urt
[WE cIunit Processes Review
Hydrogenation and Dehydrogenation by Bruce T. Alexander, Doris J. Batliner, W.
M. Meely, and F. J, O'Hara, Girdter Catalysts,
Chemical Products Division, Chemetron Corp., Louisville, K y .
b
Hydrogenation of acetylenic hydrocarbons and propadiene to mono-olefins continues
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Yield, selectivity, and catalytic life were emphasized in varied organic hydrogenation studies
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CONSIDERABLE INCREASE of interest has taken place in fundamental studies; oil and fat hydrogenation; acetylenes, olefins, and aromatics; petroleum, coal, and related materials; and dehydrogenation. T h e NHa synthesis field showed a slight increase in activity, whereas hydrogenation of carbon oxides received approximately the same attention as in the previous coverage. Interest in the oxo synthesis and in hydrogenation of miscellaneous organics experienced a decline. There was a n increase in the number of catalyst preparations for hydrogenation and dehydrogenation processes. Instrumentation continued to play a leading role in fundamental studies. Field electron emission, electron microscopy, electron diffraction, x-ray line broadening, neutron diffraction, electrical conductivity, and electron spin resonance were techniques that aided in undrrstanding particular catalysts and hydrogenation or dehydrogenation. T h e Fischer-Tropsch synthesis was investigated by the Bureau of Mines, and the mechanism of the oxo synthesis was studied in detail. I n the NH3 synthesis field, variations in catalyst composition, chemisorption, and kinetic studies, and new interest in reactor design dominated the investigations. Study of selective hydrogenation of oils and fats continued. Attention was also given to the hydrogenation of fatty acids and esters, fatty alcohols, and several lesser known oils. Selective hydrogenation of acetylenic hydrocarbons and propadiene to monoolefins was reported. Interest in hydrodesulfurization and the upgrading of petroleum stocks continued, and hydrogenation of coal continued to receive some attention, primarily by noncatalytic operations. The broad field commonly referred to as the hydrogenation of miscellaneous organic compounds had many studies directed toward improving the yield, selectivity, and life of catalysts for hy-
drogenation reactions. The catalyst preparation field included leaching, fusion, mechanical mixing, dipping, and precipitation techniques, together with activation and reactivation procedures. Catalytic dehydrogenation processes were described for the production or preparation of butadiene, styrene, formaldehyde, 2,2-biquinolyls, benzonitrile, guaiazulene, ethyl and dimethylstyrenes, divinylbenzene, 2-ethylthiophene, 2,3dimethylpyrazine, vinylpyridine and vinylquinolines, N methylpyrrole, o-vinyltoluene, and carbazole, This review covers a period from about January 1960 through February 1961.
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Fundamental Studies Activity has increased considerably the past year in adsorption, kinetic and mechanism, structural, and magnetic approaches to a better understanding of hydrogenation and dehydrogenation processes and the catalysts involved. Dispersion of platinum on oxide supports has been studied by hydrogen chemisorption (87). Extremely high dispersion of platinum on alumina was demonstrated. An extensive review was completed dealing with the effect of the amount of catalyst on the velocity of catalytic hydrogenation (28). Studies of the physical properties of two samples of Raney nickel indicated to the in-
vestigators that hydrogen is held in the catalyst by substitutional replacement of nickel atoms in the lattice (55). A magnetic method was reported for determining the degree of dispersion of metals in nickel and cobalt catalysts (76). Instrumentation continued to play a leading role in fundamental studies. It was found that the field electron emission behavior patterns of nickel, palladium, and platinum are similar (20). Investigations of active noble metal catalysts by use of the electron microscope showed aggregates of platinum scattered over the surface of the support (67). A study using electron diffraction was used to understand the surface properties and the structure of the interior of nickel catalyst particles of the 500 A. size (98), and x-ray line broadening techniques were used in the investigation of platinum-alumina reforming catalysts (I). 'The magnetic structure of NiO was investigated by neutron diffraction (5). Platforming-type catalysts were investigated by microreactor equipment used for the determination of electrical conductivity. The platinum on alumina catalyst appears to be a complex energetic system that behaves as a very weak conductor with positive holes (65). Electron spin resonance studies were conducted on supported hydrogenationdehydrogenation catalysts (64). Iron oxide catalysts were exposed to gamma radiation at room temperature in a nitrogen atmosphere. T h e irradiated catalysts showed an increase of the order of 40% in their catalytic activity in the conversion of water gas to hydrocarbons (33). Optimum operating conditions of a nickel on kieselguhr hydrogenation cat-
The complete annotated bibliography of the 1960 Unit Processes Review of Hydrogenation and Dehydrogenation by Alexander, Batliner, Keely, and O'Hara. After one year this material can be obtained from the AD1 Auxiliary Publications Project, Library of Congress, Washington 25, D. C., as Document No. 6755. The price will then b e $2.50 for microfilm a n d $1.75 for photostat copies.
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SEPTEMBER 1961
767
a n v d Unit Processes Review alyst were reporttd to be determined prior to a pilot plant program by differential thermal analysis (59). The thermal decomposition of nickel and magnesium oxalates and of nickelmagnesium mixed oxalates was investigated in a hydrogen atmosphere by thermogravimetric analysis (95).
Hydrogenation of Carbon Oxides The Bureau of Mines has published a report investigating the Fischer-Tropsch synthesis in the oil circulation process using a nitrided fused-iron catalyst (76). Iron, copper, and cobalt catalysts have been reported, as well as a nickelmanganese-aluminum catalyst, for manufacturing methane or mixtures containing it from C O and hydrogen ( 9 4 ) . Precipitated iron catalysts and oxides of nickel, iron, and cobalt are being used for the hydrogenation of carbon oxides (77, 78). Foreign patent> make u p the balance of the literature pertaining to the hydrogenation of carbon oxides. Carbonyls were hydrogenated with iron catalysts ( 7 4 ) .
Oxo Synthesis The literature pertaining to the oxo synthesis was limited However, detailed attention was given to the mechanism of the reaction (53). The work indicated that the rate determining step may be the reaction of cobalt hydrocarbonyl. olefin, and C O to form a complex which decomposes to give cobalt carbonyl plus an aldehyde. There was patent interest in an organic acid-promoted COO catalyst (27). Cobalt catalysts continued to predominate the first step of the oxo process.
Ammonia Synthesis Interest still continued in varying the composition of NH3 synthesis catalysts. A catalyst formed by heating a transition metal oxide to 450' to 600' C. in the presence of an alkali metal in an inert atmosphere was reported to permit synthesis of NH3 from nitrogen and hydrogen a t 300' to 400' C. and 100 to 300 atm., with a reaction time of 0.5 to 50 seconds (25). Modifications of the
magnetite type were studied (92), and uranium was added to the iron-type catalyst (99). The investigation of the chemisorption of nitrogen on iron catalyst received special attention (80,8 7 ) . Academic studies of kinetics and mechanism continued (G9), with special emphasis on graphical differentiation for solution of rate equations ( 7 ) . The isotope effect of the exchange reaction rate of NH3 and hydrogen was determined (39). New interest was shown in reactor design. The inside diameter of the reactor was increased a t the expense of insulation thickness and size of the cavity (43). A patented furnace employs a special catalyst arrangement (74).
Oil a n d Fat Hydrogenation A wide and varied rang? of subjects was investigated and reported in the past review period. Selective hydrogenation continued to be investigated. Hydrogenation of fatty acids and esters, fatty alcohols, and several lesser known oils was also reported. Selectivity in the hydrogenation of sesame oil a t 150' to 200' C. with an active and a self-poisoned catalyst was investigated (66). A potentiometric method was used to study selectivity in the hydrogenation of sunflower oil, methyl oleate, and methyl linoleate in absolute ethyl alcohol (36). A patent revealed that unsaturated fatty acids and esters can be hydrogenated a t less than atmospheric pressure using a fluidized catalyst bed. Nickel or palladium on alumina, pumice, or silica is a suitable catalyst. Pressures of 40 to 200 mm. of Hg and teniperatures of 200' to 260' C . were used (89). The hydrogenation of methyl oleate was studied under variable catalyst concentrations, temperatures, and hydrogen dispersion rates to determine the effect of variables on the migration of double bonds of the oleoyl groups (2.0). , Fatty alcohols were produced from sunflower seed, coconut oil, or palm kernel oil a t 320' C. and 242 atm. using 2% of a cobalt-zinc-manganese oxide catalyst (40). Mixtures of cottonseed oil in hexane,
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isopropyl alcohol, and isopropyl ether were hydrogenated. Hydrogenation rates, selectivity, and trans-isomerization were compared with results obtained by conventional nonsolvent hydrogenation (2). A column-type device was used to hydrogenate oil under pressure (88). An attempt to hydrogenate soybean oil a t 180' to 200' C. and 20 kg. per sq. cm. with iron carbonyl as a catalyst resulted in lowering the iodine value to 100. At this point hydrogenation stopped ( 4 2 ) . Catalysts comprising nickel-aluminum silicates for the hydrogenation of fats were prepared by contacting solutions of Ni(NO3) 2, NiSO4, nickcl formate, and nickel acetate with finely pulverized acid-aluminum silicates (90).
Unsaturated Hydrocarbons Selective hydrogenation was given considerable attention. The catalysts used for this purpose were prepared from cobalt, chromium, copper, iron, molybdenum, palladium, platinum, rhenium, rhodium, and zinc and were dispersed on the usual carriers: alumina, carbon, calcium carbonate, pumice, and silica. Considerable effort was devoted to the reaction mechanism of hydrogen with acetylene, ethylene, propylene, and the higher hydrocarbons. Catalysts prepared from cobalt, copper, iron, and nickel, unsupported and supported on pumice and alloys of nickelcopper and nickel-cobalt, were employed to study the reaction rate for the hydrogenation of acetylene. The rate of hydrogenation of acetylene at constant acetylene pressure was found to be first order with respect to the hydrogen partial pressure (18). Raney zinc was used to hydrogenate acetylene at 60° to 100' C. At 100' C., the maximum yield of ethylene was 43y0 (37). The selective hydrogenation of acetylenic hydrocarbons and propadiene to monoolefins with 0.01 to 0.9% palladium on alumina was reported (57). The hydrogenation and double bond migration reactions of 1-butene were studied between -30" and 198' C. by use of an alumina-nickel catalyst to determine the reaction order and activation energies. The initial rate of hydrogenation is first order with respect to the hydrogen pressure and zero order with respect to the butene pressure, unless the latcer pressure exceeds 120 mm. of H g a t 0 ' C. The double bond migration was faster than the hydrogenation ( 6 ) . Kinetic data were obtained for the hydrogenation of vinylacetylene over colloidai palladium in the presence of various additives with equimolar or deficient amounts of hydrogen. Lead and copper acetates retard the hydro. genation, increasing the yield of butadiene and decreasing the amount of butenes formed (73).
The use of a CoMo04 catalyst for selective hydrogenation of butadiene to butylenes in a mixture of higher hydrocarbons was disclosed (93). A patent was issued for a process by which benzene was nearly quantitatively hydrogenated to cyclohexane when the hydrogenation was carried out in cyclohexanol (50). The hydrogenation of naphthalenes by a sodium catalyst promoted by the addition of a small amount of quinoline and acridines was patented. A greatly increased reaction rate with 90% conversion to Tetralin was claimed (97). Naphthalene was hydrogenated over a W-Ni catalyst. Data were obtained at 300 atm. on the effect of temperature, pressure, feed rate, and catalyst size (82). A WS-NiS-AlSOs catalyst was used to hydrogenate Tetralin, benzene, limonene, and a mixture of olefins. Conversion was first order with respect to liquid concentration for each feed stock at constant reaction time. The reaction velocities of benzene and Tetralin were proportional to the hydrogen pressure at 50 to 300 atm., whereas reaction velocities of limonene and the olefin mixture were independent of the hydrogen pressure (38).
Petroleum and Coal A great deal of literature has been published concerning hydrodesulfurization catalysts. Cobalt-molybdenum-ahmina catalysts have been studied at great length. One Co-Mo-A1203 catalyst, containing at least O . O l ~ oarsenic, proved very useful in the desulfurization of thermally cracked naphtha, kerosine, gas oil, and coal tar distillates (15). Catalysts containing a small amount of V z 0 5 - M g 0 have been used successfully (47). Crude benzene was desulfurized by a thorium-activated COS catalyst (21). A process for the continuous nondestructive hydrogenation of sulfur-bearing hydrocarbon oils was also reported (56). U. S. patent literature comprised most of the work. Much work has been done on hydroforming and processes for the upgrading of petroleum stocks. A considerable amount of this work concerns the preparation and testing of platinum catalysts. The use of platinum-aluminahalogen catalysts in reforming straightrun gasolines has resulted in increasing yields of reformate, higher octane numbers, and longer catalyst life (24, 84). Octane numbers of catalytic reformates were increased by the use of a Cr203A1203-Kz0-Ce203catalyst (63). The effects of nitrogen or sulfur compounds on the poisoning of platinum catalysts were studied (58). A sour hydrocarbon distillate was refined with cobalt phthalocyaninedisulfonate as the catalyst (97). An improvement of MoO3-Al203 catalysts
by prior treatment with air or an oxygencontaining gas a t 538' to 704' C. was reported for the hydrogenation of heavy petroleum fractions (45). A zeolite cracking catalyst was reported to result in greater middle oil distillate yields than is usually obtained (34). Light gas oil was cracked using a beryllia-boria catalyst and gave greater yields of gasoline, dry gas, and carbon (70). T h e mechanism of hydrocracking was studied (30). Several studies were made on the hydrogenation of coals (44, 60). Very little was published, however, concerning specific catalysts for coal hydrogenation.
Miscellaneous Organics Investigations directed toward improving the yield, selectivity, and life of catalytic hydrogenation reactions continue to make up a relatively large portion of the subject literature. A study of the hydrogenation of oleic acid to oleyl alcohol over a coppercadmium catalyst showed that selectivity of conversion, or retention of the double bond, increased with temperature and with a decrease in the copper to cadmium ratio (77). The activity of a Raney nickel catalyst employed in the hydrogenation of nitrobenzene and cyclohexene was reported to be dependent on the time and temperature of leaching the aluminumnickel alloy and on the kind and amount of transition metal (including copper) added to the alloy (48). An Adam's type catalyst consisting of 3 parts rhodium to 1 part platinum exhibited greater activity and selectivity than pure platinum catalyst, as applied to hydrogenation of the aromatic nuclei of methylphenyl carbinol, benzhydrol, phenol, ethyl benzoate, anisole, cinnamyl alcohol, and benzene (67). The hydrogenation of anthraquinones to the corresponding anthrahydroquinones over Raney nickel in the presence of small amounts of halo-hydrocarbons was the subject of a patent. I t was claimed that the presence of as little as 0.5yo halo-hydrocarbon markedly suppressed attack of the aromatic structure (86). An investigation of the rate of hydrogenation of vinyl ethers over various catalysts (palladium-calcium carbonate, spongy nickel, and platinum black, in order of activity) demonstrated the effect of the solvent medium, the rates of hydrogenation in ethyl alcohol being four to five times greater than in aqueous alkali medium (3.5). Similarly, in the hydrogenation of 2-ethylanthraquinone over Raney nickel, a dioxane solvent favored nuclear hydrogenation, whereas a mixture of dioxane and polar solvent suppressed nuclear reaction and accelerated quinone group attack (32). An extensive investigation was made
of the rate and course of low pressure hydrogenations of aliphatic, aromatic, and a,O-unsaturated ketones over platinum metal catalysts and in various solvents (79). Dinitrotoluene was reduced to the corresponding diamine in the absence of solvents or diluents by subjection to catalytic hydrogenation in the molten form, Yield was 98% with palladiumcarbon or nickel-silica catalysts ( 4 ) .
Catalyst Preparation The role of the catalyst is becoming increasingly more important in hydrogenation and dehydrogenation processes. Considerable activity was extended this past year to the preparation of noble metal catalysts, metal oxide-type catalysts, and the reduced metal-type catalysts. A suitable carrier for platinum impregnation is reported to be obtained by the calcination of hydrous alumina to y-alumina at 260' to 538' C., followed by partial hydration, resulting in a uniform compound (54). Hydrous Fez03 prepared by adding N H I O H to an FeC13 solution was found to transform on aging to a-FezOa.Hz0 at room temperature and to or-FezO3. HzO and a-Fez03 at 100' C. (57). A patent was issued for increasing the crushing strength of metal oxide pellets by adding an aqueous vinyl-type resin latex to the powdered catalyst ingredients before calcining (9). Preliminary experiments were made on the production of nickel powder from aqueous solution of its salts (46). I t was reported that complex cobalt salts at very low concentrations are promoters for changes in the hydrogenating ability of Raney nickel (23). A British patent describes a method of catalyst preparation that consists of fusing F e 3 0 4 in an electric inductance furnace in the presence of M g O (68). As part of the catalyst preparation problem, there is a continual effort to improve activity of existing catalysts and reactivate spent catalysts. The life of platinum catalysts used for reforming hydrocarbons at elevated temperatures and pressures was reported to be prolonged by treatment with a hydrogen-containing gas at a pressure lower than the pressure used in the conversion of hydrocarbons (52). Reactivation studies included the activation of cobalt and nickel hydrogenation catalysts, inactivated by sulfur poisoning, by heating jn the presence of an oxygencontaining gas at 1200' to 1750' C. for at least 1 hour (96).
Dehydrogenation of Organics Active interest in the catalytic dehydrogenation of light hydrocarbons, VOL. 53, NO. 9
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a n v d Unit Processes Review particularly for the production of butadiene, continues a t a relatively high level. Activity in this field has been concerned primarily with efforts to improve conventional catalysts and processes. Superior selectivity and longer life at high temperatures in dehydrogenating 4-carbon hydrocarbons to diolefins was claimed for A1203CrxOs-alkali type catalysts formulated with precipitated alumina gel instead of commercial Bayer-type alumina (83). A patented extruded CrZ03-Al203 type catalyst containing added bentonite is described as having greater stability, activity, and selectivity than commonly used bentonite-free catalysts for the same type (22). The selectivity of Fez03-Crz03-KzO type catalysts, as applied to the conversion OF 2-butenes to butadiene, was reported to be improved by the addition of 0.5 to 6% silica, preferably as a solution of potassium silicate ( 8 ) . Improved physical strength of CaNiPOl catalysts, with no loss in activity for dehydrogenating olefins containing a t least 4-carbon atoms, was attributed to incorporation of u p to 3070 diatomaceous earth in the formulation; physical strengths of more than twice those of catalysts without diatomaceous earth \vere reported (77). T h e addition of 10 to 30% oxygen (based on hydrocarbon) to a steamhydrocarbon mixture was the basis of a patent claiming increascd yields and longer catalyst life in the dehydrogenation of 1-butene and ethylbenzene to butadiene and styrene, respectively, over CaNiPOl catalyst ( 3 ) . A relatively large volume of journal and patent literature on dehydrogenation was concerned with processes and catalysts for the conversion of simpler alcohols to aldehydes and ketones. A copper-promoted silver catalyst was developed for vapor-phase dehydrogenation of methanol to formaldehyde (72). A high yield of water-free acetone resulted from the reaction of isopropyl alcohol over noble metal catalysts (26).
I n an unusual application of catalytic dehydrogenation, syntheses of a number of 2,2’-biquinolyls were accomplished by reaction of quinoline compounds over a palladium-carbon catdyst (75). This method of joining two A‘heterocycles was extended to I ,5-naphthyridine and a number of pyridines; steric hindrance was considered. An investigation was made of gas phase dehydrogenation of benzylamine to benzonitrile under conditions of oxidative ammonolysis over titanium vanadates (73). Addition of ”3 and oxygen to the feed reportedly had a marked effect on the selectivity and yield of the reaction. Reported yields were 46yo in the absence of NH8 and oxygen, 51% in the presence of “8, and 89% in the presence of both.
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I n a study of dehydrogenation by hydrogen transfer, guaiol was converted to guaiazulene over a palladium catalyst in the presence of a hydrogen acceptor (70). Ketones or unsaturated compounds were added as acceptors. Other terpenes were reported to undergo the same reaction. Catalytic dehydrogenaiion processes were described for the production or preparation of ethyl- and dimethylstyrenes (62),divinylbenzene (72): 2ethylthiophene ( 7 7), 2,3-dimethylpyrazine (47), vinylpyridines and vinylquinolines (79), N-methylpyrrole (49), o-vinyltoluene (85).and carbazole (37).
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Chem. 64, 208 (1960). (2) Albright, L. F., Wei, C.-H., Woods, J. M., J. Am. Oil Chemists’ Soc. 37, 315 (1960). (3) Alexander, D. S., Firko, J. (to Polymer Corp., Ltd.), U. S. Patent 2,945,900 (Julv 19, 1960). (4)’ Aliied ’Chemical Corp., Brit. Patent 832,153 (April 6, 1960). (5) Alperin, H. A.,
[email protected]. 31, 354s 11960). (6)’-Am&omiya, Y . , Shokubai 2, 1 (1960). (7) Anderson, R. B., IND.ENG.CHEM.52, 89 (1960). (8) Armstrong, W. E., Morgan, C . Z. (to Shell Development Co. , U. S Patent 2.916.531 (Dec. 8. 19591. (9) ‘Arnold, ‘M. R,’, Dienes, E. K. (to Chemetron Corp.), Zbid., 2,929,792 (March 22, 1960). (10) Baker, E. G. (to Esso Research and Engineering Co.), Zbid., 2,916,436 (Dec. 8 , 1959). (11) Balandin, A. A., Marukyan, G. M.? others, Zhur. Obshchei Khim. 30, 321 (1960). (12) Balandin, A. A,, ShuYkin, iV. I., others, Zhur. Priklad. Khim. 32, 2566 (1 959). (13) Bal’yan, Kh. V., Borovikova, N. A , , zhur. ObshcheZ Khim. 29, 2553 (1959). (14) Bashkirov, A. N., Loktev, S. M., others, Trudy Znst. Neftti, Akad. Nauk S.S.S.R. 13, 180 (1959). (15) Beavon, D. K. (to Texaco, Inc.), U. S. Patent 2,954,339 (Sept. 27, 1960). (16) Bienstock, D., Field, J. H., others, U. S. Bur. Mines, R e p . Invest. No. 5603, 1960. (17) Boelhouwer. C . . Mourik. 3 . van. ’ bvaterman, H.’ I., Chim. @ ;nd. (Parisi 83, 875 (1960). (18) Bond, G. C., Mann, R . S.;J . Chem. Soc. 1959, p. 3566. (19) Breitner, E., Roginski, E., Rylander, P. N., J . Org. Chem. 24, 1855 (1959). (20) Caspary, E. K., Krautz, E., Intern. Kongr. Elektronenmikroskopie, 4, Berlin, 1958; Verhandl. 1, p. 780, OSRAMStudien-gesellschaft, Augsburg, 1960. (21) Ciborowski. S. (to Instvtut Chemii ‘ Ogblnej), Pol: Patint 41,482 (July IO. 1958). (22) Cornelius, E. B., Milliken, T. H., Jr , Mills. G. A. (to Houdry Process Corp.), U. S. Patent 2,945,823 (July 19, 1960). (23) Csuros, Z., Petr6, J., Heiszmann, J., Magyar Tudomhnyos Akad. Kdm. Tudomhnyok Oszthlya‘nak KorlemSnyei 13, 1 7 (1 960). (24) Donaldson, G. R. (to Universal Oil Products Co. , U. S. Patent 2,915,454 (Dec. 1, 1959j. (25) .du Pont de Nemours;-L I., & Co., Brit. Patent 822,867 (Nov. 4, 1959).
INDUSTRIAL AND ENGINEERING CHEMISTRY
(26) Engelhard Industries, Inc.: Ibid., 823,514 (Nov. 11, 1959). (27) Esso Research and Engineering Co., Ger. Patent 1,028,982 (April 30, 1958). (28) Fasman, A. B.: Sokol’skii, D. V., Trudy Inst. Khim. Nauk, Akad. Naull Kazakh. S.S.R. 5, 114 (1959). (29) Feuge, R . O.? Cousins, E. R., J . Am. Oil Chemists’ Soc. 37, 267 (1960). (30) Flinn, R. A., Larson, 0. A., Beuther, H., IND.ENO.CHEM.52, 153 (1960). (31) FreYdlin, L. Kh., Gorshkov, V. I., Zzaest. Akad. Nauk S.S.S.R., Otdcl. Khim. Nauk 1960, p. 739. (32) FreYdlin, L. Kh., Litvin, E. F., Ditsent, V. E., Doklady Akad. Nauk S.S.S.R. 131, 1362 (1960). (33) Gibson, E. J., Clarke, R. W., others, Proc. U. N. Intern. Conf. Peaceful Uses At. Energy, 2nd, Geneva, 1958 29, 312 (1959). (34) Gilbert, G. R. (to Esso Research and Engineering Co.), U. S. Patent 2,916,437 (Dec. 8, 1959). (35) Golodov, F. G., Sokol’skii, D. V., Iznpst. Akad. Nauk Kazakh. S.S.R., Ser. Khim. 1959, p. 41. (36) Golodova, L. S., Sokol’skiY, D. V., Nauch. Doklady Vysshe! Shkoly, Khim. i Khim. Tekhnol. 1959, No. 1, p. 28. (37) Grotta, H. M. (to American-Marietta Co.), U. S. Patent 2,921,942 (Jan. 19, 1960). (38) Gunther, G.: Chem. Tech. (Berlin) 12, 181 (1960). (39) Gutmann, J. R., Intern. J . Appi. Radzation and Isotopes 7, 186 (1960). (40) Haidegger, E., Karolyi, J., Zalai, A, Acta Chim. Acad. Sci. Hung. 19, 23 (1959). (41) Hansford, R. C. (to Iinion Oil Co. of California), U. S. Patent 2,911,359 (Nov. 3, 1959). (42) Hashimoto, T,, Shiina, H., Yukagakzd 8, 259 (1959). (43) Hennel, W., Przemyst Chern. 38, 438 (1959). (44) Hiieshue, R. W., Anderson, R . B., Friedman, S., IND. ENG. CHEM. 52, 577 (1960). (45) Holm, ’L. R. W. (to Pure Oil Co.), U. S. Patent 2,921,023 (Jan. 12, 1960). (46) Ishibashi, S., Orii. S., Yokoyama, H. Himeji Kd,~y6Daigaku Ketikyn Hdkoku No. 11, 140 (1960). (47) Ishiguro, T.?MatsuInura, M., Murai, H., Yakugaku Zasshi 80, 314 (1960): (48) Ishikawa, J., iVip@on Kagaku Lasshi 81, 837 (1960). (49) Jeffers, F. G. (to Imperial Chemical Industries, Ltd.): Brit. Patent 832,855 (April 13, 1960). , (50) Kaarsemaker, S., Meys, J. A. (to Stamicarbon N. V.). U. S. Patent 2,927,140 (March 1, 1960). (51) Kataoka, I.: Kitamura, ‘r., Nififion Doj6-hiryogaku Zasshi 29, 403 (1958). (52) Kellogg, M. W., Go., Brit. Patrnt 827,657 (Feb. 10, 1960). (53) Kirch, L., Orchin, M., J . Am. Cheni. SOC. 81. 3597 (1959). (54) Kodh, J. H., Ji. (to Engelhard Industries, Inc.), U. s. Patent 2,922,767 (Jan. 26, 1960). (55) Kokes, R. J., Emmett, P. H.. .I. Am. Chem. Snc. 81. 5032 (1959). (56) Koome, J., Stijntje;, G.’ J. F. (to Shell Oil Co.), U. S. Patent 2,947,685 (Aug. 2, 1960). (57) Likins, M., Strotman, J. F., McCarthy, D. 0. (to Chemetron Corp.), Zbid., 2,946,829 (July 26, 1960). (58) Lin, T.-Y., Cheng, Y.-C., Wu Haii T a Hsueh, Tzu Jan K’o Hsiieh Hsiieh Pao 5 , 32 (1959). (59) Locke, C. E., Rase, H. F., IND.F,NG. CHEM.52, 515 (1960). (60) Markov, L. K., Orechkin, U. B., Trudy Vostochno-Sibir. Filiala. Akacl. Y a u k S.S.S.R. 18, 64 (1959)
(61) Maxted, E. B., Akhtar, S., J. Chem. Soc. 1960, p. 1955. (62) Modestinu-Nicolescu, A., Analele univ. “C. I. Parhon” Bucuresti Ser. jtiinje nat. No. 21, 65 (1959). (63) Moy, J. A. E., Bond, P. D., (.to British Petroleum Co., Ltd.), Brit. Patent 820,403 (Sept. 23, 1959). (64) Nicolau, C. S., Thorn, H. G., Pobitschka, E., Trans. Faraday Soc. 5 5 , 1430 (1959). (65) Nicolescu, I. V., Popescu, A., others, Rev. chim., Acad. rCp. populaire Roumaine 4, 75 (1959). (66) Nielsen. K.. Hansen. H. J. M.. ‘ Nielson, V, R.,’J. Am. O h Chemists’ Soc: 37, 271 (1960). (67) Nishimura. S.. Bull. Chem. Sod. Jaban ‘ 33,.566 (1960). ’ (68) Osterreichische Stickstoffwerke Akt.Ges., Brit. Patent 833,878 (May 4, 1960). (69) Ozaki, A., Taylor, H., Boudart, M., Proc. Roy. Soc. (London) A258, 47 (1960). (70) Pailaud, R., Hoa, H., Compt. rend. 250, 2730 (1960). (71) Polymrr Corp., Ltd., Brit. Patent 822,227 (Oct. 21, 1959). (72) Punderson, J. 0. (to E. I. du Pont de Nemours & Co.), U. S. Patent 2,939,883 (June 7, 1960). (73) Rafikov, S. R., Suvorov, B. V., KagarlitskiY, A. D., Izvest. Akad. Nauk Katakh. S.S.R., Ser. Khim. 1959, No. 1, p. 77. (74) Raichle, L. (to Badische Anilin- & Soda-Fabrik), Ger. Patent 971,320 (Jan. 8, 1959).
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After September 1962 the complete annotated bibliography can be obtained from the AD1 Auxiliary Publications Project, Library of Conqress, Washington 25, D. C. as Document No. 6755,at $2.50 for microfilm and $1.75 for photostat copies.
UM THE W O R K S . . . Manuscripts Accepted for Pub1ication within the Next Three Issues Vacuum-Compression Distillation Column
of
I/EC
Polymerization of Ethylene Oxide
R. D. Beattie and D. F. Othmer Polytechnic Institute of Brooklyn, Brooklyn, N. Y.
T. H. Baize Jefferson Chemical Co., Inc., Houston, Tex.
Impellers i n each stage of a distillation column compress the vapor slightly and lower reboiler pressure. Tray efficiencies are given for absorption, vacuum distillation, and atmospheric distillation
NVR formed by autocatalytic polymerization plugs transfer lines and causes haze in finished adducts. Some of the factors causing”polymerization are identified, and methods of reduction are outlined
Scale-up of a Novel Mixer-Settler Extractor
R. 6. long and M. R. Fenske Esse Research and Engineering Co., linden, N. J.
Vertically reciprocating perforated plates are used as mixers. Design relationships for extraction equipment are developed, and compared with large-scale experiments
A Rapid Method for Obtaining Vapor-liquid Equilibrium Data
R. S. Ramalho, F. M. Tiller, W. J. James, and D. W. Bunch The University of Missouri, Rolla, Mo.
Apparatus is designed for simple distillation with continuous feed and product removal. Mathematical treatment of the data is given Plastics-An
The Futility of Raffinate Reflux in liquid Extraction A. H. P. Skelland Illinois Institute of Technology, Chicago, Ill.
Examination of theory shows that this technique is valueless both when used alone, and when accompanied by extract reflux
I/EC Materials of Construction Review
R. 6. Seymour SUI Ross State College, Alpine, Tex.
Growth of this industry continues i n spite of a business recession and lower selling prices. Engineering uses are becoming commonplace, both because of unique properties and availability of design data Mass Transfer-An
Nylon 6 and Related Polymers
I/EC Chemical Engineering Fundamental Review
Rene Aelion Foster Grant Co., Inc., Leominster, Mass.
R. Wilke, J. M. Prausnitz, Andreas Acrivos, E. E. Petersen, and D. R. Olander University of California, Berke!ey, Calif.
In addition to the four types of nylons produced commercially, several similar polymers were studied. Properties generally fall within the range of properties of the commercial nylons, and production volume will be determined by raw material costs
Significant progress is reported, although no radically new principles were developed. Diffusion i n liquids and interfacial and convection phenomena are active fields of investigation. Piogress has been made in application of theoryand equipment design
C.
VOL. 53, NO. 9
SEPTEMBER 1961
771
