I I Hydrogenation and Hydrogenolysis

I CHEMICAL ENGINEERING REVIEWS

UNIT PROCESSES REVIEW

I

I

II Hydrogenation and Hydrogenolysis

I

THE

literature on hydrogenation processes and studies that became available in 1955 has been reviewed. This covers the hydrogenation of carbon oxides, oxo synthesis, ammonia synthesis, oil a n d fat hydrogenation, hydrogenation of acetylenes and other unsaturated hydrocarbons, hydrogenation of petroleum, coal, and related materials, hydrogenation of organic compounds, and fundamental studies o n hydrogenation catalysts. For the convenience of the busy reader interested in selected subjects, this review is arranged in tabular form with listings of subject, catalyst and literature cited.

Hydrogenation of Carbon Oxides During the past year interest has reinainrd active in Fischer-Tropsch synthesis, methanol synthesis, and other processes related to the hydrogenation of carbon oxides. However, there has been a progressive decrease in references cited in the annual reviews (see tables). Finely divided iron catalysts promoted with potassium, calcium, copper, zinc, chromium, ruthenium. tungsten, titanium, silicates, and halides under fluidized conditions have been most widel>used in Fischer-Tropsch studies. O t h e r catalysts include cobalt, thorium, m a n ganese, ruthenium, tungsten, a n d nickel. ;\lumina, kieselguhr, bentonite, silicates, and magnesia have been utilized as carriers. Synthesis of predominantly aromatic hydrocarbons over a n alumina catalyst is reported. Increased yields of olefins are claimed using a n iron catalyst in the presence of halides and sulfur compounds as regulators. T h e synthesis of methane over nickel catalysts as well as methanol synthesis over promoted zinc oxide and zinc chromate catalysts were studied. =\ process has been patented for the production of higher alcohols having more than four carbon atoms by the direct hydrogenation of carbon monoxide in the presence of ketones over a n alkalinized zinc chromate catalyst.

Oxo Synthesis I n general, the OXO process consists of the reaction of hydrogen and carbon monoxide tvith olefinic compounds to yield mainly aldehydes which m a y be converted to alcohols in a subsequent hydrogenation step. Cobalt continues to predominate as a catalyst for the first step of the process for the production of

aldehydes. I n a second step involving the hydrogenation of the aldehydes to alcohols, molybdenum sulfide, cobalt, and nickel catalysts have been studicd. One process for the production of aldehydes claims a n improvement by injecting the cobalt catalyst into the reaction zone as a n aqueous emulsion. Another improvement is claimed to increase the reaction rate by the addition of a surface active agent to a n aqueous solution of the cobalt catalyst. Increased yields of aldehydes, involving conversion to acetals, are reported. Inclusion of a m monia during the oxonation of contaminated olefinic compounds is reported to decrease the induction period for the reaction. Several processes are concerned with the removal of impurities such as cobalt and sulfur compounds from the products.

Ammonia Synthesis A study was made to determine the effect of the diffusion of nitrogen and hydrogen on the rate of ammonia formation over a n iron catalyst. An improvement is reported in the reduction of a n iron catalyst containing small amounts of alumina and potassium oxide by conducting the reduction in a fluid reactor in the presence of a previously reduced catalyst. A process is claimed which utilizes exchange reactions with manganese compounds to integrate the production of hydrogen-carbon monoxide mixtures and ammonia. T h e generation of ammonia-synthesis gases by the steam-hydrocarbon reaction under pressure is reviewed; two references relate to the production of synthesis

gases from heavy oils. Six processes are reviewed for the synthesis of ammonia from hydrogen obtained as a by-product in the reforming of petroleum naphthas over platinum catalysts.

Oil and Fat Hydrogenation Nickel continues to be the most widely used catalyst for the hydrogenation of' fats and oils. However, studies were made using a catalyst consisting of a mixture of copper and chromium oxides with copper chromite as well as a copper chromite catalyst stabilized with cobalt. .4n improved catalyst is claimed consisting of 25 to 407; nickel, 25 to 4@%copper, a n d 20 to 50% kieselguhr. Three references describe continuous processes for the hydrogenation of fats and oils. Hydrogenation inhibitors in the oil of olive drupes and pretreatments for the removal of catalyst poisons from olive seed oil were investigated. Isomerization reactions in the hydrogenation of oleic acid and the kinetics for the hydrogenation of synthetic triolein were studied.

Acetylenes, Olefins, Aromatics, and Other Hydrocarbons Several studies were made on the production of ethylene and butadiene by the hydrogenation of acetylene over palladium, platinum, nickel, copper, and iron catalysts. Reaction products and equilibrium relaticnships were investigated. T h e mechanism for the hydrogenation of divinylacetylene over R a n e y nickel also was studied. .4 comprehensive review of the literature was made on the vapor phase

MELVIN R. ARNOLD Division of National Cylinder Gas Co., The Girdler Co., Louisville, Ky. MELVIN R. ARNOLD, of the research and development group, Catalyst Department, The Girdler Co., succeeds Paul B. Boyd, Jr., of the same company as author of our review of hydrogenation and hydrogenalysis. Arnold received his B.S. from Jamestown College in 1938 and M.S. from North Dakota State Agricultural College in 1940. From 1941 to 1943 he was employed by the Du Pont Co. and joined The Girdler Co. in 1943. He has been with Girdler since then with the exception of three years (1952-55) with The Miner Laboratories. Arnold i s a member of the ACS and the Catalyst Club of Chicago. VOL. 48, NO. 9, P A R T II

SEPTEMBER 1956

1629

UNIT PROCESSES REVIEW catalytic hydrogenation of olefins over solid catalysts. R a t e equations were developed for the reaction of hydrogen and a n olefin on the surface of a catalyst. A general rate equation is developed for the catalytic hydrogenation of' olefins in solvents wherein the rate is first order with respect to hydrogen and zero order with respect to olefin. T h e liquid phase hydrogenation of 1-hexene over Adams platinum was investigated a n d correlated with d a t a obtained previously with Raney nickel, rhodium, and palladium catalysts. Reaction rates on the hydrogenation of benzene and its homologs over a tungsten sulfide catalyst were investigated. Several other catalysts including molybdenum, thorium, cobalt, iron. nickel, Raney nickel, and Raney copper were studied. T h e effects of various treatments o n the activity of a nickelalumina catalyst for the reaction of hydrogen and benzene were described. Three references relate to the purifications of crude benzene in the presence of hydrogen a n d a similar number to dealkylation reactions with aromatic hydrocarbons over alumina-silica base cataiysts with various promoters. T h e literature on the techniques of autoclave experiments on the hydrogenation of hydrocarbons was reviewed.

Petroleum, Coal, and Related Materials T h e hydrodesulfurization of petroleum and naphtha stocks continues to remain a highly active field with cobalt and molybdenum on alumina as the most widely used catalysts. Promoters frequently employed are fluorides, other halides, and phosphorus. O t h e r catalysts of prominence include tungstennickel sulfide, platinum, titanium, and molybdenum. Numerous patents were issued covering the removal of sulfur compounds from petroleum fractions and oil ; hydrodesulfurization has received much attention due to the poisoning effect of sulfur on catalysts employed in the upgrading of gasoline fractions and other subsequent treating processes in use in the petroleum field. Patents have also been issued and studies made o n improving the quality or upgrading of petroleum fractions by the catalytic reforming of hydrocarbons in the presence of hydrogen. Platinum o n alumina, with or \vithout promoters, received the most attention, but other catalysts include palladium, molybdenum oxide, tungsten-nickel sulfide, and nickel. Alumina and silica were most commonly used as carriers. Several processes are described for the hydrogenation of heavy

petroleum and shale oils to yield more valuable products. Molybdenum oxide, cobalt molybdate, tungsten, and nickel on alumina or silica were the most widely used for hydrogenating these heavy hydrocarbons. Studies were made on the hydrogenation of coals to yield liquid and gaseous products. T h e catalysts empIoyed include ammonium molybdate, nickel chloride, tin chloride, iron sulfate, and cobalt sulfate. Various processes dealing with the hydrogenation of carbonaceous matter were reviewed and evaluated. There has been less activity in the patent field. O n e patent was issued covering a process for the hydrogenation of powdered coal in a fluidizing reactor to yield a hydrocarbon-rich fuel gas. Three patents were issued on desulfurization of coal char and coke.

Organic Compounds Hydrogenations of organic compounds are grouped according to the catalyst employed. There has becn a substantial increase in the number of references abstracted as compared to the number cited during the past four years. Raney nickel catalyst was the most widely used in promoting organic hydrogenation re(Continued on page 1639)

Desulfurization unit employing G-35 catalyst, Shell Oil Co., Wood River, Ill., refinery

1 630

INDUSTRIAL AND ENGINEERING CHEMISTRY

HYDROGENATION AND HYDROGENOLYSIS

Hydrogenation of Carbon Oxides CATALYSTS Subject Fucher-Tropsch synthesis with fluidized iron catalysts Hydrocarbon synthesis by carbon monoxide hydrogenation

Catalysl

Catalyst for producing hydrocarbons, alcohols, and esters by hydrogenation of carbon monoxide Oxygenated compounds from carbon monoxide and hydrogen Alcohols and nitrogen organic compounds by catalytic hydrogenation of carbon monoxide in presence of ammonia and its derivatives Hydrocarbons or oxygenated compounds from hydrogen and carbon monoxide Iron catalyst for producing hydrocarbons from hydrogenation of carbon monoxide Iron catalysts for reaction of hydrogen and carbon monoxide to yield hydrocarbons Ox) genated compounds with high ester content by catalytic hydrogenation of carbon monoxide Liquid hydrocarbons and oxygenated organic compounds from hydrogen and carbon monoxide Liquid and gaseous olefinic hydrocarbons from hydrogenation of carbon monoxide Increased yields of C2-C4 olefins from hydrogen and carbon monoxide Increased yields of Cz-CI olefins from hydrogen and carbon monoxide

Sviithesizing alcohols from \vater gas Synthesizing alcohols from water gas Hydrocarbons and oxygen-containing organic compounds from carbon monoxide and water vapor Testing at 250 atm. of several oxide catalysts for hydrocarbon synthesis from carbon monoxide and hydrogen Catalytic conversion of carbon monoxide hydrogen mixtures to olefins and paraffins Synthesis of aromatic hydrocarbons from hydrogen and carbon monoxide Synthesiiing alcohols from Lvater gas at lower temperatures Hvdrogcnation of carbon oxidr to produce normally liquid organic compounds Normally liquid hydrocarbons from hydrogen-carbon monoxide mixtures Hydrogenation of carbon monoxide at 100 atm. to give long chain paraffins High molecular weight hydrocarbons from hydrogenation of carbon monoxide

Sintered Fe, alkali Fe containing alkali oxide to silicic acid. 1 to 1 to 1 to 7 Fe impregnated with K2Si03 or K G 0 3 Fe promoted with alkali metal and Cu o r Ag Fe containing K 2 0 and Cu Fe containing K 2 0 and Cu or ZnO Fe containing Cu, CaO, Si02 and K 2 0 Fe salt solution precipitated on kieselguhr containing other metals such as Cu, Zn, Cr, or alkaline earth Fe containing 2-5% K2O in form of K salt of phosphoric, boric, tungstic, or molybdic acid Pyrites, 3 t o lOYo K ? O as alkali metal compound Fe containing nonvolatile metal chloride or bromide Fe type catalyst regulated by volatile halide Fe type catalyst regulated by S compound and volatile halide Fe catalysts with .A1203 and K 2 0 as principal promoters plus accessory promoters CaO, CuO, Cr203, and w 0 3 Fe catalysts with SiOz, MgO, and KzO as principal promoters plus accessory promoters CaO, wo3, CuO, and T i 0 2 Fe, Co, Ni, or R u , 50% or more in nitride form, promoted with alkali metals, nonreducible oxides and salts, and others T h o n ,A1203,CrZOg, Th02-Al208, A120~-Cr203 C o and T h o 2 on kieselguhr, 2 8 7 ~Co and 1.770 T h o * , B203 may be added A1203 free of alkali-metal oxide

Addition of 0.2570 C u O to catalyst containing A1203 and K ? O Hydrogenating metal of Group VI11 with 0.01 to 0.5 time of a metal oxide promoter, and 0.5 to 5 times bentonite-type clay 5 to 30 atomic yc Mn, 15 to 4 5 7 , A1 and/or Sn. 40 t o 70% Cu and/or Aq Ru hletal tungsite

PROCESSES Subject Production of aromatic hydrocarbons from hydrogen and carbon monoxide utilizing aromatization catalyst in second step Preparation of highly active hydrocarbon synthesis catalyst for reacting hydrogen and carbon monoxide Fluidized reduction of catalyst for synthesis of hydrocarbons by hydrogenation of a carbon oxide Process for hydrocarbon synthesis from hydrogen and carbon monoxide with catalyst particles of less than one micron Process for synthesis of motor fuel hydrocarbons from hydrogen and carbon monoxide by withdrawing in a subsequent step hydrocarbonrich fractions and contacting with alumina Development of liquid-phase hydrogenation of carbon monoxide Economics of Fischer-Tropsch synthesis Catalytic hydrogenation of carbon monoxide Design and operation of fluid catalyst pilot plant for Fischer-Tropsch synthesis Review of literature on production of synthetic liquid fuels and chemicals by hydrogenation of carbon monoxide Future of synthetic liquid and gaseous fuels Fuel gas enriched with methane by hydrogenation of carbon monoxide Production of higher alcohols by hydrogenation of carbon monoxide in presence of ketones

Catalysts hletal of Group VI11 followed bv catalyst from V and/or VI Fe Fe. alkali

Fe group and Ru Fe group, A1201 Fe Fe (mill scale j

Alkalinized Zn chromate

VOL. 48, NO. 9, P A R T II

SEPTEMBER 1956

163 1


Hydrogenation of Carbon Oxides (Continued) FUNDAMENTAL STUDIES Subject Adsorption isotherms of hydrogen and cart-on monoxide on FischerTropsch catalyst Surface phenomena on catalysts for synthesis of hydrocarbons from carbon monoxide and hydrogen Rate measurements of methane and carbon monoxide from hydrogcn and carbon dioxide Mechanism of synthesis of methane from carbon monoxide and hydrogen Correlation of structure and catalytic activity of mixed catalysts for synthesis of methanol Water formation during methanol synthesis from carbon monoxide and hydrogen

Catalyst., Co, T h o * , and kieselguhr

Fe, Co, and ThOz catalvsts Ni on kieselguhr Ni ZnO type 8ZnO.Cr208, Fe

Oxo Synthesis CATALYSTS Subject Production of aldehydes or ketones from olefins, hydrogen, carbon monoxide. and alcohols by hydrogenation of these products Synthesis of aldehydes with fluid catalyst wherein catalyst is decomposed and subsequently refluidized for reuse Oxo synthesis of aldehydes, catalyst being injected as aqueous emulsion Rate of formylation of diisobutylene and mechanism for reaction Production of diethylketone from ethylene, hydrogen, and carbon monoxide Improvement in oxo reaction by addition of a surface active agent Regeneration of spent cobalt solution used to generate cobalt carbonyl catalyst for oxo synthesis Production of oxo alcohols by hydrogenation of crude product Conversion of oxo aldehydes by hydrogenation to high molecular weight alcohols Catalytic hydrogenation of oxo aldehydes to alcohols

Clltalysts

Co or Fe, alone or mixed, and one or more oxides of Ti, Zr,Mo, and LV Co carbonyl Co finely dispersed in organic liquid and emulsified Co naphthenate Fe group Co and M g salts in aqueods solution

co h l o sulfide

Co supported Xlo sulfide and P on charcoal

PROCESSES Subject Reaction of olefins and synthesis gas a t 80 to 100' C. and 50 to 250 atm. with recovery of carbonyls by contact of effluent gas with cobalt oxide at 150' to 200" C. Decreasing induction period for oxo synthesis by introducing 0.5 to 0.15% by weight of ammonia based on olefin Increasing yield of aldehydes by conversion to acetals with glycols or alcohols Hydrocondensation of carbon monoxide with I-hexene Effect of ratio of ethylene and hydrogen in initial gas, dilution with nitrogen, and the space velocity on hydrocondensation of carbon monoxide with ethylene Preparations of saturated terpene aldehydes and alcohols from diolefinic terpene hydrocarbon Method for preparation of terpene formylation products by catalytic addition of water gas to terpene hydrocarbons Alcohols from hydrogenation of oxygenated products from oxo process Removal of iron from aldehydes produced in oxo process Aluminum alcoholate reduction of oxo aldehyde mixture Hydrodesulfurization of oxo alcohols Removal of sulfur from oxo alcohols Synthesis of octyl alcohol from hydrogen, carbon monoxide, and heptene wherein crude product is extracted with alkali bisulfite solution Process for oxo synthesis wherein fluid carbonyl catalyst is recovered for reuse Demetallizing metal carbonyl containing synthesis gas in hydroformylation of olefins Treatment of aldehydes from oxo process to remove cobalt Removal of dissolved cobalt from product wherein the metal particles are separated over magnetic surfaces Separation of cobalt on magnetic surfaces and regenerating for reuse in oxo process Lubricating grease composition consisting of a metal soap produced from reaction of oleic acid and its esters with carbon monoxide and hydrogen The oxo process in the U. S.

1 632


Cotnlysts

Co carbonyls

co

co co

Raney Ni Co

co co

Co carbonyl

co Dissolved Co compound Co in solution

co Co

Literature Cited (28B)


Ammonia Synthesis CATALYSTS Subject Investigation of the catalytic reaction for the synthesis of ammonia by diaphragm method Reduction of ammonia synthesis catalyst prepared by fusing magnetite, aluminum oxide, and potassium oxide Production of hydrogen-carbon monoxide mivtures and ammonia by exchange reactions with manganese compounds Ammonia synthesis gas generation by pressure reforming of natural gas Production of ammonia synthesis gas from heavy oils Six processes reviewed for production of ammonia from hydrogen obtained as by-product in platinum reforming of petroleum naphthas Production of hydrogen by partial oxidation of heavy fuel oil for ammonia manufacture

Literature Cited

Catalysts Fe Fe hln

Oil and Fat Hydrogenation CATALYSTS Catalysts 25 to 40% Ni, 25 to 40% Cu, 20 to 50% kieselguhr Oxides of Cu and Cr with copper chromite, Zn: and Cd Ni formate Cu chromite stabilized with 57'0 co 2% Ni

Subject Hydrogenation of fats with improved catalyst at 200' C. and 6 atm. Catalytic hydrogenation of fats and fatty acids at 150" to 350" C. and 200 to 350 atm. Rate and selectivity of hydrogenation of sunflower oil High-pressure hydrogenation of inedible oils and fats at 2500 p.s.i. Hydrogenation of shad oil at 180" C. and 1 atm

PROCESSES Subject Method for continuous hydrogenation of fatty materials resulting in intimate and vigorous contact of catalyst and hydrogen Experience with continuous hydrogenation of fats and oils giving improvement in quality, output, and production losses Process of producing saturated higher fatty acids of good color Process for producing tall oil alcohols Hydrogenation of unsaturated fatty oils in presence of catalyst and high frequency alternating electric current Manufacture of edible hydrogenated fat using a continuous process on Kharkov fat combine

Cataivrti

Ni

CHEMISTRY Subjtct Kinetics of the hydrogenation of triglycerides Isomerization during hydrogenation of oleic acid Inhibitors in the oil of olive drupes Effect of several pretreatments for removing catalyst poisons from olive seed oil and its fatty acids

Cdtalysts Ni

Acetylenes, Olefins, Aromatics, and Other Hydrocarbons ACETYLENES Subject Production of ethylene by partial hydrogenation of acetylene Formation of butadiene and butene by hydrogenating acetylene Equilibrium relations between the reactions concerned with the hydrogenation of acetylene Activity of various catalysts for synthesis of butadiene from acetylene and hydrogen Mechanism of the hydrogenation of divinylacctylene in ethyl alcohol, acetic acid, or xylene

Catalysts Pd-kieselguhr Pd on steel gauze Pd, Ni, Pt, Cu, Fe, AI,Cd, Cr, Co, Ir, Mg, and Zn Raney Ni

OLEFINS Subject Rates in liquid phase hydrogenation of 1-hexene and allyl alcohol Rate equations and mechanism for the reaction of hydrogen and a n olefin on the surface of a catalyst A review of the literature on the vapor phase catalytic hydrogenation of olefins over solid catalysts Hydrogenation and polymerization of olefins Hydrogenation of 1-propylcycloheptene at 320" C.

Catalysts Adams Pt, Raney Ni, R h , and Pd

Si0~-&08-4% NiO 10% Pt on carbon

VOL. 48, NO. 9, PART II

SEPTEMBER 1956

1633


Acetylenes, Olefins, Aromatics, and Other Hydrocarbons (Continued) AROMATICS Subject Rates of hydrogenation of condensed aromatic hydrocarbons at 150 atm. and 400' C. Rates of hydrogenation of benzene and its homologs at 200 atm. and 420' C. Activity of various catalysts for the reaction of hydrogen with aromatic hydrocarbons Effect of various treatments on activity of a nickel catalyst for the reaction of hydrogen and benzene Hydrogenation of benzene and toluene

Catalysts

ws2

W WS2, S n SnOs, TiOs, T h o ? ,vzo5,Cr203, MOOa, WOa, Fez03, Fe,.SnS, MOS3, WS3, COS, and NiS 30% Ni and 70% A 1 2 0 3

vZs3,

Process for purifying crude benzene by subjecting to hydrogen at 20 to 300 atm. and 180' to 450' C. and a method for preparing catalyst

Raney Ni and mixtures of Raney c u and Raney Ni k t i v e Al208, oxide, or sulfide from left side of Group 6, and from Group Similar 8 to above

See above Process for recovery of benzene from mixtures contaminated with other unsaturated hydrocarbons and sulfur compounds by reacting with hydrogen Destructive hydrogenation of toluene at 455' to 490' C. and 1350 atm. Process for conversion of an aromatic hydrocarbon into an alkyl cycloparaffin at 450" to 800" F. and 100 to 1000 p.s.i. in the presence of hydrogen Process for dealkylation of monocyclic aromatic hydrocarbons by hydrogenolysis at temperatures above 500" C . and pressures above 100 atm. Same as above Method for dealkylating a monomethyl naphthalene by hydrogenolysis at 450' to 750' C .

98 to 40% silicon, 2 to 60% alumina impregnated with a metal Aluminum silicate and ferric fluoride

Aluminum phosphates Silica gel and Ni or C o

MISCELLANEOUS Subject Review of literature on technique of autoclave experiments on hydrogenation of hydrocarbons Catalytic reactions of hydrocarbons in the presence of hydrogen Synthesis and catalytic hydrogenolysis of 1,1,2-trimethylcyclopropane Catalytic hydrogenolysis of ethylcyclopropane and methylcyclobutane

Catalysts

Pt on carbon

Petroleum, Coal, and Related Materials DESULFURIZATION Subject A catalyst for desulfurization of hydrocarbons Catalyst for hydrofining or autofining processes Method for desulfurizing a hydrocarbon stock at 200' to 500" C . Pretreatment of high sulfur naphthas with hydrogen for removal of sulfur and other contaminants Removal of sulfur from petroleum fraction with naphthenes as donor of hydrogen Catalytic desulfurization of gas oils by hydrogenation Desulfurization of gasoline fraction by treatment with hydrogen at 500' to 700' F. and 100 to 800 p.s.i. Catalytic removal of sulfur from petroleum hydrocarbons with hydrogen from naphthenes Removal of sulfur from motor fuels under conditions to give controlled dehydrogenation of naphthenes Desulfurization of petroleum feed stock with hydrogen in excess produced from dehydrogenation of naphthenes Cracked naphtha desulfurized by reaction with hydrogen at 780' F. and 50 to 100 p.s.i. Hydrodesulfurization of petroleum stocks with simultaneous dehydrogenation of naphthenes Commercial grade desulfurized naphtha is prepared from sulfur-containing straight run and cracked naphthas Removal of thiophenes from aromatic hydrocarbon oil A highly olefinic gasoline fraction desulfurized in the presence of hydrogen under conditions to avoid hydrogenation of olefins Study of selective hydrogenation of sulfur compounds from highly unsaturated cracked gasoline Catalytic desulfurization of petroleum hydrocarbons Desulfurization of gas oil with hydrogen supplied from the hydrocarbon feed stock

~~~

1 634

~


Catalysts Co and Mo oxides on alumina with 0.1 to 6.0% F Co and Mo oxides on alumina with both F and P T i halide and P Pt

Literature Cited (4F)

(5F)

Co0-51003-A120 3 Cobalt molybdate containins F Cobalt molybdate C o and Mo oxides

Alumina Alumina Co molybdate Cobalt and molybdenum oxides and F on . 4 1 2 0 3 support

(XF)

HYDROGENATION A N D HYDROGENOLYSIS

Petroleum, Coal, and Related Materials (Continued) DESULFURIZATION (Continued) Subject Union's cobalt molybdate process for refining high sulfur stock Catalytic treatment of mineral oil hydrocarbon in admixture with added hydrogen Pilot plant study of hydrodesulfurization of crudes at 800' to 850' F. and 500 to 1000 p.s.i. Preparation of heating oil from sour virgin fuel oil by mild hydrofining Process for improving quality of heating oil under mild conditions of 400" to 700" F. and 50 to 250 p.s.i., reducing sulfur content about 35% Hydrocatalytic desulfurization of crude oil at 750' to 850" F. and 500 to 1500 p.s.i. Process of hydrodesulfurizing heavy hydrocarbons containing substantial amounts of asphaltic material Shell upgrades stock by hydrodesulfurization

Literature Cited f 74F)

Catalysts Cobalt molybdate COO,h?oOs, A1203 Cobalt molybdate on A ~ z O J Molybdenum oxide on carrier Co and h?o oxides on bauxite W-Ni sulfide

Increasing Octane Number Subject Xfethod for preparing an alumina- halogen-platinum catalyst for reforming petroleum fractions Method for preparing an alumina-halogen-platinum catalyst utilizing hexamethylene tetramine Preparation of hydroforming catalysts containing platinum or palladium Process for reforming straight run gasoline and its fractions in presence of hydrogen Two stage process for catalytic conversion of straight run gasoline Process for reforming in presence of hydrogen hydrocarbon stock in gasoline range Nonregenerative process for converting heavy naphtha to product having improved octane number Regenerative process for hydroforming naphtha with fluidized catalyst Process for manufacturing gasoline of improved octane number from h e a w virgin nanhtha Process for hydroisomerization of saturated hydrocarbons at temperatures above 750' F. and pressures in excess of 50 p.s.i. Catalytic upgrading of gasoline and naphthas in presence of hydrogen A process for selectively hydrogenating diolefins in presence of mono-olefins in naphtha, thereby improvkg quality f& motor fuel . A process for seIectively hydrogenating diolefins in presence of mono-olefins in naphtha thereby improving quality for motor fuel Method for eliminating gum forming constituents from highly olefinic hydrocarbon fraction in uresence of hvdroaen ,- 0 Slultistage process including steps of destructive hydrogenation and reforming to produce high yields of gasoline from crude oil Catalytic conversion of a mineral oil distillate in presence of hydrogen and a silicone coated catalyst Process for producing motor fuel from gas oil wherein aromatic constituents having 4 condensed rings or more are selectively hydrogenated Regenerative process for high-pressure hydrogenation of hydrocarbons in fluid bed reactor Pretreatment of naphtha stocks high in nitrogen compounds under hydrocracking conditions prior to reforming

Catalysts Pt and F on A1203 Pt and F on A1203 Pt or Pd and F on Alp03 Pt and F on A1203 0.05 to 1.5% Pt and 0.1 to 3.070 combined halogen on A1203 Pt, Pd 0.1 to 2.0% Pt, 30 to 50% ZnO, and 70 to 50% iuzo3 10% M O O Son . 4 1 2 0 3 10% MoOa on .41103

Moo3

(52F)

0.5 to 2% M o o 3 on Si02 Moos Ni-W sulfide Alumina Ni-Si02

(57F)

A1203 and/or Si02 with metal oxide or sulfide having atomic No. between 22 and 42

(291;)

I

Pt-Alp03-halide

Petroleum Residuum and Related Heavy Oils Subjgt Two stage process for destructive hydrogenation of mineral oils and shale oils for production of gasoline Destructive hydrogenation of petroleum residues giving low carbon and gas forma-

Catalysts SiOn, A1203, and Mo or W compounds

(58F) (8F)

tinn .._..

Hydrogenation and desulfurization of petroleum residues to increase yield of Diesel fuel stock Process including hydrogenation for recovery of naphtha from petroleum oil or crude residues Refining of crude Diesel oils by medium pressure hydrogenation Studies on hydrogenation of Middle East crudes for conversion to gasoline High pressure hydrogenation in processing of crude oils in Germany Hydrogenation of heavy oils wherein hydrogen is formed by action of steam on metal, such as iron, in presence of oil Isomerization of naphthenic mineral oils in presence of hydrogen Hydrogenation of Wyoming black oils in rocking autoclave Pyrolytic hydrogenolysis of nitrogen bases in hydrocarbon oil fractions

Literafur6 Cited

24% MoOa, 4.5%

COO on A1203

Silica and/or alumina containing Mo or W and Cr, Fe, Ni or Co 10% MOODon alumina, NiO or COO

Ni Ni None


(6F) (QF) (75F) (6 0 F ) ( 73F) (63F) (77F) (47F) (72~)

SEPTEMBER 1956

1635


Petroleum, Coal, and Related Materials (Confinued) Coal and Related Material Subject Catalytic studies in batch autoclave experiments on liquid phase hydrogenation of coal Kinetic studies on destructive hydrogenation of coal in stirred autoclave Chemical composition of liquid phase from hydrogenation of tar from Cheremkhovo coal Hydrogenation of Assam coal Studies in batch unit on further hydrogenolysis of residues from hydrogenated Pittsburgh coal Reaction studies on uncatalyzed hydrogenolysis of coal High temperature medium pressure hydrogenation of light oils from lignites Review of various processes for hydrogenation of coal, tar, and crude oils Pilot scale tests on hydrogenation of coal to gaseous hydrocarbons Bench scale tests on fluidized-bed and b e d - b e d hydrogenation of coal to produce gaseous hydrocarbons Hydrocarbon-rich fuel gas by hydrogenation of coal in fluidized reactor Effect of pressure on low temperature carbonization of Russian coals Sulfur removal from low temperature carbonization char with hydrogen-methane mixtures Two-step process for desulfurizing coke particles, including treatment with oxygencontaining gas followed by hydrogen Process for desulfurizing coal with low conversion to gas or vapor

Catafysts (NH4)&fo04, NiCla, SnCl?, F e S 0 4 , and CoSOa AI red mud and F e S 0 4 Fe 80% SnS and 20% NHICl

None

NaaCO?

Organic Compounds Nickel Catalysts Subject Kinetics of hydrogenation of cinnamic alcohol Hydrogenation of benzyl ester of cinnamic acid Manufacture of cyclohexanone by hydrogenation of phenol Hydrogenation of glucose to sorbitol Hydrogenation of isoprene Hydrogenation of 2-cyanoethyl glycol ethers Mixtures of unsaturated organic compounds Hydrogenation of conjugated bonds in benzalacetone Furfurylidene ketones to corresponding secondary alcohols Peculiar behavior of catalyst in vapor-phase hydrogenation of furfuryl alcohol Catalytic hydrogenation of furfural to furfurol Selective hydrogenation of furan compounds Continuous hydrogenation of synthetic resins from alkyl aromatic ketones and formaldehyde Production of 5(4-hydroxybutyl)hydantoin Reductive amination of ethylene-carbon monoxide polyketones to polyamines Catalytic hydrogenolysis of isocamphane Anomalous reduction of 7,9-dioxoperinaphthane and its methyl ester Hydrogenation of dypnopinacol and luteodypnopinacolone Nuclear reduction in biogenesis of xanthones Syntheses of DL-glutamic acid and DL-ornithine Catalytic hydrogenation of 3-methoxy-5,6-diphenyl-l,2,4-triazine Reduction of &lactones by catalytic hydrogenation Hydrogenation of 5-aminoisoxazoles Catalyzed reduction of aromatic nitro compounds to amines using hydrazine hydrate Hydrogenation of diphenylfulvene Catalytic hydrogenation of hydroxybenzaldehydes Exhaustive hydrogenation of a- and p-hydroxyacetophenone Hydrogenation of 9-anthraldehyde Catalytic reduction of aralkylethers and aralkylamines Hydrogenation of three dimethylolbenzenes Catalytic hydrogenation of nitrosochlorostilbenes Syntheses of 8- or 10-alkylated decahydroquinolines Synthesis of 2-methyl-9-ethoxycarbonyldecahydroisoquinoline Use of organic nitrite to prevent nuclear hydrogenation in reduction of anthraquinones Use of organic nitrile to prevent nuclear hydrogenation of anthraquinones Aromatic nitro compounds to amines Process for preparing phenyl hydroquinone Process for preparing hydrogenated derivatives of phenyl hydroquinone Asymmetric synthesis effected by hydrogenation of unsaturated compounds Promotion of catalyst by treatment with HzPtCle Catalyst inhibited with halogen compounds to attain selectivity Preparation of active hydrogenation catalyst Method for preparing and activating catalyst Sensitivity of catalyst to poisoning with hydrogen chloride Prepared from Ni-Cr steels Improved activity by addition of small amounts of surface-active agents Method of preparing active catalyst and its regeneration ~~

1 636

~

~~

INDUSTRIAL AND ENGtNEERlNG CHEMISTRY

Chtalysts Raney Ni with Pt added Ni Ni-kaolin, Cu-asbestos Ni on A l a 0 3 with Cr and Co Xi, Pt, and Pd Raney Ni Raney Xi, Pd o n C a C 0 3 Raney Ni Raney Xi Xi on kieselguhr Raney Xi Raney Ni and Ni on kieselguhr Xi-Cr-Si02 gel Ni, Co Ni on kieselguhr, Cu chromite, and Pd on carbon Ni on kieselguhr, Raney Ni, Cu chromite, Cu-alumina, and Pt-alumina Raney Ni, PtOn. and Cu chromite Raney Ni Ranev Ni k a G ; NI Raney Ni, Pt Raney Ni Raney Ni Raney Ni Ranev Ni. Pt. and Pd Raney N( Raney Ni Raney Ni Raney Ni, Pd on carbon Raney Ni Raney Ni Raney Ni Raney Ni Ni '

Ni Ni sulfide-alumina Raney Ni and precious metals Raney Ni and precious metals Raney Ni Raney Ni Raney Ni Ni, Zn Ni Raney Xi Raney Ni Raney Ni 25% Ni, 2% Cr. dnd 73Yo A1


Organic Compounds (Continued) Palladium and Platinum Group Catalysts Subject Catalytic hydrogenation of tetrapropylhexadiynediol Rate of hydrogenation of 2,2,3,6,7,7-hexamethyl-4-octyne-3,6-diol and 2,5,6,6tetramethvl-3;heptyne-2,5-diol .qddition o f hydrogen to tetrapropylbutynediol and bis(1-hydroxycycloheptyl) . . .. . . . _ . acetylene Hydrogenation rate of 2,5-dimethyl-3-heptyn-2,5-diol and 3,6-dimethyl-4 nonyn3,6-diol Reaction of hydrogen with p-ditolybutynediol Catalytic hydrogenation of acetic ester of 2,7-dimethyl-3,5-octadiyne-2,7-diol Addition of hydrogen to symmetric dimethyldihexylbutyediol Hydrogenation of acetylenic bonds Transformations of butylcycloheptane Reduction of 11-oxoprogesterone to 38-hydroxy-allopregnane-l1,20-dione Low pressure hydrogenation of methyl and butylketene dimers Catalytic hydrogenation of aliphatic nitro derivatives Hydrogenation of methylphenylethynylcarbinol in presence of retarders Hydrogenation of methylphenylethynylcarbinol in presence of retarders Hydrogenolysis of a- and 8-menaphthylamine . Hydrogenation of epoxidized olefinic compounds Production of adipaldehyde Process for the production of 3~u-hydroxypregnane-11,20-dione Hydrogenation of epichlolesteryl chloride Cqra!vtic reduction of diphenylalkanolamines Hydrogenation of hydroxybenzoic acids Process for the production of 3-keto-bisnor-4-cholen-22-al Method of preparing caffeine derivatives Hydrogenation of methyl-substituted benzilic acids Selectivity of noble metal catalysts for hydrogenation of acetophenone Process for preparing substituted aminodiphenylamines Lfethod for preparing highly active catalysts by reduction of their salts in liquid ammonia Rate of hydrogenation of allyl alcohol in various solvents

Cala& ts

Pt, Pd Pt, Pd Pt, Pd Pd Pd Pt-starch Pt, Pd Pd-Pb Pt on carbon Pt Pt Pt Pd Pd, LiA1H4 Pd on carbon 59& Pd on carbon Pd Pi -.

Pt Pt Pd Pd on charcoal Pt Pt, Pd Pt, Pd Pd, Ru, and R h Pt

Copper, Chromium, and Related Catalysts Subjfct Hydrogenation of hydroxy-substituted aromatic ketones and related compounds Hydrogenolysis of substituted meta dioxanes to produce 3-methyl-1-butanol Production of 2,4,4trimethylpentanol Preparation of copper catalyst and poisoning action of nitrate ion in its use for hydrogenation of ethyl stearate

CQtalVS! r

Cu chromite Cu-Cr oxide cu Cu-kieselguhr

Metal Hydrides S2r bject Transformation of the complex of cinnamaldehyde and lithium aluminum hydtide Reduction of substituted ethyl cyanoacetates Reduction of l-(p-methox~t~enz~1)-3,4,5,6,7,8-he~ahy~oisoquinoline Reduction of mesityl oxide Amide reductions Reduction of some Grignard reagent-carbon dioxide adducts to primary alcohols Xanthates reduced to mercaptans Cleavage of disiloxanes to silane Preparation of saligenin Reduction of p-substituted stilbene oxides Reducing agent for anthoxanthins Hydrogenated bis(indo1e quaternary salts ) Reduction of p-toluenesulfonic esters of carbohydrates and related compounds Action on phenylated chalcones Reduction of end group carbonyls of dipeptides Preparation of steroids Synthesis of sapogenin derivatives Action on brucine Reduction of apoyohimbine Reduction of certain 2-phenyl-4-arylideneoxazolones Review on use in organic chemistry Reduction of p-toluenesulfonate Selective reduction of oxosteroids Selective hydrogenation of aldehyde, ketone, acid chloride, acid anhydride, and ester groups in presence of other reducible groups such as double and triple bonds Reduction of esters to alcohols Reduction of methyl 3-oxo-4-etiocholenate Literature review on use for reductions Reduction of gem-chloro nitroso compounds to oximes Preparation of 5-benzyloxytryptamines Review on reduction of organic compounds

cflto1,sti

LiAlH4 LiAlH4 LiAlH, LiAlH4 LiAlH4 LiAlH4 LiAlH4 LiAlH4 LiAlH, LiAlH4 LiAlH4 LiA1H4 LiAlH4 LiAlH4 LiA1H4 LiA41HA Li AIH; LiAIHl LiAlH4 LiXlH4 LiAlH4 KaBH4, LiAlH, KaBH4 Alkali metal borohvdrl des arid alk:oxyborohydrides K or Na borohydrides NaBHa NaBH4 LiAlH4, NaBH, Metal hydrides hietal hydrides


SEPTEMBER 1956

1637


0 rga ni c Cornpo unds (Continued) MISCELLANEOUS Subject Process for the preparation of ether-substituted 1,5 pentanediols Activity of skeletal iron catalysts in hydrogenation reactions Hydrogenation of hydrocarbons with different types of unsaturated linkages and of oxygenated aromatic hydrocarbons Pure hydrocarbons from hydrogenation of alcohols, ketones, esters, and acid anhydrides Selective reduction of conjugated nitroolefins Catalytic hydrogenation of polyhydric phenols Hydrogenation of a 1,3-dioxan to 2,2,4-trimethylpentan-1 &diol Partial hydrogenation of polyunsaturated organic compounds

Catalysts Heavy metals of Groups I, 11, and IV to VI11 Fe Fe, WS2

ws 2

Fundamental Studies CATALYSTS Subject Kinetics of diffusion for complex reactions and catalytic hydrogenation in liquid phase The multiplet theory and principle of detailed equilibrium. The mechanism of hydrogenation and dehydrogenation Fundamental experiments on activity test Effect of method of developing nickel-aluminum alloys Effect of nickel-aluminum alloy composition on catalytic activity Residual aluminum in catalyst after development Treatment of Raney alloys with hydrochloric acid Problems in the pulverization of the alloys Change of work function of nickel catalyst by coating and of nickel selenide-coated nickel catalyst due to adsorption of hydrogen and ammonia Effect of gas adsorption on the contact potential difference of nickel selenide+oated nickel catalyst X-ray and electron diffraction studies on surface structure Mechanism of exchange reaction between deuterioammonia and hydrogen in presence of selenium-coated nickel catalyst Reaction capacity of hydrogen which is sorbed by a skeleton nickel catalyst Reduction of the metal-hydrogen component of the active surface of a nickel catalyst Chemisorption of ethylene on surface of nickel The reaction mechanism of ethylene on nickel surface The role of hydrogen in Raney nickel catalyst The metal-hydrogen nature of the skeletal nickel catalyst Chemistry of Raney nickel action Reaction of components of skeletal nickel catalyst with mineral oxidizing agents Specific surface of Raney nickel catalysts Surface area, activity, and heats of solution of nickel-magnesium mixed formate catalysts Energy content of powdered metal catalysts Promotion and poisoning of nickel catalyst in liquid-phase hydrogenation Poisoning of catalysts of different physical structures Effects of positive ion bombardment and heat treatment on activity of nickel catalyst Activity of a skeletal iron catalyst in hydrogenation reactions Nature of the activity of a n iron skeletal catalyst Chemisorption of nitrogen, hydrogen, and carbon monoxide on singly and doubly promoted iron catalyst Hydrogenation through metal septa Electric conductivity, catalytic activity, and surface chemistry of chromic oxide The metal-hydrogen nature of certain hydrogenation catalysts

catalys6s

Raney Ni Raney Ni Raney Ni Raney Ni Raney Ni Raney Ni Ni-Ni selenide Ni-Ni selenide Xi-Ni selenide Ni, selenium coated Ni Ni Ni Ni Raney Ni Ni Raney Ni Raney Ni Raney Ni Ni-MgO Ni, Co Ni-Si02 gel promoted w-ith Rh, Pd, Pt, Ru, and Os Ni-MgO Ni Fe Fe FesOc with 5% A 1 2 0 3 and K z 0 Fe CrzOs

"Among its many applications, hydrogenation has played a key role in the development of modern synthetic detergents. In recent years the classic Bouveault and Blanc reaction, the sodium reduction of fats to fatty alcohol, has been brought to a high chemical efficiency. Fatty alcohols are now produced in large quantity with high purity and in good yield. Alternatively, new developments in high pressure catalytic techniques have recently made important reductions in cost. These new developments in hydrogenation have contributed to the plentiful supply of the modern detergents which are now available to the American housewife." J. G. Pleasants Vice President in Charge of Research and Development The Procter & Gamble Co.

1 638


HYDROGENATION AND HYDROGENOLYSIS (Continued jrom Page 7630)

Union

actions; however, a trend in the field i n dicates increased attention to nickel in other forms. Platinum a n d palladium catalysts were employed extensively. Severa1,studies were made utilizing copper a n d copper chromite catalysts. Ruthenium a n d rhodium are reported to be active hydrogenation catalysts. Lithium aluminum hydride a n d sodium boron hydride were studied extensi\pely for many types of organic reductions.

(42A) Ibid., 49, 246-58 (1954). ( 4 3 4 ) Uekotter, Johannes, Gluchaii/ 370-6 (1952).

88,

Oxo Synthesis 47, 140-6 (1955). Gas Research Board, Brit. Patent 712,689 (July 28, 1954). Gross, H.-\V., Royen, P. A. C. (to Metallgesellschaft Aktiengesellschaft), U. S. Patent 2,727,056 (Dec. 13. 1955). Gusev, V. I., Christozvonov, D. B., Doklady Aknd. IVauk S.S.S. R. 98, 629-31 (1 954). Guyer, A., Guyer, P., others, Helv. Chim. Acta 38. 798-809 (1955). Hall. C. C.. ’Rennie. J.. ?4orId Petrolevm Congr., Pro;., 3;d Congr. Hague, 1951, Sect. IV, 25-37. Hall, C. C., Taylor, A. H., J . Inst. Petroleum 41, 101-24 (1955). Kolbel, Herbert, Ackermann, Paul, Ibid., 1951, Sect. IV, 2-14. Kratzer. hl. B. (to Stanolind Oil and Gas Company), U. S. Patent 2,704,293 (Mar. 15, 1955). Lavrovskii, K. P., Kolbanovskii, Yu. A., Dokladv -4kad. Nauk S. S.S.R. 101, 687-8 (1955). Lebedev, V. V., Trudy Inst. Goryuch. Iskopaemykh, d k a d . Nauk 3. S.S.R. 2, 138-45 (1940). Mattox, LV. J. (to Esso Research and Engineering Co.), U. S. Patent 2,707,713 (May 3, 1955). Mattox, W. J., Buchmann, F. J., Ibid., 2,708,674 (May 17, 1955). McGrath, H. G. (to 14. L V , Kellogg C o . ) , U. S. Patent 2,700,676 (Jan. 25, 1955). McGrath, H. G., Rubin, Louis, C., Ibid., 2,728,786 (Dec. 27,1955). Metallgesellschaft h.-G., Ger. Patent 763,982 (Oct. 4, 1954). Ibid., 846,691 (Aug. 14: 1952). Natta, G., f.chim. phys. 51, 702-10 (1954). Probst, R . E. (to Standard Oil Co.), U. S. Patent 2,698,862 (Jan. 4, 1955’1. Rheinpreussen Akt.-Ges. fur Berghau und Chemie, Brit. Patent 728,602 (Apr. 20, 1955). Riblett, E. W., McGrath, H . G. (to M. Mi. Kellogg Co.), U. S. Patent 2,702,814 (Feb. 22, 1955). Ruhrchemie 21.-G., Lurgi Gesellschaft fur LVarmetechnik m. b. H., Brit. Patent 711,406 (June 30,

Fundamental Studies Numerous fundamental studics were m a d e in the field of catalytic hydrogenation. T h e kinetics of diffusion for complex hydrogenation reactions in the liquid phase were studied. T h e multiplet theory was applied to describe the mechanism of hydrogenation reactions. Considerable work was done to define factors which influence the catalytic activity of R a n e y nickel. O t h e r studies o n skeletal nickel catalysts relate to the reaction i a p a c i t y of sorbed hydrogen a r d the nature of the metal-h!-drogt,n bond. T h e effects of positive ion bombardment o n the activity of a nickel catalyst also A seiirs of studies were investigated. made o n a selenium-coated nick+,l catalyst includes determinations on the change of work function and contact potential difference d u e to the adsorption of hydrogen a n d ammonia, a n d a n investigation of’ the mechanism of the exchange reaction be tween deu terioammonia a n d hydrogen. T h e activity of a skclrtal iron catalyst for promoting hydrogenation reactions was studied, a n d it was established that the metal-hydrogen bond is less stable t h a n in nickel catalysts. Investigations included the chemisorption of hydrogen, nitrogen, a n d carbon monoxide on a promoted iron oxide catalyst. Experiments were drscribed on the electrical conductivity, catalytic activit)., a n d surface chemistry of chromium oxide.

1954)

BIBLIOGRAPHY Hydrogenation of Carbon Oxides (1A) Anderson, H. C., Wiley, J. L., Newcll, A., U. S. Bur. Mines, Bull. No. 544 (1954). ( 2 h ) Arnold, H . R., Herrick, E. C. (to E. I. du Pont de Nemours 8r Co.), U. S. Patent 2,726,218 (Dec. 6, 1955). (3.4) Badische Anilin- und Soda-Fabrik, Ger. Patent 825,398 (Dec. 17, 1951). (4X) Bashkirov, A. N., Loktcv, S. X f . , Izvest. Akad. .Vauk S. S. S. R., Otdel. Tekh. .Vauk 1954, No. 8, 147-53. (5‘4) Batcheider, H. R., Selson, H. W., Mech. Eng. 78, 11-14 (1956). (6.4) Brown, J r . , J. H., Martin, G. R. (to The Dow Chemical Co.), U. S.Patent 2,711,420 (June 21, 1955). ~ .. ~ (7.4) Davis, H. G., Wilson, T. P. (to

Carbidr and Carbon U. S. Patent 2,717,259

(37A) (38A) (39X)

(40A)

(41A)

1bzh.,-712,686 ( J u l y 28, 1954). Ibzd., 714,839 (Sept. 1, 1954). [bid., 718,386 (Nov. 10, 1954). Ibzd., 728,074 (April 13, 1955). Ibzd., 728,715 (Apr. 27. 1955). Ibid.; 730;487 ( h i a y 25; 1955). Sastri, M. V., Viswanathan, T. S., f. Sci. Ind. Research (India) 13B, 590-1 (1954). Seelig, H. S., rVeck, H. I. (to Standard Oil Co.), L.S. Patent 2,727,055 (Dee. 13, 1955). Teichmann, C. F., Grahame, J. H . (to Texaco Development Corp.), U. S. Patent 2,714,116 (July 26, 19551. Uchida: Hiroshi, Ichinokawa, Hideo, Ogawa, Kiyoshi, Repts. Goat. Chem. Ind. Research Inst., Tokyo 50, 285-94 (1955). Uchida, Hiroshi, Todo, Naoyuki, Ogawa, Kiyoshi, Ibid., 48, 266-76 (1953).

(1B) Anglo-Iranian Oil Co. Ltd., Brit. Patent 719,863 (Dec. 8, 1954). (2B) Biribauer, F. A,, Staib, J. H., Mertzweiller, J . K. (to Esso Research and Engineering Co.), U. S. Patent 2,726,199 (Dec. 6, 1955). (3B) British Petroleum Co. Ltd., Brit. Patent 715,744 (Sept. 22, 1954). (4B) Ibid., 721,956 (Jan. 19, 1955). (5B) Buchner, Karl, Hagemann, August (to Ruhrchemie Aktiengesellschaft), U. S. Patent 2,701,816 (Feb. 8, 1955). (6B) Buchner, Karl, Stader, Hermann, Ibid., 2,701,265 (Feb. 1 , 1955). (7B) Carter, C. E., Gwynn, B. H. (to Gulf Research and Develooment Co.), L. S. Patent 2,718,792 (Dee. 27, 1955). (8B) Caterall, M‘. E. (to Standard Oil Development Co.), U. S. Patent 2,700,687 (,Jan. 25, 1955). (9B) Chemische Verwertungsgesellschaft Oberhausm m. b. H., Brit. Patent 719,573 (Dec. 1, 1954). (10B) Eidus, Ya. T., Ershov, N. I., Terent’eva, E. hi., Imest. Akad. h h u k S. S. S. R., Otdel. Khim. Nauk 1954, 882-9. (11B) Eidus, Ya. T., Puzitskii, K. V., Guseva, I. V.,Ibn’d., 1954, 890-7. (12B) Fasce, E. V.,Mertzweiller, J. K . (to Esso Research and Engineering Co.), U . S. Patent 2,705,729 (Apr. 5, 1955). (13B) Hale: C. H., Ibid., 2,726,268 (Dee. 6 , 1955). (14B) Kearby, K . K., Ibid., 2,713,074 (Julv 12. 1955). (15B) Marti;, .2.’ R.: -Chemistry 3 Industr? 1954, 1536-7. (16B) hfertzweiller, J. K. (to Esso Research and Engineering Co.), U. S. Patent 2,709,714 (iMay 31, r n r c , 1722).

(17B) Mertzweiller, J. K., Kimberlin, Jr., C. N., Ibid., 2,709,713 (May 31, 1955). (18B) h.Iertz\;.eiller, J. K., Smith, \V. hf., Ibid., 2,725,401 (Nov. 29, 1955). (19B) Mikeska, L. A., Morway, A. J., Ibid.; 2,719,124 (Sept. 27, 1955). (20B) Naragon, E. A, Millendorf, A . J., Ibid., Vcrgilo, J. H. (to The Texas Co.), U S. Patent 2,699,453 (Jan. 11, 1955). (21B) Owen, J. J., Buchmann, F. J. (to Esso Research and Enrineerinq Co.), U. S. Patent ?,706,20; (Apr. 12, 1955). (22B) Owen, J. J., hlertzweiller, J. K . (to Standard Oil Development Co.), U. S. Patent 2,699,454 (Jan. 11, 1955). (23B) Reynolds, P. LV., Lamb, S. A. (to Imperial Chemical Industries (Nov. 15, Ltd.), U. 1955). S. Patent 2,723,997 (24B) Ruhrchemie A.-G., Brit. Patent 726,135 (Mar. 16,1955). (25B) Russum, L. W., Hengstebeck, R. J. (to Standard Oil Co.), U. S. Patent 2,728,798 (Dec. 27, 1955). (26B) Sherwood, P. W., Petroleum Processing 8, 241-8 (1953). (27B) Smith, W.M. (to Esso Research and Engineering Co.), U. S. Patent 2,713,073 (July 12, 1955). (28B) Sueta, Hideo, et al. (to Mitsubishi Chemical Industries Co.), Jap. Patent 3321 (June 9, 1954).


SEPTEMBER 1956

1639

UNIT PROCESSES REVIEW (29B) Taylor, A. W. C., Harding, J. B. (to Imperial Chemical Industries Ltd.), U. S. Patent 2,723,998 (Nov. 15,1955).

Ammonia Synthesis (1C) Bauch, W. A. (to Esso Research and Engineering Co.), U . S. Patent 2,707,706 (May 3, 1955). (2C) Eiekmeyer, A. G., Marshall, W. H., Chem. Eng. Progr. 51, 418-21 (1955). (3C) Paull, P. L. (to Texaco Development Corp.), U. S. Patent 2,706,147 (Apr. 12, 1955). (4C) Pfeiffer, C., Sandler, H. J.,Petroleum Rejner 34, No. 5, 145-52 (1955). (5C) Roiter. V. A.. Korneichuk. G. P.. others, Zhur.’ Fiz. Khim. 28, 16381 51 (1954). (6C) Stark:Virgh, U. S . Patent 2,714,060 (July 26, 1955). (7C) Weber, George, Oil Gas J . 54, No. 20, 80-3 (1955).

Oil and Fat Hydrogenation (1D) Allen, R. R., Kiess, A. A,. J . A m . Oil Chemists‘ SOC. 32, 400-5 (1955). (2D) Ayerbe, Felix Ramos, Grasas y acrites (Seville, Spain) 5 , 154-9 (1954). (3D) Bamag Ltd., Brit. Patent 723,887 (Feb. 16, 1955). (4D) Csuros, ZoltAn, Gtczy, Istvhn Szab6, Dknes, Acta Chim. Acad. Sci. Hung. 2, 33-56 (1952). (5D) Dunmire, Russell P., U. S. Patent 2,724,689 (Nov. 22, 1955). (6D) Empresa Nacional “Calvo Sotelo” de Combustibles Liquidos y Lubricantes, Span. Patent 212,632 (June 9, 1954). (7D) Zbid., 215,121 (June 14, 1954). (8D) Hoffmann, A. N., Montgomery, 3. B. (to Hercules Powder Co.), U. S. Patent 2,727,885(Dec. 20, 1955). (9D) Kane, J. G., Kulkarni, K. B., J . Sci. Znd. Research (India) 13B, 890 (1954). flOD) Moreno, 3. M. M., Ayerbe, F. R., Ole‘agineux 9, 697-702 (1954). (11D) Opie, J. W. (to General Mills, Inc.), U. S. Patent 2,715,641 (Aug. 16, 1955). (12D) Swicklik, L. J., Hollingsworth, C. A,, Daubert, B. F., J . A m . Oil Chemists’ Soc. 32, 69-73 (1955). (13DI Ven-zerova. N. V.. Ashkinazi. Z. hl.. Myasloboino-Zhirhvayu Prom. 19; NO. 7, 16-8 (1954). (14D) Waisgluss, Fernando, Brenner, R . R., Industria y quimica (Buenos Aires) 17, No. 1, 13-18 (1955). (15D) Zharskii, A. M., Novikova, ‘I?. M., others; Masloboino-Zhirocava Prom: 19, NO, 7, 18-20 (1954). \

I

Acetylenes, Olefins, Aromatics, and Other Hydrocarbons ( I E ) Caipetta, F. G.: Hunter, J. B. (to T h e Atlantic Refining Co.), U. S. Patent 2,721,226 (Oct. 18, 1955). ( 2 E ) Clark, Alfred (to Phillips Petroleum Co.), U. S. Patent 2,706,211 (April 12, 1955). (3E) Clough, Harry (to Imperial Chemical Industries Ltd.), U. S. Patent 2,709,193 (May 24, 1955). ( 4 E ) Zbid,, 2,709,194 (May 24, 1955). ( 5 E ) Eyring, Henry, Parlin, R. B., others, Research Council Israel,

1640

Spec. Publ. No. 1 (L. Farkas Mem. Vol.), 152-80 (1952). (6E) Fuener, Wilhelm von, Oettinger, Willi, others (to Badische Anilinund Soda-Fabrik Akt.-Ges.), U. S. Patent 2,708,180(May 10, 1955). (7E) Gonikberg, M. G., Nikitenkov, V. E., Zzvest. Akad. h’auk S.S.S.R., Otdel. Khim. Nauk 1954, 936-44. (8E) Hetzel, S . J. (to Sun Oil Co.), U. S . Patent 2,698,869(Jan. 4, 1955). (9E) Hoelscher, H. E., Poynter, W. G., Weger, E., Chem. Reus. 54, 575-92 (1954). (10E) Isagrlyants, V. I., Esayan, G. T., others, Doklady Akad. Nauk S.S.S.R. 94, 883-5 (1954). (11E) Kazanskii, B. A , , Lukina, hf. Yu., Ovodova, V. A., Bull. Acad. Sci. U.S.S.R., Div. Chem. Sci. 1954, 759-61. (12E) Khromov, S . I., Balenkova, E. S., others, Zhur. Obshchei Khim. 24, 1360-4 (1954). (13E) Lozovoi, A. V., Senyavin, S. A., Sbornik Statei Obshchei Khim. Akad. hrauk S.S.S.R. 2, 1035-42 (1953). (14E) LozovoI, A. V., Senyavin, S. A,, Zhur. Obshchei Khim. 24, 1803-9 (1 954). (15E) Lozovoi, A. V., Senyavin, S . A., Vo1’-Epshtein, A. B., J . App. Chem. (U.S.S.R.) 28, 159-65 (1955). (16E) Lukina, M. Yu., Ovodova, V. A., Kazanskii, B. A., Doklady Akad. h’auk S.S.S.R. 97, 683-6 (1954). (17E) Nonnenmacher, Helmut, Fuener, 1%‘. von (to Badische Anilin- und Soda-Fabrik Aktiengesellschaft), U. S. Patent 2,705,733 (Apr. 5, 1955). (18E) Reitz, Ortwin, Fuener, Wilhelm von (to Badische Anilin- und SodaFabrik Aktiengesellschaft), U. S . Patent 2,706,209 (Apr. 12, 1955). (19E) Rubinshtein, A. hf., FreIdlin, L. Kh., Borunova, N. V., Zzoest. Akad. Nauk S.S.S.R., Otdel Khim. hiauk 1955, 766-7. (20E) Shiba, Tadao, Reptf. Gov. Chem. 2nd. Research Znst., Tokyo 49, 278-9 (1 954). 21E) Zbid., pp. 280-2. 22E) Ibid., pp. 287-322. (23E) Tsutsumi, Shigeru, Terada, Hirotsugu, J . Chem. Soc. Japan, Znd. Chem. Sect. 57, 208-10 (1954). (24E) Urban, Wilhelm, Starker, Herman (to Scholven-Chemie Aktiengesellschaft), U. S. Patent 2,701,267 (Feb. 1, 1955). (25E) Vishnevskii, N. E., Maiorov, D. M., J. Appl. Chem. L‘.S.S.R. 28, 369-76 (1955). (26E) LVatt, George LV., Walling, Jr., M. T., J . Phys. Chem. 5 8 , 7-10 (1955). (27E) Yamanaka, Tatsuo, Refits. Sci. Research Inst. ( J a p a n ) 30, 123-30 (1954).

I

Petroleum, Coal, and Related Materials (1F) Abbott, iM. D., Liedholm, G. E., Sarno, D. H., Oil Gas J. 54, No. 11, 92-4 (1955). (2F) Anglo-Iranian Oil Co. Ltd., Brit. Patent 713,832 (Aug. 18, 1954). (3F) Ibid., 719,231 (Dec. 1, 1954). (4F) Zbid., 719,627 (Dec. 8 , 1954). (5F) Ibid., 719,640 (Dec. 8, 1954). (6F) Zbid., 721,302 (Jan. 5, 1955). (7F) Zbid., 721,357 (Jan. 5, 1955). (8F) Anhorn, V. J., Montgomery, C. W. (to Gulf Research and Develop-


ment Co.), U. S. Patent 2,700,014 (Jan. 18, 1955). Badische Anilin- und Soda-Fabrik, Brit. Patent 719,543 (Dec. 1, 1954). Basak, I. N. G., Bose, S . K., others. J . Sci. Znd. Research (India) 14B, 284-91 (1955). Baumgarten, P. K.,Hoffman, E. J., Wadley, E. F. (to Standard Oil Development Co.). U. S. Patent 2,694,671 (Nov. 16, 1954). Baumgarten, P. K., Hoffman, E. J.. Wadley, E. F. (to Esso Research and Engineering Co.), U . S. Patent 2,717,861 (Sept. 13, 1955). Becker, R., World Petroleum Congr., Proc. 3rd Congr., Hague 1951, Sect. IV, 68-80. Berg, Clyde, Petroleum Processing 7, 186-9 (1952). Birthler, R., Szkibik, C., Chem. Tech. (Berlin) 6, 373-8 (1954). Blanding, F. H. (to Standard Oil Development Co.), U. S. Patent 2,701,230 (Feb. 1, 1955). Boelhouwer, C., Waterman, H. I., others, J. Znst. Petroleum 41,21 1-14 (1955). British Petroleum Co. Ltd., Brit. Patent 728,505 (Apr. 20, 1955). Zbid., 728,506 (Apr. 20, 1955). Zbid., 728,755 (Apr. 27, 1955). Bronson 11, S. O., Morbeuk, R. C., Sweetser, S . B. (to Esso Research and Engineering Co.), U. S. Patent 2,717,857(Sept. 13, 1955). Ibid., 2,717,858 (Sept. 13, 1955). Brown, K . M. (to Universal Oil Products Co.), U. S. Patent 2,697,064(Dec. 14, 1954). Charlet, E. M., Lanneau, K. P. (to Esso Research and Engineering Co.), U. s. Patent 2,717,864 (Sept. 13, 1955). (25F) Dent, F. J., Conf. intern. gareification integraie hoitille extraite, Liege 1954, 113-24. Dent, F.J.? R G ,rombustibili 8, 61 1-38 (1 954). Docksey, P. P., Federick, W. B., Porter, H. T. (to T h e British Petroleum Co. Ltd.), U. S. Patent 2,726,193 (Dec. 6, 1955). Donaldson, G. R. (to Universal Oil Products Co.): U. S. Patent 2,723,946 (Kov. 15, 1955). Fleck, R . N. ( t o Union Oil Company of California), U . S. Patent 2,722,504 (Nov. 1, 1955). Fleck, R . N., Bills, J. L. (to Union Oil Company of California), U. S. Patent 2,726,195 (Dec. 6, 1955). Gas Research Board, Brit. Patent 712,744 (July 28, 1954). Glenn, R . A,, Fuel 34,201-12 (1955). Gorin, Everett, Zielke, C. W. (to Pittgburgh Consolidated Coal Co.), U . S. Patent 2,717,868 (Sept. 13, 1955). Haensel, Vladimir ( t o Universal Oil Products Co.), U. S . Patent 2,631,136 (Mar. 10, 1953). Ibid., 2,698,829 (Jan. 4, 1955). Hammar, C. G., Tliorld Petroleum Congr., PrGc. 3rd Congr., IfGgue 1951, Sect. IV, 295-307. Hemminger, C. E. (to Standard Oil Development Co.), U. S. Patent 2.696.460 fDec. 7. 1954). Hendridks, G. “.’(to Union Oil Company of California), U. S. Patent 2,728,710 (Dec. 27, 1955). Hoekstra, James (to Universal Oil Products Co.), U. S. Patent 2,689,226 (Sept. 14, 1954). Johnson, C. A , , Schuman, S . C. (to

HYDROGENATION AND HYDROGENOLYSIS Hydrocarbon Research, Inc.), U. S. Patent 2,707,698 (May 3, 1955). Zbid., 2,707,699 (May 3, 1955). Joyce, Jr., T. P. (to Gulf Research and Development Co.), U. S. Patent 2,700,015 (Jan. 18, 1955). Kearby, K. K.. Kirshenbaum, Isidor, Gilbert, G. R . (to Esso Research and Engineering Co.), U. S. Patent 2,728,713 (Dec. 27, 1955). ( 44F 1 Keith, P. C. (to Hydrocarbon Research, Inc.), U. S. Patent 2,707,700 (Xfay 3, 1955). (45F) Knyazeva, kl. S.? Lanin, V. ‘4., others, Zzoest. Akad. h h u k S.S.S.R., Otdel Tekh. iVauk 1955, No. 4, 142-3. Langhout. van Zijll W.C., Stijntjes, G. J. F., others, J . Znst. Petroleum 41, 263-72 (1955). Law, R. D., Petroleum Refiner 34, No. 11. 219-20 (1955). Mason, R. B., Kimberlin, Jr., C. N. (to Esso Research and EnpineerI.), U. S. Patent 2,721,169 4 ”

r n c c ,

(49F) McAfee, Jerry (to Gulf Research and Development C o . ) , U. S . Patent 2,723,943 (Nov. 15, 1955). (5OF) SfcAfee, Jerry, Montgomery, C. W., others, Petrokum Refiner 34, S o . 5, 156-62 (1955). ( 5 l F ) IlcKinley, J. B., Henke, A. hl. (to Gulf Research and Development Co.), U. S. Patent 2,726,148 (Dec. 6, 1955). McKinley, J. B., Kline, R. E. (to Gulf Research and Development Co.), U. S. Patent 2,718,535 (Sept. 10, 1955). (53F) Murrav, M. J., Haensel, Vladimir (to Universal Oil Products Go.). U. S. Patcnt 2,689,208 (Sept. 14. 1954). ( i 4 F ) Murray, M. J., Haensel, Vladimir. Grote, H. IV. (to Universal Oil Products Co), U. S. Patent 2,717,230 (Sept. 6, 1955). (55F) Nicholson, E. W. S. (to Esso Research and Engineering Co. ), U. S. Patent 2,717,855 (Sept. l ? ? 1955 ). (56F) Oblad, ‘\. G., Milliken, Jr., T. H.! Heinemann, Heinz (to Houdry Process Corp.), L’. S. Pater.t 2,700,013 (Jan. 18, 1955). !57F) Ibid., 2,703,308 (Mar. 1, 1955). (58F) Oettinger, Willi, Nonnenmachei. Helmut, other3 ( t o Badische Anilin- und Soda-Fabrik Aktiengesellschaft), U. S. Patent 2,706,705 (Apr. 19, 1955). Pelipetz. M. G., Salmon, J. R.. others, IXD.ESG. CHEM. 47, 2101 3 (1 955). Pier, hf., Fuener, W. von. others, I170rld Petrolmum Congr., Proc. 3rd Congr. Hague 1951, Sect. IV, 8190. Porter, F. i V . B. ( t o British Petroleum Co. Ltd.), U. S. Patent 2,706,703 (Apr. 19, 1955). Zbid., 2,718,490 (Sept. 20, 1955). Reed, H. C., Berg, Clyde, Leffert. C. B. (to Union Oil Co. of California), U. S. Patent 2,694,622 (Nov. 16, 1954). (64F) Schmidt, Rudlolf, Gunther, Gerhard, C h m . Tech. (Berlin) 7, 31623 (1955). (65F I Schongut, S.. Paliva 34, 237-43 (1954). (66F I SiSakov, N. V.: Paliva 34, 8-11 (1954). (6-F) Standard Oil Development Co.,

Brit. Patent 717,012 (Oct. 20, 1954). (68F) Ibid., 717,062 (Oct. 27, 1954). (69F) Stevenson, D. H., Mills, G. A , , Petroleum Refiner 34, No. 8 , 117-21 (1955). (70F) Sudzilovskava. M. S.. Robozheva. E. V., Trudy Vsehyuz. LVauch.Issledoi atel. Zmt. Iskusst. Zhidkogo Toplira i Gaya V N Z G I 1954, No. 6, \

I

71)-45

Wiiler,-‘S. IV., Pelipetz, M. G., World Petroleum Congr., Proc. 3rd Congr., Hague 1951, Sect. IV, 9107. (72F) Wetzel, J. W. (to Houdry Process Corp.), U. S. Patent 2,704,758 (Mar. 22, 1955). (73F) Zimmerschield, W. J., Shalit, Harold (to Standard Oil Co.), U. S. Patent 2,726,991 (Dec. 13, 1955). (:IF)

Organic Compounds (1G) Adamson, D. W., Wilkinson, Samuel (to Burrouqhs Wellcome & Co.), U. S. Patent 2,682,543 (June 29, 1954). (2G) Anderson, R . C., Univ. Microfilms (Ann Arbor, Mich.), Publ. No. 10,830, 72 pp. : Dissertation Abstr. 15, 334 (1955). ( 3 G ) Antropov, L. I., Pochekaeva, T. I., Zhur. Fiz. Khim. 27, 1710-17 (1953). ( 4 G ) Arcus, C. L., Smyth, D. G., Chemistry Industry 1954, 404-5. (5G) Arundale, Erving, Mikeska, L. A. (to Esso Research and Engineering Co.), U. S. Patent 2,721,223 (Oct. 18, 1955). ( 6 G ) Balandin, A. A., Ponomarev, A. A , , DoXlady Akad. .Tad S.S.S.R. 100, 917-20 (1955). (7G) Balcom, D,, Fuist, A , , J. A m . Chem. SOC. 75, 4334 (1953). (8G) Baltazzi, E.? R o h s o n . Robert, Chemistry C3 Industry 1953, 541. ( 9 G ) Bal’yan, Kh. V., J . Gen. Chem. U.S.S.R. 24, 511-16 (1954). (10G) Bal’yan, Kh. V., Zhur. Obshchei Khim. 24, 501-6 (1954). (11G) Bertho, Alfred, Bosch? Hans, Ann. 584. 23-39 (1953). Blanc;, R . B:, Gibson, D. T., J. Chem. SOC. 1954, 2487-9. Bruesch, J., Karrer, P., Helu. Chim. Acta 38, 905-8 (1955). Buvalkina, L. A., Sokol’skiI, D. V., J . Gen. Chem. 1’S.S.R. 24, 833-7 (1954). ( l 5 G ) Buvalkina, L. A., Sokol’skii, D. V., Zhur. Fir. Khim. 28, 961-9 (1954). ( 1 6G) Chemische Werke Hiils G. m. b. H., Ger. Patent 826,974 (Jan. 7, 1952). (17G) Coffman, D. D.. Farlow, M. W. (to E. I. du Pont de Nemours & Co., Inc.), U. S. Patent 2,728,777 (Dec. 27, 1955). (18G) Coffman, D. D., Hoehn, H. H., Maynard, J. Y . , J . A m . C h m . SOC. 76, 6394-9 (1954). (19G) Cooper, L. E., Lacey, R . N. ( t o British Industrial Solvents Ltd.), U. S. Patent 2,700,685 (Jan. 25, 1955). (20G) Cornubert, Raymond, Eggert, H. G., others, Bull. sot. chim. France 1954, 522-36. (21G) Dahn, H., Zoller, P., Solms, U., Helv. Chim. Acta 37, 565-74 (1 954). (22G) Danilevskii, L. P., Sultanov, A. S., Doklady Akad. Nauk U.S.S.R. 1953, NO. 2, 34-7. ( 2 3 G ) Djerassi, Carl, Gorman, Marvin,

others, J . A m . Chem. SOC.77, 56871 (1955). Dornow, Alfred, Fust. K. J., Chem. Ber. 87, 985-90 ( 1 954). Dornow, .4lfred, Hahmann, Otto, Oberkobusch, Rudolf, Ann. 588, 40-4 119543. Dornow: Alfred, kVinter, Gerhard. Vissering, Wilhelm, Chem. B o . 87, 629-33 (1954). E. I. du Pont de Ncmours & Co. Brit. Patent 709,450 (May 26, 1954). fitablissements Huillard, Brit. Patent 710,447 (June 9, 1954). Feldstein: Aaron, Vander Werf, C. A , , J . A m . Chem. SOC.76, 162631 (1954). Fontaine, T. D., Doukas, H. hl. (to Secretary of Agriculture), U. S. Patent 2,716,116 ( h u g . 23, 1955). Freidlin, L. Kh., Rudneva, K. G., Doklady Ahad. ,?.‘auk S.S.S.R. 100, 723-6 (1955). Freidlin, L. Kh., Rudneva, K. G., Sultanov, A. S., Bull. Acad. Sci. U.S.S.R., Diu. Chrm. Sci. 1954, 435-8. Gasson, E. J , , Wild, A. hf., others ( t o The Distillers Co.), U. S. Patent 2,704,774 (%far. 22,1955). Gaylord, N. G.! E.rprientia 10, 423-4 (1954) Germain, J. E., Gault, F., Bull. soc. chim. Frame 1954, 792-7. Goldman, hfartin, J . A m . Chem. SOL.76, 4032-3 (1954). Greensfelder, B. S., hloore, R. J. (to Shell Development Co.), U. S. Patent 2,674,634 (Apr. 6, 1954). Gverdtsiteli, I. M., Mikadze, Sh. G., Sbornik State; ObshcheI Khim., Akad. .Tauk SS.S.R. 2, 952-5 (1953). Zbid., pp. 956-9. Zbid., pp. 960-2. Hasegawa, Hiroshi, J . Chem. SOC. Japan, Ind. Chem. Sect. 58, 334-42 (1955). Hill, C. M., Hill, hi. E., J . A m . Chem. Soc. 75, 4591 (1953). Hogg, J. A , , Beal, P. E., Lincoln, Jr., F. H. ( t o The Upjohn Co.), U. S . Patent 2,715,621 (Auq. 16, 1955). Hogg, J. .\., Sathan, A . H., Lyttle, D. A , , Hanze, A . R. (to T h e Upjohn Company), U. S. Patent 2,701,808 (Feb. 8, 1955). Horii, Zenichi, Jnpan. J . Pharm. & Chem. 27,426-59 (1955). Isaev, Y . B., Doklady Akad. Nauk S.S.S.R. 100. 1087-90 (19553. Ivanov, D., ivanov, c.; others, Comfit. rend. acad. bulgare sci. 6 , NO. 3, 33-6 (1953). Jain, A. C., Mittal, 0. P., Seshadri, T. R., J . Sci. Znd. Research (India) 12B, 647-8 (1953). Jutisz, hfarian, Meyer, D. M., Ptnasse, Lucien, Bull. SOC. chim. France 1954, 1087-91. Kato, Jiro, Ishihara, Hitoshi, Hiwatashi, Osamu, J . Agr. C h m . Soc. Jaban 27. 498-500 (1953). . Kazanskii, B. A . . Gostunskaya, I. V., Granat, A. hl., Bull. Acad. Sci. U.S.S.R., Dir,. Chem. Sci. 1953, 601-6. Kazanskii, B. A., Tcmkina, V. Y . , Ser. Fir.-Mat. i Ertestuen. Nauk NO. 6 , 91-3 (1954). Kelecsenyi-Dumesnil. Eric, Bul!. SOC. chzm. France 1955, 81 5-1 6. Kern, Emil (to Schweiz. Sprengstoff-Fabrik A.G.), U. S. Patent 2,726,151 (Dec. 6, 1955).

VOL. 48, NO. 9, P A R T II

SEPTEMBER 1956

164 1

UNIT PROCESSES REVIEW (55G) Khromov, S. I . . Balenkova: E. S., Kazanskii, B. A , . Zhur. Obshchi Khim. 24,1562-6 ( 1 954). (56G) Kiprianov, G. I., Veitsman, .4.M., Ukrain. Khim. Zhur. 19, 662-3 (1953). (57G) Klimov, B. K., Bogdanov, I. F., Trudy Inst. Goryuch. Isopaemykh Akad. h’auk S.S.S.R. 3, 140-66 (1 954). (58G) Kolobiclski, Marian; LViernann, Joseph, Compt. rend. 238, 1039-41 (1954). (59G) Kubomatsu, Teruc, Science ,2nd Ind. ( J a p a n ) 28, 140-2 (1954). (60G) Kubomatsu, Teruo, JVatanabe, Shoji, Science and Ind. ( J a j a n ) 28, 272 (1954). (61G) Landa, Stanislav, hlosteck9, Jiil, Collection of Czechoslou. Chem. Communr. 20, 430-5 (1955). (62G) Lewis, J. R., Shoppee, C. W., Chemistry & Industry 1954, 933. (63G) Lev, Dean E.? Univ. Microfilms (Ann Arbor, hiich.), Publ. No. 12,043, 149 p p . ; Dissertation Abstr. 15, 1173-4 (1955). (64G) Lindlar, Herbert (to Hoffmann-La Roche Inc.), U.S. Patent 2,681,938 (June 22, 1954). (65G) LukeS. Rudolph, Trojlnek, Jan, Bllha, Karel. Chem. Listy 49, 717-22 (1955). (66G) Lutz, R. E., Rinker, Jr.: E. H . , J . A m , Chem. SOC.77, 366-9 (1955). (67G) hfack, C. H., Bickford, W. G., hlarklev, K . S. (to Secretary of Amiculture’i. U . S. Patent 2,%?7,048 (DK. 13. 1955). (68G) Magerlein, B. .I., Levin, R . H. (to Upiohn Co.), U. S. Patent 2,686,793 (Aug. 17, 1954). (69G) Mathers. A . P., Pro, M. J., J.A m . Chem. Sac. 76; 1182 (1954). (TOG) RfCtaver, Maurice, Bull. sot. chim. France 1954, 614-15. (71G) hticovic, V. M., MihailoviC, M. Lj., Serbian Acad. Sci. Monographs 237, Sect. Nat. Sci. and Math. No. 9, 1-193 (1955). (72G) htitra, A . K.; Karrer, P., Helu. Chim. Acta 38, 1-4 (1955). (73G) hfitsui, Sekio, Kasahara, Akira, Endo, Noboru, J . Chem. Soc. Japan, Pure Chem. Sect. 75, 234-6 (1954). (74G) Xfousseron, M., Jullien, J., Trar. SOC. pharm. Montpellier 8, 60-2 (1948). (75G) Muller, Eugen, Metzger, Horst, Fries, Dorla, Chem. Ber. 87, 128293 (1954). (76G) Nazarov, I. N., Shvekhgeimer, G. A , . Rudenko. V. A , , Zhur. 0bshche.t Khim. ‘24, 329-37 (1954). (77G) Norgaydeli, A . I., Sbornik Statei Obshchei Khim., Akad. Nauk S.S.S.R. 2, 1636-8 (1953). (78G) Ibid., pp. 1629-31. (79G) Norgaideli, A. I., Gonadze, G. M . , J . Gen. Chem. ( U . S . S . R . ) 25, 97-9 (1955). (80G) Norymberski, J. K., Woods, G. F., Chemistry C8 Industry 1954, 518-19. (81G) Okajima, Yakutaro, J . Pharm. SOC. . Japan 74, 784-5 (1954). (82G) Pallaud, Robert, Delaveau, FranCoise, Bull. SOL. chim. Frnnce 1955, 35-7. (83G) Peppiatt, E. G., Wicker, R . J.. Chemistry & Industry 1954, 932-3. (84G) Perrot, Roger, Wodey, Pierre, Compt. rend. 240, 100-2 (1955). (85G) Polonovski, Michel, Pesson, Marcel, Rajzman, Pesia, Compt. rend. 238, 1134-6 (1954). (86G) Reid, E. B., Siegel, J . R . , J . A m . C h m . Sac. 76, 938-9 (1954).

1 642

(87G) Rice, L. Xi., Grogan, C. H., Reid, E. E., J . A m . Chem. Soc. 77, 616-21 (19%). (88G) Salmanoff, A,: French Patent 984,412 (Julv 5, 1951). (89G) Schlesinger, Albert, Weiner, Nathan, Gordon, S. h t . (to Endo Products Inc.), U. S. Patent 2,712,016 (June 28, 1955). (90G) Schlesinger, H. I., Brown, H . C., U. S. Patent 2,683,721 (July 13, 19541 (91G) Schumb: W. C., Robinson, D. W., J . A m . Chem. Sod. 77, 5294 (1955). (92Gj Shah, I. R . C.. Krilkarni, A. B., Joshi, C. G., J . Sci. Ind. Research (India) 13B, 186-8 (1954). (93G) Shepherd, D. ,4,, Pedexon. K. I,. (to The Upjohn C o . ) , U. S. Patent 2,701,805 (Feb. 8, 1955). (94G) Shoppc, C . FV,, Stephenson, R. J., ChemiJtrj Industry 1954, 311. (95G) Smith, C. LV, (to Shell Development C o . ) ,C . S. Patent 2,704,771 (hfar. 22. 1955). (96G) Smith. H . ri., Shacklctt, C . D., J. A m . Chem. SOC. 76,4950-2 ( 1 954). (97G) Socitti. des usines chimiques KhBnePoulenc, Brit. Patent 712,300 ( J u l y 21, 1954). (98G) Sokol’skii, D. V., Eryhanov, A . I., Doklady Akad. .\‘auk S.S.S.R. 93, 503-5 (1953). (99G) Sokol‘skii, D. V., Levchenko, L., Vestnik Akad. Nauk Kazakh. S.S.R. 11, No. 1 (LVhole No. 106), 92105 (1954). (100G) Speeter, hl. E. (to T h e Upjohn C o . ) , U . S. Patent 2,703,325 ( M a r , 1 > 1955). (101G) Steadman, T. R. (to B. F. Goodrich (30.1. U. S. Patent 2,673,886 (Eciar. 30. 1954). 102G) Sugimoto, Norio, Kugita, Hiroshi. Fujita, T., J . Pharm. Sac. Japan 75, 177-9 (1955). 103G) Sugimoto, Xorio, Oshiro, Susumu, Saito. Seiichi, Ibzd., 75, 180-3 11955). 104G) Shaw, G., Sugo\vdz, G., J . Chcm. SJC.1954, 665-8. 105G) Theilacker, Walter, Drtjsalcr, H. G.. Chem. Ber.87.1676-84(1954). 1 0 6 ~ Trevby, ) L. w., Sci. J . ~ o j coli. . Sci.24, 3-18 (1954). (107G: Umhoefer, R . R . (to Food Xlachiners and Chemical Corp. ), U. S. Patent 2,720,531 (Oct.’ll; 1955). (108G) Ibid., 2,720,532 (Oct. 11, 1955). (109G) IYatt, G . W.,Broodo, .4rchie, others, J . A m . Chem. SOC. 76, 5989-93 (1954). (110G) LVeinmayr, Viktor (to E. I. du Pont de Nemours & Co.), U. S. Patent 2,714,614 (.4ug. 2, 1955). (111G) \$-illiams: J . L. R. (to Kodak Research Labs.), J . Org. Chem. 19, 1205-14 (1954). (112G) IVinstrom, Leon 0. (to Allied Chemical & Dye Corp.), U. S. Patent 2,716,135 (Aug. 23, 1955). (1 13G) Yeh, Ping-Yuan, others, Furrnosan Sci. 7, 27-30 (1953). (114G) Young, D. S. (to Eastman Kodak Co.), U. S. Patent 2,704,772 (Mar. 22, 195.5). (115G) Young. D. S., Rodgers, G. F. ( t o Eastman Kodak Co.), U. S. Patent 2,704,773 (hfar. 22, 1955). (1 16G) Zal’kind, Y. S., Tyutyunnikova, E. V., Sbornik Statei Obschci Khim., Akad. Nauk S.S.S.R. 2, 1302-7 (1953).


(117G) Zorbach, W. W., J . A m . Chern. SJC.75, 6344-5 (1953).

Fundamental Studies ( 1 H ) Azuma, Katsuhiko, Kobayashi, Akio, Shokubai No. 10, 1-10 (1954). ( 2 H ) Ibid., pp. 11-13. ( 3 H ) Balandin, A. A., Doklady Akad. Nauk S.S.S.R. 97. 449-52 11954). (4H) Elovich, S. Yu., Phblemy Ktnetiki i Kataliza, Akad. iVauk S.S.S.R. 6 , Geterogennyi Kataliz, 375-403 ( 1949). ( 5 H ) Ewing, V. C.: Ubbelohde, A. R . , Proc. Roy. Soc. (London) A230, 301-1 1 (1955). ( 6 H ) Freidlin, L. Kh., Rudneva, K . G., Bull. Acad. Sci. U.S.S.R., Diu. Chem. Sei. 1954. 417-21. ( 7 H ) Freydlin, L. Kh.,’ Rudneva, K . G., Doklady Akad. Nauk S.S.S.R. 91, 1349-52 (1953). ( 8 H ) Ibid., pp. 569-72. ( 9 H ) Ibid., pp. 1171-4. (10H) FreIdlin, I,. Kh., Rudneva. K . G.. Izvest. Akad. Nauk S.S.S.R.. Otdd. Khim. #auk 1954, 1082-8. (11H) Freidlin, L. Kh., Rudneva, K . G.. Sultanov, A . S., Bull. Acad. Scz. I/.S.S.R., Diu. Chem. Sci. 1954, 435-8. (12H) Jenkins, G. I., Rideal, Eric, J. C h m . SOC.1955, 2490-6. (13H) Ibid., pp. 2496-500. (14H) Kaneko, Yoshihisa, Shokubai No. 10, 20-5 (1954). ( 1 5 H j Kubomatsu, Teruo, Science and Ind. ( J a p a n ) 28, 236-9 (1954). (16H) Kubomatsu, Teruo, Ibid., pp. 31820. (17H) Kubomatsu, Teruo, Ibid., pp. 344-7. (1 8 H ) Kubomatsu, Teruo, Sugimoto, Chikae, Ibid., 28, 321-3 (1954). (19H) Kubomatsu, Teruo, Watanabe, Shoji, Ibid., 28, 214 (1954). (20H) Kubomatsu, Teruo, Watanabe, Shoji, Zbid., pp. 300-2. (21H) Kubomatsu, Teruo, IVatanabe, Shoji, Ibid., pp. 342-3. (22H) h?atsui, Toshiji, Azuma, Katsuhiko. Shokubai, No. 10, 14-19 (1954). (23H) Rienacker, G., Schubert-Birckenstaedt, M., others, Z. anorg. u. allgem. Chem. 279, 59-73 (1955). (24H) Rubinshtein, A. M., Problemy Kinetiki i Kataliza, Akad. ,t’auk S.S.S.R. 6 , Geterogennyi Kataliz, 127-36 (1949). (25H) Schubert-Birckenstaedt, Margarete, 2. anorg. u. allgem. Chem. 276, 227-35 (1954). (26H) Smith. H. A , , Chadwell, Jr., A. J . , Kirslis, S. S., J . Phys. Chem. 59, 820-2 (1955). (27H) Sokol’skii. D. V., Bezverkhova, S. T., Doklady Akad. Nauk S.S.S.R. 94, 493-6 (1954). (28H) Sokol‘skii, D. V., Problemy Kinetiki i Katalira, Akad. Nauk S.S.S.R. 6, Geterogennyi Kataliz, 157-70 (1949)/ . \ - -

~

Uchida, Hiroshi, Kurita, Minoru, J . Chem. Soc. Japan, Ind. Chem. Sect. 57, 527-30 (1954). Weller, S. W., Voltz, S. E., Z . physik. Chem. (Frankfurt) [N.F. I, 5, 100-13 (1955). Woodcock, R . F., Univ. Microfilms (Ann Arbor, Mich.), Publ. No. 13,193, 58 pp.; Dissertation rlbstr. 15, 1327 (1955). Zderic, J. A,, Univ. Microfilms (Ann Arbor, Mich.), Publ. NO. 13,301, 134 pp. ; Dissertation .4bstr. 15, 1327 (1955).

I I Hydrogenation and Hydrogenolysis

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