SEPTEMBER 1959
I/EC
Briefs I/EC's articles on . · ·
CHEMISTRY AND CHEMICAL ENGINEERING IN THEORY AND PRACTICE
The why, what, a n d significance of technical articles in this issue. Clip these Briefs for r e a d y reference and easy filing en 3 X 5 or other suitable c a r d .
. . . b e g i n on p a g e 9 7 4
I / E C
B r i e f
I/EC
Brief
Ind. Eng. C h t m . 51, 974-80 (1959)
Staff-Industry C o l l a b o r a t i v e Report
I n d . Eng. Chem. 51, 997-1004 (1959)
2,4-D Weed Killer and Derivatives
Determining Maximum Heat Load in Equipment Design
T h e Dow Chemical Co. has been in commercial production of 2,4-D and its derivatives since 1945. Last year, the company made 47 different products and formulations based o n 2,4-D and its esters and amine salts. Some of these formulations have resulted from Dow's o w n field research on the handling of specialized w e e d control problems. Dow's 2,4-D plant at Midland, Mich., uses the standard commercial process. First, 2,4-dichlorophenol is reacted with monochloroacetic acid in the presence of sodium hydroxide to produce the sodium salt of 2,4-D. T h e mixture is then acidified to precipitate the 2,4-D as fine white crystals. T h e product is treated further to form a variety of esters and amine salts. T h e plant takes special precautions to prevent the escape of 2,4-D into the atmosphere.
Heat removal capacity is often a limiting factor in the safe operation of large-scale equipment w h e n exothermic decomposition reactions are encountered. To avoid uncontrollable temperature rise with its attendant hazards of fire and explosion, the maximum rate of heat evolution must be matched by an equal heat-removal capacity. A simple differential thermal analysis method has b e e n developed for measuring rates of heat evolution from small samples, which gives data that can be used readily in the design of largescale equipment. T h e apparatus is standardized electrically. W. R. DEASON, W. E. KOERNER, and R. H. MUNCH Organic Chemicals Division, Monsanto Chemical Co., St. Louis 77, Mo.
HOWARD J . SANDERS and RALPH F. PRESCOTT
I/EC
B r i e f
I / E C
B r i e f
Ind. Eng. Chem. 51, 1005-10 (1959)
Flooding Characteristics and Separation Efficiencies of Pulsed Sieve-Plate Extraction Columns P L A N T COSTS A N D E C O N O M I C S I N THE C H E M I C A L PROCESS I N D U S T R Y Seven articles from representatives of the chemical process industry tell the story of annual investment and growth in this rapidly expanding field begin on page 981
Generalized flooding and mass transfer correlations were developed from experimental data in the unclassified and declassified literature for pulsed sieve-plate extraction columns. T h e flooding correlation is based on 665 data points and permits the prediction of total flooding velocities with an average deviation of 2 0 % from the experimental values for systems in which water is the continuous phase. T h e mass transfer correlation is based on 285 data points and permits the prediction of over-all transfer unit heights with an average deviation of 16.4% from the experimental values. This correlation applies to systems in which mass transfer occurs from the dispersed phase to the aqueous continuous phase and where the major resistance to transfer is in the dispersed phase. Nomographs facilitate design calculations. L. D. SMOOT, B. W. MAR, and A. L. BABB Department of Chemical Engineering, University of Washington, Seattle, Wash.
CLIP AND
FILE FOR READY REFERENCE VOL. 5 1 , NO. 9
•
SEPTEMBER 1959
11 A
Eastman Briefs FOR
SEPTEMBER c
^O-C-C-OH
c
I I C-C-C-C-C-OH
0
2,4-Dimethylpentanol
-O-C-C-OH H y d r o q u i n o n e β - H y d r o x y e t h y l Ether Form solid Melting point 101-102°C. Boiling point, 0.3 mm 190-200'C. Hydroxyl number, mg.KOH/g 555-565
Form Specific gravity, 20°C Boiling point, 760 mm Color, APHA
liquid 0.8201 158.5-161° C. solution in methanol Eastman C h e m i c a l Products, Inc. Kingsport, Tennessee B11
"
Please send more data on these chemicals:
B8
B9
B11
B12
B13
Name
T.tle
Company
Address
Zone No.
State
CLIP AND FILE AOvr.TISIMÏHÎ
Circle Nos. 1-1, 1-2, 1-3, 1-4, 1-9 an Readers' Service Card
12 A
INDUSTRIAL AND ENGINEERING CHEMISTRY
I/EC Ind.
B r i e f
Eng. Chem. 51, 1011-14 (1959)
Longitudinal Mixing in a Pulsed Sieve-Plate Extraction Column
B. W . MAR and A. L. BABB Department of Chemical Engineering, University of Washington, Seattle, Wash.
I/EC
Eng. Chem. 51, 1023-6 (1959)
Equilibrium compositions used in the study of isomerization have generally b e e n calculated from free energy data. This is not a favorable case for the application of calorimetric data and discrepancies b e t w e e n calculated and directly observed compositions have raised questions as to the true values. It was the purpose of this work to resolve these questions. Equilibria were determined b y direct analysis of carefully ieomerized hexanes. H i g h and low temperature were studied using active dual functional and Friedel-Crafttype catalysts, respectively. From those data a corrected equilibrium picture has b e e n developed covering a tem perature range of 100° to 750° F. These results show the equilibrium dimethylbutanes con tent to be less than predicted from free energy data. At 750° F., 2 1 % dimethylbutanes is formed vs. 2 7 % predicted. J. A. RIDGWAY, Jr., and W I L L I A M SCHOEN American Oil Co. (Texas), P.O. Box 401, Texas City, T e i .
B r i e f
I/EC
B r i e f
Eng. Chem. 51, 1015-18 (1959)
Perforated Plate Column Studies by the Box Method of Experimentation
Ind.
DONALD A. DECHMAN and M A T T H E W VAN W I N K L E The University of Texas, Austin 12, Tex.
I/EC
Eng. Chem. 51, 1027-30 (1959)
Hydrodesulfurization of Coke
T h e purpose of this study was to verify the applicability of the Box method of experimentation for correlating efficiency and pressure drop with operating and design variables of a perforated plate column. T h e i n d e p e n d e n t variables w e r e reflux ratio, vapor mass velocity, weir height, and hole diameter. A second-order polynomial equation with all possible second-order inter actions included was selected. T h e constants were evalu ated b y a least squares fit of 246 data points and with 28 data points selected b y the Box design technique. T h e lack of fit variance and confidence limits were estab lished for each equation. T h e Box correlations for efficiency and pressure drop agreed with experimental data in the range of its design. Comparison of the two equations for efficiency showed the Box-designed equation to be satis factory.
Ind.
Ind.
B r i e f
New Data for Estimating Hexane Isomer Equilibrium
This investigation was u n d e r t a k e n to correlate the effects of plate geometry, pulsing conditions, liquid properties, and liquid flow rates o n longitudinal mixing in a pulsed sieve-plate extraction column 2 inches in diameter. Experimental data for the hexane-water, benzene-water, and carbon tetrachloride -water systeir s were obtained using steady-state and delta injection techniques. Empirical correlation of the data permits estimation of continuous phase Peclet numbers with an average deviation of 17% from the experimental values. A nomograph facilitates the calculation. Back-mixing can be decreased b y use of higher con tinuous-phase flow rates, smaller plate spacings, and smaller holes in the plates.
Ind.
I / E C
Because fluidized coking of high-sulfur residual stocks produces coke with a relatively high sulfur content, a study was undertaken to develop methods of reducing the sulfur level to about 1 %. Treatment with various gases, according to procedures described in the literature, was not satis factory. Coke produced from fluidized coking of a high sulfur residuum was effectively desulfurized w h e n preoxidized with air at low temperatures (650° to 700° F., atmospheric pressure) to a 90 to 9 4 % coke yield and then treated with hydrogen at about 1400° F. and 1 to 3.5 arm. Sulfur con tent was reduced from 7 to 1% after 2 hours at atmospheric pressure and after 1 hour or less at 3.5 arm. R. BURGESS MASON Esso Research Laboratories, Esso Standard Oil Co., Baton Rouge, La.
B r i e f
I / E C
B r i e f
Eng. Chem. 51, 1019-22 (1959)
Polymeric Fats from Stearic, Oleic, and Short-Chain Dibasic Acids
Ind.
Eng. Chem. 51, 1031-4 (1959)
Catalytic Reactions of Butylamines over Alumina
To develop n e w outlets for edible fats and simultaneously develop products required by the food industry, polyesters of glycerol, short-chain dibasic acids, and some fatty acids of food fats were prepared and characterized. T h e polymers which w e r e formed possessed a n u m b e r average molecular weight below 1700 and ranged from low melting waxes (35.7 to 67.1 ° C.) to a liquid which would not crystallize at —60° C. Viscosities can be controlled b y varying composition. If the polyesters are edible, as anticipated, they should be useful as pan greases in the manufacture of baked goods, as slab dressings in the manufacture of candies, and as surface coatings for food products for which a glossy, rela tively inert finish is desired. R. O. FEUGE and AUDREY T . GROS Southern Utilization Research and Development Division, U. S. Department of Agriculture, New Orleans 19, La. CLIP A N D
T h e reactions of butylamine and dibutylamine in the gas phase at 380° to 430° C. over aluminum oxide were investigated. T h e effects of variation in space velocity, temperature, and conditions of catalyst activation have b e e n studied. From the observed kinetics, dibutylamine and Λ'-butylidenebutylamine are intermediates in the reaction of butyl amine to form b u t è n e and butyronitrile. Variation in activation conditions leads to changes in specific surface activity of different extent for the dehydrogenation and deammoniation reactions, confirming previous indications that at least two different kinds of catalytically active sites are present on the surface of the alumina. WALLACE S. BREY, Jr., and DAVID S. COBBLEDICK Department of Chemistry, University of Florida, Gainesville, Fia.
FILE FOR READY REFERENCE
VOl.
5 1 , NO. 9
•
SEPTEMBER 1959
13 A
I/EC
B r i e f
I/EC Ind.
Ind.
Eng. C h e m . 51, 1035-8 (1959)
Automatic Cascade for the Production of Nitrogen-15 A small automatic isotope separation cascade was constructed and operated to evaluate the use of the HNOj-NO chemical exchange reaction as a method of separating nitrogen-15 on a large-scale basis. Successful operation of the cascade over a long period of time demonstrated the technical feasibility of the chemical process and the cascade design. T h e most sensitive technical scale-up problem was found to b e the design of the nitric acid refluxers. T h e most important economic factor was the favorable disposition of large quantities of by-product sulfuric acid. G . M . BEGUN, J . S. DRURY, and E. F. JOSEPH Chemistry Division, Oak Ridge National Laboratory, Oak Ridge, Tenn.
I/EC Ind.
B r i e f
Eng. Chem. 51, 1045-6 (1969)
Ion Exchange Casting Resin A strongly acid ion exchange resin which could be cast in relatively large pieces was n e e d e d for ceramic research. T h e condensation of/>-phenolsulfonic acid and formaldeh y d e in the presence of amines gave a resin which could be made into cups and small tanks with a maximum dimension up to 11 inches. T h e s e castings were stable to small moisture changes and could be exposed to the drying effects of air for 1 hour or more without cracking. Beads made with this resin showed unusual stability to complete drying and rewetting. T h e resin should be useful in chemical processing where restrictions in size and shape of pieces b y conventional resins or lack stability of beads to complete drying and rewetting is now a limiting factor. L. V. PEAKES, A. A. ORLANDO, and A. L. JOHNSON W. Keith McAfee Laboratory, Universal-Rundle Corp. New Castle, Pa.
B r i e f
I/EC
Eng. Chem. 51, 1039-42 (1959)
Ind.
B r i e f
Eng. Chem. 51, 1047-60 (1959)
Improved Cascade Impactor for Measuring Aerosol Particle Sizes
Chemical Additives Control of Frictional Characteristics of Lubricants
Various parameters affect the impaction process in a cascade impactor for determining the particle-size distribution of aerosols and sprays. Studies on the jet-to-slide distance which affects the sharpness of classification, and on wall-to-slide distance which affects the loss of particles on the wall were emphasized particularly. A n improved cascade impactor containing round jets and slides was designed and calibrated. Probems encountered in the calibration process were studied and solved. Studies of the wall loss that may be expected for each stage of the impactor were made. This improved impactor and modified versions have b e e n used to determine the particle size distribution of air pollutants, therapeutic and biological aerosols, and cigarette smoke.
Special antifriction lubricants are required for noise-free operation of mechanisms containing wet clutches, such as automatic transmissions. Performance characteristics that are affected by the frictional nature of the lubricant include clutch lockup duration and shock, torque capacity, wear and fading tendencies, and audible frictional vibrations. A laboratory friction test apparatus (modified four-ball wear tester) has b e e n utilized in studies of the several parameters that influence the design of practical power transmission fluids. Experimental data illustrate effects of antifriction additive type and concentration, interaction of additivies, lubricant degradation, and clutch facing materials.
R. I. M I T C H E L L and J . NI. PILCHER Battelle Memorial Institute, 505 King Ave., Columbus, Ohio
S. R. SPRAGUE and R. G. C U N N I N G H A M Shell Oil Co., Wood River, III.
I/EC Ind.
B r i e f
I/EC
B r i e f
Eng. Chem. 51, 1043-4 (1969)
Regenerating Weak Base Anion Exchangers. Chlorate in Caustic Soda
Effect of Ind.
Chlorate in standard liquid caustic soda was suspected as the cause for oxidation of weak base anion exchangers used in demineralization. Static tests verified that chlorate is a good oxidant in acid, but no oxidation was noted in neutral or alkaline media. Column tests showed that chlorate is selectively adsorbed in the presence of large excesses of hydroxide and is not completely removed by acid during normal cycle. It was concluded that chlorate in caustic soda could be a source of trouble. Preliminary laboratory cycling tests indicated increased rinse water requirements with resins subjected to only 10 cycle» in which the régénérant contained a quantity of chlorate which might b e found in commercial standard grades of caustic soda. Rayon grade or solid forms should be used in field practice.
Eng. Chem. 51, 1051-2 (1959)
Fast Flow Rate Deionization. Pressure Drops and Removal of Trace Quantities of Metal Ions Little information has b e e n published relative to the efficacy of mixed bed deionization at fast flow rates of feeds containing trace impurities. This study, undertaken to extend k n o w l e d g e in a field of basic interest for treating nuclear reactor waters and boiler condensates, delineates the extreme efficiency of mixed bed deionization e v e n on a micro scale. H e a d loss data of basic engineering importance are also established. Rapid mixed b e d deionization permits material savings in equipment cost and housing space and provides water of highest quality. B. N. DICKINSON, I. M . ABRAMS, and LEO BENEZRA Chemical Process Co., 1901 Spring St., Redwood City, Calif.
I R V I N G M. ABRAMS and LAURANCE H. DONNALLY Chemical Process Co., Redwood City, Calif.
CLIP A N D
FILE FOR READY REFERENCE VOL. 5 1 , NO. 9
•
SEPTEMBER 1959
15 A
