APRIL 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
. . . begin on page 570 I/EC
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I/EC Brief
Ind. Eng. Chem. 50, 570-6 (1958)
Staff-Industry Collaborative Report Chemicals from Wood One answer to the problem of disposing spent sulfite liquor is to use it as a raw material for useful products. Today, spent liquor is a source of chemicals, yeast, fuel, and road binder. Marathon's process for making chemicals from wood is based on a three-stage lime precipitation of spent liquor's lignosulfonates, followed by metallic ion addition and desulfonation. T h e fractional precipitation gives an inorganic fraction and two organic fractions. T h e inorganic one is re-used in a cooking acid system, while the organic fractions are processed further. These end up as mixed salts of lignosulfonic and wood sugar acids, lignosulfonates, and partially desulfonated lignosulfonates. W h e n concentrated and dried, the products are sold as dispersants, tanning agents, water treating compounds, and for other uses.
Ind. Eng. Chem. 50, 585-90 (1958)
Equipment for Miniature Pilot Plants Collecting engineering data on a small scale generally requires the construction of a miniature pilot plant. This article describes some useful items of equipment which are commercially available for this purpose, including pumps, flowmeters, distillation and extraction equipment, powder feeders, centrifuges and filters, reactors, mixers and piping. A typical miniature pilot plant is illustrated. C. H. STOCKMAN and R. E. LYNN, Jr. Reseach Center, B. F. Goodrich Co., Brecksville, Ohio
CHESTER PLACEK, BRUCE J . BUHMANN. and RICHARD T. GALGANSKI
I/EC Brief
I/EC Brief Ind. Eng. Chem. 50, 591-3 (1958)
Collecting of Engineering Data on a Small Scale
Chemical Engineering Kinetics. Use in the Scale-Up of Chemical Processes
SCALING UP A PROCESS A Panel Discussion 577
T h e design and specification of commercial chemical reactors are important phases of the work of the chemical engineer. Such designs are usually based on laboratory and pilot plant investigations of processes; the scale-up is carried out by means of chemical engineering kinetics. T h e techniques of chemical engineering kinetics are summarized; the rate equation is developed by the twostep procedure, followed by use in the reactor design. T h e modern trend is toward elimination of successive stages of pilot plant experimentation by means of direct scale-up calculations; its limitations are indicated. Determination of a typical rate equation is described in some detail. W I L L I A M F. STEVENS Northwestern Technological Institute, Evanston, III.
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FILE FOR READY REFERENCE VOL. 50, NO. 4
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APRIL 1958
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Ind. Eng. Chom. 50, 594-8 (1958) Ind. Eng. Chem. 50, 611-12 (1958)
Economics of Process Development Three new quantitative indexes, presented for evaluating the economic attractiveness of proposed research and de velopment projects, consider the time equivalence of money, availability of capital and development effort, and computed confidence factors which may be weighted to achieve the desired degree of conservatism. The indexes are derived easily from either venture worth or interest rate of return analyses. Methods are discussed for optimum prosecution of de velopment programs to increase these attractiveness in dexes—micro pilot-plant techniques in conjunction with sound interpretive theory are particularly important. It is concluded that where high profits are forecast, it is fre quently economically sound to proceed directly from such micro-scale results to full scale commercial operation. KENNETH M. WATSON Lake Zurich, I I I .
Chlorination of Euxenite Concentrates Conventional chlorination of the mineral euxenite by treatment with chlorine gas has been modified by addition of an alkali salt to the initial process. A 95% conversion of the metals to anhydrous chlorides is reported for the process. Euxenite, carbon, and sodium chloride reacted with chlo rine at 500° C. to form anhydrous chlorides which were separated into three fractions liquid titanium tetrachloride, solid chlorides of tantalum and niobium, and a nonvolatile residue containing the water-soluble chlorides of uranium, iron, rare earths, and thorium. The alkali salt additive appears to be practical in the direct chlorination procedure and suitable for production scale equipment. A. W. HENDERSON, S. L. MAY, and K. B. HIGBIE U. S. Bureau of Mines, Albany, Ore., and Washington, D. C.
I/EC Brief
I/EC Brief
Ind. Eng. Chem. 50, 613-16 (1958)
Ind. Eng. Chem. 50, 599-602 (1958)
Scale-Up Problems in the Plutonium Separations Program
Ion Exchange Separation of Uranium from Thorium
Early during World War II, a major problem in develop ing an atomic bomb was separating plutonium on a com mercial scale. Most of the processes conceived today were in some measure under study then, and this article describes the solution to some engineering problems encountered. The precipitation method was selected for development and, because of the time factor, process and plant design had to proceed simultaneously. Ultramicro scale and labora tory beaker experiments were extrapolated to full scale plant. Pilot plant data by supplying mechanical data contributed substantially to early successful operation of the plant. This early development program showed that radio chemical processes can be scaled up from laboratory data with good confidence.
Uranium has been separated and concentrated from sodium carbonate solutions of Monazite sand residues using strong base ion-exchange resins, particularly Amberlite IRA-400. The uranyl tricarbonate anion, [ U G ^ C C ^ ] - 4 , is believed to be the active species in this exchange. The interference of anions present in monazite process solutions on the exchangeability of the uranyl carbonate complex was evaluated, and exchange data were obtained on a solution prepared from a typical sample of concentrates of Brazilian sand. The use of strong base exchangers in carbonate systems as a means of exhaustive removal of uranium from thorium is indicated.
O. F. H I L L and V. R. COOPER Hanford Laboratories Operation, General Electric Co., Richland, Wash.
R. H. POIRIER, G. D. CALKINS, G. A. LUTZ, and Α. Ε. BEARSE Battelle Memorial Institute, Columbus, Ohio
I/EC Brief
I/EC Brief Ind. Eng. Chem. 50, 617-18 (1958)
Ind. Eng. Chem. 50, 603-10 (1958)
A Ballistic Piston for Investigating Gas Phase Reactions The ballistic piston apparatus makes possible the in vestigation of either the kinetics of gas phase reactions or the volumetric properties of gases under high pressures and temperatures which cannot be attained in conventional equipment. The apparatus is suitable for investigations at apparent temperatures as high as 10,000° Γ. and for pressures of 100,000 pounds per square inch or more. The apparatus is described and the measurements made with associated instrumentation are discussed. Differential equations describing the processes taking place are derived and methods of solving these equations are included. Examples of pressure-time and temperature-time relation ships are given. P. A. LONGWELL, H. H. REAMER, N. P. WILBURN, and Β. Η. SAGE California Institute of Technology, Pasadena, Calif.
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Some N-Disubstituted Amides of Long-Chain Fatty Acids as Vinyl Plasticizers .V-Disubstituted amides of the major individual and mixed component acids of cottonseed and peanut oils have been prepared and subjected to a preliminary screening evaluation as primary plasticizers for vinyl resins. The morpholide of oleic acid, the unsaturated fraction of selectively hydrogenated cottonseed or peanut fatty acids, and the partially epoxidized morpholide of the unsaturated fraction of cottonseed acids were found to exhibit excellent plasticizer characteristics, tempered to a degree by their questionable thermal stability. Equally satisfactory morpholide plasticizers can also be obtained from many other vegetable, animal, and fish oils by application of the principles and treatments described. FRANK C. MAGNE, ROBERT R. MOD, and EVALD L. SKAU Southern Regional Research Laboratory, Southern Utilization Research and Development Division, New Orleans 19, La.
FILE FOR READY REFERENCE VOL. 50, NO. 4
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APRIL 1958
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Ind. Eng. Chem. 50, 619-20 (1958)
Inhibition of Resin Acid Isomerization
Ind. Eng. Chem. 50, 627-32 (1958)
Size Reduction of Dried Pellets Containing Serratia marcescens
Recent work on the thermal isomerization of individual resin acids indicated that most of the changes occurring when pine gum is processed into rosin could be avoided by controlling acidity during processing. A series of resins "whose composition varied from that of ordinary rosin to that of the acid portion of pine gum was prepared b y adding varying amounts of alkali to the pine gum before the turpentine was distilled from it. Thus it was possible for the first time to prepare a hard resin that contained an appreciable quantity of levopimaric acid. T h e partially neutralized resins made in this w a y should be more resistant to oxidation, show less tendency to crystallize, a n d be more effective in certain types of reactions than ordinary rosin. T h e y can be used for preparation of soaps, paper size, a n d precipitated metal résinâtes.
Suitable operating conditions for pulverizing dried pellets containing Serratia marcescens were investigated. Three types of equipment were tested: a ball mill, a fluid energy reduction mill, and a high-speed centrifugal mill. T h e chief factors affecting the grinding of the pellets were the type of feed material and the intensity of grinding. In general, the viable cell recovery in the powder d e p e n d e d chiefly upon the particle size, lowest recovery being associated with finest grinding. T h e particle size of the powder d e p e n d e d u p o n the intensity of grinding. It was possible to grind pellets from centrifuged cells to a mass median diameter below 5 microns. T h e high-speed centrifugal mill was the most satisfactory in operation, product control, a n d product characteristics.
V I R G I N I A M . LOEBLICH and RAY V. LAWRENCE U. S. Department of Agriculture, Naval Stores Research Section, Naval Stores Station, Olustee, Fla.
V. F. PFEIFER, CHAS. VOJNOVICH, H. G. MAISTER, E. N. HEGER, AND W. M . BOGART Northern Utilization Research and Development Division, U. S. Department of Agriculture, Peoria, I I I .
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I/EC Brief
Ind. Eng. Chem. 50, 621-2 (1958) Ind. Eng. Chem. 50, 633-6 (1958)
Shallow and Deep Catalytic Dehydrogenation of Petroleum C.-Aromatic Fraction
Formation of Biuret from Urea
T h e petroleum C 8 -aromatic fraction contains two valuable components—ethylbenzene for dehydrogenation to styrene and xylenes for oxidation to phthalic acids. Exploratory experiments indicate that the C 8 -fraction can be catalytically dehydrogenated on a recycle basis or on a once-through basis to produce styrene a n d xylene. For example, dehydrogenation at 575° C. gave a 4 5 % per pass yield of styrene (based on ethylbenzene) together with a 35% survival of ethylbenzene and a 77 to 8 8 % survival of xylene, d e p e n d i n g on the feed. Dehydrogenation at 700° C. gave a 60 to 6 9 % per pass yield of styrene together with a 3 % survival of ethylbenzene a n d a 64 to 77% survival of xylene. Styrene of 99 + mole % purity was obtained from the catalyzates by distillation.
T h e presence of biuret as an impurity in urea used in fertilizers is of considerable concern to both the agriculturalist a n d the urea manufacturer. Biuret is injurious to certain species of plants e v e n at low concentration. Q u a n titative measurements on the amount of biuret formed under various conditions of time, temperature, water content, ammonia partial pressure a n d partial pressure of water vapor over urea solutions, a n d melts are presented. These results indicate operating conditions necessary to minimize the amount of biuret produced in urea manufacture. C. E. REDEMANN, F. C. RIESENFELD, and F. S. LA VIOLA Research Division, The Fluor Corp., Ltd., Whittier, Calif.
B. B. CORSON, W. J. HEINTZELMAN, and F. J . PAVLIK Mellon Institute, Pittsburgh, Pa.
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I/EC Brief
Ind. Eng. Chem. 50, 637-44 (1958)
Ind. Eng. Chem. 50, 623-6 (1958)
Continuous Freeze-Drying Of Serratia
marcescens
An investigation was undertaken of the effects of various conditions on the ability of Serratia marcescens strain 8 UK to survive continuous freeze-drying and storage. A rather unusual continuous freeze-dryer was used. Factors affecting he drying of S. marcescens in the continuous freeze-dryer and the storage of the dried product are discussed, including protective materials, variations in feed materials, harvest time in the fermentor, moisture content in the dried product, pH control, temperatures in the heating section, and belt speed. 5". marcescens was dried successfully to a moisture content of 1 % , a suitable level for good storage stability, with a recovery of viable cells of 80% or higher. A production rate of 50 to 55 grams of dried material per hour could be maintained in continuous operation. H. G. MAISTER, E. N . HEGER, and W . M . BOGART Northern Utilizatton Research and Development Division, U. S. Department of Agriculture, Peoria, I I I .
Fluid-Bed Pretreatment of Bituminous Coal and Lignite. Direct Hydrogénation of Chars to Pipeline Gas To learn the type of coal pretreatment n e e d e d to produce nonagglomerating, reactive chars for fluid-bed hydrogénation to pipeline gas, fluid-bed pretreatment of low-rank coals in various atmospheres was investigated in a benchscale unit at atmospheric pressure a n d maximum temperatures of 400° to 720° F. Optimum pretreatment temperature was 600° F. for bituminous coals a n d 500° F. for lignite. Agglomeration of high-volatile bituminous coal was greatly reduced after pretreatment in air or nitrogen. High yields of pipeline gas containing 70 to 80 mole % of methane plus ethane were obtained at 1350° F. Pretreatment operations similar to commercial fluidized carbonization appear applicable to feed preparation for dry coal hydrogénation. Κ. C. CHANNABASAPPA and H. R. LINDEN Institute of Gas Technology, Technology Center, Chicago 16, I I I .
CLIP AND FILE FOR READY REFERENCE VOL. 50, NO. 4
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APRIL 1958
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Eng. Chem. 50, 645-8 (1958)
Cascade Impactor for Adiabatic Measurements Particle-size distribution data are required for the ra tional design, proper selection, and evaluation of equipment for dust and mist collection. In many chemical processes, aerosols are s u s p e n d e d in gases saturated with vapor at temperatures of 30° to 200° C. I n the present work, a small and compact "in-line" cascade impactor and accessory equipment for adiabatic particlesize determinations were developed. This impactor has b e e n used on many processes in plants throughout the country. Aerosols s u s p e n d e d in process gases containing over 3 0 % water vapor have b e e n measured successfully. J . A. BRINK, Jr. Monsanto Chemical Co., Everett, Mass.
Eng. Chem. 50, 663-72 (1958)
Combustion of Metals in Oxygen As part of a study of methods of producing high tempera tures, the combustion of metals in oxygen was investigated. T h e basic objective was developing techniques to produce and utilize high temperature sources. Metals which b u r n to produce high temperatures are discussed in terms of their location in the Periodic Table. T h e "skating s u n " phenomenon suggests a high tempera ture radiation source. Metals are classified d e p e n d i n g o n whether they ignite above or below their melting point. T h e operating characteristics of p o w d e r e d metal-oxygen flames are described in detail. T h e work reported is primarily fundamental research, although combustion of aluminum can yield a source of high intensity thermal radiation. P o w d e r e d metal-oxygen flames are highly effective in cutting through thick sections of concrete and various ceramic materials. A. V. GROSSE and J . B. CONWAY Research Institute of Temple University, Philadelphia, Pa.
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I/EC Brief Ind.
Eng. Chem. 50, 649-50 (1958)
Corrosion of Metals in Ethylene Glycol Solutions
Ind.
Variables affecting corrosion of individual cooling system metals in uninhibited glycol solutions were investigated, b o t h with and without solution renewal. Corrosion rates of metals at p H 4, 7, 9, or 11 are linear or decrease with time. Considering all metals investigated, solutions at p H 6 to 9 cause least corrosion. Addition of chloride ion u p to 200 p.p.m. increases corrosion rate, particularly for aluminum and solder. T h e most marked •effect of glycol concentration is with steel; increase in glycol content decreases the corrosion rate. Increase in tempera ture from 80° to 220° F. generally increases corrosion rates. T h e data will aid in interpretation of service performance of antifreeze solutions but not necessarily predict complete service behavior. R. J. AGNEW, J. K. T R U I T T , and W. D. ROBERTSON Texaco Research Center, The Texas Co., Beacon, Ν. Υ.
Smog Chamber Studies of Unleaded vs. Leaded Fuels As automobile exhaust gas has b e e n implicated as a major source of smog-producing chemicals, the effect of tetraethyllead and halogen scavengers used in anti knock fluids was investigated. Experiments w e r e carried out in two large glass reaction chambers equipped with air-sampling systems, on three fuels, with and without antiknock addition. Statistical analysis of the data shows that addition of tetra ethyllead to gasoline does not contribute materially to the Los Angeles smog problem. F. V. MORRISS, CALVIN BOLZE, and JOHN T . G O O D W I N , Jr. Midwest Research Institute, Kansas City, Mo.
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Eng. Chem. 50, 673-6 (1958)
Eng. Chem. 50, 657-62 (1958)
Corrosion Inhibitors in Automotive Coolant Media T h e action of some common corrosion inhibitors, in auto motive coolant media, on the polarization characteristics of steel was investigated. T h e classification of these materials as anodic and cathodic polarizers or as corrosion accelerators in coolant environ ments generally correlated with results of an accelerated stationary glassware corrosion test and simulated vehicle cooling system test developed at this laboratory. T h e anomalous nature of the results of the triethanolamine a n d sodium nitrite materials indicates the n e e d for further investigation with the other metals comprising the auto motive cooling system. Application of this technique also revealed the effect of concentration change on inhibitor effectiveness. M I L T O N LEVY Coating and Chemical Laboratory, Aberdeen Proving Ground, Md.
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Eng. Chem. 50, 677-82 (1958
Kinetic Studies of Formation of Atmospheric Oxidants Kinetic studies were made to clarify the mechanisms of oxidative smog formation and the roles of various pollu tants. Calculations of the kinetic balance of inorganic reactions suggest that only a small fraction of "oxidant" may be ozone and that, during smog peaks, "nitric o x i d e " indicated on recorders may be free radical-nitric oxide complexes. Mass spectrographic and chemical studies indicated that ozone—1-hexene reaction is much faster than previously reported. T h e variety of products suggested α-carbon oxidation rather than ozonide formation. Some products appeared to continue to liberate iodine from neutral but not from alkaline iodide reagent. T h e deviations of these reagents were evaluated for pure ozone. Ozone-olefin reactions may be important in smog chemistry as sources of organic free radicals. BERNARD E. SALTZMAN U. S. Department of Health, Education and Welfare, Cincinnati 2, Ohio
FILE FOR READY REFERENCE VOL. 50, NO. 4
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Ind. Eng. Chem. 50, 697-702 (1958) Ind. Eng. Chem. 50, 683-90 (1958)
Heat Transfer to a Gas-Phase Chemical Reaction A study has b e e n made of heat transfer to a flow system which undergoes a nearly instantaneous chemical reaction. Experiments and theory have shown that an order-ofmagnitude increase in the convection heat-transfer coefficient may result from dissociation and association reactions in the gas phase. Heat-transfer coefficients can be predicted from conventional correlations w h e n effective thermal conductivities a n d effective specific heats are used. W I L L I A M SCHOTTE E. I. du Pont de Nemours &, Co., Inc., Wilmington, Dei.
Vapor Transfer through Barriers T h e investigations of a number of workers in the field provide adequate data which permit a rather satisfactory correlation of vapor transport with adsorption characteristics. T h u s , vapor transport can be analyzed for both plastic films and for microporous barriers. This would indicate that the correlation is generally applicable. Data on a total of 14 systems are available, covering water vapor, and inorganic and organic vapors in transport through barriers such as plastic films, paper, and silica and carbon powders. T h e powders in compressed form represent microporous barriers. KARL KAMMERMEYER Department of Chemical Engineering, State University of Iowa, Iowa City, Iowa
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I/EC Brief Ind. Eng. Chem. 50 691-6 (1958)
Ion Fractionation by Permselective Membranes. Factors Affecting Relative Transfer of Glycine and Chloride Ions T h e feasibility of complex ion fractionations, using ion selective membranes, was studied. T h e relative transference of two ions sharing the same cation was strongly affected by current density, relative concentrations, and ion mobilities in the solution and membrane phases. Fluid flow pattern and ionic diffusivities were of lesser importance. Equations qualitatively predict the relative transport of ions. Efficiency of fractionation depends upon mobility ratios, thermodynamic equilibrium of the ions b e t w e e n phases, and permselectivity of the membranes. This report contributes to the understanding of complex fractionations and presents a mathematical approach, useful in the design of fractionating equipment.
Ind. Eng. Chem. 50, 703-6 (1958)
Reduced Crude Oil-Dipropylene Glycol. Liquid-Liquid Extraction System This investigation represents part of an over-all study on liquid-liquid extraction of heavy petroleum oil stocks a n d fractions with higher molecular weight glycols and similar materials. Dipropylene glycol was selected as the extracting agent because of suitable selectivity, water solubility, and density. Extraction temperatures of 160° and 212° F. were utilized. T h e selectivity of the dipropylene glycol for the low viscosity-gravity-temperature components was very good, with the selectivity at 160° F. relatively greater than that at 212° F. F. F. PAPA-BLANCO and M A T T H E W VAN W I N K L E Department of Chemical Engineering, University of Texas, Austin, Tex.
A. T. D BENEDETTO and E. N. LIGHTFOOT University of Wisconsin, Madison, Wis.
I/EC Brief Ind. Eng. Chem. 50, 707-10 (1958)
Correlation of Vapor-Liquid Equilibrium Data Integrated forms of the Gibbs-Duhem equation are commonly used to correlate liquid phase activity coefficients. Determination of the best values of the constants in these equations from experimental data requires that a series of i n d e p e n d e n t estimates of the same quantity be properly averaged. This can be done, if the relative reliability of each quantity is known which, in turn, requires an analysis of experimental error. Sources of experimental error are discussed, and the necessary statistical concepts are reviewed. For the case in which the chief source of experimental error is measurement of the composition, equations are derived for the Margules and V a n Laar equations, assuming constant absolute error and constant per cent error. T h e method is illustrated by calculating the Margules constants for the system heptane-toluene. It can be used for other problems in which a series of measurements of varying reliability must be averaged. JOHN W. TIERNEY Purdue University, Lafayette, Ind. CLIP AND
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APRIL 1958
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