AUGUST 1958
I/EC Briefs l/EC's articles on . . .
CHEMISTRY AND CHEMICAL ENGINEERING IN THEORY AND PRACTICE
The why, what, and significance of technical articles in this issue. Clip these Briefs for ready reference and easy filing on a 3 X 5 or other suitable card
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I/EC Brief I n d . Eng. C h e m . 50, 1119-23 (1958)
STAFF-INDUSTRY COLLABORATIVE REPORT I n d . Eng. C h e m . 50, 1106-14 (1958)
Pentaerythritol After a rapid growth period, market d e m a n d for penta erythritol has leveled off in recent years. M u c h activity aimed at developing n e w uses is now u n d e r way, in an in tense effort to overcome serious overcapacity in the industry. Shrinking profit margins have caused manufacturers to carefully look over integrated operating plants. O n e good example is Hercules' Louisiana, Mo., site where ammonia, methanol, formaldehyde, and sodium formate are made, in addition to pentaerythritol. Manufacturing details at the site are spelled out, and the full industry situation is presented. MORTON S A L K I N D , H. F. A H E R N , and A. A. A L B E R T
Preparation, Homopolymerization, and Copolymerization of «Acyloxyacrylic Esters N u m b e r of α-acyloxyacrylic esters were prepared, to evaluate the homopolymers and several copolymers with other vinyl monomers as coating and molding resins. T h e monomers readily homopolymerize to give clear, colorless masses; softening points and hardness charac teristics may be varied by changing the acyl and ester substituents. Ethyl α-acetoxyacrylate produced a hard, clear-cast polymer which would not melt without decomposition; the butyl ester was fusible. T h e ethyl ester could be bulkpolymerized with styrene to give clear, fusible products except at low styrene ratios, but showed poor copolymeriza tion characteristics with vinyl acetate. T h e a-acyloxyacrylate copolymerized readily with methyl methacrylate in all ratios, giving clear, fusible masses, indicating its use as modifier in manufacturing poly(methyl methacrylate) cast articles and molding resins. T H O M A S M . LAAKSO and CORNELIUS C. UNRUH Research Laboratories, Eastman Kodak Co., Rochester 4, N.Y.
I/EC Brief
I/EC Brief
I n d . Eng. Chem. 50, 1115-18 (1958)
Continuous High Pressure Synthesis of 3-Aminopropionitrile T h e reaction of acrylonitrile with ammonia was studied, to find the conditions that would give maximum yields of 3-aminopropionitrile. A continuous high pressure reactor was used to study the variables: mole ratio of ammonia to acrylonitrile, contact time, temperature, and quantity of water in the ammonia. It was s h o w n statistically that increasing the water content increased the yield of 3-aminopropionitrile. It is possible to prepare 3-aminopropionitrile in yields of approximately 8 0 % based o n acrylonitrile using 5 0 % aqueous ammonia in a mole ratio of 7 to 1 over acrylonitrile at a temperature of 105° to 110° C. and a contact time of 1-2 minutes. T h e compound is sufficiently stable for examinaion of its reactions.
I n d . Eng. C h e m . 50, 1124 (1958)
Copolymerizability of Ethyl «-Acetoxyacrylate An earlier study has b e e n extended to a more quantitative investigation of the copolymerization behavior of ethyl α-acetoxyacrylate with styrene, methyl methacrylate, vinyl acetate, and ethyl acrylate. Ethyl α-acetoxyacrylate resembles ethyl acrylate very closely in copolymerizability, b u t has little resemblance to vinyl acetate. C. C. UNRUH and T . M . LAAKSO Research Laboratories, Eastman Kodak Co., Rochester, Ν. Υ.
EDWIN M. S M O L I N and L. CLAIR BEEGLE Research Division, American C y a n a m l d , Co., S t a m f o r d , Conn. CLIP AND
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Eng. Chem. 50, 1125-6 (1958)
Hydrogenolysis of Sorbitol To develop uses for sugars obtained from saccharification of wood residues, the kinetics of sorbitol hydrogenolysis has b e e n studied by the U. S. Forest Products Laboratory. Glycerol in 4 0 % yield can be obtained from sorbitol, which is better than w h e n sugar is used directly. Other principal products are xylitol, erythritol, and propylene and ethylene glycols. Proportions and yields together with time at which they are obtained d e p e n d on the catalyst and reaction conditions. IRA T. CLARK Forest Products Laboratory, U. S. Department of Agriculture, Madison, Wis.
Eng. Chem. 50, 1135-8 (1958)
Hydrocracking an Aromatic Extract to Naphthalene and 100-Octane Gasoline Light catalytic cycle oil can be separated by extraction with sulfur dioxide into a raffinatc containing paraffins and naphthenes and an extract containing aromatics and sulfur compounds. Hydrocracking the extract can produce 1 6 % naphthalene and 5 5 % of 100-octane gasoline in a single step. T h e preferred extract contains 9 0 % aromatics a n d boils in the 200° to 250° C. range. Most-active catalysts are alkalized chromia, vanadia, and cobalt-molybdenum oxides on alumina. Best conditions for hydrocracking with alkalized chromia-alumina catalyst are 1.0 space velocity, 525° C , 800 p.s.i., and a hydrogen-hydrocarbon ratio of 3000 cu. feet per barrel. T h e gasoline produced contains 90% aromatics and less than 0.1% sulfur. ALAN K. ROEBUCK and B. L. EVERING Research Department, Standard Oil Co. (Indiana), Whiting, Ind.
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Eng. Chem. 50, 1127-30 (1958)
Eng. Chem. SO, 1139-42 (1958)
Organoaluminum Halides as Hydrogénation Catalysts
Esterification of Methylolated Rosin To increase utilization of rosin, its reaction with formaldehyde and esterification of the reaction products were studied. M u c h of the formaldehyde adds to the rosin as methylol groups. T h e alcohol groups thus introduced were esterified with drying oil fatty acids and also interesterified with drying oils. In some respects, the varnishes thus formed were superior to those made from ester gum and linseed oil. This provides a n e w method for preparing surface coating materials from rosin and drying oils.
Ethyl aluminum bromides of composition ranging from Al2Et3Br3 to Al2Et1.5Br4.5 have b e e n found to catalyze the hydrogénation of Tetralin to Decalin. Typical conditions are 350° C , 3000 p.s.i.g., and 5 weight % catalyst. The composition and physical state of this novel hydrogénation catalyst have been studied. It is concluded that the actual catalyst is not the original organoaluminum halide but a solid decomposition product. The composition of this solid varies with that of the organoaluminum halide charge; hence, it has not b e e n possible to associate the catalytic activity with any unique compound.
JACOB C. M I N O R and RAY V. LAWRENCE Naval Stores Station, U. S. Department of Agriculture, Olustee, Fia.
J. A. RIDGWAY, Jr. American Oil Co., Texas City, Tex.
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Eng. Chem. 50, 1131-4 (1958)
Isomerization of Bicyclo (2.2.1 ) -2,5-heptadiene to Cycloheptatriene A practical method has been developed for the preparation of 1,3,5-cycloheptatriene (tropilidene) from bicyclo(2.2.1 -2,5-heptadiene. This operation, a vapor phase thermal isomerization, carried out at temperatures of 400° to 475° C. and at short vapor residence times, gives yields up to 50 mole % of cycloheptatriene. As a result, this unique compound is available to organic synthesis in quantities heretofore impossible. W. M. HALPER Shell Chemical Corp., Torrance, Calif. G. W. GAERTNER Shell Development Co., Denver, Colo.
Eng. Chem. 50, 1143-8 (1958)
Pilot-Plant Production of Ground Senatia
marcescens
T h e development of a process for preparing relatively large amounts of fine powder containing high concentrations of Serratia marcescens was investigated. Powdered concentrates of 5. marcescens were produced by suitable combinations of fermentation, centrifugation, pelleting, freeze-drying, and grinding. T h e complete process incorporated p H control throughout fermentation, and the use of a continuous, controlled solids-discharge centrifuge, a continuous freeze-dryer, and a high-speed centrifugal grinding mill. T h e powder contained about 2 1 % of the viable cells present in the fermented liquor, and had a viable cell count of about 1400 Χ 10 9 per gram. It exhibited good storage stability, and was suitable for creating slow-settling aerosols. V. F. PFEIFER, CHARLES VOJNOVICH, H. G. MAISTER, V. E. SOHNS, E. N. HEGER, and W. M. BOGART Northern Utilization Research and Development Division, U. S. Department of Agriculture, Peoria, III.
E. W. S W I F T and G. E. POLLARD Shell Chemical Corp., Denver, Colo. CLIP AND
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Eng. Chem. 50, 1157-60 (1958)
Eng. Chem. 50, 1149-62 (1958)
Experiments on an Industrial Venturi Scrubber
Refractometer for Continuous Process-Stream Analysis A sensitive differential refractometer developed for the continuous analysis of two-component liquid process streams includes a wide choice of refractive index spans, from 0.1 to 0.0004, the latter with precise measurement to ±0.000004; complete elimination of the adverse effects of stream tem perature variation; and a highly stable and robust design, easy to apply, install, and maintain, but operable under the most severe plant conditions. T h e refractometer has b e e n extensively used for inprocess analyses of aqueous solutions of organics and for mixed fluorinated hydrocarbons. L. G. GLASSER and D. J . TROY Engineering Research Laboratory, Engineering Department, E. I. du Pont de Nemours & Co., Inc., Wilmington, Del.
In a statistically designed experiment, the collection efficiency of an industrial Venturi scrubber on phosphoric acid mist was measured. The variables studied included gas velocity, liquid rate, liquid injection velocity, and number of injection orifices. The collection was correlated with these variables. T h e pressure drop across the Venturi scrubber was correlated with the operating variables. T h e particle-size distributions of the acid mists entering and leaving the Venturi scrubber were determined with a cascade impactor. T h e collection efficiency of the scrubber was dependent on mist particle size. Efficiencies of 98% were obtained on particles 1.0 micron in diameter, com pared to 7 8 % on 0.5-micron particles. J. A. BRINK, Jr., and C. E. CONTANT Monsanto Chemical Co., St. Louis, Mo.
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Eng. Chem. 50, 1153-6 (1958)
The Glass Effect in Distillate Fuel Stability Glass containers are often used for storing fuels during stability studies. T h e nature of the glass has a pronounced effect on the rate of degradation of some distillate fuels. Of 13 fuels studied, 10 degraded less rapidly in soft glass than in borosilicate glass, while three fuels showed no difference. Treating the bottles with strong acid or alkali before use caused only minor changes in degradation rates. T h e glass effect w h e n operative, is due to inhibition by soft glass and not to acceleration by borosilicate glass. Because borosilicate containers appear to be essentially inert, they should be better for fuel stability studies than soft glass containers. J. G. CHRISTIAN, A. J. CHIANTELLA, J. E. JOHNSON, and H. W. CARHART Naval Research Laboratory, Washington 25, D. C.
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Eng. Chem. 50, 1161-4 (1958)
Theory of Aerosol Filtration Fibrous filters of low porosity are widely used to remove particles from gases. Although filtration efficiency has been carefully investigated and a n u m b e r of theoretical analyses exist, no satisfactory general correlation of efficiency with the important dimensionless groups has b e e n developed. T h e present theory of removal b y fibrous filters is re viewed and extended. A method of correlation based o n an analysis of the diffusion equation is suggested. Experi mental data, taken from the literature, are in agreement with the form of the efficiency function predicted from the theory. W h e n the Reynolds n u m b e r and impaction parameter are less than 1, the impaction mechanism seems to be of little importance. T h e method should prove of value in filter design and correlation of experimental data. S. K. FRIEDLANDER Department of Chemical Engineering, The Johns Hopkins University, Baltimore 18, Md.
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AIR POLLUTION
Eng. Chem. 50, 1165-8 (1958)
Reaction of Nitric Oxide with Activated Carbon and Hydrogen
Five article* starting page 1157 Biennial Review page 1175
This investigation was undertaken as a primary step in attempts to remove nitric oxide from exhaust gases by chemical reaction. A contact time of 0.8 second allowed complete reduction of nitric oxide b y activated carbon or by hydrogen on activated carbon at 600° to 700° C. T h e products are nitrogen and carbon oxides or water. These results qualify either reactant for use in certain industrial applications and warrant further work in at tempting to apply the reactions to automobile exhausts. G. BEDJAI, H. K. ORBACH, and F. C. RIESENFELD Research Division, The Fluor Corp., Ltd., Whittler, Calif.
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Eng. Cham. 50, 1169-72 (1958)
Absorption of Sulfur Dioxide from Air. Oxidation in Drops Containing Catalysts
Ind.
Droplets of sulfuric acid formed b y absorption of sulfur dioxide and oxygen from air by fog droplets nucleated by oxidation catalysts may be important in air pollution. Rates of acid formation were measured w h e n dilute drops of manganese, iron, copper, and nickel sulfates were ex posed to air containing sulfur dioxide. T h e reaction b e tween solutions of sulfur dioxide and o x y g e n in the presence of manganese sulfate is zero order with respect to both reactants and the rate is proportional to the square of catalyst concentration; it is retarded by small concentrations of acid. A mathematical analysis was developed for the steadystate absorption of sulfur dioxide b y drops of catalyst solu tions. T h e calculated rate of conversion of sulfur dioxide in a natural fog is about 500 times the rate of photochemical oxidation of sulfur dioxide in air in intense sunlight.
Eng. Chem. GO, 1181-8 (1958)
Osmionic Demineralization Unlike electrodialysis, this new method for demineralizing water, based on permselective membranes, does not utilize electricity as a prime power source. Ions are driven through membranes by the potential derived from differ ences in salt concentration b e t w e e n two fluid streams—e.g., saturated brine and brackish water. From calculations based on laboratory data, the process is economically competetive with the best methods now available for brackish water demineralization. T h e prin ciples and types of ionic cells are discussed from the stand point of minimum product cost. GEORGE W. MURPHY State University of New York College for Teachers, Albany, Ν. Υ.
H. F. JOHNSTONE and D. R. COUGHANOWR University of Illinois, Urbana, I I I .
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I/EC Brief Ind.
Eng. Chem. 50, 1173-4 (1958) Ind.
Eng. Chem. SO, 1189-92 (1958)
Photochemical Formation of Air Contaminants from Automobile Exhaust Vapors. Effects of Different Motor Fuels
Production of Carbon Disulfide
Because automobile exhaust is a major factor in develop ment of the type of smog that accumulates periodically over the Los Angeles Basin, there is interest in reducing its con tribution by modification of the type of fuel consumed. Under controlled experimental conditions maintained during comparison of two fuel blends, the composition of exhaust gases and their capabilities for participation in photochemical reactions resulting in smog were shown to depend on the make-up of the charging fuel—specifically, amounts and types of olefins in the fuel blend. T h e exhaust products of two fuels, consumed under the same conditions and in the same engine, differed signifi cantly in their effect on photochemical formation of eye irritants, aldehydes, organic peroxides, and ozone.
Alternatives were investigated to the traditional method of manufacturing carbon disulfide, which uses high tem peratures and expensive raw materials. For the reaction 2COS = C 0 2 + CS2, the activation energy was 50,000 cal. and the space velocity was 34 h r . - 1 CS2 at 440° C. and 500 hr.-» C (extrapolate) at 500° C. For the reaction C + S2 = CS 2 , the activation energy was 13,000 cal. Coal charcoal was as reactive as natural beech charcoal. Coke was relatively unreactive. A process based on the system carbon monoxide plus sulfur operating at 500° C. is an alternative. A sample of artificially prepared coal charcoal may be used as a sub stitute for beech charcoal. Coke might replace charcoal if used in a pulverized form. H. N. MADON and R. F. STRICKLAND-CONSTABLE Department of Chemical Engineering, Imperial College of Science and Technology, London S.W. 7, England
PAUL P. MADER, JOSEPH G L I K S M A N , MARCEL EYE, and LESLIE A. CHAMBERS Air Pollution Control District, County of Los Angeles, Los Angeles 13, Calif.
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Eng. Chem. 50, 1193 (1958)
Decontaminating Radioactive Water Ind.
Eng. Chem. 50, 1175-80 (1958)
Air Pollution Review 1956-57 T h e period has b e e n marked by greatly increased re search activity in Europe, Russia, and America, o n nature and levels of pollutants, reactions b e t w e e n pollutants, effect of pollution on health, and control measures. Fallout from nuclear explosions has perplexed specialists, and a voluminous literature has b e e n built u p . Pollution from engine exhausts and from industry has had special attention. KINGSLEY KAY Department of National Health, Ottawa Canada
Polymer coagulants used to coagulate and precipitate large dosages of several types of ferruginous, calcareous, and glauconite shales were slurried in contaminated tap water to remove radioactive nuclides by absorption and base exchange. Dosages of high molecular weight polyelectrolyte required for coagulation were found to be very small. Various types of shale remove radioactive contaminants from water, but the effectiveness depends on the chemical properties of the nuclides and the chemical properties of shale. T h e radioactive nuclides used as contaminants were: Sr9»-Y*>, CeI37-Ba13% Ru'W-Rh"*, Ce'^-Pr 1 ", and a fission product mixture, MFP. W h e n using these polyelectrolytes as coagulants the maximum possible removal of radioactive material was obtained by slurrying the shale for 30 minutes followed by adding the coagulant, 5 minutes of rapid mixing, and 15 minutes settling. W I L L I A M J . LACY and WALLACE DE LAGUNA Oak Ridge National Laboratory, Oak Ridge, Tenn.
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Ind. Eng. Chem. 50, 1207-10 (1958)
Effect of Heat Treatment on Silica Gel Ind. Eng. Chcm. 50, 1194 (1958)
Continuous Dissolution of Copper by Nitric Acid T h e effects produced b y varying acid flow rate and acid concentration on the rate of continuous dissolution of copper by nitric acid have b e e n studied. Rate of dissolution increases markedly w h e n the acid concentration is increased from 3 to 4.37^ or higher; over the range of mass velocities studied, rate of dissolution is either nearly i n d e p e n d e n t of mass velocity or decreases as the mass velocity is increased. T h e experiments were carried out at 29 ° C. ± 1 °. ROBERT L. JOHNSON, MERK HOBSON, and JAMES H. WEBER Department of Chemistry and Chemical Engineering, University of Nebraska, Lincoln 8, Neb.
Silica gel is one of few solids that have sufficient specificity and capacity of adsorption to be useful as industrial adsorbents. It is used to fractionate mixtures of hydrocarbon gases and is easily regenerated by heating. T h r o u g h controlled conditions of manufacture, silica gel can be tailored to separation processes involving various mixtures. Heat treatment offers one means of controlling pore volume and pore size distribution necessary for selective adsorption. Selective adsorption requires adsorbents with structural and chemical characteristics to suit the individual process. Temperature of retorting offers one means of modifying the structure of an adsorbent to meet process specifications. Heat treatment of an amorphous silica gel decreased the total pore volume and surface area of the gel, but did not appreciably modify its pore size distribution. MYRON MALANCHUK and EDWARD B. STUART Chemical Engineering Department, Engineering Research Division, University of Pittsburgh, Pittsburgh 13, Pa.
I/EC Brief
I/EC Brief Ind. Eng. Chem. 50, 1211-12 (1958)
Ind. Eng. Chem. 50, 1195-1200 (1958)
Diffusion of Gases in Porous Media Countercurrent diffusion of carbon dioxide and nitrogen through porous plugs of compressed potassium perchlorate was studied, to determine the effect of varying plug porosity and length on the diffusion coefficient. The effects of porosity variation through the range of values 0.2 to 0.4, and plug lengths of 1, 2, 4, and 8 inches on diffusivity are reported. T h e ratio of the diffusivity or diffusion coefficient to the free diffusion coefficient, plotted as a function of porosity, is compared with but does not confirm a relationship proposed by an earlier investigator. There has been little previous work in this field. Experimental apparatus is simple, yet provides quick and accurate measurement of the quantities necessary for evaluating the flow pattern equation for unsteady-state, one-dimensional, countercurrent gas diffusion in porous media samples. R. F. DYE and J . M. DALLAVALLE School of Chemical Engineering, Georgia Institute of Technology, Atlanta Ga.
I/EC
Solubility Relationships in Hydrogen Peroxide Solutions Containing Pyrophosphate and Stannate Inhibitors As most industrial quantities of hydrogen peroxide solutions are usually stored, shipped, and handled in aluminum containers, cloudy and unfavorable solutions may result from corrosion of the aluminum ions. Solubility studies were made for hydrogen peroxide solutions varying p H and concentrations of aluminum, stannate, and pyrophosphate ions. Hydrogen peroxide solutions of p H 4.5 to 5.5 containing pyrophosphate only will not precipitate solids until the aluminum ion concentration exceeds the solubility of aluminum hydroxide. These solutions can contain as much as 40 p.p.m. of aluminum before precipitation occurs. W h e n 50 p.p.m. of stannate is used in the hydrogen peroxide solutions with or without pyrophosphate, precipitation will occur w h e n the aluminum ion concentration reaches 0.3 p.p.m. These data contribute to the understanding of factors influencing solubility under various conditions. G. C. HOOD, R. J. EVANS, and G. J. PI EROTTI Shell Development Co., Emeryville, Calif.
BriefJF
Ind. Eng. Chem. 50, 1201-8 (1958)
Packed Column Performance of Carbon Dioxide— Monoethanolamine System Three commercial packings were evaluated in a tower 8 inches in diameter for absorption of carbon dioxide (8 to 12% by volume) from air b y (18 to 20%) monoethanolamine in water solutions. Liquid flows were varied from 1500 to 6000 lb./hr.-sq. ft. at gas rates of 661 and 970 lb./hr.-sq. ft. The height of transfer unit for Tellerettes was proportional to Z, -0 · 57 . Mass transfer efficiencies of ceramic Berl saddles and steel Raschig rings were equal. T h e effect of liquid flow on performance was more complex than in the case of Tellerettes. T h e Tellerettes were 23 to 7 2 % more effective in mass transfer than other packings and presented 46 to 78% lower pressure drop than Raschig rings. Flow pattern effects e n g e n d e r e d by packing geometry influence mass transfer efficiency as well as inherent packing surface.
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AARON J. TELLER University of Florida, Gainesville, Fla. HARRY E. FORD Harshaw Chemical Co., Cleveland, Ohio CLIP AND
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