogata, Y., J. Soc. Chem. Ind., J a p a n , 44, Suppl. Binding 427 (1941). (29) Pajeau, R., Bull. SOC. chiin. France, 1949, 590-1. (30) Pajeau, R., and Fierens, P., Ibid., pp. 587-9. (31) Rothstein, E., and Saville, R. W., J. Chem. SOC.,1949, 1946-9. (32) Ibid., pp. 1950-4. (33) Ibid., pp. 1954-8. (34) Ibid., pp. 1959-61. (35) Ibid., pp. 1961-8. (36) Schrnorling, L. (to Vniversal Oil Products CO.), U. S. Patent 2,481,158 (Sept. 6, 1949).
Vol. 43, No. 9
(37) Shah, D. N., and Shah, N. M., J. Univ. Bombay, Sect. A, 18, 25-8 (1949). (38) Shishido, K., J. SOC.Chem. Ind., J a p a n , 45, Suppl. Binding 16972 (1942). (39) Shishido, K., and And& S., Ibid., 44, Suppl. Binding 361b-3b (1941). (40) Smyth, G. M., and Moran, A. E. (to American Cyanamid C o . ) , U. S. Patent 2,496,894 (Feb. 7 , 1950). (41) Somerville, W. T., and Spoerri, P. E., J. Am. Chcm. SOC.,72, 2185-7 (1950). (42) Ungnade, H. E., and Crandall, E. W., Ibid.. 71, 3009-10 ( 1949). (43) Van Ber'g, C. F. (to Standard Oil Developmcnt C o . ) , U. S. Patent 2,523,168 (Scpt. 19, 1950). (44) Walsh, D. C.. and Schutze, H. G. (to Standard Oil Development Co.), U. S. Patent 2,521,431 (Sept. 5 , 1950). (45) Ibid., 2,521,432 (Scpt. 5, 1950). (46) Wilson, S. D., and Shih, S.-C., J . Chinese C h e m Soc., 16, 8.5 91 (1949). (47) Zapp, Robert. Societh in Accomandita, Ital. Patent 433,469 (Aug. 10, 1948). RECEIVED July 3, 1951
HA L OG ENAT10N
__ EARL 1. MCREE and O G D E N R. PIERCE
m@!
PURDUE UNIVERSITY, LAFAYETTE, IND.
A n upward trend i s evident in the production of chlorine and chlorinated organic compounds. M a n y new chlorine plants are in the process of construction or in operation. Research in the Geld has been especially concentrated on the preparation of the gamma isomer of benzene hexachloride and also the preparation of chlorinated olefins and polymers. Hydrocarbon chlorinations have received less emphasis, with the investigations confined mostly to improvement of established techniques. Several reviews have appeared which summarize various chtorination processes. The area of fluorination shows a decline in the study of processes for the synthesis of fluorocarbons and an increase in the preparation of fluorinated olefins and polymers. The reactions of functional group compounds have also been thoroughly investigated. A book embracing this field has been published which will materially aid both the academic researcher and the industrial chemist.
T
HE production of chlorine and chlorinated products is still increasing. This trend is certain t o continue, for in March 1951 chlorine production was 207,106 short tons as contrasted t o 167,091 short tons in March 1950 (98). A comparison of tbe production figures for several important organic materials for the months of January 1950 and January 1951 indicates the increasing utilization of chlorine in the organic chemical industry (99).
cch, lb.
CsHsC1, lb. DDT, lb.
2.4-0,
Ib.
January 1951
January 1950
28,339,500 37,298,506 7,684,104 1 843 750 6 344 '516 905:237
16,776,561 25 790 686 3:364 :448 463,329 2,369,220 326,352
:
CaHaC16, Jb. Gamma uomer
CHLORINATION Several excellent reviews of various chlorination processes have appeared during the past year. Crawford (19) discusses the application of the Deacon process t o the manufacture of phenol and the chlorination of other organic compounds. A review on the preparation, properties, and uses of methylene chloride is given b y Hebberling ( 4 7 ) while Kainer (69) presents a survey of the patent literature dealing with the production of vinyl chloride. PARAFFIN HYDROCARBONS
The chlorination of methane (86) using various light intensities :md reaction pressures in the presence of small amounts of oxygen,
argon, nitrogen, and hydrogen chloride showed t h a t the reaction was inhibited by each of the additives, with the strongest inhibitory effect caused b y oxygen. A study of t h e preparationof methylene chloride (61) from methane, methyl chloride, or a mixture of the two indicated t h a t the best conversion was obtained using a mixture of reactants in a mole ratio of chlorine :methane :methyl chloride of 1: 0.8:0.7. At 380" to 450' C. in a packed tube, a 74% conversion of methylene chloride was obtained. Foster (16)prepared ethyl chloride in a n 80% conversion from chlorine and ethane at 450-500" C. at a contact time of 0.3-0.5 second followed b y passage of the reaction products over a mixture of copper chloride and alumina at 15" C. and 3-second contact time. Randall (81) chlorinated simple aliphatic hydrocarbons using a mixture of the hydrocarbon and tetrachloroethane with chlorine at 400" C . in the presence of cupric chloride. T h e chlorination of propane in this manner yielded: CHCI,, 1%; CClr, 3.5%; C2HCI8, 26%; CzC14, 32.8%; CzHzClr, 31.2%; CBCII, 4%; and C2C18, 1%. The selective substitution of saturated hydrocarbons containing tertiary hydrogen atoms in the presence of other hydrocarbons was accomplished using chlorine in t h e presence of phosphorus pentachloride, ninc chloride, and chlorides of rare earth metals under anhydrous conditions (1). The reaction can also be conducted with nitrosyl chloride or a mixture of chlorine and metal nitrates and nitritea capable of forming nitrosyl chloride b y their interactions (8). Humphrey and Mitchell (66) chlorinated hydrocarbons in the liquid phase using actinic light and employing a technique in which the partially chlorinated mixture was passed over a n adsorbent t o remove color bodies and sludge, and then rechlorinated t o obtain a substantially higher chlorine content. A chlorine content of 60% or higher was obtained with hydrocarbons containing 10 to 16 carbon atoms b y photochemical reaction with
September 1951
INDUSTRIAL AND ENGINEERING CHEMISTRY
1975
chlorine at 75" to 85" C. until the ohlorine content reached 25 to 35%, followed by an increase in reaction temperature of not more than 12" C. per hour until the temperature reached 160" to 170" C. (99). OLEFINS AND POLYMERS
Chlorine and ethylene ( f 4 ) a t 440' C. and 30 pounds per square inch, in a mole ratio of 5.6:1,gave vinyl chloride in good yield. Reaction of ethylene with hydrogen chloride (14) at 190' C. and 150 pounds per square inch in the presence of copper chloride and zinc chloride formed ethyl chloride in 99% yield. Barton et al. ( 5 ) prepared vinyl chloride in high yield by thr reaction of acetylene and hydrogen chloride a t 150" C. using a catalyst composed of activated carbon impregnated with 10yo by weight of mercuric chloride. A modification of this reaction (104) employed a reaction temperature of 180" to 200" C. using :i catalyst composed of activated carbon highly impregnated with mercuric chloride. Acetylene was converted to tet,rachloroethylene in good yield by burning an intimate mixture of acetylene and chlorine in a proportion l : 3 a t 600"to 950' C. a t a gas flow rate of 20 meters per second ( 2 7 ) . Pyrolysis of 1,l-dicbloroethane (76) a t 500" C. using a reactor packed with nonporous, iron-free gravel produced vinyl chloride in 70% yield. Kaganoff ( 5 8 ) chlorinated polyst,yrene by dissolving the polymer in liquid chlorine and allowing the chlorine t o evaporate leaving behind the chlorinated product. Chlorinat'ion of isoprene polymers (8)in carbon tetrachloride solution using a mixture of air and chlorine with ultraviolet light radiation produced a product having substantially the same properties as chlorinated natural rubber. Reid (82) chlorinated polybutadiene in carbon tetrachloride solution a t 10" to 40" C. until a precipitata formed followed by photochemical chlorination until the precipitate redissolved, t o obtain a product suitable for use in place of chlorinated natural rubber. Polymer chlorination followed by treatment of the mixture with a small amount of iodine produced a material x i t h improved stability toward light, oxidative aging, and hydrolytic deterioration (106). AROMATIC HYDROCARBONS
The preparation bf benzene hexachloride, especially the gamma isomer, has received much attention during the past year. De Waal (21)chlorinated benzene, saturated with the alpha isomer of benzene hexachloride, at 35" C. in light until a precipitate of this isomer formed, decanted the mother liquor, and repeated the chlorination until a fraction rich in the gamma isomer was obtained. Photochemical chlorination of benzene (SO) in carbon tetrachloride solution a t -20" C. using a mixture of chlorine and carbon dioxide produced benzene hexachloride of high insecticidal activity. This same reaction was also conduct'ed in the absence of a solvent (31). I n both cases, no hydrogen chloride was formed. A process (32)for obtaining a saturated solution of the gamma isomer in benzene comprised cooling the chlorinated mixture t o precipitate the alpha and beta isomers and recirculation of the mother liquor through the chlorination reactor. A variation of the usual chlorination procedures consists of irradiation of the chlorine separately from the benzene and mixing the two reactants in the dark (97). It, is claimed that the crystallization of benzene hexachloride on the light source, which is usually immersed in the reaction mixture, is avoided. I n a study of the chlorination of benzene (89) it was found that the yield of monochlorobenzene as compared to dichlorobenzene was increased by increasing the amount of ferric chloride catalyst and the rate of addition of chlorine. Increased reaction temperatures reduced the yield of monochlorobenzene and increased that of dichlorobenzene slightly. Webb (101) treated a mixture of benzene and monoclilorobenzene with chlorine a t 30" to 40" C. in the presence of a Friedel-Crafts type cat:ilyst to produce :L high
COURTEBY
E.
I. D U PONT DE NEMOURS b. C O
INC.?
Room in Which flow, Temperature, and Pressure of Freon Fluorinated Hydrocarbons A r e Indicated and Recorded
yield of dichlorobenzenes containing principally p-dieh1oi.uh11zene. The chlorination of toluene (84)in light at 25" C. indicated the important effect on initiating the thcrnial dark reaction of \\.all surface and showed the thernxil reaction t o be of second ordcr. Diethylbenzene and chlorine ( 6 3 )a t SO" to 120" C. in the pwwncc of phosphorus trichloridt: or phosphorus pcntachloridc gavc i t 75y0 yield of bis(chlorocthy1 jtxrizene. Jl-ibaut and Blorni (108)treated naphthalene with chlorine in the vapor phasc i n the presence of iodine at 250' C. t o obtain a mixture of chloi,onaphthalenes in a ratio of 9: 1 of thc alpha to beta isomers n l i i i c a t 340" C. the ratio appmachcd 1 : l . Chlorination of mettiyl-. naphthalene ( 1 0 ) a t 2&400" C. in the vapor phase a t a cont:ict time of 5 seconds produced (chloroniethy1)naphthalene in :I roiiversion of 74%. OXYGEN-CONTAINING COMPOUNDS
Chlorination of a series of acids and csters (11) in thc v:ii)oi' phase with irradiation showed that the carboxyl group aloric t l i rects the substitution into the beta position while the m r t i l ~Icarboxy group directs to the alpha position. Blume et al. (;.; ) prepared tetrachlorophthaiic anhydride in 72% conversion h j treating phthalic anhydride with chlorine a t 200" to 270" C. in t h c presence of molybdenum chloride. The chlorides of iron a i i t i sulfur were found to produce extensive side reactions. Chloriiiation (24)of a mixture of acetic acid and acetic anhydride ;it 70" to 110' C. gave monochloroacetic acid in a yield of 50%. SULFUR-CONTAINING COMPOUNDS
Devaney (20) prepared chlorothiophenc b y the simu1t:iiic~oiis introduction of chlorine and thiophene into :I tubukir reactoi, using a mole ratio of 5.6: 1 of thiophone to cliloriiie. Thc yiclds of 2-chlorothiophene rmgcd from 60 to 85% dqwnding O J ~ the. fecd rate, with smaller amounts of polyclilorotliioj~lir.iic.Iwiiig formed. Another process ( 6 7 ) cniployrd n i l iodine mtalyst xt it rcm%ion temperature of S O o C. u i d g:ivv 2-chlorotliiol~hc~iic in a 71 yo yic.ld.
1976
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 43. No. 9
Bigc4ow ( 5 4 ) prepared perfluoi~ornc~tti~~lethyl ketone by fluorination o f tlit. ketone a t 120" to 135' C. .-I I,trgt. amount of cleavage products was f o i ~ n c I, ~t The use of bromine trifluoridp it. a f l u o r i n a t i o n a g e n t i s rpvicxwrd t)). Gutmnnn ( 3 3 ) . Unsaturated hyc1rocarl)ons g:ivts t ) c s t tf'r yields of products with rot)iilt t v i ~ i u o ride ( 4 3 ) than do the saturated ori('s; Ilaszeldine (35, 38, 4 0 ) studied thv a('tion of cobalt trifluoride on aminc ~vnsable to obtain the perfluoritiatcri amiiie in most cases, although the >.icsltis were generally low. The reactioii ( 9 ) of a partially fluorinated 1ubric.atirig oil a t 200" to 400" C. with cobalt tvifluoricie gave a stable, nontoxic material iiic9rt to osidizing agents. Cady (f2) desc.ri1)r.s a catalyst for fluorination coniprisiiig copper plated with silver, cobalt, manganese, or cerium. Fluorination ( 7 ) of a lubricating oil fraction a t 200" to 500" C. was accomplished by passing a misture of the oil and fluorine into a molten misture of 70% silver fluoride arid 3OvO COURTESY E. I . DU PONT D E N E M O W l 00.. INC. silver difluoride followed by a second pass through a high concentration of Drying Units for Removing Last Traces of Moisture from Freon Fluorinated Hydrocarbons molten silver difluoride. Liquid-phase Wuter content of Rnlthed produet Is not mwr than 10 pwtr per 1,000,ooO fluorination ( 8 ) of a lube oil fraction a t 150" t o 400' C. was conducted using either solid silver difluoride, cobalt trifluoride, or manganesr triCoonratlt and Hartough (18) prepared pentachlorothiolane by fluoride. McBee and Robb (68-7f) employed lead tetrareaction of chlorine with 2-chlorothiophene a t -30" C. Chlorinfluoride for the vapor-phase fluorination of both saturated and ation of thiophene (16) at 84" to 102" C. gave tetrachlorothiolane unsaturated halocarbons, halohydrocarbons, and hydrocarbons while more exhaustive chlorination at 70' C. produced heptafor the preparation of fluorocarbons in good yield. chlorothiolane ( 1 ; ) . t Fluorination (66,80) of polychloroheptanes with a miuture of Kamlet (60) chlorinated carbon disulfide in the presence of hydrogen fluoride and antimony pentachloride gave chloroiodine at 15" C. followed by treatment with a mixture of methanol fluoroheptanes in good yield. These materials can be reatiilj. and ether t o yield perchloromethyl mercaptan in 62T0 yield. converted t o the completely fluorinated heptane by various agents such as silver difluoride or cobalt trifluoride. BroinoFLUORINATION trifluoromethane (100) was prepared by fluorination of carbon The subject of fluorine compounds is covered extensively in a tetrabromide with a mixture of antimony trifluoride and I J ~ o recent book by Simons el al. (92). Several researchers (62) mine a t 180' to 220' C. in BO t o 70% yield. have presented a survey of fluorination methods as well as a discussion of the chemical and physical properties of various types of OLEFINS AND POLYMERS fluorinated materials. A brief review of the field was given by Gutmann ( 3 4 ) . Fluoroprene (87) was prepared in 68% yield by the vaporFLUORINE A N D METAL FLUORIDES
Swinehart (94)describes the electrolytic generation of fluorine by electrolysis of a mixture of hydrogen fluoride and potassium fluoride using a carbon cathode and a carbon anode coated with a thin layer of nickel. Polarization of the anode is claimed to be considerably reduced. Fluorination of activated carbon (91), mixed with mercuric chloride, a t 400' to 600' C. yielded a mixture of fluorocarbons boiling over the range of 95" to 160" C. and having at least eight carbon atoms per molecule. The reaction of fluorine with benzene ( 4 6 ) in the presence of gold-plated copper turnings gave perfluorinated products in 39% yield. Haszeldine and Smith (df,4.a) found that fluorination of alicyclic rather than aromatic hydrocarbons gave better yields of fluorinated products. A study (28) of the reaction of benzotrifluoride, 1,4-bis(trifluoromethyl)benzene, and 1,3,5-tris(trifluoromethyl)benzrne with fluorine led to the conclusion that addition of one fluorine atom occurred first, changing the aromatic character of the ring t o that of a cyclohexadiene. Trichloroethylene (45)reacted with fluorine at various temperatures to give a variety of chlorofluor0ethant.s and ethylenes as well as polymers. Holuli and
phase reaction of vinylacetylene with hydrogen fluoride a t 20" to 100" C. in contact with charcoal impregnated with a miscvl oxide of mercury and nitrogen. Gorhrnour (29) pioducwl hesafluoro-Zbutyne by treatment of 'L,:~-tiirIiloroh~saHuol.o-~butene with zinc and alcohol at 70' C. I3ot.h licsafluoi~obut:tdiene and hesafluorocyclobutene were obtaiueti as by-produrti. .\ study of the effect of temperature, contact time, diluents, and materials of construction on the vapor-phase dehydroch1orin:ttion of chlorofluoroethanes a t BOO' C. was made by Huskin?; et nl. (56). The compound CC13CHF2 was converted to CCI,=C'F, in a conversion of 78%. 8-Chloro-a,@-difluorostyrene (I,?) was prepared by dechlorination of the cwrresponding ethj.1benzeiie and found to polymerize with difficulty. hlcUee and Sanford ( 7 3 ) prepared 2,4,Gtris(trifiuoromethyI)st~-rc~ie :tiid found it would not polymerize using ordinary techniques. Several olefins (19)containing a trifluoromethyl grouping Lvrre prepared by the reaction of an alkyl Crignard with estcrs of trifluoroacct,ic acid followed by dehydration of the alcohol formeti. Henne el aE. (49) studied the effect of an adjacent triHuoromethyl grouping on an unsaturated linkage and concluded th:tt the inductive effect of the Huorine polarizes the olcfinic bond so
September 1951
INDUSTRIAL A N D ENGINEERING CHEMISTRY
1977
that the carbon atom next to the fluorinated grouping is more Haszeldine and Smith (44)have determined the boiling points, negative and causes directive addition to occur. In the case of densities, refractive indexes, and surface tensions of various classes hesafluoro-2butyne (51), the addition of acetic acid at 50" to of fluorocarbons. 60" C. gave the expected acetate in 40 to 55% yield and triL I T E R A T U R E CITED fluoroacetone in 3470 yield. Ayers, G. W., and Harton, E. E., J r . , C . S. Patent 2,542,107 T h e addition of alcohols to fluorinated olefins in the presence of (Feb. 20, 1951). a I)ase received much attention. B u r et al. ( 4 ) reacted allyl Ibid., 2,584,764 (April 10, 1951). alcohol with chlorotrifluoroethylene to obtain the allyl ether in Banus, J., Emelbus, H. J . , and Hasseldine, R. N., J . Chem. 4 5 5 yield while tert-butyl alcohol gave the corresponding ether SOC.,1950, 3041-5. i n 90yCyield. The reaction (95) of chlorotrifluoroethylene, 1,lBarr, J. T., et al., J . Am. Chem. Soc., 72, 4480-2 (1950). Barton, D. H. R., and Mugdan, AT., J . Sac. Chem. I u d . (Londiciilorodifluoroethylene, and l-chloro-2,2-difluoroethylenewith don), 69, 7Er9 (1950). vai,ioiis alcohols a t autogenous pressures in the presence of a Bartovics, A., U. S. Patent 2,537,641 (Jan. 9, 1951). base a t 40" to 100' C. produced the corresponding ethers in good Benner, R. G., Ibid., 2,549,565 (April 17, 1951). !.ield. Park et d.(77, 7 8 ) studied the additions of chlorine, Benning, A. F., Ibid., 2,521,626 (dept. 5 , 1950). Ibid., 2,541,190 (Feb. 13, 1951) bromine, and various alcohols to trifluoroethyiene and tetraBoyd-Barrett, H. S., Holker, J . R., Steiner, H. h I . E., and fluoroethylene. Using 1,2-dichloro-3,3,4,4tetrafluoro-l-cycloPetrocarbon. Ltd.. Brit. Patent 633.097 (Dec. 12. 1!)49). butene in the presence of a base they obtained a 75% yield of Bruylants, A., Tits, M., and Dauby, R., Bull. sac. C l h i m . Belges, the corresponding l-alkox~-2-ckloro-3,3,4,4tetrafluoro-l-cyclo58, 310-23 (1949). Cady, G. H., U. S. Patent 2,510.864 (June 6, 1950). butene ( 7 9 ) . The reaction of chlorotrifluoroethylene with Campbell, K . N., Knoblock. J. O., and Campbell, J3, K.. trifluoromethyl iodide or bromotrichloromethane in the presence J . A m . Chem. SOC.,72, 4380-4 (1950). of ultraviolet light and perosides gave the corresponding 2Cherniavsky, A. J., Brit. Patent 635,013 (March 29, 19501. chloro-1-iodohexafluoropropane and l-bromo-2,3,3,3-tetraCohen, S. G., Wolosinski, H. T.. and Scheuei, P. J., J . A m . Chem. SOC.,72, 3952-3 (1950). cliloro-1,2,2-trifluoropropane(50). Coonradt, H. L., and Hartough, H. D., E. S.Patent 2,533,773 3 1 c k and Sanford ( 7 2 ) prepared polymers of (trifluoro(Oct. 17, 1950). methyl)- and chloro-( trifluoromethy1)styrenes by emulsion Ibid., 2,525,774 (Oct. 17, 1950). polJ.merizat.ion techniques. Tetrltfluoroethylene (83) was polyIbid., 2,549,576 (April 17, 1951). Crawford. R. M., Chem. Eng. Progress. 46, 483-5 (1950). merized in an aqueous suspension containing a small amount of Devaney, L. W., U. S.Patent 2,533,098 (Dec. 5 , 1950). nionosuccinic acid peroxide a t 30" C. and 350 pounds per square De Waal, H. B.. Ibid., 2,550,046 (April 24, 1951). inch. Sauer (88) polymerized hexafluoropropylene with tetraDickey, J. B., Ibid., 2,541,465 (Feb. 13, 1951). fluoroethylene in an aqueous suspension of ammonium persulfate Ihid., 2,541,466 (Feb. 13, 1951). Eaker. C. M., Ibid., 2,539,238 (Jan. 23, 1951). and sodium pq-rophosphate a t 55" to 64" C.and 250 to 650 atmosFinger, G . C., et al., J. .4m. Cheni. Soc., 73, 115-~55, pheres. The product formed clear, tough films of extreme stabil(1961). ity. Dickey (22, 2.9) prepared copolymers of a-fluoro methFoster, R. T., and Imperial Chemical Industries, Ltd.. Brit. acrylamides and a-fluoromethyl acrylonitriles with acrylinitrile, Patent 639,435 (June 28, 1950). styrene, and methyl methacrylate. A series of polymers (96) Fruhwirth, 0.. and Walla, H., U. 5. Patent 2,538,723 (.Jan. 16, 1951). was Q b t a i n d from various ctilorofluoro-olefins and halogenated aGilbert, R., and Bigelow, L. h.,J . Ana. C'hem. Soc., 72, methylstyrene which had desirable molding and coating proper2411-17 (1950). ties. Gochenour, C. I., C. S. Patent 2,546,997 (.kpril 3, 1951 I. Gorise, M.,Ibid., 2,513,092 (June 27, 1950). Ibid., 2,524,970 (Oct. 10, 1950). MIXELLANEOUS Ibid., 2,529,803 (Nov. 14, 1950;. Gutmann, V., Angew. Cheni., 62A, 312-15 (1950). The reaction of a metallic sdit of trifluoroacetic acid with free Gutmann, V., Osterreich. Chmi.-2.. 31, 165-9 (1950). iodine produced trifluoromethyl iodide in good yield (39, 48). Hasseldine, R. N., J. Chem. Soc., 1950, 1966-9. Ibid., pp, 2789-92. The silver salt gave an 8770 yield while sodium, potassium, Ibid., pp. 3037-41. mercury, lead, and barium salts gave lower yields. The reaction Ibid., 1951, 102-4. of the CF, free radical with hydrogen-containing compounds gave Ibid., pp. 584-7. fluoroform and with carbon tetrachloride yielded chlorotiiHasseldine, R. N., Research (London),3, 43G1 (1950). Haszeldine, R. N.. and Smith, F., J . Chem. SOC.,1950, 2689-94, fluoromethane (5). Acetylene (57) reacted with trifluoromethyl Ibid., pp. 2787-9. iodide t o form 3,3,3-trifluoro-l-iodopropenewhich on oxidation Ibid.,pp. 3617-23. yielded trifluoroacetic acid. This reaction wasl extended to 1Ibid.. 1951. 603-8. iodoheptduoropropane ( 3 6 ) to produce heptafluorobutyric Hauptschein, M., and Bigelow, L. A , , J . Am. Chem. Soc., 72, 3423-6 (1950). acid. Haworth, W. Tu'., Smith. F., and .kppleton, E. V.,Brit. Patciit A series of polyfluorobenzenes and mesitylenes was prepared 630,606 (Oct. 18, 19491. bj- Finger et al. ($5) by means of the Schieman reaction. In a Hebberlins, H., Seife7lrOZe-Fette-Wachse, 76, 21 1-13 (1950). siniilar manner, various monofluoroisoquinoiines were obtained Henne, A - L . , and Finnegan, W. G., J . A m . Chem. Soc.. 72, 3806-7 (1950). ( 8 6 ) . Hydrolysis of nuclear-halogenated benzotrifluorides ( 6 4 ) Henne, A. L., and Kaye, S., I b d . . 72, 3369 (1950). with 1 0 0 ~ osulfuric acid followed by esterification produced Henne, A. L., and Kraus, D. W. Ibid., 73, 1791-2 (1951). various benzoic acid esters otherwise difficult to obtain. ReacHenne, A. L., Schmits, J. V., and Finnrgan, W. G . , Ihid.. 72, tion of perfluorotoluene ( 6 7 ) with concentrated sulfuric acid gave 4195-6 (1950). pentafluorobenzoic acid in 25Y0 yield. 2,4,6-Tris(trifluoroHenne, A. L., and Zimmer, W.F., Ibzd.. 73, 1103-4 (1951) I b i d . , pp. 1362-3. niethyl>l,3,5-triazine ( 7 6 ) on treatment with ethanol and Holub, F. F., and Bigelow, L. A , , Ibid., 72, 4879 84 (1950). hydrochloric acid formed ethyl trifluoroacetate in 92% yield Humohrev. E. L.. and Mitchell. E.. U. S. Patent 2.530.699 Kitration (66) of l,l,l-trifluoropropane at 395" C. gave both (Nbv. i l , 1950). l,l,l-trifluoro-3-nitropropaneand l,l,l-trifluoro-2nitroethane. Huskins, C. W., Tarrant, P., Bruesch, J. F., and Padbury. J. J., IND. ENG. CHEM., 43, 1253-6 (1951). Asimilarreaction(90)at 437't0462' C.gavea 1670yieldof l,l,l(57) Johnson, C. E., Wohlers, H. C.. and Wagner, G. AI.. I-. S. triAuoro-S-nitropropane and a 25% yield of trifluoroacetaldehyde. Patent 2,540,675 (Feb. 6, 1951). Both N-bromotetrafluorosuccinimide ( 5 2 ) and trifluoroacetyl (58) Kaaanoff. S . D., Ibid., 2,513,330 (July 4, 1950). hypobromite (53) have been found to be excellent bromination (59j Kainer, F., Kolloid-Z., 113, 121-8 (1949). (60) Kamlet, M. J., U. S . Patent 2,545,285 (March 13, 1951) agents.
1978
INDUSTRIAL A N D ENGINEERING CHEMISTRY
(61) Ketslakh, M. M., Rudkovskii, D. M., and Suknevich, I. F., Zhur. Priklad. Khim., 23, 215-19 (1950); J. Applied Chem., U.S.S.R.,23,221-4 (1950). (62) Kirk, R. E., and O t h e r , D. E., ed., “Encyclopedia of Chemical Technology,” Vol. 6, pp. 738-69, New York, Interscience Publishers, 1951. (63) Kress, B. H., Brit. Patent 625,281 (June 24, 1949). (64) Le Fsve, G. M., and Scheurer, P. G., J . A m . Chem. SOC.,72, 2464-5 (1950). (65) McBee, E. T., U. S. Patent 2,537,777 (Jan. 9, 1951). (66) McBee, E. T., Hass, H. B., and Robinson, I. M., J . Am. Chem. Soe., 72, 3579-80 (1950). (67) McBee, E. T., and Rapkin, E., Ibid.,73, 1366 (1951). (68) McBee, E. T., and Robb, R. M., U. S. Patent 2,533,132 (Dec. 5, 1950). (69) Zbid., 2,533,133 (Dec. 5, 1950). (70) Zbid., 2,544,560 (March 6, 1951). (71) Zbid., 2,545,430 (March 13, 1951). (72) McBee, E. T., and Sanford, R. A., J . A m . C h a . Isoc., 72, 4053-5 - - - ~- (1950). .----,(73) Zbid., pp. 5574-5. (74) Niagara Alkali Co., Blume, P. W., et al., Brit. Patent 631,008 (Oct. 25, 1949). (75) Norton, T. R., J. Am. Chem. SOC.,72, 3527-8 (1950). (76) N. V. de Batsafache Petroleum Maatachappij, Brit. Patent 633,211 (Dec. 12, 1949). (77) Park, J. D., et al., J. Am. Chem. Soc., 73, 1329-30 (1951). (78) Park, J. D., Lycan, W. R., and Lacher, J. R., Ibid., 73, 711-12 (1951). (79) Park, J . D., Snow, C. M., and Lacher, J. R., Ibid., 73, 2342-5 (1951). (80) Perkins, M. A., U. S. Patent 2,549,988 (April 24, 1951). (81) Randall, M., Z6id., 2,547,139 (April 3, 1951). (82) Reid, R. J., Ibid., 2,537,630 (Jan. 9, 1951). (83) Renfrew, M. M., Ibid., 2,534,058 (Dec. 12, 1950).
Vol. 43, No. 9
(84) Ritchie, M., and Winning, W. I. H., J. C h a . Soc., 1950, 357983. (85) Ibid., pp. 3583-90. (86) Roe, A., and Teague, C. E., Jr., J . Am. Chem. SOC.,73, 687-8 (1951). (87) Salisbury, L. F., U. S. Patent 2,519,199 (Aug. 15, 1950). (88) Sauer, J. C., Ibid., 2,549,935 (April 24, 1951). (89) Sen Gupta, 8. B., Chakravarti, D. P., and Dutta, A. P., J. Indian Chem. SOC.,Znd. Eng. News Ed., 11, 1 3 9 4 5 (1948). (90) Shechter, H., and Conrad, F., J. Am. Chem. SOC.,72, 3371-3 (1950). (91) Simons, J . H., U. S. Patent 2,522,968 (Sept. 19, 1950). (92) Simons, J. H., ed., “Fluorine Chemistry,” Vol. 1, New York, Academic Press, Inc., 1950. (93) Spina, J. A., U. S. Patent 2,511,818 (June 13, 1950). (94) Swinehart, C. F., Zbid., 2,534,638 (Dec. 19, 1950). (95) Tarrant, P., and Brown, H. C., J. Am. Chem. SOC.,73, 1781-3 (1951). (96) Te Grotenhuis, T. A., and Swart, G. H., 0. S. Patent 2,548,504 (April 10, 1951). (97) Towle, W. L., U. 6. Patent 2,534,485 (Dec. 19, 1950). (98) U. S. Dept. of Commerce, Bur. of the Census, “Facts for Industry, Inorganic Chemicals,” M19a-31 (1951). (99) U. 8. Tariff Commission, Chemical Division, “Facta for Industry,” Series 6 - 2 7 5 and 86 (1951). (100) Waterman, H., U. S. Patent 2,531,372 (Nov. 21. 1950). (101) Webb, G. A.,Zbid-, 2,527,606 (Oct. 31, 1950). (102) Weissert, F. C., Behrend, E. B., and Rriant, R. C., Zbid., 2,537,627 (Jan. 9, 1951). (103) U’ibaut, J. P., and Bloem, G. P., Rec. trav. chim., 69, 586-92 (1950). (104) Yamasuga, K., and Chiba, K., J . SOC.OTQ. Synthetic Chem.. J ~ J K I7, X ,125-33 (1949). RECEIVED June 19, 1951.
Hydrogenation and Hydrogenol ysis HAROLD W. FLEMING THE GIRDLER CORP., LOUISVILLE, KY.
During 1950 there have been important developments of the Fischer-Tropsch process, including initial operation of the first commercial synthesis plant in the United States, a moving “fixed catalyst bed‘’ with liquid coolant, and a nitrided iron catalyst which appears to resist oxidation and deposition of free carbon during the synthesis. Selective hydrogenation of acetylenic compounds in gas streams containing ethylene and hydrogen may make available large quantities of ethylene for the chemical industry. The petroleum industry continues to investigate the hydrogenation of double bonds for the production of aviation gasoline, saturation of aromatic hydrocarbons in catalytic cycle stock, and destructive hydrogenation of gas oils. The trend in ammonia synthesis studies is toward the use of a fluidized “fixed bed” of promoted iron catalyst to obtain higher conversions per pass. There i s increased interest in a supported copper chromite type of catalyst and in the substitution of other metals such as nickel, cobalt, zinc, and cadmium for copper.
OR the first time this review includes the Fischer-Tropsch process, with a brief summary of the earlier literature added t o t h e fuller coverage of theliterature made available in 1950. T h e hydrogenation of coal is not reviewed because the Bureau of Mines is the principal contributor in this field and their work is summarized each year in a n annual report (19, 17, bS, 30, 3 1 , 4 0 , 4 l , 4 8 , 5 9 , 5 5 , 8 9 , 1 0 1 , 1 1 8 , 252, 153, 1 6 5 , 1 6 6 ) .
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FISCHER-TROPSCH PROCESS The historical development of the Fischer-Tropsch process has been summarized in many publications (3, 81-84, 149, I@, 164). Because the process has not been included in these annual
significant information Obtained from the operation of cornmercial and pilot plants in Germany and the United States will be discussed briefly before the more detailed summary of the literature for 1950 is given. All the German Fischer-Tropsch p l a n t s i n 1938-44 (141-14s) were operating according t o t h e Ruhrchemie process using the CoTh02-Mg0-kieselguhr catalyst at 180’ to 220’ C., a t either 1 or 10 atmospheres pressure, and with two or three stages with product recovery after each stage. T h e average yield of hydrocarbons ranging from propane-propylene t o waxes of 2000 molecular weight was 150 grams per cubic meter of (2H2 1CO) gas. T h e space velocity employed was 60 t o 100 volumes of feed gas per volume of catalyst per hour. T h e only outstanding procese development using the cobalt catalyst recycled about three volumes of end gas from the first stage per volume of fresh gas with product condensation after each cycle. This resulted in an increase of 30% in the throughput without sacrifice of yield. The recycle-process gasoline has a 50 to 55 motor octane number as compared with 46 for the older process without recycle.
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