AUGUST 1956
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Ind. Eng. Chem. 48, 1231 (1956) Ind. Eng. Chem. 48, 1242 (1956)
Trends in Cyclotron Design T r e n d s in the development of cyclotrons are briefly traced over the period since the machine was first proposed b y E. O. Lawrence in 1930. Recent trends in design goals are (1) better energy definition, (2) the r e a d y variability of b e a m e n e r g y , (3) the acceleration of h e a v y particles, such as nitrogen, (4) markedly increased beam currents, (5) more d e p e n d a b l e operation, and (6) higher energies in the mesonproducing range. T h e s e goals are being approached through such design features as improved b e a m deflectors and analyzers, larger p o w e r supplies a n d more flexible oscillators, improved ion sources, and the development of n e w magnetic field configurations to improve b e a m focusing and to provide phase adjustment for relativistic particles. It now appears possible to produce large currents of protons in the 1000-m.e.v. energy range with a fixed-frequency cyclotron having an azimuthally varying magnetic field. Such a machine n o w b e i n g studied at the Oak Ridge National Laboratory is briefly described. ROBERT S. LIVINGSTON Oak Ridge National Laboratory, Oak Ridge, Tennessee
Removal of Deuterated Boric Acid from Heavy Water by Ion Exchange Resin Ion exchange methods were investigated to remove boron from high purity deuterium oxide after boric acid anhydride had b e e n a d d e d in an atomic water boiler to obtain data on the transport mean free path of thermal neutrons. After preliminary experiments a setup was devised w h e r e b y 2700 liters of h e a v y water containing 50 mg. of boron per liter were passed through an ion exchange column and the boron content r e d u c e d to 0.012 mg. per liter. T h e purity of the deuterium oxide was u n c h a n g e d , and the yield was almost 100%. T h e column was successfully deuterized and dedeuterized. LOUIS SILVERMAN and WANDA BRADSHAW Atomics International, A Division of North American Aviation, Inc., Canoga Park, Calif.
Ind. Eng. Chem. 48, 1248 (1956) Ind. Eng. Chem. 48, 1238 (1956)
Peroxide Decomposition in Aqueous Homogeneous Reactor Fuels T h e decomposition of peroxide in uranyl sulfate solutions has b e e n found to be first order in peroxide and i n d e p e n d e n t of the uranium concentration. T h e rate also appears to b e i n d e p e n d e n t of the acidity of the solution as long as n o excess acid is present. First-order specific reaction-rate constants have b e e n determined at 5 3 ° , 7 8 ° , and 100° C. A conductance method has b e e n d e v e l o p e d for following the decomposition at excessively fast rates which preclude successful use of standard chemical methods. Catalytic effects caused b y probable corrosion and fission product species present in homogeneous reactor solutions have b e e n studied b y this technique. Allowable operating power levels for aqueous homogeneous reactors have b e e n estimated from the data. M . D. S I L V E R M A N , G. M. WATSON, and H. F. McDUFFIE Oak Ridge National Laboratory, Oak Ridge, Tenn.
Water for Nuclear Engineering T h e outlook for adequate supplies of water of suitable quality for nuclear energy development is more favorable in some parts of the country than in others. Competition for water in some areas is intense a n d may pose real limitations on the development of nuclear installations. Development engineers and other scientists responsible for expansion of nuclear engineering projects are u r g e d to give early and thorough attention to water requirements with reference to existing or potential availability of water supplies. T h e program of waste disposal from nuclear installations also must be p l a n n e d carefully so that receiving streams and u n d e r g r o u n d waters will not b e rendered dangerous or unsatisfactory for subsequent use. It is imperative that leaders in the field of nuclear engineering lend their support and actively participate in programs that h a v e as their objective the development and conservation of water supplies for all beneficial uses including expansion of nuclear energy installations. S. K. LOVE and W. F. W H I T E U. S. Geological Survey, Washington 25, D. C.
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AUGUST 1956
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CHEMICAL PROCESSES Ind. Eng. Chem. 48, 1252 (1956)
Electrolytic Reduction of Phthalic Acid A continuous cell in which catholyte flows as a film be tween the mercury cathode and a porous porcelain cell diaphragm gives almost theoretical current efficiencies, has a low resistance and many times the production capacity of batch cells of comparable size. The cathode poisoning problem is eliminated by use of a mercury cathode which can be removed from the cell, washed, and recycled. Phthalic acid can be reduced electrolytically in the cell to cyclohexadiene dicarboxylic acids, which are interesting intermediates for polymeric products. The continuous cell also shows promise in the reduction of organic com pounds other than phthalic acid. PAUL C. C O N D I T California Research Corp., Richmond, Calif.
Ind. Eng. Chem. 48, 1268 (19S6)
Recovery of Aconitic Acid from Molasses A study to recover aconitic acid from sugar cane molasses resulted in development of two processes. T h e first was based o n use of methanol to precipitate over 9 0 % of the aconitic acid as calcium aconitate. T h e second is an extrac tion process to recover the acid directly, using methyl ethyl ketone as the solvent. Ternary solubility data were determined for several sys tems. Pseudo-countercurrent extractions resulted i n over 90% recovery of aconitic acid. Preliminary cost estimates were prepared to produce 1 million a n d 4 million p o u n d s of aconitic acid annually b y these processes a n d b y an ion exchange process. T h e sol v e n t extraction process appears most economical a n d com mercially feasible. ERNEST A. REGNA and PAUL F. BRUINS Polytechnic Institute of Brooklyn, Brooklyn 1, Ν. Υ .
Ind. Eng. Chem. 48, 1278 (1956) Ind. Eng. Chem. 48, 1258 (1956)
Acetaldehyde by the Chisso Process
Condensation of Acetone to Mesityl Oxide
Methods for hydrating acetylene and separating and purifying acetaldehyde were studied, in order to increase the efficiency of conversion and recovery, reduce the heat and power required, and simplify equipment and processing. · The Chisso process uses hydration heat for rectifying acetaldehyde, eliminates recycling of acetylene, and produces higher yields than the German process. Mechanical and operating losses of acetylene are low, and the plant required is simple and relatively inex pensive.
T h e rate of condensation of acetone to mesityl oxide a n d water has b e e n determined using a sulfonated polystyrenedivinylbenzene ion exchange resin (Dowex 50-X8) in the hydrogen form as catalyst. T h e reaction was carried out in a tubular flow reactor using fixed b e d s of catalyst u n d e r isothermal steady-state conditions. T h e experimental work covered temperatures from 30° to 75° C , resin sizes of 20 to 25, 30 to 35, a n d 120 to 140 mesh, a n d space velocities from 0.00417 to 0.0761 liter/(min.)(equiv.). Although the resin catalyst became black during the reaction, no deactivation was apparent over the period of observation. Diacetone alcohol was a major reaction b y product a n d traces of resinous materials were also noted.
DONALD F. O T H M E R , K I C H I R O KON, and TAKEO IGARASHI Polytechnic Institute of Brooklyn, Brooklyn 1 , Ν. Υ., and Shin Nippon Chisso Hiryo K.K., Tokyo, Japan
F. G. KLEIN and J . T . BANCHERO Department of Chemical and Metallurgical Engineering, University of Michigan, Ann Arbor, Mich.
Ind. Eng. Chem. 48, 1287 (1956)
Propylene Oxide—Methanol Liquid-Phase Reaction Ind. Eng. Chem. 48, 1263 (1956)
Cyanoethylation of Cotton Fabric A pilot plant study was undertaken to investigate nonuniformity in production of cyanoethylated cloth. By careful control of reaction conditions, especially temperature, 45-yard lengths of standard print cloth were cyanoethylated within limits of 0.40 to 0.42 cyanoethyl addition per anhydroglucose unit. This evenness of modification existed even between single yarns and fibers and along the length of individual fibers. The uniformity attained was within the limits of differenti ation by any standard test. LUCIEN H. GREATHOUSE, H. J . JANSSEN, W. N. BERARD, and C. H. HAYDEL Southern Regional Research Laboratory, New Orleans, La.
T h e effect of temperature, sodium hydroxide concentra tion, a n d initial reactant quantities u p o n the rates of the homogeneous, liquid-phase reactions b e t w e e n methanol and propylene oxide to form l-methoxy-2-propanol, and betweeD l-methoxy-2-propanol a n d propylene oxide to form methoxy dipropylene glycol were investigated w h e n reactions occurred individually a n d consecutively. Indi vidual reactions were conducted batchwise at an alco hol to oxide mole ratio of five to one. T h e two consecutive reactions were conducted simultaneously starting with an equimolal mixture of reactants. T h e range of catalyst concentrations studied was 0.03 to 1.5 weight %; the temperature range investigated was from 35 to 100° C. T h e rate of the uncatalyzed reaction b e t w e e n methanol and propylene oxide was determined over the range from 45° to 145° C. a n d is of the same order of magnitude as the catalyzed reaction for sodium hydroxide concentrations below 0.01 weight %. H. A. PECORINI and J. T. BANCHERO Department of Chemical and Metallurgical Engineering, University of Michigan, Ann Arbor, Mich.
VOL. 48, NO. 8
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AUGUST 1956
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I n d . t n g . l , h c m . 4S, ΊΖ9Β (19DO)
Mixed Acid Nitration of Toluene
Ind. Eng, Chem. 48, 1320-9 (1956)
Few rate data h a v e b e e n obtained for the two-phase nitration of toluene b y mixed acid w h e r e concentrations of acids h a v e b e e n i n t h e r a n g e of commercial nitrations. A miniature, continuous flow, stirred reactor with a n internal volume of 1.26 ml. was u s e d to study the rate of reaction over a range of acid concentrations. Reaction rates a thousandfold greater than those re ported previously w e r e m e a s u r e d o v e r w i d e ranges of temperature, acid composition, phase ratio, a n d flow rate. Actual rates are far higher than w o u l d have b e e n predicted b y extrapolating previous correlations for this reaction. It was not possible to measure rates using acids of sufficient strength to show detectable concentrations of the nitronium ion.
Cellulose Lacquers Included here are condensations of the eleven papers presented in the symposium, "Significant Recent D e v e l o p ments in Cellulose Lacquers," h e l d at the Dallas, Tex., ACS meeting in April 1956. T h e complete symposium is scheduled for publication in Part II of the August 1956 issue of Official Digest, Federation of Paint and Varnish Production Clubs (available August 15). End of Symposia
HENRY M . BRENNECKE and KENNETH A. KOBE University of Texas, A u s t i n , Tex.
Ind. Eng. Chem. 48, 1330 (19S6)
Levulinic Acid as a Basic Chemical Raw Material Ind. Eng. C h e m . 48, 1305 (1956)
Toluene Nitration Kinetics T h e rate of nitration of toluene to mononitrotoluene was studied in a continuous-stirred tank reactor at 35° C. u n d e r conditions w h e r e mass transfer b e t w e e n phases d i d not affect reaction rates. T h e acid compositions u s e d were within the range of commercial nitration practice. Reaction rates w e r e d e t e r m i n e d , a n d w e r e four to five times those previously reported for the same phase com position, because of more intense agitation. T h e distribution ratio of nitric acid b e t w e e n acid and organic phases generally favors the organic p h a s e , b u t is strongly d e p e n d e n t on the sulfuric acid concentration in the acid phase. This must be considered in design work. ALLEN J. BARDUHN and KENNETH A. KOBE University of Texas, A u s t i n , Tex.
Levulinic acid can be formed b y acid degradation of low grade cellulose material. Because supplies from this source could b e large, a search for industrial uses was initiated. A literature review shows many suggested applications but very few actual uses. T h e reactivity of levulinic acid enables the formation of a w i d e variety of compounds. Some reactions were conducted with levulinic acid de rived from cellulose and with α-angelica lactone, the simplest derivative of levulinic acid. T h e levulinyl group has b e e n introduced into vinyl chloride polymers b y vinyl levulinate and into cellulose acetate b y transesterification. T h e l e v u linyl group appears to improve the tensile strength and to change other properties of the polymers. α-Angelica lactone, /3-angelica lactone, γ-valerolactone, a n d dimethylpyrrolidone, all from levulinic acid, exhibit good solvent properties. REID H. LEONARD Newport Industries, Inc., Pensacola, Fla. Ind. Eng. Chem. 48, 1342 (1956)
Superfine Thermoplastic Fibers Ind. Eng. C h e m . 48, 1316 (1956)
Pyrolysis of Oil Shale Oil shale was retorted in a fluidized solids system at 250° to 465° C. (482° to 857° F.), and 625 to 50 mm. of mercury, to determine the effect of pressure o n rate of pyrolysis. T h e rate of oil-shale pyrolysis corresponds to that for a first-order reaction, in that it is proportional to the amount of organic material remaining undecomposed. T h e effect of pressures b e t w e e n 625 and 50 mm. on the rate of retorting was insignificant over the temperature range studied. T h e work indicates larger values of ^ than reported in the literature at the lower temperatures, and good agreement with more recent work at higher temperatures in a fluidized solids system. LEO DlRICCO and PAUL L. BARRICK University of Colorado, Boulder, Colo.
A process is described w h e r e b y it is feasible to produce submicron organic fibers from a variety of thermoplastic materials i n c l u d i n g nylon, polystyrene, poly(methyl methacrylate), poly(ethylene terephthalate), and polytrifluorochloroethylene. A n extruder forces a hot thermoplastic melt through a row of fine orifices into two converging streams of high velocity heated gas, usually air. Fiber diameters are determined b y four basic process variables— air and nozzle temperatures, air pressure, and polymer feed rate. Proper balancing of the variables yields fiber mats that possess high filtration efficiency w h e n tested with a 0.3-micron-diameter liquid aerosol. Smoke pene tration values are reported for various polymers and conditions. Nylon is the material most readily suited to production of the finest fibers and, hence, is the highest in smoke collection efficiency. Polytrifluorochloroethylene, however, shows promise for achieving both good filtration performance and high chemical and thermal resistance. VAN A. WENTE Naval Research Laboratory, Washington 25, D. C.
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AUGUST 1956
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Ind. Eng. Chem. 48, 1347 (1956)
Ind. Eng. Chem. 48, 1366 (1956)
Synthesis of Hydrogen Persulfides
Heats of Combustion of Organic Compounds
T h e h y d r o g e n persulfides are easily made, are very reactive, and may have considerable industrial interest if good synthesis yields can b e obtained. T h e quantitative results of a n investigation of the synthesis of a mixture of h y d r o g e n persulfides from inorganic acids a n d sodium polysulfide are presented. T h e variables studied were temperature, sodium polysulfide composition, sodium polysulfide concentration, acid type, acid concentration, and mixing conditions. Synthesis yields of u p to 7 0 % were obtained and the results of the investigation suggest that higher yields are possible.
A method for calculating heats of combustion of organic compounds from structural features d e p e n d s o n the straightline relationship b e t w e e n the molar oxygen balance and the molar heat of combustion of a homologous series. Intercept and slope values have b e e n determined for 61 structural features from published data for approximately 1500 compounds. T h e average difference b e t w e e n o b served a n d calculated heats of combustion is 1 to 2%. T h e method allows checking the accuracy of the values assigned as contributions of functional groups to heat of combustion, and should b e particularly helpful in choosing tailor-made compounds with specific e n e r g y features, in the field of explosives.
H. P. MEISSNER, E. Ft. CONWAY, and H. S. M I C K L E Y Department of Chemical Engineering, Massachusetts Institute of Technology, Cambridge 39, Mass.
G. R. HANDRICK Arthur D. Little, Inc., 30 Memorial Drive, Cambridge 42, Mass.
Ind. Eng. Chem. 48, 1354 (1956)
Mechanism of Wash Primer Action Information was obtained o n the structure of w a s h primer film W P - 1 , the mechanism of its formation, a n d its mode of action in retarding corrosion and enhancing paint adhesion o n iron surfaces. X-ray a n d electron diffraction, electron and optical microscopy, infrared spectroscopy, and paramagnetic resonance techniques were used. An iron surface coated with wash primer generates a protective oxide film, supplies chromate for repair of any dama g e to such a film, supplies a zinc phosphate film analogous to the film produced in phosphate treatment, and superimposes o n these an organic film which acts as a good m e chanical protection and a b o n d for subsequent paint films. A tentative picture of the mechanism of wash primer action is d e v e l o p e d from these data.
Ind. Eng. Chem. 48, 1375 (1956)
Heats of Combustion of Some Organic Nitrogen Compounds A method for calculating the heats of combustion of nitrogen compounds, paraffins, acetylenes, olefins, amides, a n d aromatic compounds is based on the n u m b e r of oxygen atoms necessary to b u r n the compound to carbon dioxide (gas), water (liquid), a n d nitrogen (gas). T h e oxygen in a N O , group is not counted. T h e simple linear relationship gives results that agree with existing data very accurately a n d can be u s e d to predict unmeasured values. Experimental values are given for 21 nitrogen compounds. J. A. Y O U N G , J . E. K E I T H , P. STEHLE, W. C. DZOMBAK, and HERSCHEL HUNT Department of Chemistry, Purdue University, Lafayette, Ind.
JEROME KRUGER and M . C. BLOOM Naval Research Laboratory, Washington 25, D. C.
Ind. Eng. Chem. 48, 1361 (1956)
Pressures and Forces along Cylindrical Bubbles in a Vertical Tube T h e pressure distribution a n d forces acting o n a b u b b l e rising in still water at room temperature in a smooth vertical tube of 2-inch bore were measured as b u b b l e s passed fixed points in the water at the tube wall. T h e pressure is constant within each b u b b l e and approximately equal to the h e a d of water above the b u b b l e . Kinetic energy h e a d is partially converted into pressure h e a d for a short distance below the b u b b l e tail in b u b b l e s less than 30 inches long. A shear stress acting d o w n w a r d o n the tube wall results from downflow around the b u b b l e . T h e assumption of "free fall" of the water from the b u b b l e nose gives a good approximation of the distribution of water around bubbles 1 to 50 inches long. These data are of importance in understanding slow cocurrent gas-liquid flow in vertical tubes.
Ind. Eng. Chem. 48, 1379 (1956)
Forced Heat Convection in Pipes Nuclear reactors and some other kinds of heat sources are operated essentially to warm a fluid that passes through a tube, the wall heat flux remaining constant. An analysis of the temperature distribution, assuming p l u g flow of the fluid, is presented. T h e results should b e of interest in the kinetics of zeroorder processes that occur at the wall of a tubular chemical reactor. LEONARD TOPPER Johns Hopkins University, Baltimore, M d .
A. D. K. LAIRD and DUNCAN CHISHOLM University of California, Berkeley, Calif.
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