BRIEFS Summary of papers published in this month's research quarterly, I&EC Process Design and Development
PREDICTING THE EFFECT OF HYDROCARBON INJECTION O N BLAST FURNACE OPERATION
CARBONACEOUS DEPOSITS O N SILICA-ALUMINA CRACKING CATALYST
The results of tests of hydrocarbon injection in the blast furnace indicate that the amount of coke displaced relative to the quantity of hydrocarbon injected can vary widely. A basis for explanation of the wide variation in hydrocarbon to coke displacement ratios is developed. It is shown that there are three process paths for hydrocarbon injection, and the displacement ratio of a given test depends on the path or combination of paths followed. An added factor which can influence the results appreciably is the effect of injection of the blast additive on gas utilization in the furnace. The principles utilized in the study of displacement ratios are applied to evaluation of eight blast additives comprising heavy fuel oil, natural gas, coke-oven gas, hydrogen, carbon monoxide, nitrogen, oxygen, and carbon dioxide.
Coked silica-alumina cracking catalyst removed from a commercial fluid cracking unit has been studied using electron microscopy and differential thermal analysis. Endothermic decomposition of the deposit in the absence of air was observed above 800' C . Since mixtures of carbon black and fresh catalyst were not affected by high temperature treatment, it is suggested that the endotherm observed was caused by cracking of the deposit into volatile fragments. Oxidation characteristics of the coked catalyst were studied and kinetic data obtained. Sufficient oxygen is apparently adsorbed on the catalyst to support oxidation, since rapid reaction was not appreciably hindered by substituting a helium atmosphere for air. Pretreatment with hydrogen of fresh catalyst prior to coking in the laboratory seemed to prevent formation of one type of coke observed with the untreated sample.
H. E. W. Burnside, ESSOResearch and Engineering Co., Liihden, N . J.
James W. Hall and Howard F. Rase, Department of Chemical Engineering, T h e University of Texas, Austin, Tex. APPLICATION OF HEAT-TRANSFER PRINCIPLES TO A METALLURGICAL PROCESS PROBLEM. RELATIONSHIP OF LADLE PREHEATING TO TEMPERATURE LOSSES
The chemical engineer plays an important role in process research and development activities in the steel industry. The use of material and energy balances, the concepts of unit operations, and the principles of heat and mass transfer are being applied to an increasing number of metallurgical process problems. This paper presents a simple example of the application of heat-transfer principles to a metallurgical process problem. The conclusions are applicable to many other high-temperature heat-transfer studies.
ESTIMATION OF SPOUT DIAMETER IN A SPOUTED BED
Spout diameters, d,, were measured for eight materials in two semicircular columns of 4- and 6-inch diameter, respectively, using air as the spouting medium. The quantity d, in a spouted bed is proportional to the square root of the mass flow rate of air. A generalized equation IS proposed for estimating d, under various conditions, requiring only the mass flow rate of air and the column diameter as primary information.
M . A. Malek, L. A. Madonna, and Benjamin C.-Y. L u , University of Ottawa, Ottawa, Ontario, Canada
W. M . Danver, J . K. McCauley, and F. C. Langenberg, Crucible Steel Co. of America, Pittsburgh 73,Pa. EFFECT OF EQUILIBRIUM LINE CURVATURE O N MASS TRANSFER CALCULATIONS THE SIGNIFICANCE OF FLUID DYNAMICS IN THE BLAST-FURNACE STACK
To improve the productivity and thermal and chemical efficiency of the blast furnace process, it is important to establish favorable fluid-flow characteristics in the blast furnace stack. These characteristics are related to the permeability of the burden materialsore, coke, and limestone-within the stack, the particle size and distribution of solids, and gas velocity, density, viscosity, pressure, and temperature. The application of chemical engineering techniques and process engineering analysis indicated that considerable improvement in blast furnace operation would result from various procedures for beneficiating the burden materials. The chemical engineering aspects of beneficiation processes such as sintering, pelletizing, and briquetting are discussed, together with the resulting improvements in fluid-flow characteristics and blast furnace performance.
J. C. Agarwal and W. L . Davis, Jr., United Stales Sleel Corp., Apjlied Research Laboratory, Monroeville, Pa.
PLUTONIUM ELECTROREFINING
The production of large amounts of high purity plutonium metal by bomb reduction techniques is a difficult and time-consuming task. Electrorefining processes have been developed that provide good yields of the pure metal in a compact form of high density on either the 500-gram or 3.5-kg. scale. Because of the operational simplicity, the method is also ideally suited to the economical processing of plutonium metal scrap.
L. J . Mullins, J. A. Leary, A . N . Morgan, and W. J . Maraman, Los Alamos Scientific Laboratory, University of California, Los Alamos, N. M .
Previous methods of combining individual phase resistances have been based upon using the slope of the equilibrium curve. This article shows that when curvature of the equilibrium line is large, the procedure should be based upon the slope of a chord connecting two specific points on the equilibrium curve. Application of this procedure has been extended to mass transfer through bubble trays, and equations have been derived whereby the point efficiencies, Eo@and Eo&,may be properly estimated from individual phase resistance. An example calculation shows that for large equilibrium line curvature the previous method can be in error by as much as 307&
C. A. Plank and E. R. Gerhard, University oflouisville, Louisville, K y , HOLDUP STUDIES IN A PULSED SIEVE-PLATE SOLVENT EXTRACTION COLUMN
The total holdup of dispersed organic phases in a pulsed sieveplate solvent extraction column was intensively studied in onecolumn geometry to determine the actual phase velocities. The column was 2 inches in diameter and contained 43 plates with a 2-inch plate spacing. The plates were made of 19-gage, Type 304 stainless steel perforated with '/a-inch-diameter holes to give a 23% free area. Hexane, benzene, and methyl isobutyl ketone were used as the individual dispersed phases with water as the continuous phase. The effects of pulse amplitude, phase flow rates, and pulsation frequency on the dispersed phase holdup were studied. Dispersed phase holdup was found to be a minimum at the transitiun frequency between mixer-settler and emulsion types of column operation. For the systems studied this frequency can be predicted from a simple empirical correlation. The results have been used in the analysis of continuous phase longitudinal mixing data to be reported later.
G. A. Sehmel and A. L. Babb, University of Washington, Seattle, Wash. VOL. 5 5
NO. 1
JANUARY 1963
69
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INDUSTRIAL A N D ENGINEERING CHEMISTRY
BRIEFS POLYMERIC LIGANDS. SEPARATION OF URANIUM FROM SOLUTIONS AND ORE LEACHES WITH SALICYLIC ACID-FORMALDEHYDE POLYMERS
Uranium is extracted as uranyl ion from solutions, using salicylic acid-formaldehyde polymers. Use of the technique described gave uranium of good purity in high yields.
R. C. DeGeiso, L. G. Donaruma, and E. A . Tomic, E. I . du Pont de Nemours C8 Go., Inc., Wilmington, Del.
ONE-STEP CATALYTIC CONVERSION OF ETHANOL TO BUTADIENE IN FLUIDIZED BED
An exhaustive and intensive study has been made on the application of the fluidized bed technique to the catalytic conversion of ethanol to butadiene; improvement in the conversion of ethanol to butadiene has been phenomenal. AlzOa-ZnO (60:40) is the best catalyst in both fixed and fluidized bed operations. A maximum conversion of 72.8y0 of ethanol to butadiene is obtained, against 55.8y0in the fixed bed operations, under optimum conditions. No liquid product is usually found in the fluidized bed.
S. K . Bhattacharyya and B. N . Avasthi, Indian Institute of Technology, Kharagpur, West Bengal, India
SUPERHEATED VAPOR AS A DRYING AGENT IN SPINNING FIBER
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Superheated vapor is an attractive drying agent, but its applications have been limited. Now its use has been extended to th drying of highly viscous materials, a difficult operation when air is used. Dry spinning of synthetic fiber with superheated solvent vapor as a drying agent produces a stronger, finer fiber. The recovery plant is simpler than that required in air drying, and the spinning chamber is smaller. Thus, the equipment area is greatly reduced. This method using superheated vapor is expected to produce high quality fiber and to improve production.
Tetsuo Yoshida and Tsutomu HyidG, Faculty of Engineering, Osaka City University, Osaka, J a j a n
USE OF NEW SOLVENTS FOR EVALUATING CHEMICAL CELLULOSE FOR THE VISCOSE PROCESS
Two new cellulose solvents, alkaline sodium ferric tartrate and cadmium oxide-ethylenediamine (cadoxene), have been investigated as to their utility in providing methods for predicting the behavior of a cellulose in the viscose process. The relationship between the viscose filterability and particle count of a chemical cellulose and its rapid solution characteristics in the new solvents has been investigated. Color of cadoxene-cellulose solution has been correlated with color of original pulp and corresponding regenerated product. The dissolving characteristics of a wide variety of pulps and chemically modified celluloses in the new solvents have been related to the chemical and morphological features of the cellulose fibers. These new solvents show substantial promise for rapid characterization of viscose filterability potential and end product color of chemical cellulose.
D . K . Smith, R. F. Bampton, and W. J . Alexander, Rayonier Inc., Whippany, N . J .
DESIGN PRINCIPLES FOR ANNULAR-BED ELECTROCHROMATOGRAPHY
A cylindrically symmetric arrangement is proposed for an electrochromatograph, in order to eliminate thermal bed-face effects. Theoretical analysis of the thermal and electrical behavior of a simplified model has been made. For a given geometry and a specified separation, the following relations apply : The product of residence time and applied voltage is constant. At relatively long residence times, power input is proportional to the maximum temperature rise in the unit; at any preset power input, the maximum allowable concentration then becomes proportional to the square of the residence time. These reiations can be used to maximize the separation capacity of any given unit.
Ray M . Hybarger, Charles W. Tobias, and Theodore Vermeulen, Unzverszty of Calafornaa, Berkeley 4, Calif. ELECTROCHEMICAL REDUCTION OF NITROBENZENE AT CONTROLLED POTENTIALS
Nitrobenzene was reduced electrochemically at a mercury cathode at various controlled potentials in acid electrolytes. Potential control to f l mv. was achieved by use of a recently developed instrument which is capable of supplying the high currents required to obtain sufficient quantities of product to make a complete analysis of the product mix. Of nine possible products, only four were obtained in measurable quantities. The composition of the product mix is a sensitive function of both the potential and length of electrolysis.
W. H. Harwood, Continental Oil Co., Ponca City, Okla. Ray M . Hurd and Wade H. Jordan, J r . , Tracor, Inc., 1701 Guadalufie St., Austin, T e x . PHOTOCHEMICAL AND THERMAL PRODUCTION OF TITANIUM TRICHLORIDE
The rate of the gas-phase reduction of titanium tetrachloride by hydrogen to form titanium trichloride and hydrogen chloride was measured in a batch reactor over the temperature range 430’ to 500’ C. The reaction rate appears to be first order with respect to both titanium tetrachloride and hydrogen giving an over-all empirical second-order rate expression. The temperature dependence of the specific reaction-rate constant indicates an activation energy of 41 kcal. per gram-mole. Traces of mercury vapor catalyzed the reaction. The reaction is also photon-catalyzed, with the rate being increased many orders of magnitude over the thermal rate. The photochemical reaction permits the production of titanium trichloride near room temperature where titanium trichloride formation is thermodynamically favored ; whereas to obtain practical rates in the thermal reaction, temperatures around 800” C. are commercially employed where thermodynamically titanium trichloride formation is much less favored.
Rodney R. Beyer and David M . Mason, Department of Chemical Engineering, Stanford University, Stanford, Calif. SALINE WATER CONVERSION BY PHENOL ADDITION
The two-phase system from addition of phenol to a saline solution is utilized to desalinize one phase by countercurrent flow of the phases. The phenol is separated primarily by cooling, the remaining phenol being removed by liquid-liquid extraction with benzene. The desalinization is carried out at pH 5 and at room temperature or below, reducing scaling and corrosion. Estimated costs are 59 to 77 cents per 1000 gallons in a 10,000,000gallon-per-day plant. The investigation has been carried to the pilot-plant stage.
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A . F. Reid and A . H. H a l f , H a l f and Reid, Dallas, T e x . EFFECT OF YIELD STRESS O N THE POWER LAW CONSTANTS OF FLUID FOOD MATERIALS DETERMINED IN LOW SHEAR RATE VISCOMETERS
CORRESPONDENCE
The power law constants, including the yield stress of several food materials, were determined employing a single cylinder viscometer. The values of the constants were compared when the yield stress was neglected and when it was considered.
Comments on an article by Liang-Tseng Fan and Yong-Kee Ahn, “Critical Evaluation of Boundary Conditions for Tubular Flow ENG.CHEM.PROCESS DESIGNDEVELOP. 1, 190 Reactors” [(IND. (1962)].
S. E. Charm, Massachusetts Institute of Technology, Cambridge 39, Mass.
M . G. Lorenz, Esso Re.rearch and Engineering Go., Linden, N . J . VOL. 5 5
NO. 1
JANUARY
1963
71
