JUNE 1959
I/EC Briefs I/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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Ind. Eng. Chem. 51, 720-6 (1959)
STAFF-INDUSTRY COLLABORATIVE REPORT
Ind. Eng. Chem. 51, 731-2 (1959)
A New Continuous Chloride Ion Analyzer
Silica-Alumina Petroleum Cracking Catalyst Significant technical advances have led to development of catalytic cracking which has produced by-products such as plastics and synthetic rubbers, and founded n e w industrial complex, the petrochemical industry. W. R. Grace & Co., Davison Chemical Division, has a n u m b e r of synthetic fluid cracking plants; the one at Lake Charles, La., is described. Davison produces petroleum reforming and specialty catalysts, sulfuric acid, sodium silicate, a variety of other products for chemical and fer tilizer industry. Davison used a continuous process for producing silicaalumina gel slurry. All raw materials are closely controlled by flow rates and recording rotameters. Final spray dried catalyst is composed of microspheroids of 20 to 80 microns in diameter. W I L L H. SHEARON, Jr., and W. R. FULLEM
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Direct measurement of chloride ion concentration was n e e d e d in areas w h e r e old titration techniques were too time-consuming. A n analyzer required a sensing element that would withstand continuous operation under a variety of conditions. Silver and silver chloride salt formed into a structurally sound electrode withstood erosion and abrasion and con tinued usage without loss of measuring ability. Thermo compensation made possible determinations b e t w e e n 10 and 10,000 p.p.m. at 0° to 80° C. Lower concentrations were measured accurately at constant temperature. Measure ment was limited b y anomalous effects of oxidizing agents, or b y substances that form insoluble salts with silver. T h e analyzer will find use in a variety of applications where continuous chloride analysis is required for product control. It can be used to monitor streams that receive industrial wastes. ROBERT H. JONES and THOMAS J . KEHOE Beckman Instruments, Inc., 2500 Fullerton Road, Fullerton, Calif.
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Ind. Eng. Chem. 51, 733-8 (1959)
Explosions in Butadiene Systems Ind. Eng. Chem. 51, 727-30 (1959)
The Galvanic Cell Oxygen Analyzer A process analyzer for traces of oxygen in petrochemical plant streams is based on the electrochemical reduction of oxygen in a silver-lead galvanic couple. T h e analyzer is little affected by operating variables and has given partsper-million oxygen analyses with excellent reliability and minimum maintenance. W. J . BAKER, J . F. COMBS, T . L. Z I N N , A. W. W O T R I N G , and R. F. WALL Monsanto Chemical Co., Texas City, Tex.
An explosion in 1951 in a butadiene storage drum caused extensive damage to Polymer Corp.'s butadiene extraction unit. Butadiene peroxide seemed the most likely cause of the blast, and as only meager, information existed on the exact behavior of butadiene, oxygen, and butadiene perox ide, this system was studied. Oxygen reacts readily with butadiene to produce an insoluble polymeric peroxide, which, being heaviest, settles to the bottom of a container in concentrated form. This peroxide layer is unstable and presumably self-heating, and at about 180° F. decomposes violently with about the same expansive force as commercial explosives such as trinitrotoluene. T h e peroxide hazard can b e minimized b y addition of p-tert-hutyl catechol or sodium hydroxide solution or dilu tion with a n inert solvent such as b e n z e n e . D. S. ALEXANDER Research and Development Division, Polymer Corp., Ltd. Sarnia, Canada
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Eng. Chem. 51, 739-40 (1959)
Diffusion Flames for Producing Titanium
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Although titanium is now produced batchwise, a con tinuous process is desirable and could be developed using a diffusion flame formed from titanium tetrachloride and sodium. Experiments with such a system showed that mass production rates of the order of 0.03 gram of titanium per second can be achieved for each 1-cm. radius of liquid sodium droplet. H o w e v e r , additional experiments are necessary to determine the best method for recovering the titanium. Based on experimental results, estimated value for the thermal conductivity of the multiple-component gas mixture in the shell b e t w e e n the droplet and the flame surface is 0.00268 cal./(cm.)(second) (° K . ) .
Eng. Chem. 51, 749-52 (1959)
Alkyl Silicate Derivatives in Aviation Hydraulic Fluids with Hydrolytic Stability Alkyl silicate derivatives were synthesized and tested for hydrolytic stability at 400° F. T h e most stable compounds contained both tert-alkoxy groups and alkyl groups of two or more carbon atoms. T h e excellent hydrolytic stability of these compounds enhances their utility in such fields as aviation hydraulic fluids. R. L. PEELER and S. A. KOVACICH California Research Corp., Richmond, Calif.
A. E. FUHS Gas Dynamics Laboratory. Northwestern University, Evanston, III.
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Eng. Chem. 51, 741-4 (1959)
Recovery of Fission Product Cesium from Acidic Wastes Fission product cesium is present in chemical processing wastes from plutonium recovery operations at Hanford. It can be recovered from acidic waste solutions by precipita tion with several metal ferro-, ferri-, and cobalticyanides. Cesium recovery is limited primarily b y the large amount of iron in the waste streams. In the presence of iron, best cesium recovery is obtained with zinc ferricyanide or zinc cobalticyanide. A novel method for recovery of cesium in the absence of iron uses ammonium ion and nickel ferrocyanide. Typical schemes for cesium recovery are discussed, and the behavior of other fission products in these processes is mentioned. H. H. VAN T U Y L and R. L. MOORE Hanford Laboratories Operation, General Electric Co., Richland, Wash.
Eng. Chem. 51, 753-8 (1959)
Organometallics in Lubrication Organometallics are often effective in reducing the fric tion and wear of rubbing metals. A systematic study was made in b e n c h equipment with representative compounds, including tetraethyllead, (methylcyclopentadienyl)manganese tricarbonyl, and di-n-butyltin sulfide, alone or as addi tives in fluid lubricants, u n d e r many test conditions. Worn surfaces were studied b y electron diffraction and emission spectroscopy. Inorganic solids, produced on the surfaces by thermal degradation of the organometallic due to localized frictional heating, were detected and usually identified. Some solids, including recognized solid lubri cants, were derived wholly from the additive—i.e., without chemical attack of the surfaces. Our expanding technology requires n e w approaches to lubrication problems. Organometallics should be con sidered for their potential utility. It is likely that end-use applications can b e developed. MORTON ANTLER Chemical Research Division, Ethyl Corp., Detroit 20, Mich.
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Eng. Chem. 51, 745-8 (1959)
Effect of Retarders and Promoters on Polymerization of a-Methylstyrene Thermal or peroxide-catalyzed polymerization of amethylstyrene is sluggish in systems containing over 50 mole % monomer; polymerization with alkali metals is more effective but subject to impurities. Poly(propylene glycol ether), w h e n a d d e d at concentra tions of 500 p.p.m. or less, causes the sodium-catalyzed polymerization of α-methylstyrene to proceed at practical rates and to high molecular weight. Specific effects of various impurities are described. G I F F I N D. JONES and RALPH E. FRIEDRICH Physical Research Laboratory, The Dow Chemical Co., Midland, Mich.
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Eng. Chem. 51, 759-62 (1959)
Chelating Ion Exchange Resins To increase the selectivity of ion exchange resins toward closely related cations, resins have b e e n prepared which incorporate chelating compounds into the resin structure. Such resins were made b y condensation of formaldehyde with resorcinol, /3-resorcylic acid, resacetophenone, oaminophenol, and 8-quinolinol. T h e equilibrium absorption of several divalent cations over the p H range 1 to 10 has b e e n measured for these resins and, for comparison, for two commercial cation exchangers. T h e chelating resins showed capacity comparable to the commercial resins and in general superior selectivity. T h e 8-quinolinol resin was very effective in chromato graphic separation of cobalt from copper and in removal and recovery of traces of copper from relatively concentrated salt solutions. LLOYD D. PENNINGTON Southern Oregon College, Ashland, Ore. M A X B. W I L L I A M S Oregon State College, Corvallis, Ore.
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Eng. Chem. 51, 763-4 (1959)
Resistance to Stress Corrosion of 1 2 % Chromium Stainless Steel Stress corrosion tests of 1 2 % chromium stainless steel were made in 0.5% acetic acid saturated with h y d r o g e n sulfide. For the materials tested, resistance to stress corrosion in creased u n d e r the following conditions: increased temper ing temperature above 1000° F., addition of secondary alloying elements, decreased in hardness, decreased ap plied stress, and vapor-blasted rather than an as-ground finish. R. E. LOCHEN and E. R. M I L L E R Atlis-Chalmers Research Laboratory, Milwaukee, Wis.
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Eng. Chem. 51, 779-82 (1959)
Autoignition of Liquid Fuel Sprays T h e autoignition process for a liquid fuel spray plays an important role in the operation of compression ignition engines. A n u m b e r of kinetic processes are involved in autoignition; some of them can occur simultaneously. Autoignition with air temperatures at fuel injection of 600° to 1000° K. and air pressures from 15 to 30 atm. was studied in the shock tube mainly b y high speed photography and pressure transducer measurements. Ignition lag data for a n u m b e r of hydrocarbon fuels are presented. Formation of a shock w a v e caused b y the explosive reaction of fuel during autoignition is possible. D e p e n d e n c e of shock formation o n the duration of fuel injection and on air pressure and temperature is briefly discussed. GEORGE J . M U L L A N E Y General Electric Research Laboratory, Schenectady, Ν. Υ.
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Eng. C h e m . 51, 765-70 (1959)
Flow, Power Requirement, and Pressure Distribution of Fluid in a Screw Extruder T h e simplified equations for flow of a viscous material through a screw extruder are derived, considering the importance of flow both in the direction of the channel and in the plane transverse to the channel. It is important to calculate the volumetric flow rate across a plane p e r p e n dicular to the axis of the screw. Consideration of the flow and pressure profiles in the plane transverse to the channel indicates that ûow in the channel is affected b y the clearance b e t w e e n the land and barrel surface. Expressions for the power requirement compatible with these flow relations are presented. W. D. M O H R and R. S. M A L L O U K Polychemicals Department, E. I. du Pont de Nemours &. Co., Inc., W i l m i n g t o n , Del.
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Eng. Chem. 51, 783-6 (1959)
Heat of Mixing in the System Nitrogen-Methane For extensive studies on the removal of nitrogen from natural gas and the liquefaction of natural gas, accurate data about the behavior of a nitrogen-methane mixture were required. Calculations based on published data show that the heat of mixing is positive and relatively small—40 B.t.u./lb. mole for a mixture of 5 0 % nitrogen and 5 0 % methane (heat of evaporation for nitrogen is 2800 B.t.u./lb. mole). Therefore, no appreciable inaccuracy is introduced in process calculations, as far as enthalpy balances are con cerned, if heat of mixing is neglected. For consideration of equilibrium conditions, however, the positive heat of mixing has a noticeable effect—a tend ency against mixing—which makes the vapor concentrations, especially of the diluted components, higher than expected in ideal mixtures. H E L M U T KNAPP American Messer Corp., 405 Lexington Ave., New York 17, Ν. Υ .
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Eng. C h e m . 51, 787-90 (1959)
Collapse of Steam Bubbles in Water
AIR POLLUTION— A Serious Problem Physiological effects of air pollutants and analytical methods, new work on automobile exhausts and gasoline vapors, and sulfur dioxide in air pollution begins on page 771
T h e absence of theoretical predictive equations a n d the paucity of empirical generalizations predicting the rate of boiling heat transfer prompted this investigation into one of the series of steps involved in the mechanism of boiling, the collapse of saturated vapor bubbles in cool liquid. T h e steam-water system was investigated for various degrees of instability ranging from 1° to 20° F. Instan taneous and mean heat transfer coefficients for complete collapse were determined b y photographic measurements of the progressive collapse of vapor bubbles a n d found to b e proportional to the products of b u b b l e diameter, latent heat of vaporization, and vapor density. Coefficients were on the order of 10 4 B.t.u./(hr.) sq. ft. ( °F.) for bubbles 1 cm. in diameter, indicating extremely high transfer rates. Comparison showed no agreement with theory. OCTAVE LEVENSPIEL Bucknell University, Lewisburg, Pa.
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HIGH PRESSURE COMPRESSORS
Ind. Eng. C h e m . 51, 791-6 (1959)
Correlating Latent Heats and Entropies of Vaporization with Temperature These important functions are essential in process and plant design. Entropies come from latent heats, on which there are few experimental values. The use of entropies of vaporization aids many calculations, but they are pub lished for only a few fluids used in power generation or refrigeration. The convenience of their use is seldom possible. By correcting for nonideality of the gas and the com pressibility of the liquid, new equations and nomograms were developed thermodynamically. Latent heats and entropies of vaporization may be immediately evaluated with an accuracy comparable to that from calorimetric measurements for some 500 compounds from the equations and simply used nomograms. Ready methods of applying to other compounds are given.
4 stage, 14" stroke Norwalk compressor, installed in 1937 and operating satisfactorily at maximum speed today. User states " N o carbon problem or indications of overheating of any sort."
DONALD F. O T H M E R and DAVID Z U D K E V I T C H Polytechnic I n s t i t u t e of Brooklyn, Brooklyn 1, Ν. Υ.
JOURNAL OF CHEMICAL AND ENGINEER ING DATA will
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July 15, 1959 Subscription to V o l . 4 is p r i c e d at $ 6 . 0 0 f o r members a n d $12.00 f o r n o n m e m b e r s . A d d r e s s o r d e r s f o r JCED or CEDS to Circulation D e p a r t m e n t , Journal of Chem ical and Engineering Data, 1155 Sixteenth St., N . W . , W a s h i n g t o n 6 , D. C.
Issues of Chemical and Engineering Data Series w h i c h p r e c e d e d this j o u r n a l a r e a v a i l a b l e at $ 3 . 5 0 each ( V o l . 1, N o . 1; V o l . 2 , N o . 1; V o l . 3, N o s . 1 a n d 2 ) .
This 5 stage, 14" stroke, heavy-duty tandem compressor is Norwalk's modern counterpart of the 1937 model shown at top. Develops 3000 lb. p.s.i.g. in capacities up to 31,000 c.f.h. Every Norwalk compressor is test-run a t the factory, then taken down for complete inspection before re assembly and shipment. Norwalk makes compressors from single stage to six stages; from 125 to 25,000 psi pressure; for gases listed below: ACETYLENE
ETHYLENE
AIR
HCL
ARGON
HELIUM
CERTAIN
HYDROGEN
HYDRO CARBONS
NITROGEN
CO and CO.,
NITROUS OXIDE
ETHANE
OXYGEN
For full details, write for Catalog 44
NORWALK COMPANY, INC. SOUTH NORWALK, C O N N E C T I C U T Established Î86U Circle No. 84 on Readers' Service Card
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