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Staff-lndustry C o l l a b o r a t i v e Report Acrylates and Methacrylates. Ester Manufacture and Markets
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The Chemical Industry—A Nuclear Future? Part I I . Reactor Physics
The Rohm & Haas process for methyl and ethyl acrylate involves reaction of acetylene, carbon monoxide, methyl or ethyl alcohol, nickel carbonyl.and hydrogen chloride in a continuousprocesswhich requires very accurate control of feed rates. Methyl methacrylate is made in a continuous process starting with conversion of acetone cyanohydrin to methacrylamide sulfate; reaction with methanol then produces methyl methacrylate. Acrylates and methacrylates give polymers with outstanding transparency and aging properties. Considerable variation in hardness, minimum film-forming temperature, etc., can be obtained by copolymerization. Principal markets discussed are cast sheet, molding powders, emulsion polymers, solution polymers, water-soluble polymers, unsaturated polyesters, specialty elastomers, and chemical intermediate.
Nuclear reactor physics is primarily of concern to the physicist. On the other hand, the potentially attractive use of such reactors to provide space and process heat and for radiation processing, and the chemical nature of fuel processing and the associated chemical production of radioisotopes, impel the chemist toward a modest familiarity with the subject. W. R. TOMLINSON, Jr. The Johns Hopkins University, Operations Research Office, Bethesda, M d . Ind. Eng. Chcm. 51,1339-44 (1959)
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MORTON SALKIND, E. H. RIDDLE, and R. W. KEEFER Ind. Eng. Chem. 51, 1328-34 (1959)
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Zone Freezing in Demineralizing Saline Waters Photochemistry in the Solar Furnace
To determine the technical feasibility of zone-freezing demineralization of saline waters, segregation of solutes during carefully controlled freezing experiments on aqueous solutions was studied. Results are applied to suggested processes for demineralization on a large scale. Segregation depends sharply on freezing rate, solution concentration, degree of agitation, and thermal geometry. In two-stage zone freezing, more than 99.9% of dissolved salt has been removed from solutions containing 3 grams per liter with a pass rate of 1 inch per hour. From solutions containing 3 0 + grams per liter (sea water concentration), pass rates of the order of 0.15 inch per hour are required. This research has demonstrated the technical feasibility of the method. Estimates of the cost of water produced by one of the continuous processes proposed compare favorably with those calculated for other demineralization processes at a similar stage of development.
The focal spot of the solar furnace can be used as a cool, intense light source. Liquids as well as gases can be handled at the focus of the solar furnace as they absorb only selected wave lengths. For this reason photochemical light absorption can take place at ambient temperature and below. This use of the solar furnace can become important when an i n situ light source is required. The photoreduction of eerie ion in perchloric acid solution was studied as an illustration of such a use. The stoichiometry and kinetics of this reaction remained unchanged in the solar furnace from those observed at room temperature and with artificial light sources. RUDOLPH J. MARCUS and HENRY C. WOHLERS Chemistry Department, Stanford Research Institute, Menlo Park, Calif. Ind. Eng. Chem. 51, 1335-8 (1959)
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R. C. HIMES, S. E. MILLER, W. H. M I N K , and H. L. GOERING Battelle Memorial Institute, 505 King Ave., Columbus 1, Ohio
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Ind. Eng. Chem. 51, 1345-8 (1959)
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GUIDE FOR AUTHORS, published in February 1959 issue, page 230, gives copy requirements to be observed in preparing manuscripts for consideration. Manuscript (2 copies) should be sub mitted to the Editor, 1155 Sixteenth St., N.W., Washington 6, D. C. The American Chemical Society assumes no responsibility for the statements and opinions advanced by contributors to its publications. Views expressed in the editorials are those of the editors and do not necessarily represent the official position of the American Chemical Society. 1959 Subscription Rates Members Nonmembcrs, domestic and Canada Nonmcmbcrs, foreign except Canada
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$2.50). Claims for missing numbers will not be allowed if received more than 60 days from date of mailing plus time normally required for postal delivery of journal and claim. No claims allowed because of failure to notify the Circulation Department of a change of address, or because copy is "missing from files," Published monthly by the American Chemical Society, from 20th and NorthamptonSts.,Easton, Pa. Executive Offices, Editorial Headquarters, and Circulation Department, 1155 Sixteenth St. N.W., Washington 6, D. C. Advertising Office: 430 Park Ave., New York 22, Κ. Υ. Branch Editorial Offices: 36 South Wabash Ave., Chicago 3, 111.; 718 Melrose Bldg., Houston 2, Tex. ; 2 Park Ave., New York 16, N. Y.; 703 Mechanics" Institute Illdg., 57 Post St., San Francisco 4 , Calif.; Bush House, Aldwych, London. CHANGE OF ADDRESS: Notify Circulation Department, American Chemical Society, 1155 Sixteenth St., N.W., Washington 6, D. C. Such notification should include both old and new addresses and postal zone number, if any. The American Chemical Society also publishes: Analyt ical Oitmistry, Chemical and Engineering News, Chemical Abstracts Service, Journal of the American Chemical Socitty, The Journal of Physical Chemistry, Journal of Agricultural and Food Chemistry, The Journal of Organic Chemistry, and Journal of Chemical and Engineering Data. Kates on request.
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Preparation of Diisopropyl Using Salt Hydrate-Boron Trifluoride Complex Catalysts
Hydrodesulfurization Activity of Promoted Molybdenum Oxide-Alumina Catalysts A number of molybdenum oxide-alumina catalysts containing oxides of Group VIII elements as promoters were studied for hydrodesulfuriza tion activity. Definite optima exist in the quantities of both nickel and cobalt oxides in combination with molybdenum which yield the most active catalysts. Additional promotion in desulfurization activity was observed when two iron-group elements are added to molybdenum oxide-alumina. Other catalyst variables were studied—e.g., the effects of variations in the total amount of active elements present, the type of support used, and the method by which the catalyst is prepared. All of these factors have significant effects upon catalyst activity. HAROLD BEUTHER, R. A. FLINN, and J. B. McKINLEY
HARMON M. KNIGHT and JOE T. KELLY
Gulf Research and Development Co., Pittsburgh, Pa. Ind. Eng. Chem. 51,1349-50 (1959)
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Diisopropyl, an excellent blending component for gasoline, is readily produced by alkylation of isobutane with ethylene using Friedel-Crafts catalysts. However, an improved catalyst was sought which would give high yields without the corrosion and handling problems associated with known catalysts. Complexes of boron trifluoride with certain hydrated metal salts are active for ethylene alkylation, particularly boron trifluoride—iron pyrophosphate hydrate. With this catalyst, alkylate yields are about 265% (wt.) based on ethylene charged. The C6 fraction, 70% of the total, is about 97% diisopropyl and has a Research octane rating of 103. Total alkylate rates almost 101. These new catalysts are believed to have real potential, not only for isobutane-ethylene alkylation, but for other reactions as well.
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Research and Development Department, American Oil Co., Texas City, Tex.
Ind. Eng. Chem. 51,1355-7 (1959)
Calculating Homogeneous Reaction Rates and Orders in a Flowing Gas Reactor. Thermal Decomposition of Ethylbenzene A quick and simple method was needed for determination of specific thermal reaction rates in a flow reactor containing a gradient of tem peratures. A graphical method was developed to calculate specific reaction rates, based on total conversions and temperature profiles in the re actor. An example of this calculation is given for the dehydrogenation of ethylbenzene in the presence of steam. Use of flow reactors has several limitations for determination of kinetic data. However, the method of calculation given can be easily applied to many reaction systems normally used in the laboratory.
Synthesis and Polymerization of 3,3,3-Trichloro-1-propene One property of most plastic materials that limits their utility is their flammability. Flammability of plastics containing halogens is greatly reduced. A new synthetic route to 3,3,3-trichloro-l-propene has been found making this monomer readily available for homopolymerization or copolymerization to yield flame-resistant polymers. Polytrichloropropene and copolymers of vinyl acetate, and ethylene with 3,3,3trichloro-l-propene, have been prepared and do not support combustion. W. A. SKINNER, ERNEST BISHOP, DALE TIESZEN, and J. D. JOHNSTON Department of Chemistry, Stanford Research Institute, Menlo Park, Calif., and Ethyl Corp., Baton Rouge, La.
Ind. Eng. Chem. 51,1359-60 (1959)
EMERSON H. LEE and GEORGE D. OLIVER
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Plastics Division, Monsanto Chemical Co., Texas City, Tex. Ind. Eng. Chem. 51,1351-2 (1959)
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Association Reactions for Poly(alkylene Oxides) and Polymeric Poly(carboxylic Acids) Oxidized Asphalts in a Vertical Pilot Plant The oxidation of two asphaltic residua was studied in a pilot scale converter. The vertical type converter was stainless steel and held a charge of 10 to 30 gallons. Instruments controlled the temperature, pressure, and air rate. Process rate could be increased by increasing the temperature, pressure, air rate, or liquid level. Properties of the final product were dependent upon the temperature, pressure, air rate, and nature of the residuum being oxidized. H. M . CHELTON, R. N. TRAXLER, and J. W. ROMBERG Research and Technical Department, Texaco, Inc., Port Nechcs, Tex.
Ind. Eng. Chem. 51, 1353-4 (1959)
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Methods for insolubilizing and radically altering the physical proper ties of water-soluble high polymers by a simple, low-energy reaction were sought. Combinations of poly(alkylene oxides) or other polymer ethers with polymeric poly(carboxylic acids) have water insolubility, flexibility, heat resistance, and elastic recovery characteristics different from either component alone. This suggests extensive hydrogen bonding between ether and carboxylic groups in the polymers. The ease of formation of such association products, instantaneously and at room temperature, the ready control of such formation by a variety of inhibitors, and the wide range of properties possible in the products commend this reaction for consideration wherever in situ production of hydrophilic elastomers is desired. K. L. SMITH, A. E. WINSLOW, and D. E. PETERSEN Research Department, Union Carbide Chemicals Co., South Charleston, W. Va. Ind. Eng. Chem. 51,1361-4 (1959)
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Chromium Chloride—Alkylaluminum—Catalyzed Polymerization of Propylene
Metallic and nitrogenous constituents of petroleum fractions not only poison catalysts used in cracking, reforming, and isomerization, but also promote corrosion. The severity of their removal by hydro génation processes often results in costly hydrogen consumption by side reactions. Almost all of the metals (V, Ni, Fe) and 80 to 85% of the nitrogen were removed from both California crude and coker gas oil by a nonhydrogen consuming process using aqueous hydriodic acid at 700° F. Sulfur removal was also high (70 to 80%). The hydriodic acid is partly converted to iodine. Oil and iodine recoveries were only 90 to 95%, and some corrosion was encountered. If these troubles were overcome, the process would probably first be used for treatment of low grade crudes and refractory stocks. W. E. GARWOOD, W. I. DENTON, R. B. BISHOP, S. J. LUKASIEWICZ and J . N. MIALE Research and Development Laboratory, Socony Mobil Oil Co., Inc., Paulsboro, N. J .
J. F. GILLESPIE and J. W. L. FORDHAM Diamond Alkali Co., Painesville, Ohio
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Removal of Nitrogen and Metals from Petroleum Stocks with Hydriodic Acid
The anhydrous chromium chlorides were investigated as Ziegler catalyst components along with triethyl- or triisobutylaluminum for propylene polymerization. Chromium trichloride with the trialkylaluminum yields a catalyst, but the chromium dichloride-triethylaluminum combination was in active under the conditions used. The polypropylene prepared with the chromium trichloride-triethylaluminum catalyst is a moderately regular polymer of high molecular weight. The rate of polymerization and the molecular weight of the polymer can be controlled by varying certain polymerization factors. The chromium modification of the catalyst acts like the analogous combination derived from titanium trichloride. However, a significant difference is the greater activity of the latter. The lesser activity of the chromium catalyst suggests its evaluation in the polymerization of the more active polar monomers, where the catalyst can be poisoned by the monomer.
Ind. Eng. Chem. 51,1365-8 (1959)
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Ind. Eng. Chem. 51,1377-8 (19S9)
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Effect of Nitrogen Compounds on Hydrodesulfurization of Petroleum Fractions An Experimental Study of Heat Transfer to Nitrogen-Oil Mixtures
Previous investigations of catalytic hydrodesulfurization examined the role of olefins and sulfur compounds. This article describes the effects of some nitrogen compounds on catalytic hydrogénation of sulfur compounds and olefins A catalytically cracked gasoline (0.62% sulfur) and a synthetic mixture of η-heptane and heptenes (0.5% sulfur as thiophene) were processed over two laboratory-prepared catalysts: nickel-alumina and cobalt-molybdena-alumina. Olefin hydrogénation was inhibited more than desulfurization by addition of as little as 140 p.p.m. of nitrogen to the synthetic feed stock. The gasoline, after acid-washing to lower its nitrogen content, lost 2.5 octane numbers upon desulfurization and exhibited a larger increase in olefin hydrogénation than in desulfurization. Basic nitrogen compounds improve the selectivity for sulfur removal relative to olefin hydrogénation.
The rate at which heat is transferred to a mixture of a nitrogen and very viscous oil was measured in a vertical 5-foot heat exchanger 0.506 inch in diameter. Constant flux heat transfer coefficients were meas ured. At constant oil rate, the rate of heat transfer increased with increas ing nitrogen volumetric flow rate. The two-phase heat transfer co efficient can be approximated by the single-phase heat transfer corre lation of Sieder and Tate, using the oil properties and basing the velocity on the total volumetric throughput. R. F. KNOTT, R. N. ANDERSON, A. ACRIVOS, and Ε. Ε. PETERSEN Department of Chemical Engineering, University of California, Berkeley, Calif. Ind. Eng. Chem. 51,1369-72 (1959)
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JBSTCI3EI3F" F. W. KIRSCH, HAROLD SHALIT, and HEINZ HEINEMANN Houdry Process Corp., Marcus Hook, Pa. Ind. Eng. Chem. 51,1379-80 (1959)
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POLYURETHANE COATINGS Cross-Flow Air-Water Contactors
Condensed versions of seven discussions of one-package surface coatings, baked polyurea coatings, coatings from castor polyols, diisocyanate a d ducts coatings based on castor oil, reactions of isocyanates with drying oils, poiyether polyols, and stable pigmented coatings systems based on prepolymers
The equations that describe the relationship of gas enthalpy and water temperature as a function of position in cross-flow air-water contactors are complex and difficult to solve. This work was initiated with the intent of devising a simplified computation procedure for the design and evaluation of cross-flow contactors. Generalized design charts were developed by numerical computa tions and are presented in a form useful for design and evaluation purposes. R. S. SCHECHTER and T. L. KANG Chemical Engineering Department, University of Texas, Austin 12, Tex. Ind. Eng. Chem. 51,1373-6 (1959)
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