RESEARCH RESULTS - Industrial & Engineering Chemistry (ACS

Ind. Eng. Chem. , 1962, 54 (1), pp 97–102. DOI: 10.1021/ie50625a014. Publication Date: January 1962. Note: In lieu of an abstract, this is the artic...
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All manuscripts listed here are being considered for possible publication in one of the I/EC quarterlies. They are available to I/EC subscribers, and may be obtained at reproduction and handling cost. They should be treated in the same fashion as a personal communication. Use of the material in publications, or reference to it, should have the author's approval. Please use the printed coupon, and include payment with your order.

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Oxidation of Pyrolytic Graphite in Air between 1250' and 1850' F.

Simple Apparatus for Measuring the Film-Forming Potentials of liquids

Milton Levy Watertown Arsenal Laboratories This report presents results of an investigation of the oxidation characteristics of pyrolytic graphite as a function of time and temperature in quiescent air, utilizing a technique that permits automatic and continuous recording of oxidation rate.

P. R. Benson and W. R. Martini Atomics International A pyrolytic apparatus uses an electrically heated vertical cylinder in a capsule containing the liquid under test. T h e weight of film deposited under test conditions establishes the fouling potential of the liquid.

Ms.

No. 2

2 1 pages, including 7 j g u r e s , 2 tables.

Advanced Developments Reinforced Fabric Plastics

in

Organic

92.00

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Price 8

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Total remittance (check, money order, cash) $-(Payable to American Chemical Society) RESEARCH RESULTS SERVICE Industrial and Engineering Chemistry 1155 Sixteenth Street, N.W. Washington 6, D . C.

M s . No. 58

16pages, including Sfigures, 2 tables.

11.00

Matrix-Nonwoven Commercial Electrolytic Cell for Periodic Acid

D . V . Rosato Telecomputing Corp. The report reviews the principles that govern the limited growth and mathematical advantage in the use of nonwoven fibrous structure for plastic or ceramic matrix laminates, giving information on predicting their mechanical properties. M s . No. 8

MS*-

40pages, including 1 l j g u r e s , 1 table.

C. L. Mantell Newark College of Engineering T h e design of cells for production of dialdehyde starch is given in sufficient detail for reproduction, with reports of operating results. Rigid PVC is a major material of construction.

M s . No. 65

21 pages, including 5figures, 3 tables.

92.00

42.00

Catalytical Deposition and Grafting of Olefln Polymers Into Cellulosic Materials

A Mathematical Model for Photochemical Chlorination of Alkyl Benzenes

D. J. Bridceford Tee-Pak, Inc. A process for polymerization is described, which involves binding

R. W . Sommers, R. M . Downing, and H . M . Brcnnecke E. I. du Pont de Nemours 6 Y Go., Inc. A mathematical model derived from basic chemical kinetics

initiators or components of initiator systems to cellulosics by ion exchange. Batch or continuous processes with residence times of several seconds to a few minutes for each bath can be used.

predicts the course of batch or continuous countercurrent chlorinations as a function of liquid and gas composition and light intensity.

M s . No. 7 7

30pages, including 5figures, 70 tables.

42 00

Ms. No. 6 9

42pages, including lgfigures, 4 tables.

$2.00

Reactivity of Double Bonds of Fumaric and Maleic Esters at Elevated Temperatures

Photo-Initiated Addition of Carboxylic Acids to Higher Oleflns

Lahja Turunen Sucnska Oljeslageri A b Reactions of fumaric and maleic double bonds were investigated under conditions corresponding to the manufacture of unsaturated polyesters. Several anomalies in production are discussed.

Alfred Steitz, Jr., and T . P. Moote, Jr. Pan American Petroleum Gorp. T h e nature of the products of the reaction and factors controlling their distribution were studied, as well as the kinetics of the reaction, so that an over-all mechanism could be postulated.

Ms. No. 43

Ms.No. 104

20pages, including Gfigures, 4 tables.

92.00

Paraffin Isomerization with Hydrogen Chloride-Promoted Dual-Function Catalysts

C. H . Thomas, J .

Mooi,R. S.Bartlett, and R. A . Sanford

23pagcs, including I j g u r e s , 3 tables.

$2.00

Catalytical Hydrogenation of Nitrosamines l o Unsymmetrical Hydrazines

Sinclair Research, Inc. A catalyst comprised of a precious metal on a boria-alumina support, promoted with hydrogen chloride, is effective for butane, pentane, and hexane isomerization in the 550' to 750' F. range.

G. W . Smith and D . N . Thatcher E . I. du Pont de Nemours @ Go., Inc. T h e catalytic hydrogenation of nitrosamine to hydrazines is enhanced by the presence of dissolved salts in the reaction medium.

Ms. No. 57

M s . No. 108

16 pages, including 1 figure, 6 tables.

$1.00

77pagcs, including 5figures, 2 tables.

VOL. 5 4

NO. 1

$1.00

JANUARY 1 9 6 2

97

R E S E A R C H RESULTS Pressure Hydrogenolysis of Paraffins. System

Kinetics in a Flow

Critical Evaluation of Boundary Conditions for Tubular Flow Reactors

T h e kinetics of hydrogenolysis reactions of ethane, propane, and butane were studied in a flow system a t 1000 p.s.i.g., 1000° to 1300' F., and a t the stoichiometric feed ratio for complete conversion to methane, and compared ivith published pyrolysis data.

Liang-tseng Fan and Yong-Kee Ahn Kansas State University T h e three sets of boundary conditions most frequently used for design and analysis of isothermal tubular flow chemical reactors are critically re-examined. Differences and relations among concentration profiles and conversions are numerically evaluated.

Ms. .Yo, 113

M s . ,vo. 208

E. B. Shultz, Jr., and H . R. Linden Institute of Gas Technology, Chicago

Z j p a g e s , including djigures, 4 tables.

$2.00

24 pages, including 2 4 j p r e s .

s2.00

Kinetics of the Catalytic Dehydration of Primary Alcohols Ammonium Nitrate Propellants Based on a Polyester-Acrylate Binder

J . E. Stauffer and W. L. Kranich Worcester Polytechnic Institute

A . 0 . Dekker and G. A. Zimmerman Aerojet-General Cor$. This review summarizes development of a castable composite propellant. Typical problems associated with development of composite propellants are discussed with particular reference to use of ammonium nitrate as oxidizer.

Reaction kinetics for dehydration of primary alcohols from ethyl to hexyl over */-aluminum oxide was studied, to find Ivays of predicting kinetic behavior of a compound in a catalytic reaction from known data on a homologous compound with the same catalyst.

M s . .%lo, 1 14

15pages; including Gjgures, 3 tables.

dis. N o . 2 7 3

18 pages, including &?figures.

$1.00

57.00 Multicomponent Viscosities of Gaseous Mixtures at High Temperatures

Hydrolysis of Dialdehyde Starch. Glyoxal and Erythrose Production in Sulfurous Acid-Barium Sulflte Solutions

C . A . Wilham, T . A . McGuire, J . W . Van Clew, F. H . Otey, and C. L. Mehiretter Northern Regional Research Laboratory Direct acid hydrolysis produces glyoxal of known industrial value and erythrose which can be reduced to erythritol. Addition of barium sulfite to sulfurous acid increases yields a t higher dialdehyde starch concentrations and enhances isolation of glyoxal and erythrose.

Ms. N o . 134

73pages, including ZJigures, 1 table.

51.00

S. C. Saxena and T.K . S. Narayanan Atomic Energy Establishment Trombay, Bombay, India Binary diffusion and pure viscosity data are used to compute binary viscosities according to an expression derived from rigorous kinetic theory. T h e procedure enables calculation of m:i!ticomponent viscosities for mixtures permuting out of nine binary systems considered here.

Ms. I f o . 219

20pages, including 5 tables.

52.00

Effect of Pore-Size Distribution on Reactions in Catalyst Particles

Peter Harriott Cornell Uniuersity Simulation of the Theoretical Time-Temperature Behavior of a Supercritical Mass of a Self-Heating Chemical on a Digifal Computer

J . R. Parks Monsanto Chemical Co. An IBM 704 computer has been used to find numerical solutions of Fourier's equation, term and associated technique can be used thermal explosion of available.

Ms. N o . 158

including a nonlinear power generation initial and boundary conditions. T h e to plan and guide experiments on the any self-heating chemical, if data are

18flages, including Z j g u r e s , 4 tables.

81.00

Comparative Study of Continuous liquid Thermal Diffusion Systems

Robert Grasselli and David Frarier Standard O i l Co. (Ohio) Three liquid thermal diffusion flow systems-center feed, mixed end feed, and transverse flow-were experimentally studied at various column heights, slit widths, and temperature levels, and their separation-rate characteristics were intercompared. Ms. N o . 162

41 pages, including 1 4 j g u r e s , 7 tables,

82.00

Methods of estimating the effective diffusivity and the catalyst effectiveness factor are presented for three types of pore-size distribution. Ms.

.vo. 2 2 9

15 pages, no Jigures.

$1.00

Acid Retardation. Physical Separation of Strong Acids from Their Salts by Use of Anion Exchange Resins in the Common Ion Form

M . J . Hatch and J . A . Dillon Dow Chemical Co. Extensive studies were made of the ability of anion exchange resins to absorb strong acids reversibly by nonexchange mechanism and thereby separate strong acids and their salts. Applicability to metal pickle liquors and ore leaching liquors has been invertigated. M s . ?Jo, 233

3 2 pages, including 4Jigures, 1 table.

52.00

Coke Formation in Catalytic Cracking

TV. G . Appleby, J . W. Gibson, a n d G . M . Good Shell Development Co. T h e work was devoted mainly to a study of the influence of hydrocarbon molecular structure and molecular weight o n coke formation over several typical aluminosilicate catalysts.

M S . N o . 234

35pages, including 2jgures, 13 tables.

$2.00

N e w Techniques in Processing Urethane Elastomers

K . A . Pigott, J . W . Brittain, William Archer, Jr., B. F. Frye, R. J . Cotli, and J . H . Saunders Mobay Chemical Co. T h e processing of a new type of partially cured, solid polyurethane elastomers by extrusion, injection molding, transfer molding, blow, and compression molding i s described. Abrasion resistance, ozone resistance, tensile, and tear properties are equivalent to those obtained by casting.

Ms. N o . 173

98

17pages, including lofigurer, 5 tables.

57.00

INDUSTRIAL AND ENGINEERING CHEMISTRY

A liquid Phase Process for Acetylene Reactions J . J . Nedwick 3 Haas Go. Rohm t Operation of a condensed-phase technique for carrying out acetylene reactions under high pressure is described and its advantages with respect to safety, economy, productivity, and versatility are discussed.

'MS.A'o. 248

75jiager, including l j g u r e , 3 tables.

57.00

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Circle Nos. 81, 82, 83, 84 on VOL. 5 4

Readers' Service

NO. 1

Card

JANUARY

1962

99

RESEARCH RESULTS The 1ow.Temperature Gaseous Reduction of Iron Ore in the Presence of Alkali

Production of Aromatic Polyfluoro Compounds from Chloro. fluorocyclohexanes

Arthur McGeorge, Jr., A. Norman Hixson, and K . A . Krieger University of Pennsylvania, Philadelphia, Pa. Rates of reduction by hydrogen of pure Fen03 and selected iron ores were measured to test the reported beneficial effect of alkali metal compounds. T h e alkali apparently reacts with ore impurities, resulting in increased reduction rates rather than acting as a “promoter” in a catalytic sense.

P . Johncock, R. H . Mobbs, and TV. K . R. Musgrave The University, Durham, England T h e chlorine atoms are eliminated preferentially from chlorofluoro- and chlorofluorohydrocyclohexanes when these are passed over iron gauze a t 400’ to 500’, giving rise to polyfluorobenzenes.

Ms. YO.248a

29pages, including 7 fables, 8Jigures.

17 pages, including 1 figure, 4 tables.

$ 7 00

Nitric Acid Dissolution of Uranium-Molybdenum Alloy Reacfor Fuels

Catalytic Reduction of Nitric Oxide

Nitric oxide can be removed from the exhaust streams of combustion processes by a catalyzed reduction, using hydrocarbons or hydrogen present in the exhaust as the reducing agent. Data are given for the reduction of nitric oxide to nitrogen and to ammonia by two different mechanisms using hydrogen.

Wallace W . Schulr, Raymond E. Burns, and Edward M . Duke Hanford Laboratories Operation, General Electric Co. Nitric acid dissolution procedures for the preparation of redox process solvent extraction feedstocks from U-bfo alloy reactor fuels are discussed. Special dissolution procedures are given for preparing low-acid solutions of relatively high (0.75.M or greater) uranium content.

Ms. No. 257

Ms. No. 272

R. J . Ayen and IM.S. Peters University of Illinois

22pagess,including 4 tables, 6S;gures.

$2.00

Thomas Blanchard and J . C. Chu Polytechnic Institute of Brooklyn Heat transfer to and from jackets and coils in an agitated vessel was studied Tvith 2.0% hydrolyzed polyacrylonitrile, 3.5% poly(vinyl alcohol), and 2.0% polyacrylamide. A correlation analogous to the Chilton correlation for Nebvtonian fluids was developed.

M s . NO.2 6 2

2 1 pages, including Sjigures, 7 table.

77pages, including 3 tables, 4Jigures.

$ 1 00

Use of Ozone in Rocket Propellants

Heat Transfer of Pseudoplastic Fluids in an Agitated Tank

$2.00

Radiochemical Characteristics of Particulate Crude in the SM-1 during Core 1.

C. S. Stokes and A . G. Streng Temple University C0mparatii.e data on ozone-fuel and oxygen-fuel systems are presented. A preliminary phase diagram for the liquid OS-02-FI system a t 77.4’ K. is given. Experimental combustion of several liquid propellant systems containing ozone is described, usinq micro rocket apparatus.

Ms. N o . 276

7 8 p a g e s , includtng 4 figures, 3 tahler.

57.00

Production of Cyanogen from the Elements, Using a Plasma Jet

C. R Bergen

H . W . Leutner Temple University

Alco Products, Inc. Particulate corrosion products (crud) collected from the coolant of the Army Package Power Reactor during Core I were studied. Analysis techniques for C050, cob&,FesQ,Cr51, and lln54 are given. Relation of the findings to the mechanism of crud transport is discussed.

Cyanogen has been produced under practicable conditions for industrial applications, with yields up to l 5 % , based on carbon input, from a consumable carbon cathode with nitrogen and argon as plasma phases. Ordinary and pyrolytic graphites are used as electrode materials.

Ms. No. 263

24pages, Qjgures, 2 tables.

K . L. Lindsay Ethyl Gorp. T h e design of kinetic experiments is considered as a problem in selecting the best time intervals for measuring the composition of the reacting mixture. An approach is based on transformation of the time variable to a dimensionless variable. M s . No.

267

lQpager, including GJgures, 1 table.

$1.00

Studies with a three-cell and seven-cell electrodialysis unit indicate that this method may be used to recover fission elements, as well as acids, from radioactive waste solutions.

87.00

Vapor-Phase Halogenation of Benzene by Chlorine Trifluoride

R. E. Banks, P. Johncock, R. H. Mobbs, and W. K. R. Musgraue T h e University, Durham, England T h e reaction between benzene and chlorine trifluoride gives a highly complex product if the reagents are diluted with excessive nitrogen to moderate the reaction. Conditions can be chosen to give chiefly fully halogenated cyclohexanes, but all hydrogen atoms may not be eliminated. M s N o . 270

21 pages, including lfigure, 5 tables.

37 00

Synthesis of Polydodecylbenzene Using Hydrofluoric Acid Catalyst

E. H. Holst, A . J . Startz, J . R. Zoller, and J . E. Tessieri Texaco, Inc. Polydodecylbenzene was prepared from propylene tetramer and benzene, using hydrofluoric acid as catalyst, under conditions for maximum dialkylation. Processing variables were investigated, and heavy alkylates produced were examined for susceptibility to sulfonation.

M s . N o . 287

76pages, including 3figures, 4 tables.

$7 00

H. C. Bramer and R. D . Honk Mellon Institute

G. J . Bub, J . D . Vie, and W. H . Webb Uniuersity of Missouri, School of M i n e s and Metallurgy

77 pages, including 7 j g u r e , 5 tables.

7 1 pages, including 3 tables.

Design Criteria for Sedimentation Basins

Fractionation of Fission Elements by Electrodialysis

Ms. No. 2 6 8

iMs iVo. 2 8 6

$2.00

A n Approach to the Optimum Time Scheduling of Kinetic Experiments

100

iMs. ‘2‘0.2 7 1

$2.00

82.00

INDUSTRIAL A N D E N G I N E E R I N G CHEMISTRY

This article presents design procedures for sedimentation basins in the manner of the conventional unit-operation treatment, and shows how scale criteria derived from them may be used in small-model evaluation of alternative basin designs.

Ms. N o . 295

IQpagcs, including 7 j g u r e s , 2 tables.

Irradiation Factor Dependency. Electron Irradiation of Materials

$7.00

Exploratory Studies on

E. F. Degering U. S. Army Quartermaster Research and Engineering Center Exploratory studies on effects of irradiation-induced polymerization of vinyl monomers indicate factor dependency under the experimental conditions used with respect to atmosphere, dose rate, temperature, and the monomer system. IUS.A’o. 301

32pages, including 12jgures, 6 tables.

$2.00

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40 Chatham Rd.. Summit, N. J. A Division of Martin Marietta Corporation Representatives i n 31 countries. Writ, oxport manager for dotails. Yo. 86 on Readers' Service Card VOL. 5 4

NO. 1

JANUARY 196

RESEARCH RESULTS Rate-Determining Factors in Dialysis of Electrolytes

A N e w Hydrocarbon Elastomer.

B. H. Vromen Graver Water Conditioning Co.

E . K . Gladding, B. S. Fisher, J . W'. Colleite, and Coworkers E . I . du Pont de A'emours @ Co., Inc. Sulfur-curable elastomers from olefins and diolefins are described, with methods for synthesis. Factors that influence laboratory-scale polymer synthesis are discussed, including catalyst type, polymerization temperature, and diene sttucture.

Experiments are reported that illustrate the phenomena encountered with a number of electrolytes, and the results are related to effects that are neglected in the usual dialysis theories.

M s . N o . 306

43pages, including SJgures, 2 tables.

$2.00

Ms. N o . 332 Heats of Mixing of liquids

Experimental data for the heats of mixing of the ternary system sulfuric acid-phosphoric acid-water are presented. A general expression for predicting ternary heats of mixing from binary data gives good agreement with experimental results. M s A'o. 307

75pages, including Sfigures, 2 tables.

23pages, including 7figures, 13 tables.

A N e w Hydrocarbon Elastomer.

J . B. Knobeloch and C. E. Schwartz Universtty of Virginia

$7.00

I

$2 00

I1

J . J . Verbanc, M . S.Fawcett, E. J . Goldberg, and Coworkers E. I . du Pont de Nemours c 3 Co., Inc. A hydrocarbon elastomer synthesized from petrochemical intermediates using coordination catalysis is described. It resembles commercial diene elastomers in general appearance, is soluble in hydrocarbon and chlorinated hydrocarbon solvents, and is stable to prolonged storage.

M s . N o . 333

36 pages, including I d j g u r e s , 70 tables.

82.00

Collection Efficiency of Jet Impactors at Reduced Pressures

S. C . Stern, H . 1V. Zeller, and A . I . Schekman General M i l l s , Inc., and Collins Radio Co. Collection efficiencies of circular and rectangular jet impactors were determined at reduced pressures, using monodisperse solid homogeneous aerosols, in an effort to correlate existing theory with experimental data. T h e experiments verify the significant role of the Cunningham correction for slip in the impaction of small particles a t reduced pressures. Ms. ATo. 3 0 9

22pages, including 8Jgures, 2 tables.

$2.00

Application of Inorganic Ion Exchange Materials i n Pressurized Water Nuclear Reactors

h'orman Michael and R. F. Sterling Westinghouse Atomic Power Department Zirconium oxide and phosphate were prepared and evaluated as ion exchange materials under various operating conditions, to obtain water of high purity.

M s . LVO.374

7pages, including ZJigures, 2 tables.

67.00

Source of Dimethylhexanes in Sulfuric Acid-Catalyzed Butene Alkylation

C. A . Zimmerman, J . T . Kelly, and J . C. Dean Cities Service Research and Development Co. Isobutane was alkylated with 1-butene, 2-butene, and isobutene, and alkylate composition determined by improved gas chromatographic procedures. A modified mechanism for formation of dimethylhexanes is suggmted. M s . IVO. 335

74 pages, including 5 iables.

$7.00

Paper from Inorganic Fibers

R. A . Keppeland R. D . TWalker, Jr. Uniuersity of Florida Work with blends of glass, ceramic, and asbestos fibers is described, including procedures and conditions employed. T h e flow plan and operation of a laboratory paper machine, designed to operate on a semicontinuous basis, are given.

M s . No. 338

40pages, including lofigures, 6 tables.

$2.00

synthesis of Mercaptans

Preparation of Low Freezing Jet Fuels by Isocracking

H . 0 . Folkins and E. L. ikfiller Pure OilCo. A catalyst and process, proved in pilot plant operation, produce methyl mercaptan from methanol and hydrogen sulfide in molal yields of over 90% per pass with selectivities of around 95.

R. H. Korlowski, H. F. Mason, and J . W. Scott California Research Cor$. Three 550" to 850' F. boiling range feeds were isocracked to produce kerosine-type fuels. T h e products are evaluated as .jet fuel components. Properties in relation to composition, effects of recycle splitter cut point, once-through operation, and feed properties are discussed.

Ms. No. 3 1 5

27 pages, including 7 Jgure 12 tables.

82.00

High Temperature Inhibition of Normal Paraffin Oxidation by Alkyl Aromatics

J . J . Giammaria and H . D . Norris Socony Mobile Oil Cu., Inc. Several termination reactions are proposed to explain the inhibition of oxidation of n-heptane by aromatics such as toluene, p xylene, ethylbenzene, and cumene at 300' to 400' C. Analyses of oxidation products are presented to support the proposed reactions.

Ms. 2Yo. 379

15pages, including 3Jgures, 2 tables.

87.00

Ads. .To. 3 3 9

24pnges, including 2Jgures, 7 tables.

Electrolytic Production of Oxides

Uranium Metal from

52.00 Uranium

R. D . Piper and R. E. Leifield Adallinckrodt Chemical Works The technical feasibility of a process for reduction of uranium oxides to massive uranium metal a t 1150' C. in a fused fluoride electrolyte has been demonstrated in the laboratory. -4pplicalion to other reactive metals appears possible.

M s . hjo, 341

24 pages, including $figures, 3 tables.

82.00

Rigid Urethane Foams Derived from Crude Tall Oil Correlating Diffusion Coefficients in Binary Gas Systems

102

P. G . Gemeinhardt, E'. C. Darr, and J . H. Saunders Mobay Chemical Co.

D . F . Othmer and H. T . Chen Polytechnic Institute of Brooklyn A simple method for correlating diffusion coefficients is presented, based only on molecular weights and critical volumes. The resulting nomogram is correct within the experimental limits of most data reported on diffusion.

Foams exhibiting predominantly closed cells, containing up to 40% crude tall oil, have been made in standard processing equipment, with significant savings in cost of raw material. Processing information is given on one-shot techniques of preparing molded and slab-stock foam.

M s . h'u. 327

Ads. N o . 342

13 pages, including 4figures.

$7.00

INDUSTRIAL A N D ENGINEERING CHEMISTRY

13pages, including 2figures, 9 tables.

57.00