drogenation and Hydrogenolysis interest continued in iron-type catalysts and fluidized processes in the Fischer-Tropsch literature. The addition of thallium and cerium to the usual zinc-copper-chromite-type catalyst was investigated for the methanol synthesis reaction. Studies were made using cobalt hydrocarbonyl for the aldehyde formation step and nickel- 01 cobalt-type catalysts for the alcohol formation step of the oxo process. The oil and fat hydrogenation literature included selective hydrogenation studies employing nickel or a promoted nickel catalyst. Proper choice of selective hydrogenation catalysts at given operating conditions allowed the removal of acetylene from gas streams containing ethylene. In the ammonia synthesis field, a comparison between data obtained during a pilot plant run and laboratory data was made. Investigators continued to report hydrodesulfurisation and reforming studies of petroleum and petroleum products. High pressure hydrogenation of coal for the production of good grade aromatic-type gasoline was described. Hydrogenations of many different organic compounds were studied under various conditions with the bulk of the work relating to nickel, palladium, platinum, and lithium aluminum hydride catalysts.
drogenation catalysts has been reviemed. A tabular form has been used with a listing of subject, catalyst,
cited. a brief
has
preceding the
HYDROGENATION OF CARBON MONOXIDE
There has been active interest in Of both FischerTroPsch and methanol synthesis type Mechanisms of catalyst reduction and of exchange and hydrogenation reactions were reported. catalysts. Iron was the most studied Fischer-Tropach catalyst and was freHE literature which became available in 1953 on the hyquently proinoted by the addition of potassium, aluminum, copper, and calcium. Kieeelguhr, alumina, magnesium oxide, drogenation of carbon monoxide, oxo synthesis, oil a n d fat hydrogenation, hydrogenation of acetylenes and aceand similar substances were mentioned as carriers. Cobalt was tylenic compounds, ammonia synthesis, hydrogenation of petroalso investigated as a catalyst for the Fischer-Tropcch syntheleum and hydrocarbons, hydrogenation of coal, hydrogenation sis. 3Iethanol synthesis catalysts were primarily zinc-copperof various organic compounds, and fundamental studies of hychromite-type promoted with thallium and cerium.
the preparation
T
CATALYSTS
CATSLYSTS
Literature Cited (1A )
(C'OntinUed)
Subject catalyst,^ prepared by blending neutral precipitates of iron nitrates and alkalies with potassium silicatee
Subject Application of iron nitrides as Fischer-Tropsch catalysts
Catalyst Iron nitrides
Catalyst nitrided with ammonia for 4 to 8 hours a t 350' to 385' C. and compared with untreated catalyst
Fe,O:, Cr203, FIgo. KOH in ratio of 94:0.8:4.6:0.6
(2-4)
Iron catalyst for the conversion of carbon monoxide and hydrogen
Fe-2 to 10% finely divided C particles-100Jo alkali metal promoter
( ~ 2 ~ 4 ) Iron-type cat,alyst of high gas load
Catalyst for hydrocarbon syn- Fe catalyst containing 1% KAO thesis at 650" F. and 250 pounds and 2% A120a per square inch Catalyst giving longer life and increased yields of higher hydrocarbons
Catalyst for hydrocarbon synthesis with increased life
literat,ure Catalyst Cited Fe, Si02 in ratio of (64-4) 100:20 to 25
Fe-Cu-CaO-I< silicate
(18A)
Fe-Cu
(6QA)
capacity, high conversion capacity, and low methane formation (39~)
Fe, Cu, CaO in ratio ( 5 l A ) of 100:5 : 10 impregnated with K silicate to give an equivalent of 574
KOH
Fluidized iron catalyst for the synt,heses of hydrocarbons and oxygenated hydrocarbons
Pyrit,es ash or mag- (66.4) netite promoted NadX3, with KCI, KF, or
KpCOj Description of preparation of a catalyst suitable for fluidized operation
Fe catalyst promoted with 0.5% and O.G% IC20
(74A)
Iron catalyst for the hydrogena; tion of carbon monoxide a t 220 C. and 10 atmospheres
Fe, Cu, CuO, ltieselguhr, alkali (KgO) in ratio of 100:5:10:10:8
(58A)
Catalyst for manufacture of alcohols from carbon monoxidehydrogcn mixtures
ZnO-CrOa act'ivated (6-4) with CuO, K ~ C O J , KOII, or R b acetate
Alkali
(53A )
Adsorption studies of hydrogen and of carbon monoxide by a new catalyst
Cu-ZnO-CraOsTh02-Ce20g
(204)
Promoted catalyst for reaction of carbon monoxide with hydrogen a t 200' t o 300' C. and a pressure near atmospheric
Catalyst, for methanol synthesis a t 100" C. and 10 atmospheres
Cu-ZnO-Cr2Og
(688)
promoted
1846
September 1954
INDUSTRIAL AND ENGINEERING CHEMISTRY CATALYSTS (Continued)
Subject Poisoning action of coexisting an- Zn ions in the preparation of methanol synthesis catalyst
PROCESSES
Catalyst
Subject Longer iron catalyst life effected Fe by maintaining hydrogen concentration in the synthesis zone a t 40 to 50 volume % of total feed
Study of promoter action of copper Zn Methanol synthesis from a gas mixture consisting of water gas and hydrogen
CONDITIONING A K D REGENERATION Fe
Catalyst regenerated by recycling the entire tail-gas stream
Fe'
Catalyst maintained at a constant activit,y level by being withdrawn from reaction zone and oxidized t o remove carbonaceous matter
Fe oxide
Catalyst regenerated by oxidation with air to temperatures of 1100" F.
Finely divided Fe oxide type
Recycled gases are passed in contact with a series of synthesis catalyst beds
Fe
(49A)
Fluidized bed having constant average particle size
Fe
(44'4)
Fluidized bed process a t 350" to 650' F. and 250 t o 600 pounds per square inch
Finely divided Fe
(&?A)
(65A)
Fe
(64'4)
Separation of liquid hydrocarbons obtained from Fischer-Tropsch synthesis
AlzOs-base
(7'4 1
Stabilization of gasolines by treatment a t elevated temperatures
Bauxite or bentonite clays
Catalyst fines separated from the fluidized bed by entrainment in the product gases Yield of isobutanol increased by recycling by-product methanol to the reaction vessel Stwdy of appropriate conditions for synthesis of methanol
hpplication of elutriator to concentrate catalyst particles containing smaller carbon content
Fe
Catalyst pretreated by contacting with synthesis gas a t lower than normal pressure and space velocity
Fe type
Catalyst pretreated by reduction Fe with ammonia synthesis gas mix REACTOR DESIGK
Control of partial pressure of carbon monoxide to ensure use of iron apparatus
v
Recovery of products of catalytic hydrogenation of oxides of carbon
(I7A)
(41A)
Separation of oxygenated compounds from the products of the hydrogenation of carbon monoxide Purification of alcohols from the Fischer-Tropsch reaction
New t y e of evaporative cooling Control of the exothermic heat of reaction
(24A)
Treatment and arrangement of catalyst t o permit use of the synthesis reactor for the entire process
Catalyst regenerated by contact with carbon dioxide a t a temperature materially above the temperature of the synthesis reaction
Synthesis of hydrocarbons in a tubular reactor
Application of two-stage fluidiza- Co-MgO-Si02 gel tion technique to obtain a hydrocarbon product containing substantial quantities of olefins
Regulating the admission of feed gas to keep the catalyst in a fluidized state
Catalyst regenerated by dropping dispersed particles in a uniform shower downward through successive reaction and regeneration zones
Reactor for uniformity throughout reaction zone
(3A 1
Two-stage process under fluidized Fe conditions
Solidifiable contaminants removed from hydrocarbon synthesis catalysts by treatment with hydrogen a t elevated temperatures
Application of helical baffles to provide continuous catalyst phase
Catalyst
Literature Cited
Suppression of formation of light eases and carbon dioxide in DrocZss utilizing fluidized synt'hesis catalyst a t 500' t o 700" F.
ZnO-CuO-Th02
Catalyst regenerated with mixture of air and an inert gas maintaining a temperature difference in the catalyst bed of less than 300" F.
1847
with {quid mixtures as cooling media
Cu-Ba.chromite
(79.4) (10A)
I N DU STR IA L AN D E N GI N EER I N G CHE M IS TR Y
1848
Imii cat,a157sts rvem p ~ e t i e a t e dIvitii ammonia synthesis gas arid the i,(w.dt,sm-ere interpreted as indicating increased activity, (iurability: and versatility. Tail-gas streams, mixtures of air and inert gas, and carbon dioxide w r e used for regeneration. The recent activity relating t o reactor design for FischerT r o p x h synthesis has entailed varied efforts to provide continuous catalyst contact and close temperature control. l l o s t processes were concerned with fluidization techniques. X twost'age fluidization technique for hydrocarbon s-nthesis resulted in a product containing substant'ial quantities of olefins. Longer iron catalyst life w a . ~c~lniiiirtltiy maintaining the hydrogen con-
Catalyst
Subject Cooktnt-conducting tubes spaced geometrically in a vertical reactor
ture Cited
(%A?
Co-Th02-MgOkieselguhr
Cooling medium consisting of two organic compound? mnintained a t boiling
l'owcleied catalyst diluted with Cu
Description of a procebs for coli- Iteduced Fe tinuous hydrogenation of carbon monoxide
Subject 1.llectron and x-ray diffract,ion E'e studies
ture Cited
(40'4
(4%4 )
..idsorption characteristics of various catalyst8
Fe
(50-4)
(&A)
Co-ThOa-bInOkieselguhr
(6d.t)
(47.4)
Application of liquid-air-temperature chemisorption to determine free cobalt on surface of catalyst
(67A)
(80'1
1
Fr:m .IMP;Y ~ A I Ultraviolet and infrared spectroscopy employed to differeritiate The various aromatic hydrortw hons
Mechanism of synthesis of hydrocarbons from carbon monoside and hydrogen
(14.11
Phidenre presented that alcohols Co are precursors of hydrocarbons in Fischer-Tropsch synthesis
(28-4 1
Alcohols as intermediate products Fe of thc: Fischer-Tropsch q-nthesis
(31-4)
Results interpreted as indi t h a t complexes resemblir sorbed alcohols are formed from carbon monoside and hydrogen during synthesis and act as intermediates in the building up of higher hydrocarbons
(37A 1
Initiator of chain growth may be a n adsorbed radical formed by hydrogenation of surface carbide
Stud>. of oxygenated compo~iiiris in oil and water streams 1dent)ification of T acids anti 32 nonacid chemicd compounds in wat'er stream produced by hydrogenation of r ~ r b o n monoxide
High pressure and Ion. tenipcrature aids formation of methaiie by hydrogenation of carbon monoxide
Analyses of hydrocarbons by distillation, chromatography, spectrometric methods, and other means
FC
(7811 1
Dependence of reaction type on catalyst and conditions
Co arid Fe
(13'4 )
Study of adsorption of hydrogen and carbon monoxide and their mixtures
co
(21'4)
Cheinisorption of carbon mon- Fe, Cu, MgO in oxide should predominate over ratio 80:5:15 Fischer-Tropsch catalyst
Catrtlys t
Fe
Addition of acetylene t o synthesis gas reduces reaction temperature Operation in presence of heattransfer surfaces and a flniclized mass
centration in the syritheeis mile a t 40 t o 50 volnme % or t o i d feed. Iron equipment was employed for methanol synt1irsi.S when control of the partial preesurc of carbon monoxide W:IS maintained. Distillation, chromatography, spectromctric methods, anti other analytical techniques were employed to differentiate t,ho various compounds resulting from the hydrogenation of carbon monoxide. Electron diffraction, x-ray diffraction, and liquid-ai1,t'einperature Chemisorption st,udies were made on various iroli and cobalt catalysts. Several investigat,ors interpreted their results as giving sufficient evidence t h a t complexes resembling
Hexagonal iron carbide as a n intermediate in the carbiding of F'ischcr-Tropsch catalysts
Control of temperature in fluidized bed reactors containing SURpended catalysts Cooling medium for the coiitact reactor boiled between 190' and 250° c.
Vol. 46, No. 9
Comments on development of Fischer-Tropsch hydrocai [,on synthesis Formation of hydrocarbons from hydrogenation of rnrbon monoxide under influence of nltrasonic waves Comparison of Fischer-Tropsch synthesis n-ith Bergius coal hydrogenation process
(%'A) Possibilities of process
Fischer-Tropsch
September 1954
INDUSTRIAL AND ENGINEERING CHEMISTRY
adsorbed alcohols are formed from carbon monoxide and hydrogen during synthesis and act as intermediates in the building of higher hydrocarbons.
OXO SYNTHESIS Cobalt hydrocarbonyl continued to predominate as the catalyst for the first step of the oxo process where carbon monoxide and hydrogen react with an olefin to produce an aldehyde. Nickeland cobalt-type catalysts were frequently studied for the second step of the oxo process that involves the hydrogenation of aldehydes to alcohols. The regeneration of cobalt catalysts was carried out by oxidation a t 100' to 400' F. A process was described wherein olefins, carbon monoxide, and hydrogen in the presence of a catalyst gave liquid products containing aldehydes and dissolved metal carbonyl. This mixture was passed into a catalyst decomposition zone and the oxygenated products were hydrogenated over a sulfactive catalyst. Investigations were made to improve the alcohol yield by removing the alcohol and repeating the hydrogenation of the residue. Studies made over a large prrssure range showed that the oxo synthesis is first-order with respect to olefins and zero-order with respect to carbon monoxide and hydrogen. Investigations of the chemistry of the oxo and related reactions were made.
CATALYSTS, RECOVERY A N D REGENERATION
PROCESSES (Continued) Subject
Catalyst
Repeated hydrogenation of residue after removal of the alcohols for improved alcohol yield
10% MoSz; Kikieselguhr
Attempts to obtain the most desirable hydrogen-carbon monoxide ratio Synthetic lubricating fluids of low pour point and high viscosity index are obtained by reacting an 8-carbon oxo alcohol with phosphorous oxychloride Discussion of mechanical arrangement Utilization of oxo bottoms
Metallic soap catalyst CHEMISTRY
Subject Reaction velocity of the oxo synthesis is independent of the partial pressure of carbon monoxide and hydrogen over the pressure range of 120 to 180 atmospheres
Catalyst [Co(CO).41*
Catalyst
Subject Hydroformylation of higher carbon olefins with carbon monoxide and hydrogen
COZ(C0)8
Preparation of higher alcohols Co-kieselguhr promoted with from olefins, carbon monoxide, Ni(CO)4 and hydrogen Regenerating cobalt oxo catalysts by oxidation a t 100-400' F.
Co-MgO-thoria diatomaceous earth
Comparison of cobalt catalysts for the reaction vinyl ethers with carbon monoxide and hydrogen to give alkoxypropionaldehydes
Co and COIZ
Removal of cobalt from olefincarbon monoxide-hydrogen reaction mixture
Co type
Evidence for cobalt hydrocarbonyl as the hydroformylation catalyst
COP(C0)8
Oxo synthesis at given pressure intervals proceeds as a firstorder reaetion with respect to the concentration of the olefins
Metallic Co
Synthesis of esters from olefins, hydrogen, carbon monoxide, acetic acid
Co type
Study of the chemistry of oxo and related reactions
[CO(CO)412
OIL AND FAT HYDROGENATION
PROCESSES Hydrocondensation of carbon Raney Ni for hymonoxide with olefins and isodrogenation of condensate butylene Production of aldehydes by liquid reaction of monoolefins with carbon monoxide and hydrogen a t 100' to 180" C. and 200 to 300 atmospheres.
Co salt
Preparation of highly branched primary tridecanol
Co naphthenate for aldehyde formation; Ni-kieselguhr for alcohol formation
Description of formation of alde- Sulfactive catalyst hydes and dissolved metal carbonyl and subse uent hydrogenation t o alcohds
Partially reduced nickel catalysts were used extensively by the oil and fat hydrogenation industry. Supports such as silica gel, active charcoal, alumina, diatomaceous earth, and silica were investigated. Copper, aluminum, and magnesium were tried in varying amounts as promoters. The presence of more than 1.5% sulfur in the form of sulfate destroyed the activity of a nickel catalyst for the hydrogenation of peanut oil. Problems of selective hydrogenation, effect of pressure, effect of solvent, and pretreatment of oil were investigated. Experiments were undertaken in Russia on the refining and hydrogenation of rape oil. Studies were made on the relationship of hydrogenation with density values and refractive index values of olive oil. Temperature changes were investigated during the hydrogenation of oleic acid and methyl oleate. Attempts were made to characterize selectivity by percentage of total consumption of hydrogen needed for saturation of oil or fat specimens. CATALYSTS Subject
Catalyst
Literature Cited
Sulfur in the form of sulfate de- Ni on diatomaceous (2C) earth stroyed the activity of a nickel catalyst for the hydrogenation of peanut oil
5
Vol. 46,No. 9
INDUSTRIAL AND ENGINEERING CHEMISTRY
1850
CATALYSTS (Continued) Subject
Catalyst
Use of porous supports such as sil- Fe-Cr ica gel, active charcoal, or active earth The nickel obtained >Tasjet black in color and granular in texture
Ni formate
A noncolloidal, particulate cata- Ni-hl208-SiOs lyst was prepared by adding a n aqueous solution of a n alkali metal carbonate to a n aqueous solution of a soluble nickel salt, a soluble aluminum salt, and a n alkali metal silicate a t 79' t o 90" C. Precipitation xas made by adding a solution containing copper and manganese ions to a solution containing chromium ions
Cu-Cr-Mn
Catalyst used for preparation of saturated fatty acids from unsaturated fats and oils
1% MgO to ,41-Ni
Evaluation of activity test for comparing hydrogenation catalysts
PROCESSES Historical review of process Hydrogenation of rice-oil fatty acid a t high pressure Selective hydrogenation of soybean oil a t 260' to 350" C. and 150 to 200 atmospheres
Influence of temperature and pressure on the fat splitting of coconut oil under pressure without catalyst
(11C)
Selectivity related with percentage of total consumption of hydrogen needed for saturation of oil or fat specimen Reaction velocity constants of fat splitting calculated by means of formula of first order
HYDROGENATION OF ACETYLENES AND ACETYLENIC COMPOUNDS Various forms of platinum and palladium catalysts were investigated for use in the hydrogenation of acetylene and acetylenic compounds. Silica gel, alumina, and pumice were studied as carriers. The eelective hydrogenation of acetylene from a gas stieam containing ethylene and higher unsaturates was accomplished by proper selection of selective hydrogenation catalyst and careful control of process conditions. Mass spectrometric and infrared analyses were utilized in the study of the hydrogenation of acetylene and the exchange between hrdrogen and deuterium in unsaturated compounds. An investigation of reaction order showed the hydrogenation of acetylene to he zero-order with respect to acetylene and first-order with respect to hydrogen.
Subject Hydrogenation of acetylene to ethylene by repeated passes over a catalyst bed using a hydrogen-containing gas
Catalyst
Literature Cited
Silica gel or AI203 (ID) impregnated with 0.1 to 1%P d
Analyses interpreted as i n d i d i n g Ni that acetylene is adsorbed on the catalyst in part as a carbon complex and self-hydrogenates to ethylene
Hydrogenation of glycerides using a n industrial isoamyl alcohol aa solvent
Low temperature hydrogenation Raney Ni of cottonseed and linseed oil in benzene, toluene, and xylene Pretreatment of soybean oil with steam before hydrogenation
Finely divided Ni
Refining and hydrogenation of rape oil
Ni formate
Studies of margarine made from hTi mixtures of hydrogenated oils Ki-Cu
Autoclaving studies of palm oil under hydrogen pressure without catalyst Simultaneous hydrogenation and Ni-A1 hydrolysis of fatty oils CHEMISTRY Density and refractive index of hydrogenated olive oil
Catalyst
10% basic zinc carbonate
Hydrogenation of soybean-oil foot Ni a t 160' to 250' C. and 30 to 50 atmospheres
Hydrogenation of fats, oils, and waxes
Subject Thermal analysis and reaction rate determination of fats and oils
Literature Cited
Ni formate
-4cetylene selectively removed by Selective hydro- ( 8 D ) hydrogenation from gas stream genation catacontaining ethylene and higher lysts unsaturates Kinetic study showed reaction Ru, Os, and all (91)) metals of Group order to be zero nrith respect t o VIXI acetylene and first with respect t o hydrogen Reaction of propylene with deu- P t terium studied in the range - 18" to 130" C. over a pumicesupported catalyst Hydrogenation of acetylene derivatives
Pd
(50)
Hydrogenation rate of l,$-butynediol and its acetate over variOUP catalysts
Pt, Pd, Pt black, (7D) and Pd-starch in ethanol
Catalyst comparison for catalytic P d and Pt hydrogenation of methyl and ethyl ethers of 2,7-dimethyl-3,5octadiyne-2,7-diol
(1OD)
INDUSTRIAL AND ENGINEERING CHEMISTRY
September 1954
(AMMONIASYNTHESIS,Continued)
(HYDROQENATION O F ACETYLENES, Continued)
Subject
1851
Catalyst
Literature Cited
Subject
Catalyst
Literature Cited
Tests indicated that both natural Natural and syn- ( I E ) and synthetic catalysts can be thetic magnetite stabilized with Na containing catalysts from 0.75 to 1.00% air a t room temperature and a t pressures from essentially atmospheric to 140 pounds per square inch
Acetylene hydrogenation controlled by regulating the amount of gases supplied to the reaction and by cooling the reaction mass with circulating air Description of reactor useful for hydrogenation of acetylene
AMMONIA SYNTHESIS The preparation of a promoted iron ammonia synthesis type catalyst was described. Iron catalysts promoted by alumina alone, or with potassium oxide, or calcium oxide, or else by a mixture of alumina and potassium oxide with calcium oxide, magnesium oxide, and silica were investigated. Results were obtained that were interpreted as indicating that natural and synthetic magnetite catalysts can be stabilized with nitrogen containing 0.75 to 1.00% air a t room temperature. The ammonia concentrations throughout the bed of a pilot plant converter agreed rather closely with results predicted from work with a laboratory converter operating under essentially isothermal conditions. An ammonia synthesis catalyst when reduced by hydrogen in a surface electron microscope gave a pattern that corresponds to the dispersed parts in the grain boundaries. It was presumed that the substance in the dispersed part that takes part in electron emission consists of the combination of iron oxides and potassium oxide. No direct relation was found between the thermionic eniission of catalysts promoted in various ways and their catalytic activity. Investigations were made of the mechanism of the exchange reaction between heavy ammonia and hydrogen in the presence of platiiium.
Preparation of ammonia synthesis Fe promoted with catalyst Al, Ca, and K
(9E)
Gas mixture for ammonia synthesis from nitrogen and cokeoven gas
(dm
Latest developments in ammonia synthesis Temperature dependence of the rate of exchange reaction between deuterioammonia and hydrogen Kinetics of ammonia synthesis and decomposition a t 400' t o 450' C. and 400 millimeters of mercury
(6E)
Study of the exchange reaction be- P t black tween hydrogen and heavy ammonia in the presence of a catalyst
Experiments indicated that iron is Fe deposited in SiOl ( 6 3 ) not spread out over the surface of the silica in a monolayer but forma discrete crystal aggregates Microscopic investigation of fused Fe promoted with catalysts for ammonia synthesis K oxide
(8E)
STEAM c
1 .
RbTURN TO PRETREATMENT FATTY ACID STORAGE
CHARGE PUMP
HYDWGENATION CONVERTOR
FILTER PUMP
POST BLEACHING KETTLE FILTER PUmP STUMINQS TANK
STEAHINGS PUMP CWRTE8Y THE OIRDLER GO.
Hydrogenation Unit for Fatty
Acids
INDUSTRIAL AND ENGINEERING CHEMISTRY
1852 ( A X M ~ KS~Y NAT H E S I B , Contznued)
DESULFCRIZ ~ T I O Y (Continued)
Subject
Catalyst
Literature Cited
Subject
Catalyst
Literature C'1terl
compounds hydrogenated a t 371' to 427' C:and 500 t o 1000 pounds per square inch
Comparison of product distribution and temperature gradient between pilot plant and laboratory converter Attempts to correlate catalytic activity and thermionic properties
Vol. 46, No. 9
Fet03 promoted with &03,&O, CaO, MgO, and SiOz
(IIE)
HYDROGENATION OF PETROLEUM AND HYDROCARBONS Cobalt molybdate, nickel sulfide, tungsten sulfide, and molybdenum sulfide were investigated as catalysts for the desulfurization of petroleum and hydrocarbons. Alumina, bauxite, and alumina-silica mixtures were employed as promoters. A hydrodesulfurization process was presented claiming a new "trickle" technique to remove 85 to 90% of the sulfur from petroleum fractions a t only 80 to 85% of the cost of usual vapor phase hydrodesulfurization. . A process has been described employing a catalyst, consisting of cobalt),molybdenum, and bauxite in the ratio of 0.8:6.5:100. A catalytic reactor x-ith a stationary catalyst bed was adapted to the destructive hydrogenation of a heavy hydrocarbon stock, such as reduced or topped crude oil, in the presence of granulated molybdates or tungstates supported on suit'able carriers. Highviscosity lubricating oils were produced by treating shale oil, lignites, tars, dist.illation residues from mixed-base petroleum, bitumens, asphalts, or mixtures of heavy paraffinic and aromatic crude oils with hydrogen under pressure in the presence of a catalyst containing molybdenum, chromium, copper, titanium, and clay. Many studies were made of a platinum-on-aluminum catalyst for reforming gasoline. A process i w s described involving a homogeneous catalyst claimed to possess high activity, selectivity, and long life in continuous hydroforming of naphthas and gasolines. Hydrocarbons were reformed in a tITo reactor process whereby the catalyst was continuously withdrawn from each of the reactors and transported to the heating zone, thence back to the reactors, in order to maintain a uniform t,emperat,ure. The bulk of the studies pertaining to olefins emphasized controlled selective hydrogenation. Sickel sulfide, tungsten sulfide, molybdenum sulfide, palladium, platinum, and barium-promoted copper chromite catalysts were studied. Much of the interest shown in the hydrogenation of aromatic compounds pertained to the preparation and comparison of catalysts.
Desulfurization of heavy petroleuni oils
Xi deposited on a ( 1 3 F ) porous support
New technique t o remove 85 to Co-hlo-.41nOd 90% of the sulfur from petroleum fractions a t only 80 to 85% of the cost of usual vapor phase hydrodesulf urization
(d8F)
Desulfurization conditions were 22% Xi as NiO, 400" t o 510" C. and 100 to 1000 supported on a pounds per square inch cracking catalj st
(2:F)
Catalytic desulfurization of petroleum oils at 700" t o 800" F. and 50 to 300 pounds per square inch
(28F)
S e w desulfurization process Desulfurization of high boiling petroleum fractions a t temperatures less than 800" F. and 500 t o 5000 pounds per square inch Petroleum residuum was partially desulfurized and convert,ed largely to gas oil Desulfurization of crude oils and 6nCI4 and TiCI, asphalt a t 400" t o 800" F. and 100 t o 5000 pounds per square inch
(39Fj
Desulfurization of h j drocarbon vapors Desulfurization of hydrocarbons containing olefins Desulfurization of hydrocarbon Oxides and sulfides oil with an excess of gas t o effect of Co and Mo good flowing of the materials
(44F)
Desulfurization of cracked naphthas without the use of hldiogeii or a hj-drogen donor from an external source
3Iixtures of oxides of Co and 1 x 0
(48F)
Desulfurization of petroleum hydrocarbons ranging from light naphtha distillates to wax distillates
Co molybdate upon ( 4 9 F )
Desulfurization of refinery oils
Co, N o , bauxite in (63E') ratioof0 8 : 6 5 : 100; IT-SiS
Desulfurization of petroleum hydrocarbons
Marine sediments
A1203
DESULFURIZATION Subject
Catalyst
Petroleum fraction passed in the vapor phase t o a catalyst chamber a t a temperature of 650" t o 800' F. and a t a pressure of 25500 pounds per square inch
Metal sulfides and orides of Group
Catalytic desulfurization of petroleum hydrocarbons
Co molybdate or A I 2 0 3 in first reactor; W and Xi sulfides in second reactor
VI
P E T R O L E U M R E S I D C c h f S AIiD
Naphthenes dehydrogenated t o Co molybdate aromatic and organic sulfur
i67Fj
RELATED HEAVY OILS
Catalyst,s useful in pressure hydro- Silica-containing genation, cracking, reforming, catalyst alkylating, isomerization, and cyclization processes *
(6F)
Conversion of higher boiling petro- Montmorillonite leum fractions into lower boiling clay compounds by catalyt,ic cracking
($16')
INDUSTRIAL AND ENGINEERING CHEMISTRY
September 1954 PETROLEUN
RESIDUUMS AND
RELATED
Subject IIydrogenolysis of a heavy-residuum hydrocarbon oil to a good quality gas oil and gasoline
HEAVY OILS (COYbtinUed) Catalyst
IXCREASIKG OCTANENUMBER(Continued) Subject
Catalyst
Reforming at 950' F. and 300 0.5% Pt on actipounds per square inch vated A1208
Molybdenaalumina
Cracking of paraffin middle oils in W sulfide a high pressure atmosphere of hydrogen
Study of aromatizing cracking reactions of brown-coal-tai,middle oils in a hydrogen atmosphere
OLEFINS
Production of high viscosity lubricating oils
Reactivity of ethylenic conjugated Ni bonds toward hydrogen
Apparatus for the destructive Granulated molybhydrogenation of a heavy hydates or tungdrocarbon stock states
Interpretation of heats of hsdrogenation of olefinic substances
Thermodynamics for complex cracking reactions of paraffin hydrocarbons of 11 and 17 carbon atoms a t temperatures up t o 800" c. INCREASING OCTANE
NUMBER
Reactivating a supported catalyst used for reforming of naphtha
P t supported on AlnOa
Comparison of various catalysts for isomerization of saturated hydrocarbons
Ni, Co, Pt Fe, Cu, ~o oxide, or oxide deposited on Si02-A1203
w
Catalyst prepared for gasoline reforming
0.3% Pt in AlzO3
Preparation of catalyst for gasoline reforming
Alumina containing 0.3% Pt and
0.3% F
Catalyst for hydrocarbon conversion that minimizes cracking or controls it a t a low level
AI2O8 plus 0.01 to 1% Pt with or without halogen
Regeneration of carbonized noble metal on rare-metal catalysts, especially platinum-containing catalysts, takes place in two steps under controlled conditions Hyperforming operation carried out at a pressure of 400 pounds per square inch and at temperatures between €400' and 900" C. Catalytic reforming of hydrocar- Pt, A1~03,and combon fractions containing parafbined halogen; fins and naphthenes Pt, Si02 Gasoline fraction reformed by con- Pt-F-A1203 tact under reforming conditions with a t least two successive beds of catalyst Hydrocarbons reformed with the Pt-AhOa catalyst continuously cycled from each reaction zone t o the heating zone Homogeneous catalyst with high 0.6% Pt on AI2O3 activity, selectivity, and long life in continuous hydroforming of naphthas, gasolines, and other hydrocarbons Hydrocarbons converted into other hydrocarbons of higher octane rating in a n improved, continuous, cyclic hydroforming process
Butadiene selectively hydrogenated a t 230" t o 240" C. and 3 to 6 atmospheres
Cu0-Crz03-Cr03MgO
Selective hydrogenation of monoand diolefins
NiS-W sulfide
Liquid-phase selective hydrogenation of polyolefins t o monoolefins
MoS2 and NiS
Selective hydrogenation of cyclopropyl-1-alkenes to cyclopropylalkanes
2- Ba-promoted Cu (55F) 2Chromite catalyst
Catalytic. hydrogenation of some Ni, Pd, trisubstituted ethylenes black Description of improved apparatus and techniques for the measurements of olefinic unsaturation by quantitative hydrogenation
and
Pt (308')
Pd-C
(47W
AROMATIC COMPOUNDS Comparison of palladium-type P d sponge and P d catalyst for the hydrogenation black of benzene at 200" C.
(1F)
Hydrogenation of aromatic com- Raney Ni pounds
(QF)
Comparison made on activities of different concentrations of catalysts for the hydrogenation of benzene Ni and Co powders
(S5F)
Catalyst suitable for the hydro- 10 to 25% Mo& on genation of the aromatic conspent cracking stituents of petroleum fractions catalyst
(408')
Catalytic activity as a function of hydrogenation temperature
Hydrogenation catalyst for aromatic derivatives
Xi-Cu catalyst pre- (15F) pared from double salts
MISCELLANEOUS Study oi h drogenation catalyst using cycchexene
vzo3
Preparation of catalyst, claimed a s Ni-Mg formate good a s Raney nickel for hydrogenation of cgclohexene
(S2F)
(SSF)
Catalyst for hydrogenation and dehydrogenation of hydrocarbons Hydrogenation and dehydrogena- Ni on ALO,, ZnO, tion studies of nickel catalysts CnO3 and FezOJ on different carriers
(54F)
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
1854
(HYDROGENATION or COLI,, Continued)
HYDROGENATION OF COAL The data and experience gained while processing four typical American coals during the firat three years' operation of a demonstration plant are suminarized by the U. 8.Bureau of Mines. All four coals mere hydrogenated satisfactorily a t 500 t o 600 atmospheres resulting in a good grade of aromatic-type gasoline. h process Tvas described that consisted of the destructive hydrogenation of lignite or peat fluidized in a &earn of hydrogen a t temperatures of 900" to 1200" F. and at pressures of 500 to 2000 pounds per square inch. Chromatographic studies were made on the products of hydrogenation of t x o t'ppes of coal. Solvent fractionation and molecular distillation investigations were made on the soluble residue from a restricted hydrogcnolysis and a continuous liquid-phase hydrogenation.
Catalyst
Subject Application of chromatography to a study o f products of hydrogenation of tm-o types of coal
Cr-Cu
Chemical study of products obtained from coal hydrogenation Fuel gas of high heating value produced from the hydrogenation of carbonaceous solids a t elevated temperature and pre3sui.e Productidn oi good glade aromatic-type gasoline from hydrogenation of coal a t 500 to 600 atmospheres Demonstration r u m made on a liquid-phase hydrogenation unit and a vapor-phase hydrogexiation unit Hydrogenation of solid fuels by fluidization in a series of chambers with countercurrent passage of hydrogen Destructive hydrogenation of lignite or peat fluidized in a stream of hydrogen at temperatures of 900" t o 1200" E. and pressures of 500 t o 2050 pounds per square inch
Two-stage coal extraction and hydrogenation process
(Ira)
( 1i G )
Sn and Mo
(IlC)
Hydrogenations of organic compounds are grouped according t o the catalyst employed. Sickel catalysts were studied for many different types of hydrogenations. Inveetigators mere interest'ed in selecting the proper conditions and correct form of nickel catalyst for selectively hydrogenating carbon to carbon linkages in the presence of carbon to oxygcn linkages. Monoolefinic fatty acids m r e produced from the corresponding polyolefinic fatty acids. Precipitated nickel and copper were active hydrogenation catalysts in t,he presence of sodium hydroxide or when treated with aqueous sodium hydroxide before use. Potent,iometric investigations were made of liquid-phase hydrogcnation reactions on a skeletal nickel catalyst. Palladium black was used in a, series of experiments indicating t h a t the rate of hydrogenation of unsaturated acids generally declines with increase of t,heir molecular weights. Coxnparisons n-ere made of the tase of adsorpt,ion of organic acids on platinum cataljds. The comparative performances of plat'inum, galladiuni-, osmium-, and ruthenium-t#ype catalysts were investigated for the hydrogenation of triple and double bonds. The lithium aluminum hydride reduction of 4 P-dicarbonylcompounds m-ae found t o give primarily unsaturated alcohols. Mechanism studies w r e made of halide reductions. Selective hydrogenat,ion of carbon to carbon linkage was made in the prcsence of carbon t o oxygen linkage mith lithium aluminum hydride. Several hydrogenation studies employing copper chromite type catalysts were reported.
NICKCLCATALY~TS Catalyst
Literature Cited
Monoolefinic fatty acids contain- Raney Xi ing 8 t o 22 carbon atoms produced from the corresponding polyolefinic fatty acids
(4H)
Selective hydrogenation of a,& Ni with CNCI, or ethylenic ketones HCI present
(911. 1O H )
Xi contaminated (1fH) with chlorides
Comparison of different catalysts S i , Pt,, and P d for selective hydrogenation of doubly unsaturated conipounds
(2QH)
W-6 Raney Ni
(3011)
Selective reduction of unsaturated acids and esters
Description of procees and equipment for liquid-phase coal hydrogenabion
drogenation of coal
Catalyst-pressure relationship in hydrogenclysis of coal
Selective hydrogenation of ethylenic ketones
Hydrogenation of phenol fractions hlool of low temperature tar a t 420" 6.and X5 atmospheres
Catalyst
Literature Cited
Review of progress in various phases of coal hydrogenation
Subject
Use of coal gas for mild hydrogena- Xq. soln. of Nation of coal €IC03
Review with 25 references on hy-
Subject Historical development of the Gerinan coal-hydrogenation industry
(SG)
Hydrogenat,ion of brown coal and peat and analyses of product obtained
Wydrogenat,ion of powdered coal Soln. of tin chloa t 700" to 1050' F. and 1000 to ride, FeSOl t o which is added 10,000 pounds per square inch Si02-A120a
Vol. 46, No. 9
Selective hydrogenation of acrylic group of 2-furanacrylic acid and its deiivatives m-ae accomplished a t temperatures below 60" C. and a pressure of 50 kilograms Selective hydrogenation of steroid Raney Xi polyenes
(3511)
September 1954
INDUSTRIAL AND ENGINEERING CHEMISTRY
NICKELCATALYSTS ( C O n h U e d ) Subject
Catalyst
Hydrogenation of dibenzylidene- Raney Ni and dia~isylidenesuccinic acids a t ordinary pressure and room temperature Catalytic reduction of pyromellitic acid at elevated temperature and at least 200 atmospheres hydrogen pressure gave 1,2,4,5 - cyclohexanetetracarboxylic acid
Literature Cited
(8H)
Ni
Subject
Catalyst
(23H 1
Hydrogenation of cyclohexyl- Raney Ni ketene dimer and w-cyclohexylalkylketene dimers
(94H)
Hydrogenation of n-Mannono-r1 a ~ t o n e - l - Cto~n-Mannitol-1,B~
(R5H)
Na-Hg and Raney
Ni
Reduction of esters of hydroxy- Raney Ni imino carboxylic acids
(39~)
Preparation of alkylated cyclo- Raney Ni hexanes by hydrogenation of the corresponding alkylbenzenes
(4OH)
Catalytic reduction of xylose Raney Ni under high temperature and pressure
(43H)
Hydrogenation of unsaturated hy- Fe, Co, Ni, Pt, Pd, ( 4 6 H ) droxy acids and their esters a t or Mn 150' to 180' C. and pressures of at least 10 atmospheres Application in pharmacy of the Ni hydrogenation of lanolin a t 330" C. and 180 to 300 atmospheres Hydrogenation of vinyl ethers
KaOlI treated NiAI
Hydrogenation-dehalogemtion of
Ni-AI
(1H)
Hydrogenation and dehydrogena- Pt in acid tion of yobyrine, tetrahyrine, and of noneubstituted isoquinoline
(16H)
Pt black
($OH)
Many catalytic reductions and the P d on C chemistry of the reduction products
(44H)
Hydrogenation of petroselinic and Pt black petroselaidic acids
(48W
Comparison of ease of adsorption of organic acids on platinum catalyst
Pt
Comparison of Pt-, Pd-, OS-, and Pt on BaSO1, P d o n (63H) Ru-type catalysts for the hydroBaSOa, Os on genation of triple and double BaS04, and R u bonds on BaSOa LITHIUMALUMINUM HYDRIDE
(66H)
Reduction of ethyl oxalate by lithium aluminum hydride Reducttion of 3-chlorophthalic acid and of its three mebhyl esters
chlorobenzene and benzyl chloride Hydrogenation 19cholestenone to Precipitated Xi and cholestanol Cu in presence of NaOH
CATALYST'S
Hydrogenation of unsaturated Pt02, Pd on AI2O3, ( 1 6 H ) quaternary ammonium iodides and Raney Ni
Mild hydrogenation of ethers
14
Literature Cited (6111)
Nickel h drogenation catalvst Ni prepareJby treating an aquebus solution of a nickel salt with an alkali metal to precipitate nickel hydroxide and then reducing the washed filtered cake in aqueous suspension with hydrogen under pressure at 80' to 158" C. P.4LLADIlJM A N D PLATIXUM
Hydrogenation of commercial al- Raney Ni dol
Potentiometric study of hydrogenation reactions
NICKELCATALYSTS (Continued)
Comparative hydrogenation of un- Pd black saturated fatty acids ehowing a decline in rate with increase in molecular weight
Variation in conditions in control- Ni ling hydrogenation of castor oil
c
1855
(69H)
Ki with additives ( 1 4 H ) Pd, Pt, and benzyl mercaptan
Potentiometric investigation of Ni-A1 in alkali liquid-phase hydrogenation reactions on a skeletal nickel catalyst
(64H)
Role of intermediates in the syn- Raney Ni thesis of hydrogenated phenanthrenes
(19H)
Reduction of steroidal enol acetates with lithium aluminum hydride and sodium borohydride Reduction of some, enolizable 3dicarbonyl compounch to unsaturated alcohols Mechanism of halide reductions with lithium aluminum hydride Reduction of ergosteryl and 7-dehydrocholesteryl tosylate
Effect of reduction temperature of Ni from Ni(HC00)s; ( 3 7 H ) nickel and cobalt compounds on Co from Cothe catalytic properties of the (HCOO)2 metallic catalysts Catalytic propertirs of nickel or NiSOd or Cos04 (38H) cobalt prepared from amalgams solutions were by distillation of the mercury or used with Hg decomposition iri air cathodes
Preservation of the carboxylic group during selective reduction with lithium aluminum hydride Reduction reactions of Lthium aluminum hydride in the alicyclic series Testosterone prepared by reduction of 3-alkyl enol thioethers of A~androstene-3,17-dione
(43H)
INDUSTRIAL AND ENGINEERING CHEMISTRY
1856
LITHIUM ALUMINUMHYDRIDE (Continued) Subject
Catalyst
Literature Cited
Reduction of compounds in the lysergic acid ring system
(bOH)
Reduction of cycloheyylketene dimer and w-cyclohexylalkyl ketene dimeis
(66H)
Reduction of 3-enol thioethers of androstenedione t o 3-enol thioethers of testosterone
(57H)
Review of various processes including lithium aluminuin hydride reduction COPPBR C H R O l f I T E A N D
Electrochemical studies and the effect of hydrogen or nitrogen treatment at 300" to 35OOC. on the catalytic activity of the palliidium-hydrogen solid system were reported. The previously noted phenomena of the action of hydrogen and oxygen on platiriurn surfaces was found t,o occur on surfaces of palladium. Esplanation as given that the metal was activated by osygen-hydrogen Inistures as a result of deep-seated alteration of the surface, with t,he captured oxygen apparently acting a3 a surface-modifying admixture. The optimum amount of oxygen in respeot t o catalytic activation of palladium appeared to be that corresponding t o the formation of a monolayer.
GENER.4L
RELATED CATALYSTS
Attempts to obtain primary alco- Cu-Cr oxide hols by hydrogenation of mdioxanes a t elevated temperature and pressure Hydrogenation of cyclohevanone to cyclohevanol
Vol. 46, No. 9
(W
Cu carbonate acti- ( S H ) vated with Zn, Cr, and Ba ovides
Hydrogenation of organie sub- CuO in S ~ O Lor stances pumice stone
(60H)
Literature Cited Subject Catalyst Mechanism of reduction of iron Hematite and mag- (62) netite oxides Mechanism of exchange and hydrogenation reactions of ethylene
(14C
hlechanism of exchange and hydrogenation reactions of olefins
(15i)
Studies of hydrogen transfer reactions accompanying the cobalt catalyzed addition of carbon monoside to olefinic compounds
(17i)
Studies of redistribution of liydi ogen in olefinic hydrocarbons
Review of catalytic hydrogenation in organic chemistry
Aluminosilicate
(8Oi)
Hydrogenation of organic compounds with synthesis gas
Free energy in determination of possible cleavages in the cracking of n-paraffinic hydrocarbons
(&ii)
Hydrogenation of carborj-lie acids It u t,o alcohols
Mechanism of exchange of hydiogen gas and aqueous alkali
($Si)
Hydrogenation of glycolic acid t o ethylene glycol
Ru
NICKELCATALYSTS
Hydrogenation of organotin and lead compounds under pressure Process of hydrogenat'ion of aldehydes and ketones t,o their respective alcohols
(WH)
Proper condit,ions for the preparation of the lead soaps of unsaturated fatt,y acids and their hydrogenation to the corresponding alcohols Preparation of higher fatty alcohols by catalytic hydrogenation
Fe-Zn, Zn-hl
(3iH)
FUNDAMENTAL STUDIES The mechanism of reduction of pure natural single CI hematite and magnetite by hydrogen was studied b e t n w n 450' and 1000" C. by microscopic methods. Mechanism studies were made of exchange and hydrogenation reactions of olefins. Free energies were considered in determining possible cleavages in the cracking of n,-paraffinic hydrocarbons. InveEtigations were made \Tith Raney nickel catalysts to determine the stereochemical fate of an asymmetric center adjacent to a sulfur atom during reductive desulfurization. The role of diflerent adsorption centers in the hydrogenation of acetylene on metallic nickel was studied and the results were interpreted as indkating t h a t hydrogenation t,akcs place on centers with minute or (,lose bo minute act,ivation energies for desorption. The kinetics of the hydrogenation of crotonic acid in ethanol were studied by an isobar method.
Critical experiments t o determine Itaney Xi the source of hydrogen during reductive desulfurization
(W
Determination of the stereochem- Raney S i ical fate of a n asymmetric center adjacent to a sulfur atom during reductive desulfurization
(4i)
Role of different adsorption cen- Metallic Xi ters and kinetics of hydrogenation for the hydrogenation of acetylene
(10i)
Deuteiization schemes for tradi- Raney S i tional Raney Si type catalysts
(lii)
Kinetics of hydrogenation of cio- IianeS Xi tonic acid
(16i)
Nechanism of the hydrogenation of linolenic acid
Ilaney Xi
($27 1
PALI,ADIUX A X D P L A T I S E M CATALYSTS
Kinetics and mechanisni of catalytic hydrogenation of hydrocarbons
Solid systeni Pd-H
(12)
Effect of treatment with hydrogen or nitrogen on catalytlc activity
Fresh P d black
(22)
Pd-C
(Si)
Electrochemical study of the system palladium-hydrogen Studies of behavior changes of palladium-charcoal in hydrogenation reactions
September 1954
INDUSTRIAL AND ENGINEERING CHEMISTRY
PALLADIUM AND PLATINUal
CAT.4LYSTS (COnti?ZUed)
Subject
Catalyst
Literature Cited (1%)
S a t u r e of activation of catalyst by oxygen-hydrogen mixtures
Pd
Stereoisomerism in the series of hydrogenated thiachromans
Pd-CaCOB, Pd, P d (18i) in EtOH-Me2C0, and P d in dioxane
Stereoisomerism in the series of hydrogenated thiachromans
Pd-CaCOs
(19i)
Isotopic distribution in cholesterol after hydrogen-deuterium exchange
Pt
(7i)
Catalyzed exchange of hydrogen isotopes with steroids
Pt
Kinetic studies of oxidat>ion of hydrogen
Pt foil
1857
(MISCELLANEOUS, Continued)
Subject
Catalyst
Action of hydrogen on phosphates
(10J)
Review of early work dealing with high pressure hydrogenation of solutions of salts of metals below hydrogen in electromotive series
(1IJ)
Hydrogenation catalyst having good mechanical strength and high efficiency
MoSa-Fe
(12J)
Preparation of thermoplastics with excellent low temperature properties
Ni-kieselguhr
(1JJ)
sulfideSi02-Li02-A1203
Special treatment for aluminum supported type catalyst
(1%)
MISCELLANEOUS
Recovery of products of catalytic hydrogenation of oxides of carbon
(15J)
Hydrogenation of carbon oxides
(16J)
ii detailed description was given of an apparatus for determining the activity of a nickel catalyst, used for hydrogenation, by measuring the flow of hydrogen in and out of the reaction vessel. Another apparatus was described consisting of a bent side arm where the catalyet can be equilibrated with hydrogen before allowing contact between the catalyst and the unsaturated material in solution in the main part of the hydrogenation flask. The precipitation of vanadium from aqueous vanadate solutions by reduction with hydrogen was reported.
Catalyst
Subject Equimolar hydrogen-chlorine mistures containing about 1% nitrogen trichloride explode in the dark below a critical pressure of ab6ut 25 millimeters mercury a t 20” c.
Literature Cited
(1J)
Comprehensive review of hydrogenation and hydrogenolysis Hydrated or anhydrous nickel chloride reduced to metal by hydrogen Reactions of atomic hydrogen with ethane in a flow system over the temperature range 80’ t o 163’ C. resulting in methane as only product Paraffin wax heated a t 450” C. for 1 hour in the presence of hydrogen a t 120 atmospheres yields approximately 30% by weight of hydrocarbon boiling below looo C.
Different catalysts
(5J)
Detailed description of activity testing apparatus for hydrogenation catalyst
Ni
(6J)
Removal of impurities t o improve life of hydrogenation catalyst Apparatus for catalytic hydrogenation
Role of chromium oxide in the reduction of the carbonyl group under high pressure hydrogen
Literature Cited
Precipitation of vanadium from aqueous vanadate solutions by reduction with hydrogen a t 100’ to 100 pounds per square inch
Ni powder
(1’7J)
Simplified method of characterization of catalyst activity Composition of W-6 Raney nickel
LITERATURE CITED HYDROGENATION OF CARBON MONOXIDE
(1K) Anderson, Robert B., “ildvances in Catalysis,” Vol. 5, pp. 355-84, Academic Press Inc., New York, 1953. (2A) bnderson, Robert B., and Schultz, John F. (to the U. S.A , , as represented by Secy. of the Interior), U. S.Patent 2,629,728 (Feb. 24, 1953). (3A) Arnold, John H., and Grosselfinger, Frederick €3. (to Hydrocarbon Research, Inc.), I b i d . , 2,628,970(Feb. 17, 1953). (4.4) Badische Anilin- & Sodafabrik, Brit. Patent 682,826 (Nov. 19, 1952). (5&) Badische Anilin- & Sodafabrik, Ger. Patent 868,146 (Feb. 23, (1953). (6-4) Beck, Roland A., and Sensel, Eugene E . (to Texas Co.), U. S. Patent 2,640,845(June 2, 1.953). (7-4) Benson, Homer E., and associates (to U. S.A,, Secy. of the Interior), U. S. Patent Appl. 272, 626. (8-4)Cady, William E., and associates, IXD.ENG.CHEXI., 45,350-3 (1953). (94) Cain, D. G., and associates, Ibid., 45,pp. 359-62. (lOA) Dorschner, O., Ckem.-Ing.-Tech., 25,277-85 (1953). (11A) Easley, Joseph C., and Kellner, Hugh L. (to Gulf Research & Development Co.), U. S.Patent 2,609,345 (Sept. 2, 1952). (12A) Eastman, du Bois (to Texas Co.), Ibid., 2,632,017( X a y 17, 1953). (13A) Eckardt, H. H., D i e Tcchriik, 8, 457-65 (1953). (14A) Eidus, Ya. T., Uspeichi Khin., 20, 54-70 (1951). (154) Entreprise generale de chauffage industriel Pillard frBres gS Cie., Brit. Patent 688,915(March 18, 1953). (16.4) etablissements Brunon-Vallette & Cie. (S. Q. r. 1.) and Societe anon. de Gas ComprimB, French Patent 891,202 (March 1, 1944). (17A) Fleming, Harold W.,and Friedman, Alvin H . (to Phillips Petroleum Co.), U. S. Patent 2,615,036(Oct. 21, 1952). (18A) Gall, D., and associates, J . A p p l . Chem. ( L o n d o n ) , 2, 371-80 (1952). (19A) Garbo, Paul W.(to Hydrocarbon Research, Inc.), U. S.Patent 2,655,437(Oct. 13, 1953). (20-4) Ghosh, J. C., Sastri, M. V. C., and Kamath, G. S.,J . chim. phys., 49,500-3 (1952). (21-4) Ghosh, J. S., Sastri, M. V. C., and Kini, K. A., IND.ESG. CHEM.,44, 2453-70 (1952).
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY Gillespie, Bruce G. (to Standard Oil Development Co.), U. S. Patent 2.608.535 (AuE. 26. 1952). , , , I Hemminger, Charles E. (to Standard Oil Developinent Co.), I h i d . , 2,608,569 ( h u g . 26. 1953). Ibid., 2,651,653 (Sept'. 8 , 1953). Hogan, John P. (to Phillips Petroleum Co.), Ibid.,2,644,829 (July 7, 1953). Hogan, John P., and Friedman. Alvin H. (to Phillips Petroleum Co.). Ibid..2.608.568 iAue. 26. 1952). Holder, Clinton FI. (to Standard Oil Development Co.), Ibid., 2,626,968 (Feb. 17, 1953). Horne, Wm. A, and Crawford. Vincent L. (to Gulf Research & Development Co.), Ibid., 2,632,016 (March 17, 1953). Huisak, Karol L., and associates (to Stanolind Oil I%Gas Co.). Ibid., 2,620,262 (Dee. 2, 1952). Hydrocarbon Research, Inc., Brit. Patent 676,635 (July 30, 1952). Kagan, 13.. and associates, Izxest. A k a d . .Vauk S.S.S.R., Otdel. Iihiin. S a u k , 1952, pp, 649--57. Keith, Percival C. (to Hydrocarbon Research, Inc.), 5 . S. Patent 2,631,159 (March 10, 1953). Kini, K. A , , and associates, J . Sci. Ind.Research (India),10B, XO.10. 243-5 (1951). Koch, Herbert, Chem.-Ztg., 74, 103-6 (1950). Krebs, Robert TV., and Lewis, Warren K., Sr. (to Standard Oil Development Co.), U. S. Patent 2,627,522 (Feb. 3, 1953). Kudo, Shiro., J . Chcns. SOC.J a p a n , I n d . C h m . Sect., 55, 287-9 (1952). Kummer, J. T.. and Emmett, P. H., J. A m . Chem. Soc., 75, 5177-82 (1953). Lanning, +ni. C. (to PIiiilips Petroleurn CO.), U. 8. Patent 2,661,338 (Dee. 1, 1953). Layng, Edwin T. (to Hydrocarbon Research, Inc.), Ihid., 2,629,729 (Feb. 24, 1953). NcCartney, James T., and associates, J . P h y s . Chem., 57, 730-6 (1953). McGrath, Henry G. (to PI.W. Kellogg Co.), Brit. Patent 682.154 ih-ov. 5 . 19521. hIcGrath, Henry G., and associates (to 11.W.Kellogg CO.). U. S.Patent 2,635,111 (April 14, 1953). Manes, SIilton, and associates, J . Am. Chem. Soc., 74, 6207-9
(1952). Mayer, Iran. and Johnson, Virginia C. (to Standard Oil Development Go.), C. S. Patent 2,642,448 (June 16, 1953). Mayr, Herinann, and Narinesco, NQda,rrench Patent 893,663 (Aut I
11 1944).
~I ~
AIetallgese~lsclia~t 8.-G.. Brit. Patent 683,516 (Nov. 26, 1952). I b i d . , 690,925 (April 29, 1953). Morrell, C. E., and associates, 1x11.ENG.CHEZI.,44, 2839-43 (1952). Odell, Wm. TI-. (to Standard Oil Development Co.), U. S. Patent 2,620,313 (Dee. 2 , 1952). Podgurski, H. H., and Emmett P. H . , J Phus. Chem., 57, 15964 (1953).
Rottig, Walter (to Ruhrchemie h -G.). U. S.Patent 2,620,347 (Dec. 2, 1952). Ibid., 2,628,969 (Feb. 17, 1953) Ibid., 2,647,138 (July 28, 1953). Rottig, Walter, and associates (to Ruhrchemie A,-G. and Lurgi Gesellschaft fur Warmetechnikn~.b. H . ) , I h i d . , 2,617,774 (Kov. 11, 1952). Rubin, Louis C., and IIcGrath. Henry G. (to h4. VI. Kellogg Co.), Ibid.,2,620,346 (Dee. 2, 1952). Ruhrchemie A-G.. Brit. patent 678,963 (Sept. 10, 1952). Ibid., 680,241 (Oct. 1. 1952). Ibid., 690,432 (April 22, 1953). Ruhrchemie .4.-G. and Lurgi Gesellschaft fur Warmetechnik m. b. H.. Ibid.. 679. 785 (Seot. 24. 19523. Ibid., 688,640 (March 11, 195i). Ibid., 692,234 (June 3, 1953). Sastri, SI. V. C., and Sprinivosai1, 5. R., J . Am. Cizem. SOC., 75, 2898-2900 (1953). Sensel, Eugene E. (to Texas Co.), U. 9. Patent 2,651,652 (Sept. 8, 1953). Standard Oil Development Co., Brit. Patent 676.658 (July 30, 1952). Ibid., 678,941 (Sept. 10, 1952). Steita, Alfred, J r . , and Barnes, David K., ISD.ENG.CHEV.,45, 353-8 (1953).
Sullivan, Frederick W., Jr. (to Hydrocarbon Research, Inc.), U. S. Patent 2,626,275 (Jan, 20, 1953). ( 6 8 8 ) Terui, Soji (to Kippon Hydrogen Industries Go.), Japan Patent 505 ('52), (Feb. 19, 1952). (69A) Tomasik, Zdzislaw, 'Vafta (Poland), 8, 4 6 5 0 (1952.) (70A) Tomita, Akira, J . Chem. Sac. Japan. I n d . Chem., Sect., 54, I
446-8 (1951).
Vol. 46,No. 9
(714) Ibid., pp. 504-5. ( 7 2 8 ) Ibid.,pp, 505-7. (73-4) Union Rheinische Braunkohlen Kraftstofl A.-G., Brit, Patent 682,954 (SOT, 19, 1952). (74-4) Vandaveer, Roscoe F. (to Stanolind Oil 6: Gas Co.), U. S. Patent 2,626,274 (Jan. 20, 1953). (75-4) Vatson. Claude IT. (to Texas Co.),Ibid., 2,635,110 (April 14, 1953). (76.4) Weghofer. Hans, Rec. qrZim. ind. (Rio d e Janeiro), 22, S o . 250, 14-24 (1953). (77A) Weitkamp, A. W., and Frye, C. G.. I r n . T.':R-G. CHmi., 45, 363-7 (1953). (78A) Weitkamp, -4. TV., Seelig, Herinan 8..and associates. Ibid., 45, pp. 343-9. (79d) Wentzel, Wilhelm ( t o Ruhrchemie -1.G.and Lurgi Gesellschaft fur Wiirmetechnik m. b. H.), Brit. Patent 688,778 (March 11, 1953). (8OA) Williams, Theodore S. (to M.TV. Kellogg C o . ) , U. S. Patent 2,615,911 (Oct. 28, 1952). OXO SYNTHESIS
(1B) hdkins, Homer, and Williams. Jack L. R., J . O T ~Cizem., . 17, 980-i (1952).
(2B) Asahara, Teruzo, and associates, J . SOC.O ~ QSgizthe~. . Chem., J a p a n , IO, 538-41 (1952). (3B) ETdus, Ya. T., and associatcs, Izoest. Akad. Sauk S.S.S.R., Otdel. Iihim. Nauk., 1952, pp. 978-81. (4B) Gresham, Wm. F., and Kubico, Michael 4. (to E. I. du Pant de Nemours & Co.), U. S. Patent 2,609,397 (Sept. 2, 1952). (5B) Lamb, Sidney A , and Imperial Chemical Industries, Ltd.. Brit, Patent 667,093 (Feb. 27, 1952). (6B) Mayland, Bertrand J., and Stewart, S. Grant (to Phillips Petroleum Co.), U. S. Patent 2,638,452 (Xay 12, 1953). (7B) Rlikeska. Louis A., and Smith, Paul V., Sr. (to Standard Oil Development Co.), Ibid., 2,642,452 (June 16, 1953). (8B) Naragon, Ernest A., and associates (to Texas Co.), I b i d . , 2,626,246 (Jan. 20, 1953). (9B) Natta, G., and Ercoli, R., Chiinica e indusfria (Milan),34, 503-10 (1952). (10B) Katta, G., and Pino, P., Chiinie &. industl'ie, 63, No, 3, 467-9 (1950). (11B) Natta, G., Pino, P., and Beati, E., Ibid., 63, S o . 3, 464-6 (1950). (12B) N. V. de Bataafsche Petroleum Llaatschappij, Brit. Patent 675,719 (July 16, 1952). (13B) Owen, John J., and Fasce, Egi V. (to Standard Oil Development Co.), U. S. Patent 2,594,341 (April 29, 1952). (14B) Schreyer, Ralph C., J . Am. Chenz. Soc., 74, 3242-3 (1952). (15B) Standard Oil Developinene Co., Brit. Patent 671,608 ( M % y7, 1952). (16B) Ibid., 672,349 (May 21, 1952). ( 1 7 ~ )rbid.,682,177 ( s o v . 5 , 1952). (18B)Wender, Irving, Greenfield, Harold, and associates, J. 4 1 n . Chem. SOC., 74, 4079-83 (1952). (19B) Tender, Irving, Sternberg, H. W., and associates, Ibid., 75, 3041-2 (1953). OIL A N D FAT HYDROGENATION
(IC) .herbe, Fbliz Ramos, and Osza, Joke Martienz de la, Grasas y aceifrs (Sevilla, Spain), 2, 90.l j 2 , 11-18 (1951). (2C) Catravas, Georges N., Compt. rend.. 236, 617-18 (1963). ( 3 C ) Chimiotechnie union chimique du nord et du RhGne, French Patent 978,995 (April 20, 1951). (4C) Compagnie francaise des essences synthetiques. Ibid.,977,656 (April 4, 1951). (5C) Ilitotsumatsu, Masaji, and Takeshita, Yasuhiko, Japan. Paten%5936 ('51) (Oct. 2 , 1951). (6C) Saito, Koji, and YIori, Takajiro, V i l u n ~ i n ~( Js a p a n ) ,5, 191-2 (1952). ( 7 C ) Kana'iati, D. D., Proc. Symposium Indian Oils rata Natl. Chem. Lab. India, Poona, 1951, 169-74. (8C)Oliver, J., and Borrero, I., Grasaa Y aceztrs (Sevilla, Spain), 2, SO. 4. 7-18 (1951). (9C) Paterson, Wm. J. (to Lever Brothers C o . ) , U. S. Patent 2.645.620 (Julv 14. 1953) (1OC) Sokol'skii, D: V., and nlelekhina, L. S.,Doklady Alcad. Nauk I
I
S.S.S.R., 89, 881-3 (1953). (11C) Suito, Eiji, and Aida, Hiroshi, J . Chem. SOC.J a p a n , I n d . Chem. Sect., 54, 765-8 (1951). (12C) Takumi, Shizuo, and Kirwada, Tsutomu, Japan. Patent 1367 ('53) (April 2, 1953). (13C) Teruyama, Kenji, and associates, J . Chem. SOC.J a p a n , I n d . Chen. Sect., 54, 401-3 (1951). (14C) Thurman, Benjamin H. (to Kraft Foods Co.), U. S. Patent 2,621,191 (Dec. 9, 1952).
c C
September 1954
INDUSTRIAL AND ENGINEERING CHEMISTRY
(15C) Tsutsumi, Shigeru, Japan. Patent 4585 (’52) (Nov. 6, 1952). (16C) Tyutunnikov, B. N., and Fraler, B., Maslobolno-Zhirovaya Prom., 18, No. 1, 7-10 (1953). (17C) Ibid., NO. 2, 14-18 (1953). (18C) Ueno, Seiichi, Japan. Patent 7227 (‘51) (Nov. 20, 1951). (19C) Ibid., 128 (’52) (Jan. 18, 1952). (20C) Yonese, Chizuo, J . Chem. SOC.Japan, Ind. Chem. Sect., 54, 498-500 (1951). (21C) Ibid., pp. 500-502. (22C) Ibid., pp. 503-504. (23C) Yoshijima, Tadashi, and Tsutsumi, Shigeru, Ibid., 54, pp. 554-5. (24C) Zharskii, A. M., and associates, Maslobolno-Zhirovaya Prom., 18, NO. 7, 16-7 (1953). HYDROGENATION OF ACETYLENES AND ACETYLENIC COMPOUNDS
(1D) Badische Anilin- & Sodafabrik (Kurt Eder and Wilhelm Munster, inventors), Ger. Patent 841,141 (June 13, 1952). (2D) Bond, G. C., and Turkevich, John. Trans. Faraday Soc., 49, 251-91 (1953). (3D) Cases, EugBne, and Cheffer, Paul, French Patent 888,127 (Dec. 3, 1943). (4D) Ibid., 893,155 (June 1, 1944). (5D) Csuros, Zoltftn, GBczy, Istvftn, and Polga. Jbnos, Acta Chim. Acad. Sei. Hung., 1, 417-36 (1951). (6D) Douglas, John E., and Rabinovitch, B. S.,J . Am. Chem. SOC., 74, 2486-9 (1952). (7D) Gverdtsiteli, I. M.,and Mikadze, Sh. G., Zhur. Obshchel Khim.. 22. 1401-5 (1952). (8D) Fleming,‘ Harold W.; and’ associates, Petroleum Refiner, 32, NO. 9, 135-43 (1953). (9D) Sheridan, J., and Reid, W. D., J . Chem. SOC.,1952, pp. 2962-6. (10D) Zalkind, Yu. S.,and Kolyaskina, Z. N., Zhur. Obshchel Khim., 22, 2140-8 (1952). AMMONIA SYNTHESIS
(1E) Burnett, J. A., Allgood, H. Y., and Hall, J. R., IND.ENQ. CHEY.,45, 1675-82 (1953). (2E) Directie van de Staatsmijnen in Limburg, Dutch Patent 72,251 (April 15, 1953). (3E) Enomoto, Saburo, Shokubai, 8, 47-9 (1952). (4E) Enomoto, Saburo, and Horuchi, Juro, Proc. Japan Acad., 28, 493-8 (1952). (5E) Kaneko, Yoshihisa, Shokubai, 7, 95-105 (1951). (6E) Kiperman, S. L., and Granovskaya, V. Sh., Zhur. Fiz. Khim., 26, 1615-18 (1952). (7E) Nielson, Anders, “Advances in Catalysis,” Vol. 5, pp. 1-37, Academic Press, New York, 1953. (8E) Osumi, Yoshio, J . Chem. SOC.Japan, Pure Chem. Sect., 74,30811 (1953). (9E) Suwa, Tasuku, and Hama, Yutaka (to Showa Electro-Industries Co.), Japan. Patent 3412 (’52) (Sept. 1, 1952). (10E) Uchida, Hiroshi, Kuraishi, Miohio, and associates, Repts. Gout. Chem. Ind. Research Inst. Tokyo, 48, 12-26 (1953). (English summary) (11E) Uchida, Hiroshi, and Todo, Naoyuki, Ibid., pp. 85-96. (English summary) HYDROGENATION OF PETROLEUM AND HYDROCARBONS
Alchudzhan, A. A., Zhur. Fiz. Khim., 26, 1730-5 (1952). Anglo-Iranian Oil Co., Ltd., Brit. Patent 679,175 (Sept. 17, 1952). Anglo-Iranian Oil Co., Ltd., and Howes, Donald Albert, Ibid., 682,309 (Nov. 5, 1952). Anglo-Iranian Oil Co., Ltd., and Porter, Frederick W. B., Ibid., 690,806 (April 29, 1953). Apgell, Herbert R. (to Universal Oil Products Co.), U. S. Patent 2,635,080 (April 14, 1953). Badische Anilin- & Sodafabrik (Wilhelm v. Fiiner and Gerhard Free, inventors), Ger. Patent 843,251 (July 7, 1952). Berg, Clyde, Oil Gas J., 51, No. 46,286, 289-90, 292-3 (1953). Berger, Charles V., and Haensel, Valdimir (to Universal Oil Products Co.), U. S. Patent 2,642,383 (June 16, 1953). Bewley, Thomas, and Aller, Basil V. (to Distillers Co., Ltd.), Brit. Patent 677,091 (Aug. 6, 1952). Catravas, Georges N., Compt. rend., 236, 935-7 (1953). Ciapetta, F. G., and Hunter, J. B., IND. ENG.CHEM.,45, 14755 (1953). Cornubert, R., and Phblisse, Jean, Bull. SOC. chim. France, 1952, pp. 399-402. Crawford, Vincent L. (to Gulf Research & Development Co.), U. S. Patent 2,646,388 (July 21, 1953). De la Mare, P. B. D., J . Chem. Soc., 1952, 1602-7.
1859
(15F) Goldschmidt, T., A.-G. (Ludwig Schertel, inventor), Ger. Patent 807,814 (July 5, 1951). (16F) Haensel, Valdimir (to Universal Oil Products Co.), U. S. Patent 2,623,860 (Dee. 30, 1952). (17F) Ibid., 2,623,861 (Dec. 30, 1952). (18F) Ibid., 2,629,683 (Feb. 24, 1953). (19F) Ibid., 2,636,863 (April 28, 1953). (20F) Ibid., 2,641,582 (June 9, 1953). (21F) Haresnape, John N., and Porter, Frederick W. B. (to AngloIranian Oil Co., Ltd.), Ibid., 2,647,075 (July 25, 1953). (22F) Hartwig, Karl T. (to Universal Oil Products Co.), Ibid., 2,643,214 (June 23, 1953). (23F) Heard, Llewellyn, and Herder, Marvin J, Den (to Standard Oil Co. of Indiana), Ibid., 2,659,701 (Nov. 17, 1953). (24F) Hodgson, Maurice A. E., Reynolds, Peter W., Thomson, Ronald C., and Imperial Chemical Industries, Ltd., Brit. Patent 682,668 (Nov. 12, 1952). (25F) Hoffman, Edward J.,and Wadley, Edward F. (to Standard Oil Development Co.), U. S. Patent 2,635,435 (May 12, 1953). (26F) Hoog, H., Klinkert, H. G., and Sohaafsma, A., Petroleum Refiner, 32, No. 5, 137-41 (1933). (27F) Horne, Wm. A. (to Gulf Research & Development Co.), U. 8. Patent 2,647,857 (Aug. 4, 1953). (28F) Ind. Chemist, 29, 164-8 (1953). (29F) Jones, C. M.,PetroEeum Engr., 25, No. 7, C-27-8 (1953). and Grushko, I. E., Doklady Akad. Nauk (30F) Kasanski:, B. -4., S.S.S.R., 87, 767-70 (1952). (31F) Kellogg, M.W., Co., Brit. Patent 689,005 (March 15, 1953). (32F) Komarewski, U. I., and Erikson, T. h.,J . Am. Chem. Soc., 75, 4082-3 (1953). (33F) Langenbeck, Wolfgang, and Giller, Arnold, 2. anorg. u. allgem, Chem., 272, 64-8 (1953). (34F) Lanning, Wm. C. (to Phillips Petroleum Co.), U. S. Patent 2,627,495 (Feb. 3, 1953). (35F) Lihl, F., and Zemsch, P., 2. Elektrochem., 57, 55-69 (1953). (36F) McAfee, Jerry (to Gulf Oil Corp.), U. S. Patent 2,639,224 (Mav 19. 19531 (37F) Mison: RalphB: (to Standard Oil Development Co.), Ibid., 2,636,841 (April 25, 1953). (38F) Ibid., 2,657,175 (Oct. 27, 1953). (39F) Mason, Ralph B., and Rose, Harold J.,Ibid., 2,640,011 (May 26, 1953). (40F) Mills, Ivor W., and Johnson, Herbert L. (to Sun Oil Co.), Ibid., 2,635,081 (April 14, 1953). (41F) Montgomery, Charles W., and Brown, Charles S. (to Gulf Research & Development Co.), Ibid., 2,640,009 (May 26,, 1953). (42F) Moore, R. S.,Trimble, R. A . , and Greensfelder, B. S.,J. Am, Chem. SOC.,74, 373-5 (1952). (43F) Musaev, D. A., and Gal’pern, G. D., Doklady Akad. Nauk S.S.S.R.. 88. 71-2 (1953). -, N. V. de Bataafsche Petroleum Maatschappij, Dutch Patent 71,604 (Feb. 16, 1953). Ibid,, 75,052 (April 15, 1953). Oblad, Alex G., and Mills, George G. (to Houdry ProcesB Corp.), U. S.Patent 2,636,909 (April 28, 1953). Pack, F. C., and Planck, R. W., J . Am. Oil Chemists’ Soc., 30, 461-3 (1953). (48F) Porter, Frederick W. R., and Northcutt, Roy C. (to AngloIranian Oil Co., Ltd.), U. S.Patent 2,640,802 (June2,1953). (49F) Ibid., 2,648,623 (Aug. 11, 1953). (50F) Rab6, Gyula, and SzBkely, And&, Acta Chem. Acad. Sci. Hung., 2, 293-305 (1952) (in German). (51F) Ibid., pp. 307-16. (52F) Rab6, Gyula, and Zalai, Andrfts, Magyar KBm. Folydirat, 58, 303-5 (1952). (53F) Sherwood, Peter W., Erdol u. Kohle, 6 , 616-19 (1953). (54F) Shuikin, N. I., and associates, Izvest. Akad. Nauk, S.S.S.R., Otdel. Khim. Nauk 1953, pp. 96-9. (55F) Slabey, Vernon A., and Wise, Paul H., J . Am. Chem. Soc., 74, 3587-9 (1952). (56F) Societe chimique de la Grande Paroiese (A. Gosselin, inventor), French Patent 874,640 (Aug. 13, 1942). (57F) Zobell, Claude E. (to Texaco Development Corp.), U. S. Patent 2,641,564 (June 9, 1953). HYDROGENATION OF COAL
(1G) Blonskaya, A. I., Doklady Akad. Nauk S.S.S.R., 91, 257-613 (1953). (2G) Chaffee, C. C., and Hirst, L. L., IND.ENQ.CHBY.,45,822-38 (1953). (3G) Clarke, Edwin A., Chaffee, 6. C., and Hirst, L. L.,U. S. Bur. LMines, Rept. Invest. 4944, 1953. (4G) Gas Research Board and Dent, Frederick J., R&. Patent 695,192 (Aug. 5, 1953).
INDUSTRIAL AND ENGINEERING CHEMISTRY Gilbert, Wm. I., and Montgomery, Charles W. (to Gulf Research 8: Development Co.), U. S.Patent 2,654,695 (Oct. 6, 1953). Glenn, R. A., and DeWalt, C. W., Jr., Fuel, 32, 157-68 (1953). Kalbach, John C. (to Hydrocarbon Research, Inc.), U. S. Patent 2,639,982 (ilIay 26, 1953). Kukharenko, T. A., and Savel'ev, A. S.,Dolilady d k a d . Nauk S.S.S.R., 86, 729--32 (1952). Pampuch, Roman, Prace Badawcze Glbumego Inst. Gdrnictzaa (Ratowice),Komun., No. 69, 14 pp. (1950). Pampuch, Roman, Przemysl CItem., 31(8), 330-4 (1952). Pelipets, M. G., and associates, IXD.ESG. CHmr., 45, 806-9 (1953). Perna, F., and Pelcik, J., Paliwa, 31, 151-5 (1951). Pevere, Ernest F., and associates (to Texas Co.), U. S. Patent 2,658,861 (Sov. 10, 1953). Pier, hlatthias, 2. ElektrochenL.. 57, 456-GO (1953). Shibata, Kenao, Chem. Eny.. 60, Xo. 5 , 214-8 (1953). Skinner, L. C., Gasification and Liquefaction of Coal Symposium, Ann. Meeting Am. Inst. Mining Met. Engrs., Xew York, Feb. 20-1, 1952, 1--14. Standard Oil Development Co., Brit. Patent 693,582 (July 1, 19531, ORGANIC COMPOUNDS
(1H) Artamonov, P. A. Zhur. ObshcheE Khim.,23, 216-18 (1953). (2H) Badische Anilin- & Sodafabrik. Ger. Patent 844,891 (July 24, 1952). (3E-I) Zbid.,851,343 (Oct. 2, 1952). (4H) . . Baldwin, Wm. S., and Floyd, Don E. (to General Mills), U. S. Patent 2,656,371 (Oct. 20, 1953). (5H) Barr&,Roger, and Favreau, Leopold. C o m p f . rend., 235, 1404 (1952). (6H) Bird, R. F., and Turner, E. E., J . Chem. Soc., 1952, pp, 5050-1. (7H) Cat, A. de, Industrie chim. belge, 17, 652-64, 772-80, 838-44, 1027-42 (1952). (8H) Cluzel, Roger, and Cordier. Paul, Compt. rend., 235, 622-3 (1952). (9H) Cornubert, tl., and Kazis, C., Bull. soc. chiin. Fiance. 1952, pp. 410-13. (10H) Cornubert, R., and PhBlisse, Jean, Ibid., pp. 403-~-7. (11H) Cornubert, R., and Iteal, Max, Ibid., pp. 407-10. (12H) Dauben, Wm. G . , and associates, J . Am. Ciiena. Soc., 74, 3852-5 (1952). (13H) Dreiding, Andre S.,and Hartman, John A,, Ibid.,75, 939-43 (1953). (14H) Drua, V. A , and Sokol'ski?, D. V., Zhur. FEZ. Khim., 26, 48491 (1952). (15H) Eliel, Ernest L., and Freeman, Jeremiah P., Ibid., 26, 929-8 (1952). (16H) Epsstein, Roland, and associates, Bull. soc. chinz. Fiance. 1952, '
pp. 777-9.
(17H) Farbwerke Hoeschst vorm. Meister Lucius &. Bruning (Adolf Sieglitz and Otto Horn, inventors), Ger. Patent 855,400 (Kov. 13, 1952). (18H) Ford,,Thornas A. (to E. I. du Pont de Kemours &. Co.), U. S. Patent 2,607,807 (hug. 19, 1952). (19Hj Fry, Edward M.,J . Org. Chem., 17, 1484-91 (1952). (20H) Gershbein, Leon L., and Ipatieff, V. N., J . Am. Chem. Soc., 74, 1540--2 (1952). (21H) Gresham, Wm. F. (to E. I. du Pont de Xeniours & C o . ) , U. S. Patent 2,607,805 (hug. 19, 1952). (22H) Gupta, 6. 3., and Aggarmal, ,J. S.,J . Sci. Ind. Research (India) 11B, 303-4 (1952). (23H) Hancock, C . Kinney. ISD.ENG.CHEM.,44, 1003-6 (1952). (24H) Hill, Carl M., Hill, Mary E., and associates, J . Am. Chem. SOC.,74, 166-7 (1952). (25H) Isbell, Horace S., and Karabinos, J. V., J . Research S a t l . Bur. Standards, 48, 438-40 (1952). (26H) Janot, Maurice Marie, and associates. Bull. soc. chim. France, 1952, pp. 230-6. (27H) Karrer, P., and Asmis, H., Helc. Chim. Acta, 35, 1926-31 (1952) (in Gerniani. (28H) Kkfrnan, B&1jamin I. (to 11.JT.Kellogg Co.), U. S Patent 2,623,893 (Dee. 30, 1952). (29H) Kaaanskii, B. A., and Popova, S . I., Izuest. Akad. Nauk S.S.S.R., Otdel. Iihim. X a u k , 1952, 422-32. (30H) Khan, N.A , , J . Am. Oil Chemists' Soc., 30, 40-3 (1953). (31H) Kobashi. htsuo, and associates. J . Chem. Sac. Japan, Ind. Chem. Sect., 54, 332-3 (1951). (32H) Komori, Saburo, and associates, Ibid.,55, 237-9 (1952). (33H) Kulkarni, K. B., Bombay Technologist, 2 , 37-43 (1952). (34H) Lambert, Paulette, and Xastagli, Pierre, Compt. rend., 235, 6 2 6 7 (1952).
Vol. 46, No. 9
(35H) Laubach, G. D., and Brunings, K . E., J . Am. Soc., 74, 7 0 5 - i (1952). (36H) Lebedeva, A . I., and Almashi, L. F., DokZadg A k a d . Nauk S.S.S.R., 86, 75-8 (1952). (37H) Lihl, F., and Zemsch, P., 2. Elektrochenz.. 56, 979-85 (1952). (38H) Ibid., pp. 985-7. (39H) Lur'e, S. I., and a3sociate6, Zhw. Obschel Khim., 22, 2011-14 (1952). (40H) Kekhtiev. S. D., and associates. Doklady Akad. N a u k S.S.S.R., 86, 547-50 (1952). (41H) Mirsa, Rafat, Current S c i . (India),21, 195 (1952). (42H) Misuguchi, Jun, and Ohoshi, hlinoru, J . Chern. Soc. Japan, I n d . Chem. Sect., 53, 205-7 (1950). (43H) Ilousseron, Max, and associates, Compt. T e n d . , 235, 177-9 (1952). (44H) Mulholland, T . P. C., J . C'hem. Soc., 1952, pp. 3987-94. (45Hj 5 . V. de Bataafsche Petroleum llaatschappij, Brit. Patent 680,508 (Oct. 8, 1952). (46H) Orchin, Milton, "Advances in Catalysis," 5-01. 5, pp. 385415, Academic Press, New York, 1953. (47H) Perroncito, Giulio, Boll. chim. farm., 92, 37-41 (1953). (48H) PigulevskiI, G. V., and Artamonov, P. A , , Zhur. OhsiicheE Khim.. 22. 1140-3 (1952). Rosenkrane, Geo., and associates (to Syntex S . A , ) , U. S. Patent 2,609,378 (Sept. 2 , 1952). Sandoz, Ltd., Brit. Patent 674,061 (June 18, 1952). Schweia. Sprengstoff-Fabrik A.-G., Brit. Patent 692,268 (June 3, 1953). (52H) Smith, Hilton A,, Shacklett, Comer D., and Welch, Clark lI., J . Am. Chem. Sac., 74, 4534-6 (1952). (5311) Sokol'BkiY, D. V., Z h w . Obshchet Khim., 22, 1934-41 (1992). (54H) Sokol'skii, D. V., and Druz, J-, A., Zhur. Fiz. Khim., 26, 36170 (1952). (55H) Sokol'skii, D: V., Shostakovskii, &I. F., and associates, Zhur. Priklad. Iihlm., 25, 867-75 (1952). (56H) Spriggs, Alfred S., and associates, J . Am. Chem. Soc., 74, 1555B (1952). (57H) Syntex, 9. A,, Brit. Patent 662,400 (Dee. 5, 1951). (58H) Tsntsumi, Shigeru, and Akatsuka, Hisashi, J . Chem. Soc. Japan, Ind. Chem. Sect., 55, 105-7 (1952). (59H) Urushibara, Yoshiyuki, B I L L Chern. Soc. J a p m , 25, 280 (1952) (in English). (60H) Usines de 3lelle (Henri Martin Guinot, inventor), French Patent, 973,322 (Feb. 9, 1951). \
-
FUNDAMENTAL STUDIES
(li) Alchudshan, A. A , , Zhur. F i z . Khinr., 26, 1591-9 (1952). (2i) Ihid., pp. 1600-9. (3i) Bonner, Wm. A , , J . Am. C h n . Soc., 74, 1033-4 (1952). (4)Ibid., pp. 1034-9. (Si) Edstrom, J. O., J . Iron Steel Inst. (London), 175, 239~-304 (1953).
(6i) Fedorova. A. I., and Frumkiu. A. S . ,Zhur. Fiz. Khim., 2 7 , 24760 (1953). (71) l'ukushima, Daiid K., and Gallagher. T. F., J . Bzol. Ch(?n.,198, 861-9 (1952). (Si) Ibid., pp. 871-84. (9i) Hartuny, Walter H., and Chang. Yen-Tsai. J . Am. C'hem. Soc., 74, 5927-9 (19.52). (1Oi) Keier, N.P., Iznest. A k a d . .Tauk S.S.S.R., Otdel. Iihirn. S a u k , 1953, pp. 48-57. (11i) Khan, X. A,. Science, 117, 130 (1953). (12i) Krylov, 0. T., and Roginekii. S. %., D.iklady A k a d . S a u k S.S.S.R., 88, 293-5 (1953). (13i) Krylov, 0 . V., Roginskii, S. Z . . arid Tret'yakov, I. I., Ibid.. 92, 7 5 G (1853). (14i) Lardler, Keith J.. arid associates, J . Chem. Piius.. 21, 949- 50 (1353). (15i) Xarkham, llaria Clare, and associates, I b i d . , 20, 1 3 3 - 2 (1952). (16i) AIorrita, Fred L., and associates, J . A m . Chem. Soc., 75, 3118-21 (1953) (17i) S a t t a , G., Pino, P., and Ercoli, R., Ibid.. 74, 4496-8 (1952). (1%) Kasarov, I. N., and a%sociates,Zhur. Obshchei Rhim., 22, 1236-44 (1952). (19i) Ibid., pp. 1405-10. (209 Petrov, A. -%.,and Frost, A. V., Ibid., pp. 1773-80. (219 Rab6, Gyula, and SaBkely, Andras, Acta Chim. A4cad. Sei. Hung., 2, 273-91 (1952) (in German). (22i) Ueno, S., Matuda, M.,and Yamashita, K., Fette u . Seifen, 54, 467-8 (1952). (23i) Wilmarth, 7%'. K., and associates, J . Am. Chem. Soc., 75,454953 (1953). I
INDUSTRIAL AND ENGINEERING CHEMISTRY
September 1954 MISCELLANEOUS
(1J) A4shmore,P. G., "future, 172, 449-50 (1953). (25) Atwood, Kenton, IND.ENG.CHEM.,45, 1976-98 (1953). (35) Beidler, Edward A. (to Crowdey-Republic Steel Corp.), U. S. Patent 2,642,356 (June 16, 1953). (4J) Berlie, AI. R., and LeRoy, D. J., Discussions Faraday Soc., h-0. 14, 50-4 (1953). (5J) Boelhouvier, C., and associates, Chem. Eng. Sci., 2, 69-73 (1953). (GJ) Brauman, Pierre, and Tsangarakis, Constanten, Mbm. s e r u m s chim. btat (Paris),36, No. 2 , 198-200 (1951). (7J) Curtin, Gerald F., Jr. (to E. I. du Pont de Nemours 8: Co.), U. S. Patent 2,617,835 (Nov. 11, 1952). (85) EpsztGn. Roland, Olomucki, Martin, and Giraud, Pierre, Mbm. services chim. &at (Paris),36, 283-4 (1951). (9J) Hasegawa, Hiroshi, and Miyake, Ryoiohi, J . Pharm. SOC. Japan, 70, 187-90 (1953).
m!!
WILLARD
1861
(1OJ) Hutter, Jean Claude, Ann. chim. (Paris),8, 450-97 (1953). (llJ) Ipatieff, Vladimir N., J . Chem. Educ., 30, 110-15 (1953). (125) Johnson, Herbert L., and Stuart, Archibald P. (to Sun Oil Co.). U. S. Patent 2,649,419 (Aug. 18, 1953). (135) Jones, R. Vernon, and associates, IXD.ENG.CHEM.,45, 111722 (1953). (145) LapessB, G. V. E., French Patent 977,108 (March 28, 1951). (155) McGrath, Henry G. (to >I. W. Kellogg Co.), U. S. Patent 2,632,765 (March 24, 1953). (16J) McGrath, Henry G., and Hill, Luther R. (to M. W. Rellogg Co.), U. S. Patent 2,640,844 (June 2 , 1953). (175) O'Brien, R. N., and associates, Trans. Can. Inst. Mining M e t . , 56, (in Can. Mining Met. Bull., 499, 673-6 (1953). (185) Tyutyunnikov. B. N., and Fraier, B., Masloblno-Zhiroaaya Prom., 18, No. 3, 10-11 (1953). (19J) Watt, Geo. T.V., and Parker, Sidney G., J . Am. Chem. Soc., 74, 1103-4 (1952).
NITRATION dec.
CRATER
HERCULES POWDER CO., WILMINGTON, DEL.
Continuous nitration processes continue to b e of interest. Two Biazzi units for the manufacture of nitroglycerin have been put in service at government facilities. Also such a unit for the commercial manufacture of nitrobenzene has been installed in West Virginia. A continuous unit for the nitration of cellulose has been patented. The study of nitration of amines to yield their nitro derivatives remains active, as well as the production of nitroparaffins.
ITRATION in its broadest sense covers the treatment of organic compounds with nitric acid or its equivalent t o produce both nitrates and nitro compounds. As in the past reviews, this is a resume of articles and patents pertinent to the art of nitration published since the 1953 review (6).
NITRIC ACID ESTERS ildditional units for the manufacture of nitroglycerin by the Biazzi continuous process have been installed in the United States a t government facilities. An article published by Klassen and Humphrys (I6) describes the manufacture of nitroglycerin by the Biazzi continuous process at the Calgary Works of the Canadian Industries Ltd. The authors describe the various pieces of equipment and discuss the plant operation. A comparison between the batch process and the continuous process is made with comments concerning the advantages of the Biazzi unit. Also in West Virginia a continuous Biazzi unit for the nitration of benzene has been installed and put in operation. A general procedure for the nitration of sugars or derivatives of sugar is described by Honeyman and others ( I S ) . T h e method consists of treating a suspension of the sugar derivative in acetic anhydride with a mixture of acetic anhydride and about 50% excess of fuming nitric acid, the temperature being kept at 0" C. iZfter nitration is complete, about 1 hour, the product is recovered by pouring the solution in ice water, after which it is stabilized. The authors point out that mixtures of acetic anhydride and fuming nitric acid may decompose violently a t room temperature; hence, such a mixture should be made only as needed. Aqueous and nonaqueous solution procedures for the preparation of nitrated alcohols are described by Nichols, Magnusson, and Ingham ( 2 2 ) . The reaction is carried out by the addition of nitric acid to oxirane compounds such as ethylene oxide, propylene oxide, and epichlorohydrin. Factors influencing the yield of nitrated product were determined. An increase in temperature increases the yield of product. Also, investigation was
made of the t.u.0 major side reactions, glycol formation and polymerization. A patent granted to Nitroglycerin -4ktiebolag ( 2 3 ) describes reacting an aldehyde or a ketone with nitroform in the presence of an inert solvent for the reaction components to produce trinitroalcohols. Suitable solvents are water, alcohol, dioxane, or carbon tetrachloride. A process for the continuous nitration of cellulose is described by R a m s q (85). The method consists of suspending a strip of cellulose so that it sags downwardly between the points of SUBpension, and the valley of the freely moving strip is immersed in the bath of nitrating acid, which may move countercurrent to the movement of the strip. According to Cherubin ( 6 ) . cotton linters when nitrated with mixed acids without swelling show a difference in reactivity between two fractions which are thought to correspond to the crystalline and amorphous regions of the cellulose fiber.
NITRO COMPOUNDS Lauer and Soland ( 1 7 ) found that the nitration of benzene containing 91.5 mole % monodeuterobenxene gave nitrobenzene containing 74.9 mole % of monodeuteronitrobenzene and mdinitrobenzene containing 60.9 mole % monodeutero-m-dinitrobenzene. Since these are the concentrations expected if there is no hydrogen isotope effect, these studies confirm a previous report by Melander based on tracer studies that loss of a hydrogen ion cannot be a rate-influencing step in aromatic nitration. The use of nitryl chloride as a nitrating agent was investigated by Price and Sears ( 2 4 ) who found its activity can be promoted with such compounds as hydrogen fluoride, aluminum chloride, and boron fluoride. Its application appears to be limited to aromatic substances of intermediate activity. Highly reactive aromatics as phenol and anisole tend to give oxidative degradation, while deactivated aromatics as nitrobenzene are recovered unchanged.
NITROAMINES
T h e production of tetryl from dinitrochlorobenzene and dimethylamine or mixtures of the latter with methylamine is described by Desseigne ( 7 ) . T h e procedure consists of treating an
