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By L. D. Godshall

The latest revised edition of Mr. C. A. stetefeldt's book on the Lixiviation of Silver-Ores, which appeared very recently, contains no mention of the volatilization of silver in chloridizing-roasting—an omission which is the more remarkable in view of the fact that in former editions of the work this important subject was noticed. Moreover, Mr. Stetefeldt has discussed it to some extent in his paper on " The Stetefeldt Furnace," * in which he criticised certain statements made by me before the Colorado Scientific Society in May, 1893, in a paper entitled " A Review of the Russell Process;" ? and Mr. Morse, in his paper on " The Lixiviation of Silver-Ores by the Russell Process at Aspen, Colorado," $ has given statistics showing the loss of silver by volatilization (including the dustloss, which Mr. Morse estimates at not more than 1 per cent.) on more than 30,000 tons of ore roasted, to have been 9.16 per cent. The matter must certainly be deemed important enough to warrant me in returning to it, and offering, with the aid of the figures made public since my first paper, a reply to the criticisms of Mr. Stetefeldt. The passages of my paper which he deemed to be " ques-

Jan 1, 1897

By William R. Webster

This is a subject which our Institute has made peculiarly its own. In the first volume of its Transactions the analysis of steel received attention, and every subsequent volume has borne witness to the acuteness and industry of our members in the investigation of this subject. The keynote mas struck, in this as in so many other lines of progress, by A. L. Holley, in his paper on " Tests of Steel," read at the Easton meeting of October, 1873 (Trans., ii., 116)—an essay which may rank as a classic by reason of .its elegant form, logical force, and clear prevision of all the bearings of its theme, Taken together with the brief report of the discussion which followed it (in which Dr. Drown emphasized the effects of heat-treatment and mechanical handling, and Dr. Sterry Hunt the importance of minute variations in chemical composition, and of possible isomeric and allotropic conditions), it constitutes, after the lapse of twenty-five years, an admirable and adequate introduction to the long list of technical papers which have succeeded it. Three years later came the epoch-making papers of Dr. C. B. Dudley on the relation between the chemical composition and physical properties of steel rails, which, with the voluminous discussion they evoked, constitute a special volume, published by the Institute, and full of useful suggestions. If Dr. Dudley could be induced to resume this investigation, he would doubtless be able to solve many points still uncertain or disputed. But I cannot undertake to review the history of this subject, as represented in our Transactions—still less to restate all the contributions to it which have been made in books or in papers before other technical societies, since the initiative was taken by the Institute. My more modest purpose is to indi-

Jan 1, 1899

By E. W. Murbach

The oxidation of uranium carbide by oxygen at various pressures, and by air, has been investigated at temperatures up to 600°C. Arc-melted and cast uranium carbide displays oxidation behavior that appears to be dependent on its treatment after melting. ccReactive" uranium carbide, which results from exposure of freshly melted material to laboratory air, ignites in oxygen at about 275° to 350°C depending on pressure, and in air at about 350°C. The product of the initial oxidation appears to be UO2+.. Continued heating produces U30,. The initial oxidation rate is poportional, roughly, to the square root of the oxygen pressure. The activation energy determined for the initial oxidation reaction is 7.1 kcal, from 400° to 600°C in 10 mm of oxygen. AN investigation of low-decontamination methods for reprocessing uranium carbide reactor fuels is being carried out at Atomics International. One of the reprocessing cycles includes oxidation of the fuel at relatively low temperature (300° to 500°C) and reaction of the product oxide with carbon at elevated temperatures (above 1500°C) to produce uranium carbide. A number of small-scale experiments have been carried out in which uranium carbide was oxidized in air and oxygen at various pressures to measure reaction rates and to obtain other information concerning the oxidation process. In initial experiments with arc-melted UC, ignition was observed at about 275°C in oxygen or 350°C in air. However, similar experiments by Neymark' at 426°C in air showed no ignition. It was soon determined that the difference in oxidation behavior was due to the treatment of the UC following arc-melting. Neymark's experiments were carried out with freshly melted UC while those reported in the

Jan 1, 1963

By E. A. Gulbransen, K. F. Andrew

In a recent communication14 we have reported on the kinetics of the reactions of zirconium with O2, N2 and H2 as a function of the time, temperature and pressure variables. A systematic study was made and the results correlated with fundamental theories of gas-metal reactions. This paper will present a similar study for titanium. Titanium and zirconium are members of the IV group of the periodic table and possess many similar physical and chemical properties as a result of their similar electronic configuration for the outer electrons. The two metals are relatively inert to both gas and liquid phase corrosion at room temperature. However, at moderate temperatures the metals become active and react readily with the common gases including O2, N2 and H2 which are of interest in this study. A study of the kinetics of these gas-metal reactions is of interest for three reasons: (1) to understand the rate of reaction of titanium and its role in the behavior of high temperature alloys; (2) to understand the practical difficulties of the reduction, refining and working of titanium; and (3) to correlate the data with fundamental theories of gas-metal reactions and crystal structure predictions. Literature Survey Several review papers8 and books4243 exist on the preparation and properties of titanium and its alloys. THE METAL Titanium has, at room temperature, a hexagonal lattice of the zinc type. Hagg19 gives a value of 2.953A for the (a) axis, a value of 4.729 for the (c) axis and a density of 4.427 at 20°C. Burgers and Jacobs6 have observed the transformation of the hexagonal to the body-centered cubic structure at 880°C and have established a value of 3.31 for the cube edge and a density of 4.31. TITANIUM-OXYGEN Carpenter and Reavell6 using a pressure change method have studied the reaction at temperatures of 742° and 1000°C and for a pressure of one-fifth of an atmosphere. The probabilities for reaction are calculated from kinetic theory and they report a value of 10-5 for O2 at 1000°C and 10-6 at 740°C. The titanium-oxygen system has been investigated by Ehrlich.10,11 Five phases are observed. Between (TiO2 and TiO1.90) an alpha-phase, consisting ofarutile lattice, is found. A beta-phase is observed between (TiO1.80 and TiO1.70). A gamma-phase is homogeneous between (TiO1.56 and TiO1.46) and has a structure of the corundum type. The delta-phase exists between TiO1.25 and TiO0.6 and has a sodium chloride structure. From TiO0.42 to Ti the metal structure is observed. The surface oxide films have been studied by Hickman and Gulbransen.20 The rutile structure is observed in the temperature range studied, 300 to 700°C. Three crystalline modifications of TiO2 exist: rutile and anatase which are tetragonal and brookite which has an orthorhombic structure. Anatase is reported36 to exist in two forms: I and II. Anatase II changes to anatase I at 642°C. Anatase I is stable up to 915°C where rutile becomes the stable modification. At 1300°C rutile transforms to brookite which melts at 1900°C. The monoxide, TiO, may be prepared from the dioxide by high temperature reduction with carbon or magnesium. Its melting point is 1750°C. TITANIUM-NITROGEN Carpenter and Reavell6 report that at 1000°C a linear rate law is observed. The probability of reaction is given as 10-8 at 1000°C. Fast12 has studied the solubility of nitrogen and its effect on the mechanical properties of the metal. The crystal structure of TiN has been shown by several workers2'21'44 to follow the sodium chloride structure. However, the calculated density is found to differ from the pycnometric value. This is studied by Brager3,4 in detail. He has suggested that the titanium sites in the lattice are only partially filled at low temperatures. As the temperature of preparation is raised the vacant sites become occupied which expands the lattice and increases the hardness and density. An (a) value of 4.22Å is given for room temperature. TITANIUM-HYDROGEN The solubility and the crystal structures observed in this system have been reviewed in a recent book by Smith.40

Jan 1, 1950

By R. D. Pehke, J. F. Elliott

The solubility of nitrogen in liquid pure iron has been measured as a function of pressure and temperature. Sieverts' Law is obeyed at all pressures up to 1 atm and the temperature coefficient of solubility is 8 x 106 %/°C. The solubility of nitrogen in liquid iron alloys has been studied by the Sieverts' method and by the sampling method. The solubility is decreased by Al, C, Co Cu, Ni, 0. Si atzd Sn, and it is increased by Cr, Cb, Mn, Mo, Ta, W, and V. Interaction coefficients eN, for the effect of these elements on nitrogen dissolved in liquid iron, are reported. 1 HE effect of nitrogen upon the properties of steel may be desirable or not, depending upon the composition, processing treatment, and the use of the product. To understand the behavior of nitrogen in the various steelmaking processes, it is necessary to have reliable fundamental data pertaining to the solubilities, rates of solution, and chemical reactions of nitrogen in steel, particularly in the liquid state. In an effort to extend our knowledge in these areas, an investigation of the thermodynamics and kinetics of the solubility of nitrogen in liquid iron alloys was undertaken. The thermodynamic aspects of the study are presented in this paper. The solubility of nitrogen in liquid pure iron has received the attention of several investigators whose results are summarized in Table I. Reasonable agreement among the more recent researches1-l8 is found for the solubility of approximately 0.044 wt pct at 1600°C and 1-atm pressure of N,, for the temperature coefficient of solubility being small but positive, and for adherence to Sieverts' law for pressures up to 1 atm. The solubility of nitrogen in a number of binary liquid iron alloys has been studied: Fe-A1,3 Fe-As,16 Fe-C,3, 71 18, 19, 20 Fe-Cr ,5,7, 10, 11, 15 21 Fe-Co,'4, '6 Fe-Cu,'6 Fe-Mn,10, 11, 18 Fe-Mo,13, 16 Fe-Ni,10, 11, 13, 15, 16 Fe-O,16, 17, l9 Fe-p,7 Fe-S,l6 Fe-Sb,16 Fe-Se,lg Fe-Si,4) 97 '77 187 19>2° Fe-Sn,16 and Fe-v.51 '3 A few ternary systems have been studied, most of which were reviewed by ~angenberg" who applied the methods suggested by WagnerPz3 Chipman,24 Darken and G~rry, and Morris and Buehl26 for predicting solubilities in multicomponent alloys. Langenberg22 and Humbert and Elliott15 compared the solubilities computed from simple binary alloy systems with experimental measurements of nitrogen solubilities in liquid iron containing two or more alloying elements. The interaction coefficients for nitrogen in

Jan 1, 1961

By H. E. Wilborg

This chapter deals with those sands employed by the foundries for the manufacture of cores and molds used in the casting of such common metals as steel, gray iron, ductile iron, aluminum-based alloys, and copper-based alloys. Most metal is cast in "green sand" molds in which the sand mixture, consisting primarily of silica, clay, and water, forms a plastic material. This plastic material is rammed around a pattern in a split box called a flask, then the box is separated, the pattern is withdrawn, and the metal poured. These green sand molds are broken apart when the metal has solidified. The sand is then remixed and a new mold made for the next casting. To a lesser extent silica sand is mixed with resins or oils and, after forming, the mixture is hardened either by heat or chemical reaction. In any case, the foundry mold or core is used just once before being broken up and remixed for manufacturing another core or mold. By far the greatest consumption in the foundry is of those types of sand high in silica, low in clay (under 0.5%) and occurring in numerous locations thoughout the United States.

Jan 1, 1975

By D. C. Seidel, M. C. Fuerstenau, R. J. Roman

The role of surface charge in soluble salt flotation, which was developed in Part I, is extended to relate the theory to the specific phenomena of KCI-NaC1 separations. Temperature-collector solubility relationships, metal ion activation, and particle size effects are discussed. The initial paper in this series developed and presented the hypothesis that one of the mechanisms of soluble salt flotation may involve electrical attraction between the collector and mineral surface. This hypothesis was developed from a combination of experimental data and free energy calculations, and details of the logic are presented in this first paper.* The studies have indicated that KC1 has a positive surface charge and NaCl a negative charge. KC1 can therefore be floated with sulfonate ion (RSO;) or with an aqueous polar species such as the aqueous amine chloride, RNH3C1(,,). The chloride end of the RNH3C1(,,) molecular dipole is probably negative and will be attracted to the positive surface of the KC1 particles and absorb (actually probably fit into a vacant chloride site) on the mineral surface. The amine end of the collector molecule would extend into the solution phase and provide the air avid surface required for flotation. NaCl particles are floated by such collectors as aqueous molecules of fatty acid salt, RCOONa(,,), in which the positive inorganic end of the dipole is attracted to the negatively charged surface of the NaCl and, in this case, adsorb and probably fit into a vacant sodium site on the surface. The aminium cation, RNH~, should also be a collector for NaC1. For certain collectors, actual precipitates of the collector must be formed before a sufficient amount of the polar aqueous molecule is present to effect flotation. In a system of this type there is a three-way equilibrium between: Aqeous Molecular Solid Precipitate - A of the Collector (Not Dissociated) . Ionic Species (Dissociated). The controlling equilibrium is probably between the precipitated form of the reagent and the aqueous

Jan 1, 1969

By J. L. Gregg

RECENTLY there has been considerable interest in the production and use of, extra hard alloys composed primarily of tungsten and carbon. Dr. Hoyt's recent paper1 gives a good description of these alloys and describes their performance when used as tools. There are a number of these alloys on the market sold under various trade names, and it is the purpose of this paper to describe the results of an investigation of the structure of five of these alloys by means of microscopic and X-ray methods. The samples studied were in the form of small tools or wire-drawing dies, which were either purchased or supplied as samples. They were in some cases not supplied by the original makers but were furnished by the agents in this country, and we wish to call attention to the fact that they may not be truly representative of the materials supplied under the various trade names. No performance data are given and no inference as to the inferiority of one alloy as against any other is made K Schröter2 recently described methods for polishing alloys of this type for microscopic examination and has presented photomicrographs of several alloys. However, he did not identify their constituents or describe methods for their identification.

Jan 1, 1929

As already said Pattin's map and the later one of Evans' showed coal in several places in Ohio as early as 1750, and possibly 1748; the reference on the latter map was' to an exposure near Bolivar, in Tuscarawas County, as well as along the Hocking River. So far. as now known, it 'was not mined in either place until 1810. George Croghan, in descending the Ohio with his party in 1765, mentions an "Alum Hill" which they saw near the present site of Pomeroy, probably an exposure of saline deposits, but does not mention coal. As settlement north of the Ohio River was prohibited until 1787, no coal was mined until long after that date. In 1785 a survey of seven ranges in the Ohio country was made, the line running west from a point on the north bank of 'the Ohio River, due north of the western termination of the southern boundary of Pennsylvania. The surveyors noted, "from hence to Stoney Brook between two very steep and high Ridges; it is eight yards wide, its bottom is of Slate and Sand Stone, and in many parts of it are large pieces of excellent Coal washed by, the Rains from the Neighboring Hills."' This was the present Yellow Creek, and the coal was from some of the lower measures. The Scioto Company published a pamphlet in French in 1787, to promote the sale of their lands and emigration to them, in which was said,

Jan 1, 1942

By Keith G. Wallace

Small scale open pit mining of the Lucky Mc property in the Gas Hills district of central Wyoming was started in the spring of 1954 and the first uranium ore went to Vitro's mill in Salt Lake City that July. Shortly after mining started it became apparent that accurate ore control for mining purposes would be an absolute requirement. A systematic drilling program was initiated in the spring of 1955, and has been continued up to the present time. Two main mining areas have been developed. Mine 1, at the site of the original ore discovery in the Gas Hills, covers a mineralized zone roughly 600 x 2800 ft. This orebody was outlined and developed by drill holes on 50-ft centers. Approximately 1300 holes were drilled in the area before preliminary mining plans were made and mineable reserves calculated. Reserve estimates were based almost entirely on chemical assays of drill hole samples.

Jan 10, 1958

By Cyril Wells, Robert F. Mehl

THE practical importance of a knowledge of the rates of diffusion of carbon and of alloying elements in steel has often been pointed out 1,13 This importance ties chiefly, though by no means only, in the study of carburizing and in the study of reactions involved in the eutectoid inversion in steel The present paper is one of a series in which the rates of diffusion of carbon and of alloying elements in y-Fe and their mutual effects are measured with precision The present paper reports the results of meas¬urements of diffusion coefficients D of manganese in -y-Fe over wide ranges of temperature, and concentration, and of the effect of carbon and impurities and of grain size upon these diffusion coefficients [$] Data on the rate of diffusion of manganese in y-Fe have been reported by Fry2 and by Paschke and Hauttmann 3 Claussen4 calculated the diffusion coefficient D from Fry's data as 3 X 10-10 sq cm per sec at 960°, which will be shown to be incorrect by many orders of magnitude Paschke and Hauttmann gave a rough value of 9 6 X 10-8 sq cm per sec at 1400° Neither of these workers considered the variation of D with concentration and with temperature, and neither studied the effect of carbon METHOD AND MATERIALS Method -The method employed is identical with that used earlier 5 Owing to the volatility of manganese and the consequent loss of manganese from the outer surfaces of the welded diffusion bars, these surfaces were discarded The diffusion anneals were performed in argon, except one (test 18) in which hydrogen was employed for purposes noted below The temperatures reported are accurate to about 3° and constant within I°C , the diffusion times are reported to the nearest half hour The specimens were furnace-cooled after the diffusion anneal at about 2° per min Layers, usually 0 004 in thick, parallel to the welded interface, were machined from the specimens after the diffusion anneal and analyzed for manganese to 0 01 per cent Mn, the distances of these layers from the interface was measured to ±0 0002 in The concentration-penetration curves obtained were analyzed by both the Grube and the Matano solutions e The D values calculated by these two methods do not differ appreciably 5 The Grube solution was used except in tests in which the effect of concentration upon D was greater than 50 per cent, in such cases the Matano method, which explicitly provides for the variation of D with concentration,1 is the more reliable In general, the number of layers machined from the zones of variable composition were large enough to permit the use of the average layer composition as that of the center of the layer In 3 of the 30 tests, however, this is not justified, and the D values

Jan 1, 1941

By J. W. Lacey, F. H. Brinkman, J. E. Faris

This paper presents an analysis of the high-pressure, gas-driven LPG-slug process, based on fluid flow tests in areal models. Two types of tests were made. One series was made in low-pressure models which permitted observation of fluid movement. Three completely misci-ble analog fluids were used. A second series of tests was made in high-pressure models using methane, propane and a light refined oil saturated with methane at room temperature and 1,550 psig. Under the test conditions of room temperature and a pressure level of 1,550 psig, the phase diagram for the fluids used is similar to those for many of the field systems where the process is considered for use. A method for using these laboratory data to calculate field performance of the process is outlined. As a result of this work, it is concluded that small banks of LPG (5 per cent HV or less) are not effective in increasing oil recovery in horizontal reservoirs. Znstead, where small banks are used, the driving gas quickly penetrates the LPG bank because of fingering and channeling; and from this point on, the process behaves essentially as an immiscible gas-injection project. The validity of this conclusion was substantiated by: (1) laboratory studies of the effect of rate, model size and mobility ratio on miscible displacement in areal models; and (2) calculation of field recovery, which compared closely with actual field recovery. INTRODUCTION Field applications and pilot tests of the gas-driven, LPG-bank, oil-recovery process are on the increase. Most of these tests are employing small banks (2% to 5 per cent hydrocarbon volume) of LPG, which is miscible with both the driving gas and the oil in place, in an effort to attain an effective yet economical miscible displacement of oil by gas. The expectation of miscible displacement with small banks is based on the concepts that: (1) lengths of solvent-oil mixed zones, measured during miscible displacements in long slim cores, are representative of those that will occur in the field; and (2) areal sweep efficiencies5 measured in electrolytic model studies are applicable to miscible displacement in reservoirs. Our experimental evidence indicates that the mixed-zone lengths and sweep efficiencies mentioned are not applicable to miscible displacement in reservoirs. In this paper we present an evaluation of the gas-driven, LPG-bank oil-recovery process based on fluid flow experiments in areal models. These results are used to predict the performance of a field pilot test of this process, and the results are compared with the actual test results. THE EFFECTIVENESS OF LPG BANKS The effectiveness of LPG banks of various sizes in accomplishing miscible displacement of oil by gas was determined by displacement tests in a model representing one-quarter of a confined five-spot pattern. The model, 12 X 12 X 1/4 in. in size, was packed uniformly with glass beads. It was operated at a pressure of 1,550 psig and at room temperature; the fluids used were methane, propane and refined oil saturated with methane at 1,550 psig. The saturated oil had a viscosity of 1.2 cp at room temperature. The results of these tests are shown in Fig. 1, where recovery is plotted as a function of the volume of fluid injected for: (1) an immiscible-gas drive with an oil-to-gas viscosity ratio of 85; (2) three sizes of LPG banks; and (3) two completely miscible displacements with mobility ratios of 85:1 and 10:1. (The miscible displacement data plotted are the averages of several tests.) The results show that a 2½ per cent bank of LPG does not increase oil recovery over that obtained by immiscible-gas drive. The 7 and 17 per cent banks are, respectively, about 30 and 50 per cent effective (with reference to the M = 85 miscible-displacement curve) in increasing oil recovery at the point where 2½ hydrocarbon volumes (HV) of fluid have been injected. The percentage effectiveness of the banks at a given volume of fluid injected is defined as Recovery by Bank — Recovery by Gas Drive Recovery by Miscible Recovery by Flooding Gas Drive We conclude from these results that banks of LPG smaller than about 5 per cent HV in an individual stratum will cause from little to no increase in oil recovery. This finding was substantiated by work in low-pressure models, which permitted visual observation of fluid movements. In these tests, three completely miscible fluids having the same viscosity ratios as those used in

By Dale S. Preece

INTRODUCTION In 1975 Congress passed the Energy Conservation Act to establish a U. S. Strategic Petroleum Reserve (SPR) with a capacity of 750 million barrels of crude oil. The most economic storage medium was determined to be salt caverns leached in salt domes in Louisiana and Texas. Salt caverns existed at several sites when the reserve was created. These were obtained by the U. S. Department of Energy (DOE) and used to initiate SPR oil storage. In order to meet the storage capacity approved by Congress, new caverns also had to be leached. To support the resulting design effort, finite element computer programs have been used to determine the creep closure and structural stability of salt caverns Using site specific material properties including creep models, elastic moduli and fracture data, the finite element analyses have replaced earlier empirical approaches to cavern design. This report presents results of such finite element analyses to determine the best cavern roof shape and the minimum pillar to diameter ratio, P/D. These numerical predictions indicate that the current cavern design is safe. FINITE ELEMENT AND MATERIAL MODELING The finite element program used in this study has existed for approximately four years. Its theoritical basis (Key, et al, 1980) and application are well documented It was originally developed to predict the creep around mined openings In bedded rock salt for the Waste Isolation Pilot Plant (WIPP) The program was tested by modeling the creep of salt around a drift and by comparing the results with the predictions of eight other structural computer codes (Morgan, et al, 1981) Since then the program has had continual use for calculations to support the WIPP (Miller, et al, 1982) For about two years the

Jan 1, 1984

By Clarence Zener

THE heat-treatment of steels will not pass from the stage of an art into that of a science until the mechanism of the phase transformations associated therewith is thoroughly understood. Such an under- standing will involve two distinct types of inquiry: (I) the direction of the trans- formation, (2) the speed of the transformation. The first type of inquiry, which involves only the equilibrium relations between the various phases in steel, is the subject of the present and of a succeeding article; the second type, which involves the kinetics of transformations, will be the subject of a later article. In order that a theory of equilibrium relations may give useful information, certain experimental data must be put into the theory. It is customary for these data to be of a thermal nature. In the system discussed here in steel such thermal data are very scarce. In medium-alloy steels another type of data might possibly be used. In these steels the concentration of solute is so low that it may be possible to use the approximation of dilute solutions, an approximation that leads to linear relationships. The unknown functions, or constants, may then be determined in some cases from the binary iron- alloy system and in other cases from the ternary iron-carbon-alloy system. From the functions, or constants, so determined may then be computed the equilibrium relations in more complex medium-alloy steels. In the present article this second approach is used, the necessary experimental data being obtained from the simple binary and ternary equilibrium diagrams. FUNDAMENTAL EQUATIONS In this article are derived the equilibrium relations between the gamma, alpha and cementite phases. In these three phases all important alloying elements except carbon form substitutional solutions, each alloying atom occupying a potential site for an iron atom. Carbon, on the other hand, forms an interstitial solution. In the face-centered cubic gamma phase, the interstitial positions are at the center of the unit cube and at the centers of the cube edges. There are therefore four interstitial positions per unit cell, or one per iron atom. In the body- centered cubic alpha phase, the interstitial positions are probably at the face centers, and also at the centers of the edges, which are crystallographically equivalent to the face centers. There are therefore six interstitial positions per unit cube, or three per iron atom. In cementite, (Fe, Alloy)3C, the carbon atoms may be regarded as filling all the lattice positions of a given type. The introduction of the fundamental equations of equilibrium has presented the author with a quandary. These equations are formally so similar to other equations that have been derived1,2 for related systems that they may appear to some readers

Jan 1, 1946

By D. W. Fuerstenau, P. C. Kapur

The kinetics of green pelletization in a laboratory balling drum have been studied, using pulverized limestone as a model system. The growth characteristics of green pellets were found to be extremely sensitive to the moisture content of the material. Empirical kinetic equations, which incorporate a function of specific surface of the pellets as the criterion for growth potential, have been found to describe growth in a nucleation region and in a ball growth region. The rate constants in the kinetic equations are strongly dependent on the moisture content of the material being pelletized. Size distributions of the balls at different stages of pelletiz-ing are also discussed. In many industrial chemical processes, particulate matter can only be utilized if it is in an agglomerated form, such as pellets. Pelletizing is now widely used in iron ore technology1, and it has also been applied to a number of diverse fields such as the production of cement-kiln feed2, fertilizers3, and fluorspar4. Recently, it has been proposed to pelletize dispersion-type ceramic nuclear fuel elements5. In iron ore technology, for example, the production of agglomerates by pelletizing involves two major steps: 1) the preparation of green balls by rolling particles in a suitable balling device and 2) the firing of the green balls to form compact, strong bodies upon sintering. The critical step in a successful iron ore pelletizing operation is generally considered to be the balling operation1. In this paper, which is not concerned with the sintering of green pellets, the words green pelletizing and balling will be used interchangeably. Green pelletizing, or balling, will be defined as the process of forming larger bodies by rolling fine particles on a surface without the application of direct pressure. Two recent literature surveys6" indicate that in spite of the considerable amount of industrial pelletizing, very little is known about the fundamental principles of balling and its kinetics. The first reported research on the kinetics of pelletizing is the work of Newitt and Conway-Jones8. Using silica sands of different sizes in a batch laboratory balling drum, they found that the average green pellet diameter increased linearly with time at constant drum speed, and qualitatively the growth rate increased with moisture content. Generalized conclusions cannot be drawn from their research since the materials which they pelletized were sand and sand-silt mixtures rather than comminuted materials. Moreover, Newitt and Conway-Jones used testing sieves to estimate the size distribution of the green pellets, and this technique limited the range over which they could study the growth kinetics of the pellets. Bhrany and co-workers9 investigated the kinetics of balling iron ore fines on disk pelletizers ranging in diam from 1 to 18 ft. In their investigation, balling was carried out as a continuous operation, and growth kinetics were studied in terms of retention time of the material on the disk. Although the feed material in their study was quite coarse (the maximum size being about 1/2 in.), they also found qualitative relationships between pellet growth and water content, and feed size. In the present investigation, a number of innovations were introduced that refined the experimental measurements and established the reproducibility of balling experimentation. This enabled extension of the range of measurements to include study of agglomerate nucleation phenomena in the fractional mm size. This paper presents a detailed analysis of the nucleation and growth of green pellets in a laboratory balling drum. MATERIALS AND METHOD Pulverized limestone of specific gravity 2.72 was used as a model system in these studies. It has already been established that the balling characteristics of limestone and silica are similar to those of iron ore concentrates 2,8,10, depending on physical, rather than chemical, properties of the particles. The size distribution of the limestone was determined by a wet-dry sieving technique in the sieve range and by a sedimentation balance in the sub-sieve range. Fig. 1 presents the size distribution of the limestone used in this research. This figure shows that the material is finer than 200p (65 mesh) and that 25% of it is finer than 12. The specific surface area of this powder, as measured by BET gas adsorption methods,

Jan 1, 1964

By J. P. Matoney, E. J. Sandy, D. A. Dahlstorm

INTRODUCTION Before an understandable discussion concerning coal-dewatering processes can be initiated, it is necessary to define some terms of usage. The many different meanings and interpretations of terms preclude development of standard definitions so that the terms which are defined in this chapter should be regarded mainly as working terms intended to facilitate communication. A coal slurry ' might be defined as a watery suspension carrying particles of fine coal and other assorted material ranging upward in size from the finest clay particles. Some particles may be in the colloidal sue range and exhibit characteristics of suspended colloids. The dilution of the system generally is such that it is in a condition of independent particle subsidence. In some coal mining areas a slurry is regarded as a suspension of fine coal and other materials having a dilution that cannot be economically dewatered by filtration. A coal slime may be regarded as a slurry containing particles of such size range that 50 per cent or more (by weight) will pass a 200-mesh sieve. Slime suspensions generally are difficult to handle without special treatment in conventional sedimentation equipment. A coal sludge is defined as a slurry that has been partly dewatered by sedimentation usually to a thick or viscous consistency where further dewatering can be most readily facilitated by filtration. Culm and silt are terms characteristic of coal-preparation practice which should be defined. In anthracite terminology, culm is the generally coarse residue or waste accumulation of coal, bone and rock from preparation plants most of which are no longer functional. Culm has a wide range of sizes, some rather coarse, and except to differentiate it from silt, the term is of limited interest in this discussion. In anthracite terminology, silt is the accumulation of waste fine coal, bone and slate settled out from preparation plant water in excavated basins. Silt is generally made up of particles ranging in size from 3/32-in. round-opening screen to the very finest sues. Silt is also referred to at times as sludge, fines, slush, and mud and is the partly dewatered derivative of what has been previously defined as slurry. In the terminology of the bituminous coal producing areas, the word culm commonly corresponds to slurry or slime, depending upon the size distribution of the suspended solids. Editor's Note: Because of the numerous and varied contributions of the associate authors of this chapter, the text does not differentiate between sections authored by each individual as is the case in most chapters of this book.

Jan 1, 1968

By Thomas Fraser

UP to the present, there has been no large coal-producing industry in any of the South American countries. Since colonial times, the great mineral and agricultural wealth of that continent has led the people to activities other than the development of manufacturing industries based on coal; and climatic conditions are such that there has been very little demand for solid domestic fuel. However, there are extensive and widely distributed reserves of coal in South America that would make the development of a modern coal industry feasible. That factor is of the utmost significance now, when it is believed that the South American countries are entering the pioneer phase of a broad industrial development. Coal Fields Great areas of coal-bearing formations of Cretaceous and Tertiary ages occur generally throughout the Andean uplift and extend into the coastal range of the Caribbean region far east of Caracas. Thus the west coast countries have adequate reserves of coal, which include a wide range of types and classes. In the eastern part of South America, east of the Cordillera, as in North America, the coal measures are of Carboniferous and Permocarboniferous ages. The principal known deposits in this area are in the southern States of Brazil. Permocarboniferous coals ranging in rank from lignitic to anthracitic are found in the States of Rio Grande do Sul, Santa Catarina, Parana and Sao Paulo. In the great.interior plateau of Brazil, south of the Amazon River, are extensive areas of Carboniferous strata that may contain coal deposits. There are widely scattered reports of findings of coal in' wells and stream beds in northern Piaui and Goias. In the Rio Fresco Valley, explorers have observed outcrops of two beds of anthracite and have brought to Rio de Janeiro samples from these beds. The Fresco is a tributary of the Xingu River that enters the Amazon from the south, but coal could not be shipped by water since the Rio Fresco area is in the upper part of the Xingu Valley, and there is a formidable series of rapids between that area and the lower level of the Amazon River basin. It is doubtful if coal deposits in this general area will be of economic importance for many years to come. Fig. 1 shows the general location of known coal fields of South America that have been explored sufficiently to indicate the presence of workable reserves. The coal deposits of the Andean region are similar in occurrence and general characteristics, as well as in age, to the coals of the Rocky Mountain region of North America. Although the coal fields obviously

Jan 1, 1952

By D. Harrington

During the past few years, there has been a trend toward the use of rock-dusting, rather than relying on humidifying, or the use of water, to limit or prevent explosions in the coal mines of the United States. This is partly because British coal mines have adopted rock-dusting and, at least in a sense, have condemned the use of water. Moreover, during the past few years, particularly in the latter part of 1922 and in 1923 and 1924, several explosions with heavy loss of life occurred in coal mines of the United States that were known to have more or less extended sprinkling, or humidifying, systems. The sentiment created by these disasters quickly caused a distrust of explosion-prevention methods requiring use of water and simultaneously caused more or less of a stampede into rock-dusting. Much of the wholesale condemnation of watering methods was without adequate knowledge, or at least without adequate consideration, of local conditions in each case, and rock-dusting was adopted largely without sufficient knowledge of how to rock dust safely or correctly. However, mines that had been using watering methods and had suffered these recent serious disasters (notably Dolomite, Dawson, and Castle Gate) instead of abandoning the use of water when operations were resumed after the disaster, greatly extended their watering systems. At the same time they took other precautions as to electricity, ventilation, blasting, etc., and supplemented the watering system with rock-dusting where the latter was likely to be the more effective. The trend toward rock-dusting during the past year or two (succeeding the recent mine disasters) is very similar to the rapid movement toward watering, or humidifying, methods, about 1910 to 1912, after a series of disastrous mine explosions. The Phelps-Dodge Corpn., which operates a large property at Daw-son, N. M., after an explosion in its No. 1 mine in February, 1923, decided that it is dangerous to have all its "explosion-prevention eggs in one basket" and so adopted what may now be termed the Western coalmine explosion-prevention system, in which both rock-dusting and watering are used, supplemented by other up-to-date mining methods and practices; such as exclusive use of modern electric safety lamps, with magnetically locked flame safety lamps for testing purposes; use of

Jan 1, 1925

By Charles R. Wraith

The property of the Roan Antelope Copper Mines, Ltd., is situated at Luanshya, north central part of Northern Rhodesia, and is connected with the main line of the Rhodesia Railways, Ltd., by a 24-mile branch line from N'dola. Most of the material and supplies that are not available in Africa are shipped into the country via Beira, on the East Coast of Africa, a distance of 1473 miles from Luanshya and the nearest ocean port. The output of copper is shipped by rail to Beira and thence by boat to the market. Passenger travel is mostly via Cape Town, a distance of 2162 miles from Luanshya. Excellent passenger trains operate on regular schedules between Cape Town and Northern Rhodesia. Luanshya is 13" south of the equator at an elevation of 4000 ft. above sea level, and has a mild healthful climate. During the rainy season, from October to March, the rainfall averages 53 in. The area is profusely covered with vegetation. An ample supply of water for industrial and domestic purposes is available throughout the year. The more important supplies for smelting purposcs, such as wood, coal, limestone, silica, quartzite, and clay for "dolly" mud, are conveniently available. Excellent grades of coal, coke and firebrick are obtained from the Wankie Colliery Co., Ltd., Southern Rhodesia. The Wankie colliery has just completed the erection of equipment for the manufacture of silica brick. An ample supply of quartzite of good grade is available for this purpose. Silica brick is also obtained from the Belgian Congo and from India. Limestone is quarried from a large deposit a few miles from Bwana Mkubwa, which is 30 miles by rail from the smelter. An abundant supply of clay for " dolly " mud and for lining launders is available within a short distance of the smelter. Metallurgy Copper is contained in the ore as chalcocite, chalcopyrite and bornite. Chalcocite predominates in the eastern end of the orebody almost to the exclusion of other copper minerals. The amount of chalcocite decreases with a corresponding increase of chalcopyrite and bornite toward the western extension, where the latter predominate.

Jan 1, 1934

By S. R. Titley

The recent emphasis placed upon the use of molybdenum as a geochemical indicator has stimulated considerable inquiry into the behavior of molybdenum in the zone of oxidation. This paper represents a summary of recent and continuing experimental work and calculations in an investigation of a portion of the system Mo-Fe-S-H20 and treats the stability of various iron and molybdenum compounds with respect to oxidation potential and pH. Using experimentally determined free energy values for ferrimolybdite, diagrams of the stability fields of this mineral have been calculated with respect to ilsemannite (?), molybdenite, pyrite and limonite. This theoretical approach is the one utilized by Garrels3'4 in studies of the relationships of various minerals in the zone of oxidation. Use of this approach is particularly suited to the study of geochemistry in the zone of supergene processes because of the low temperatures, low pressures and other relatively easily determined and duplicated factors that exist in the near surface environment. Such a study of molybdenum, however, is complicated by several factors. One of these is the fact that the strong amphoteric behavior of molybdenum makes possible a wide variety of substances and complexes whose exact chemical natures are unknown. The second factor is the dearth of thermodynamic data for many of the simplest of the possible compounds and ions important to the study. For the purpose of this study, the problem of complexes has been approached through considering only the simpler possibilities realizing that the complexes and systems so treated may be gross oversimplifications. All the complexes considered, however, have been suggested in the chemical 2,7,9,12 or geologi-cal literature. EXPERIMENTAL WORK Studies of the behavior of molybdenum ions and ferrimolybdite have been carried out in aqueous sys- tems, and reactions have been followed by simultaneous measurement and recording of pH and oxidation potential. A major problem involved in this study was the long periods of time necessary for equilibrium to be established in some of the systems considered; in a few instances, these periods exceeded four weeks, that is, four weeks during which measured conditions changed continuously. Another problem, in some instances, was the indeterminate nature of the reactions that have taken place. Because of the tendency of molybdenum to complex, reactions which take place under some of the more extreme imposed conditions of oxidation and acidity or alkalinity are unknown. However, useful data for the present work were obtained from studies of the molybdate ion and ferrimolybdite between pH 2 and 8 and under only moderately oxidizing to nonoxidizing conditions. Instruments used in the experiments were a Hewlitt-Packard Model 412A VTVM, a modified Beckman Zeromatic pH Meter and two Varian model 11 recorders. pH was measured between glass and calomel electrodes and Eh was measured between calomel and platinum electrodes. Conditions of pH were varied with 1N H2SO4 and 1N NH4OH and 1N NaOH. Eh was varied with gaseous nitrogen, oxygen or aqueous H202. Ambient temperature was essentially uniform at 24ºC and was increased in the reaction vessel by the positioning of a magnetic stirrer whose temperature was sufficient to bring the temperature to 2S°C in the reaction. The temperatures of reaction did not vary more than 1/2ºfrom 25°C. Two reactions were investigated, the ferrimolybdite-limonite-water reaction and the reduction of molybdate ion. Studies of both reactions yielded useful data that were used in preparation of the Eh-pH diagrams. The traces of the reactions are shown on Fig. 1. Ferrimolybdite-Limonite- Water: Studies of this reaction involved analysis of the solution of ferrimolybdite and simultaneous formation of ferric hydroxide. The data are summarized on Fig. 1. In this reaction, equilibrium was attained at various pH's when coexistence of the two solid phases (ferrimolybdite and ferric hydroxide) was attained. At the proper pH, controlled by the amount of ferrimolybdite and thus the dissolved content of molybdate species, both phases were observed and reaction times to complete the transition were on the order of weeks. The reac-

Jan 1, 1963