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By Orville R. Lyons, A. C. Richardson

THE Coal Division of Battelle Memorial Institute, during the course of an investigation conducted for a coal producer, carried out extensive sampling of the fine-coal section of a preparation plant. The information obtained during the testing period was used to evaluate the overall plant operation and provided the basis for. recommended changes in the plant flowsheet. Included in the information were data for the results obtained when using a Bird centrifuge to dewater the particular coal being treated. At the completion of the investigation, the coal producer gave Battelle permission to publish the operating data for the Bird centrifuge in order to make this information available to the coal industry. The authors wish to take this opportunity to express their appreciation to this company and its officials for their willing cooperation in the matter of publication. Description of Preparation Plant: The preparation plant on which the data were obtained is primarily a jig plant. The coal being washed is a low inherent moisture, friable, Pocahontus-type. The washed coal from the jig is dewatered and sized at 1/4 in. by a Parrish-type dewatering and sizing screen. The minus 1/4-in. coal and the underflow water from the shaker screen flow to a sludge tank where, after the coal settles, the coal is conveyed by a flight conveyor into a pump sump. The pump, a 300-gpm sand pump, delivers a mixture of fine coal and water to a Bird centrifuge which produces a dewatered cake and an effluent. At the time when the investigation was made, the centrifuge effluent was returned to the sludge tank and the cake product was mixed with a coarser size of coal prior to loading into railroad cars. The semiclarified water from the sludge tank overflowed into a pump sump from which it was pumped to the jig. As originally designed, the preparation plant was intended to operate with a closed water system but it was found, soon after operations started, that for various reasons this could not be done. In order to provide for removal of excess water from the system and to aid in maintaining the desired minimum percentage of solids in the circulating water, the plant was operated to provide from the sludge tank a continuous overflow of water and fine solids that was sent to waste. The centrifuge feed represents approximately 35 tons per hour of minus 1/4-in. coal in the form of a pulp averaging 38 pct solids. Sampling Procedure: In order to obtain basic data for determining the relationships existing in the fine-coal section of the preparation plant, samples were obtained for: (1) the centrifuge feed, (2) the centrifuge cake, (3) the centrifuge effluent, and (4) the circulating water. The sampling was arranged to start on a Monday, in order to begin operations with a sludge tank full of fresh water, and was continued long enough to allow sufficient time for fine solids to build up within the water system or for a two-day, four-shift operating period. All samples were taken at half-hour intervals except when plant stoppages occurred. After a stoppage the plant was

Jan 1, 1951

By E. P. McCurdy, W. J. Tait, A. E. Craig

The Circuitron herein described applies current from the classifier motor circuit and energy from the sound of grinding media to move an oscillating disc. The disc through a photoelectric cell controls the speed of the ore feeder and consequently the amount of ore delivered to the mill. THE Telluride Mines, Inc. at Telluride, Colo., is operating a flotation concentrator recovering lead, zinc, and copper with some gold and silver. The nominal capacity is 500 tons per 24 hr. The ore, which comes from several different mines, is characteristic of the district, changing from extremely tough rhodonite to soft gouge. The ore is crushed and washed, recrushed, and delivered to the mill bin at about % in. to serve as ball mill feed. Details of Grinding Circuit The material from the fine-ore bin is carried over a belt feeder driven by a Reeves vari-speed device. The belt discharges to a No. 86 Marcy ball mill, which operates in closed circuit, with jigs and a 6-ft Dorr classifier. A Massco density controller holds the density of the classifier overflow at a predetermined point. The overflow, which contains about 5 pct + 48 mesh, goes to the flotation section. Manual Operation Before the adoption of automatic control for the grinding circuit, this work was all done manually by the operator. The bin gate was set to deliver 40 to 50 lb of ore per lineal foot of belt, and the speed of the belt was adjusted by the operator to deliver at the rate of about 500 tons per 24 hr. As the ore changed in hardness, specific gravity, or in the amount of moisture, or, as the size of the feed changed due to bin segregation, crusher setting, or other causes, the operator made corresponding changes in the rate of feed by manipulation of the Reeves control. Sometimes these changes occurred so rapidly that they caused sharp, pronounced surges, which created very considerable unbalance from normal conditions in the grinding circuit and, more critically, in the flotation section. Since it is not possible for the operator to anticipate or follow such changes closely, a very considerable unbalance from normal conditions may occur, which will require a drastic change in the rate of feed. These surges upset the fineness of grind and interfere radically with the balance between tonnage and reagent control. All of this tends to reduce the grade of concentrates, increase the loss in the tailing, and thus decrease the recovery of values. The Circuitron Some years ago, The Mine and Smelter Supply Co., in conjunction with the operators at the Telluride Mill, undertook to build a device that would give close control of the rate of feed from the ore bin and to coordinate with this a related device that would regulate the amount of sand load on the classifier rakes. Emphasis was strongly laid on the fact that such a control must apply to the entire grinding circuit and must include the feed to the ball mill, the classifier sand return, and the density of the classifier overflow. If this could be done successfully, we felt that the circuit could be operated under best possible conditions, with compensations

Jan 1, 1951

By J. F. Myers, F. M. Lewis

The paper reports the development of a large, slow speed ball mill closed circuited with a hvdro-scillator. This increased grinding efficiency 28 pct over conventional units. AS the title indicates, this is a progress report for the first year of experimental operation of a relatively large diameter, slow speed ball mill with 1-in. balls, with and without various classifiers, and including a hydroscillator. Several years ago the authors came to the conclusion that if any further progress were to be made in our flotation process, an understanding of the chemical and physical reactions and the control thereof, in the grinding circuit, was essential. It may be stated, at this point, that the preparation of a correct feed for the flotation process is still the number one objective of our grinding studies. This progress report deals with grinding "per se," and not with the chemical and physical reactions as the result of grinding. Prior to this time we had taken the naive position, that since grinding had been practiced by the industry for some fifty years or more, it had been well exploited and developed by a host of investigators. Consequently, we had given the matter only superficial attention. At the start of our study, we were aware of the fact that some difference in opinion existed, but we were not prepared for the controversial evidence that developed nor for the extent to which the experts differed in their viewpoints. There seemed nothing else to do but to tour the continent and decide for ourselves what was right and what was wrong, read all the published literature and visit with anyone who had ideas about the matter. This we did over the next few ensuing years. Since our study has met with some measure of success, we report, herewith, these data that ultimately they may be of help to other investigators. In 1944 it became necessary to increase our grinding capacity and at the same time to grind the sulphide portion a little finer. This provided the impetus to put our ideas into effect. As has been previously described, our grinding flowsheet at that time consisted of a 6x12 rod mill, followed by two 5x10 ft, and one 6x12 ft trunnion overflow ball mills, with conventional rake classifiers. Naturally, we first considered all the possibilities of altering or adding to the existing equipment. It became evident that if any appreciable increase in grinding efficiency could be obtained, it would pay to scrap the existing small mills and classifiers and install one big mill with adequate classification. Trying to determine just how much more efficient a big mill could be, in which were incorporated all

Jan 1, 1951

THE primary interest in the subject of this chapter lies in the fact that various heats of steel made to the same chemical specification do not always-have the same properties. The properties considered here, of course, are those inherent in the ingot immediately after solidification and not qualities imparted by variations in subsequent mechanical or thermal treatment. The expression "made to the same chemical specification" is used because some of the variations in properties are due to variations in chemical analysis within the specified ranges of those elements commonly specified and determined. Other variations in properties are due to variations in those constituents of steel (elements or compounds) that are not ordinarily included among the elements specified, thus not a part of the specified "composition." The term "constitution" is used to include not only the specified composition but also the nature and distribution of every element or compound contained in the steel entering the ingot mold; also included are items such as aluminum oxides and nitrides, presence of soluble gases, and dispersion of nonmetallic particles. When it is considered that the constitution of steel is determined by the addition or absorption into the bath of all such constituents from whatever source, it follows that constitution is of necessity the final result of steelmaking practice. It is the agency through which steelmaking practice operates to control the properties of the steel. The term steelmaking practice is here used in the broad sense, meaning the control of all the materials entering the steel and of the conditions under which the process is carried out. Steelmaking practice, thus defined, establishes the chemical system within which the reactions between components must proceed in obedience to the laws of chemistry. Thus the chemical constitution of the steel is established and, through constitution, the properties of the metal are established. In the preceding chapters it has been shown how the constitu-

Jan 1, 1951

By C. W. Sherman, J. Chipman, H. I. Elvander

THE pronounced and usually deleterious effects of sulphur on all ferrous metals and the resultant necessity for its control in metallurgical processes have stimulated many investigations of the system iron-sulphur. The data required for thermodynamic study of the behavior of sulphur in molten iron and steel include the activity and free energy of the dissolved sulphur and its heat of solution. Such data are also of theoretical interest since there is all too little information available concerning solutions of nonmetallic solutes in metallic solvents. It was the purpose of this investigation to attack the problem very directly by a study of equilibrium at several temperatures in the reaction H2 (gas) + S = H2S (gas) [1] K1 = PH2S /PH2 as where the sulphur is present in the liquid iron in amounts up to several percent by weight. Such a method of attack is not new since several careful studies have already been reported. It is planned, however, to extend the study to other metallic solvents and particularly to determine the effects of the various alloying elements on the activity of sulphur in liquid iron. This paper presents the results on molten iron-sulphur alloys containing up to 4 pct sulphur in the temperature range 1530°-1730°C. Literature Review The significant researches on dilute molten solutions of sulphur in iron include those of Chipman

Jan 1, 1951

By H. H. Kellogg

Equations representing the standard free energy of formation as a function of temperature, for thirty metallic chlorides, are presented and plotted on a free-energy vs. temperature diagram. The use of these data for calculations on reduction of metallic chlorides, refining of metals with chlorine, and chlorination of metallic oxides and sulphides is illustrated. CHLORINE metallurgy' has attracted metallur- gists for more than a century because the unusual properties of the metallic chlorides—low melting point, high volatility, and ease of formation from the oxides—make possible many useful extractive processes. Interest in chlorine processes is undergoing a renaissance due to present availability of chlorine at relatively low prices, and to recent advances in technology. During the present century there have accumulated a considerable number of reliable values of the thermodynamic constants for the metals and their chlorides. These data permit the calculation of free-energy equations for many metallurgically important reactions. Consideration of free-energy values makes possible certain predictions of the direction and extent of a given reaction, as well as the effect of temperature, pressure, and composition upon the result. Reaction rate, although not predictable from free-energy data, is usually sufficiently great at elevated temperatures that diffusion of the reactants and products to and from the zone of reaction determines the actual rate. Thus, if the free-energy indication is favorable, the chances are good that a high temperature metallurgical reaction will proceed at a reasonable rate, if adequate provision for rapid diffusion has been made. This paper presents standard free-energy equations for a number of metallic chlorides, based on data which are scattered throughout the literature. The equations are presented in a form that simplifies their use, and typical examples are given of the application of free-energy data to metallurgical processes. Free Energy of Reaction The free-energy change (AG) of a reaction is the true measure of the "driving force" of the reaction under a given set of conditions, and this is related to the standard free-energy change (AGO) of the reaction as follows: For the reaction: bB + cC = dD + eE ?G = ?G°+RTln ADd. AEA / ABb. ACc where A, = activity of constituent (i) T = absolute temperature, OK R = gas constant The criterion of a spontaneous reaction from left to right, at constant temperature and pressure, is a negative value for the free-energy change (?G). The standard free energy of the reaction is equal to the free energy of the reaction when all the reactants and products are at unit activity, since under these conditions the second term on the right-hand side of eq 1 is equal to zero. The concept of activity is treated fully in many textbooks on chemical thermodynamics1 and in a recent article by Chipman.2 Briefly, the activity (A,) of a constituent (i) is a measure of the reactivity of this constituent relative to its reactivity in some arbitrary standard state. For liquids and solids the standard state most often used is the pure liquid or solid constituent. Thus the activity of a pure liquid or solid in a metallurgical reaction is equal to unity. Gases under moderate pressure and at elevated temperatures behave very nearly as 'idea1 gases,' and the standard state is chosen as the gas at 1 atm pressure. The activity of an ideal gas is therefore equal to its partial pressure, and this relation is sufficiently exact for real gases in most metallurgical reactions. For a liquid or solid solution there is in general no simple way to express the activity of a constituent as a function of its concentration, and activity must be determined by experiment. A few solutions follow a so-called 'ideal' behavior, and if the pure constituent is chosen as the standard state, the activity of a constituent in an ideal solution becomes equal to its mol fraction. When a reaction reaches a state of thermodynamic equilibrium at constant temperature and pressure, AG becomes equal to zero and eq 1 reduces to: [ADd . AEe ?G°=RTln Abb ¦ Ac c equilibrium [2] The brackets surrounding the activity term are used to emphasize that each of the activities is an activity under equilibrium conditions—not just any arbitrarily assigned value. The bracketed term is the equilibrium constant (K) of the reaction. Eq 2 makes possible the calculation of equilibrium activities for a given reaction, if AGO is known at the desired temperature. The standard free-energy equations presented in this paper were calculated from the fundamental thermodynamic values of enthalpy of formation at 298°K (AH°,), standard entropy at 298°K (So298), heat capacity as a function of temperature (Cp), and enthalpies of transition, fusion, vaporization, and sublimation for the various constituents. Where possible the data reported in the recent "Selected Values of Chemical Thermodynamic Properties," published by the Bureau of Standards," were used. A large number of data came from the publications

Jan 1, 1951

Jan 1, 1951

By R. L. Slobod, B. H. Caudle, E. R. Brownscombe

An earlier publication has discussed three methods lor obtaining relative permeability data on small core sample-: and the apparatus and technique for the capillary pressure displacement method. This paper describes the apparatus and technique for the solution gas and the dynamic displacement methods and presents a routine procedure for obtaining oil-gas and water-oil relative permeability data. Theoretical and experimental considerations are presented to show that the end effect commonly associated with the dynamic flow mechanism is extremely small where constant rates are employed in the flowing phase. An effect of flow rate on relative permeabilities obtained by the dynamic system is found only when gas is one of the flowing phases and this effect is ascribed to a form of channeling in the capillary system. The apparatus and procedure* used to obtain relative permeability data with three phases flowing are described and some preliminary results of the use of this method are shown. INTRODUCTION In a previous publication from this laboratory there appeared a brief discussion of the concepts behind three basic methods for obtaining relative permeability data.' These three methods were called the capillary pressure displacement method. the solution gas displacement method, and the dy. namic displacement method — the names being suggestive of the type of process used for obtaining the desired saturation prior to making the permeability measurements. In the same publication, the apparatus and technique for the capillary pressure displacement method were described and some typical results obtained by this method were presented. This paper will present: 1. The routine procedure used to obtain complete relative permeabilitv data (In small core samples with two phasec flowing; 2. The experimental techniques for the solution gas and dynamic displacement methods for obtaining relative permeability data; 3. The results of some studies on the mechanism of fluid flow through consolidated porous media; and, 4. The preliminary results on the determination of relative permeability for a system in which three phases are flowing. TECHNIQUE AND APPARATUS FOR THE DETERMINATION OF RELATIVE PERMEABILITY WITH TWO PHASES FLOWING In order to obtain relative permeability data on a small core sample which will describe the various phases of reservoir depletion. it is necessary that the methods used duplicate, as closely as possible, the various mechanisms involved in rescbrvoir depletion. It is important that. in any type of relative permedbility determination. the core be originally at virgin reservoir conditions with respect to the fluids within the pore *paces. (for example. oil used to displace water from core until connate water saturation estahlished). and that the subsequent saturation changes in the core be analagous to tile reservoir depletion mechanism for which the data are to he used. PROCEDURE OF DETERMINING RELATIVE PERMEABILITY DATA WITH TWO PHASES FLOWING A standardized procedure has been set up for obtaining relative permeability data and other information on small core samples. This procedure essentially consists of 11 steps as shown below: 1. Determination of tile capillary pressure curve.'! This information is used to help select samples for relative permeability determinations and to charactrrize. in general. the pore size distribution of the sample. 2. Determination of the specific permeabilities to air, oil. and water. These values are those on which the relative pern~eahility calculations are based. 3. Reduction of the core to connate water by an oil drive using the high speed centrifuge. 1. Determination of the critical gas saturation value and the associated relative permeability to oil by the solution gas drive method. 5. Determination of the relative permeabilities to oil and gab in the region where both phases are flowing by the capillary presqure method. 6. Reduction of the sample to residual oil in the centrifuge by an air drive. and the determination of the relative permeability to gas at this point.

Jan 1, 1951

Jan 1, 1951

By Rudolph G. Wuerker

THE Krupp-Renn Process,[1] has been successfully used to treat low-grade iron ores, laterites, titaniferous sands, and other minerals, and before World War I1 25 units were built by the Krupp-Grusonwerk, Magdeburg, Germany. J. J. Howard[2] has shown theoretical advantages of the pyro-metallurgical treatment over conventional approaches; and the process was described by R. Durrer[3].

Jan 1, 1951

By Elmer R. Kaiser

Industry Adopts Research: Seventy-Ave years ago Thomas A. Edison began in a modest way and with limited funds to gather about him men of various talents to form the first industrial research laboratory. His laboratory at Menlo Park, N. J., became famous for many discoveries and inventions, but possibly the most important of all may yet be the industrial research laboratory itself. Today, private industry operates 2500 research laboratories in which 135,000 persons' are directly and indirectly creating new processes and products and improving old ones, as well as developing new information to help keep the fountain of knowledge from running dry. In this change-making function, the scientific personnel comprises 41 pct; the technical personnel 26 pct; and the balance, 33 pct, nontechnical. The term "industrial research" has become so broad as to include almost everything beginning with the search for and discovery of the laws governing the properties of matter and energy to the development and testing of processes, methods, and equipment. These classes of investigation commonly merge so that no sharp boundary can be traced between them. The National Research Council therefore defines industrial research as "the endeavor to learn how to apply scientific facts to the service of mankind."' Currently, expenditures for research by industry are variously estimated at between $450,000,000 to $700,000,000 a year,' or about twice the expenditure for 1940. The President's Scientific Research Board" estimated that the national research and development for 1947 (excluding atomic energy) was as follows: A few companies spend as much as 5 pct of their gross receipts for research, but 1% to 2 pct is considered a good proportion by many." Shortages: Commendable as is the record of growth and accomplishment of science in industry, it is only a beginning. America and the rest of the world have merely sampled the fruits of industrial research; most industries have yet to make research the key to their future. A top research consultant, T. A. Boyd, of General Motors, states ". . . perhaps 90 per cent of all companies still have no research laboratories."Y or example, of more than 17,000 manufacturing concerns whose gross sales exceed $500,000 a year, less than 2500 have research laboratories. A still smaller proportion of the 184,230 manufacturing establishments in 161 industriese have or could afford their own research facilities. Yet, the small and mediurn-sized com,panies with less than 250 employees each, produce one half of the dollar volume of manufactured products.' How are these companies to participate in and share the benefits of research? Boyd gives two reasons for the inadequate number of laboratories in industry: Many people still do not appreciate the importance of research, nor understand its tremendous potentiali-

Jan 1, 1951

By B. T. Wykoff

This paper describes an important function of mining in Southeast Missouri. The practice is a necessary procedure to prevent disintegration of the pillars. Although the technique is peculiar to this district, it might have application in other mines using room and pillar method. CONSIDERING the subject alone, this paper would cover only a mechanical treatise of pillar roping. Because the St. Joseph Lead Co. originated the practice, it is proper to give a short introduction to the company. It is also proper to describe pillars and discuss their purpose to justify expending large sums of money to preserve them after the surrounding area has been thoroughly mined. Because the St. Joseph Lead Co. originated the practice of back pinning with wedge bolts, patch plates and channel irons, and the pouring of substitute pillars of concrete, these too, are mentioned. The Southeast Missouri Division of the St. Joseph Lead Co. is the largest lead producer in the United States. About 95 pct of the present producing mines are in St. Francois County, which begins 60 miles south of St. Louis. The entire lead ore production of this county, at the present time, is mined and milled by this company, treatment plant capacity being about 22,000 tons per day. This area is also the oldest, lead having been mined at Mine La Motte, in Madison County, in 1723. Estimated production of all the various companies that have mined here is about 7,000,000 short tons of pig lead. Method of Mining The lead occurs in the ore as galena. Galena is found either in the form of disseminated or solid streaks, of varying thickness. Ore stratum is the Bonne Terre dolomite, which is about 350 ft thick, but almost all the ore is in the lower 100 ft. Ore is mined by room and pillar method in open stopes. These stopes vary in height from 7 ft to 200 ft, depending on the thickness of the pay ore in that spot. Back, or roof, is supported entirely by pillars. In a majority of stopes, after the loose scales are mined down, the back has remained solid for many years (fig. 1). Under ideal conditions pillars are spaced to form an equilateral triangle and are as small and as far apart as the height of the stope and the character of the back will permit. They vary in diameter from 10 ft to 50 ft and are from 18 ft to 50 ft apart, measured from the outer edges. In general, the pillars are approximately 12 ft in diameter, and 25 ft apart. The spacing is very uncertain because of the vagaries of the ore trend, the desire to better support breaks in the back, and the attempt to spot out the thinner ore by not placing one in the core of the ore body. Use of Structural Steel Channels In stopes where the back is bad because the overlying formations are thin with wet, weak and shaly

Jan 1, 1951

By J. L. Lamon, W. Crafts

Study with the electron microscope of the carbides in vanadium-chromium-molybdenum steels after tempering up to 1000 hr at 600 teelsto 1400°F confirmed that alloy carbides are formed at the secondary hardening temperature by decomposition of the plate-like iron carbides. It was also demonstrated that vanadium carbide persists as much smaller particles than do chromium- or molybdenum-bearing carbides. Conditions conducive to the formation of fine vanadium carbides are indicated to be favorable for high temperature strength. IN order to determine the effects of long exposure at high temperatures on vanadium-bearing steels, a survey has been made of their hardness and carbide structure. The behavior of carbides in the tempering of martensite was studied by X ray diffraction and electron microscope examination of electrolytically extracted residues in greater detail than in an earlier investigation.' A group of steels with about 0.25 pct carbon and containing chromium up to 5 pct, molybdenum up to 1 pct, and vanadium up to 1 pct was either quenched or annealed and then tempered for peri- ods of up to 1000 hr at 600° to 1400°F. Their hardness after tempering agreed with the Hollomon and Jaffe2 relation of equivalency of time and temperature, and with the degree of secondary hardening predicted from composition. Further, the appearance of the carbides indicated that the time and temperature equivalency relation was also applicable to the degree of carbide development. The mechanism of the tempering of martensite was demonstrated more clearly than in the earlier study. It was confirmed that carbides develop from martensite as poorly defined plates of the Fe2C type carbide followed by thickening of the plates with a transition to Fe,C. Finally the plate structure deteriorates into a lacy mass from which alloy carbides emerge as chunky particles that grow slowly with further increase of tempering temperature. Vanadium carbide derived from tempered martensite was found in characteristically small particles that tended to grow very slowly. The addition of chromium or molybdenum to a steel with predominant vanadium carbide tended to introduce carbides of a chromium- or molybdenum-bearing type having a somewhat larger particle size. The Cr,C, type carbide particles were larger than those of the V,C, type and somewhat smaller than the carbides in steel containing both Cr,C and M,C. Similar observations were made of the carbides in the pear lite of annealed steels. It appeared that high temperature properties would be benefited by the retention of the fine carbide particles that result from a balance of composition and heat-treatment designed to produce a maximum amount of vanadium carbide. Procedure: The steels used in the investigation were made with a base of Armco iron in a high-frequency furnace at the Union Carbide and Carbon Research Labs., Inc. The steels were deoxidized

Jan 1, 1951

By R. F. Mehl, W. Batz, C. Wells

Diffusion coefficient values for carbon in austenite covering a wide range of temperature and composition have been determined employing statistical methods. In addition, the relation between concentration and each of the following, D (diffusion coefficient), Q (activation heat of diffusion), and A (the constant in the diffusion equation), has been obtained. A study of the rates of diffusion of austenite was published in Metals Technology in 1940.' The present investigation is an extension of the earlier work, undertaken (1) to obtain values of the coefficient of diffusion, D, over a much wider range of carbon concentration, and (2) to provide data in all ranges of concentration and temperature in such abundance that statistical methods could be employed to evaluate the accuracy of the data with unusual precision. Composition of Materials: Composition of materials used in this research program are listed in table I. These materials, all forged to about 1 1/4 in. rounds, consist of a high-purity iron, Armco iron, a large number of laboratory-made plain carbon steels containing amounts of impurities normally expected in high-quality commercial steels, and three silicon steels. Since it was known at the time these steels were being made that impurities in the amounts present were unlikely to affect carbon diffusion rates' significantly, the effort made to obtain high-purity steels was not as persistent as it otherwise would have been. Procedure: In general, the procedure followed by Wells and Mehl and described' in detail in an earlier publication' is the one used by the present authors. However, certain modifications have been made which it is believed allow diffusion data to be interpreted more objectively and correctly. These are described completely under appropriate subheadings which follow. Experimental Procedure: Experimental procedure includes (1) the preparation of specimens by welding steels of different carbon contents, (2) the heating of these for certain times at selected temperatures in order to diffuse carbon along the specimens across the welded "interface," and (3) the determination of the carbon distribution across the diffusion zone. Preparation of Specimens: Prior to welding steel of one carbon content to iron or steel of another carbon content, surfaces to be welded are machined perpendicular to the longitudinal axis of cylinders which are about 3/4 in. in diam and 1 1/2 in. long. The prepared, flat, parallel surfaces are brought together and butt-welded electrically. Evidence of a good weld is given in fig. 1. Welding temperature

Jan 1, 1951

By S. R. Zimmerley, S. F. Ravitz

High-grade cobalt concentrates were produced from the complex Blackbird ore with very good recovery in continuous pilot-plant operations in which a low-grade bulk cobaltite-pyrite flotation concentrate was roasted in a multiple-hearth furnace to oxidize the pyrite selectively. The cobaltite was floated from the resulting calcine. THE existence of the cobalt-copper deposits in the Blackbird district, Lemhi County, Idaho, has been known for many years. However, these deposits have not yet been exploited successfully because of the low grade of the ore, absence of information on ore reserves, and lack of feasible methods for concentrating and recovering cobalt from the ore. In 1941, when it appeared that World War II might interfere seriously with imports of cobalt from overseas, the U. S. Bureau of Mines started an extensive mining and metallurgical investigation of the Blackbird deposits. Exploration by trenching and drilling1 indicated that ore reserves were adequate to warrant consideration of large-scale exploitation. A process for producing high-grade cobalt concentrates from the ore was developed at the Salt Lake City Station of the Bureau,2 and hydrometallurgical procedures for producing cobalt metal or oxide from the concentrates were developed at the Boulder City Station.3 The Howe Sound Co., through a subsidiary, the Calera Mining Co., carried out further exploratory work, which increased probable ore reserves to a tonnage commensurate with a large investment in mine, mill, transportation facilities, and refinery. Simultaneously, the metallurgical staff of the company, working in cooperation with the Bureau of Mines, further investigated the metallurgical problems. It was the opinion of both groups that pilot-plant testing was required to translate laboratory results into plant operation. In general, the Blackbird ore has a high content of pyrite and some pyrrhotite and contains 0.5 to 1 pet cobalt and 1 to 2 pet copper, which are present essentially as cobaltite and chalcopyrite. The copper can be recovered readily as a high-grade concentrate by selective notation. The cobalt then can be recovered as a bulk sulphide concentrate assaying 4 to 5 pct cobalt, but no satisfactory procedure for separating the cobalt from the pyrite and pyrrhotite directly by flotation had been found. The method developed by the Bureau for producing a high-grade cobalt concentrate is essentially an application of the old Horwood process of selective roasting.4 The bulk sulphide concentrate is roasted to form an oxide coating on the iron mineral particles, and the calcine is then treated by flotation. The oxide coating prevents the iron minerals from floating so that it is possible to obtain a high recovery of cobalt in concentrates assaying more than 20 pct cobalt. Laboratory tests by metallurgists of both the Bureau and the Howe Sound Co. had indicated the optimum roasting temperature to be 425° to 450°C. At lower temperatures the rate of oxidation of the iron minerals is too low, whereas at higher temperatures substantial quantities of cobalt are rendered water-soluble. Because of its high sulphur content (35 to 40 pct), the bulk concentrate tends to continue to burn after it has reached the optimum roasting temperature. Although excessive temperatures could be avoided in the small-scale laboratory furnaces, there was considerable doubt that the temperature could be controlled properly in industrial equipment. To provide material for the pilot-plant tests, the Calera Mining Co. installed a small, temporary flotation mill at the Blackbird property and treated

Jan 1, 1951

By Brahm Prakash, R. Schuhmann

Chemical conditions for flotation and nonflotation of quartz with oleic acid as collector and barium, calcium, aluminum, iron, and tin as activators were studied using a simple vacuum-flotation technique in glass-stoppered graduates. The detailed study of barium activation led to an interpretation based on ideal Langmuirian chemi-sorption. FLOTATION of quartz is of practical importance as something to be avoided in soap-floating many types of ores. Clean, unactivated quartz is not floated with fatty acids and soaps, such as oleic acid and sodium oleate, in the quantities normally used for flotation. However, data in the literature indicate that almost any multivalent cation will activate quartz if given an opportunity. Thus, a common problem is to prevent activation of quartz by the various inorganic cations inevitably present in flotation pulps. Wark and his coworkers1 have demonstrated the reversibility of the chemical reactions and adsorptions involved in the activation, depression, and collection of the common sulphide minerals. The procedure in much of their work was to bring a mineral surface to equilibrium with solutions of known pH, collector concentration, and activator concentration, and then to test the floatability of the mineral by contact-angle measurement. From the data, graphs were constructed with pH and reagent concentrations as coordinates. These graphs show fields of flotation and fields of nonflotation, separated by narrow transition regions whose locations are shown by so-called contact curves. From the shapes and locations of the contact curves, which roughly separate fields of flotation from fields of nonflotation, a quantitative understanding of the interaction of the reagents with each other and with the minerals often can be deduced. The study of quartz flotation to be described in this paper follows in broad lines the approach of Wark and coworkers. That is, pH, activator concentration, and collector concentration were varied to find equilibrium conditions of flotation and non- flotation, and the results are presented graphically by means of contact curves. However, instead of testing for floatability by measuring the contact angle on a polished surface, a simple vacuum flotation technique was developed and used. Purified oleic acid was the collector and terpineol the frother. Barium activation was studied in some detail, and exploratory studies were made of activation with calcium, aluminum, ferric iron, and stannic tin. Preparation of Materials Quartz: Large lumps of high-grade vein quartz were crushed dry in a cone crusher and rolls. The —20, +28-mesh portion was screened out and used in the subsequent steps. This material was passed through a high-intensity magnetic separator to discard iron, then leached twice with hot concentrated HCl and washed repeatedly with distilled water. The cleaned sand was then wet ground with porcelain balls in a porcelain pebble mill, deslimed repeatedly by settling and decantation to discard —800-mesh material, and again washed with hot HCl followed by distilled water. The resulting stock of quartz was stored under water. Chemical analysis gave 99.8 pct SiO2. Table I gives the size analysis of the quartz used for flotation tests. Calculations from these data, using shape factors given by Gaudin and Hukki9 indicate a specific surface of about 500 cm2 per g. Blank flotation tests in distilled water, and in water with added frother, showed the prepared quartz to be completely nonfloatable and thus indicated the absence of organic contamination. Oleic Acid: The preparation of oleic acid was based on fractional vacuum distillation of methyl oleate2,3 followed by regeneration of oleic acid, and finally fractional crystallization of oleic acid from acetone solutions at low temperatures." The pure oleic acid was stored in a refrigerator. The iodine number of the oleic acid was found to be 90.0 (theoretical 89.93). Oleic acid was used in the form of a dilute water solution of sodium oleate, after preliminary flotation tests showed no effects of form of addition and order of addition of reagents when an adequate conditioning time (that is, 30 min) was provided. Other Reagents: Sodium hydroxide solutions low in carbonate were prepared by first making 1:1

Jan 1, 1951

By R. C. Buehl, J. P. Morris

ACTIVITY values for sulphur dissolved in liquid iron and slags as functions of composition and temperature are needed in applying thermodynamics to sulphur-control problems in iron- and ' steel-making. The purpose of this investigation was to determine the effect of carbon on the activity of sulphur in the metal phase. The method employed was the same as that used in an earlier investigation' concerning the effect of silicon on sulphur activity in liquid iron. A study was made of the conditions of equilibrium in the reaction between hydrogen gas and sulphur dissolved in iron-carbon alloys. The chemical equation for this reaction can be written as follows: S (in liquid Fe-C alloy) + H2 (gas) = H2S (gas). It was found that the activity coefficient of sulphur in liquid iron increases as the carbon content increases. At 2.3 pct carbon and 1600 °C, the activity coefficient of sulphur is twice its value in carbon-free iron, and at carbon saturation it is more than six times as great. The effect of temperature on sulphur activity was found to be small. Previous work on the reaction between hydrogen gas and sulphur dissolved in liquid iron has been reported by several investigators2,³,4 but only recently have studies been made of the effect of alloying elements. Silicon1 is known to have a pronounced influence on the activity of sulphur in iron, its effect being similar to that shown by carbon as described in the present report. Kitchener, Bockris, and Liber-man5 recently have published a preliminary report of their work on the effect of carbon on sulphur activity in iron. Their experiments were made at 1570°C and carbon saturation in the melt. Under these conditions they found that the activity coefficient of sulphur was approximately doubled by the presence of carbon. This is a much smaller effect than that found in the present work. Experimental Method: The apparatus and procedure were essentially the same as those used in the earlier investigation of the effect of silicon on sulphur activity.' Briefly, the method was as follows: A molten iron-carbon alloy was brought to equilibrium at constant temperature with a mixture of H2 and H2S of constant composition by bubbling the gas through the metal. Samples of the melt were

Jan 1, 1951

THE problem of reaction rates in the open-hearth process is essentially that of trying to form a fairly clear picture of the "chemical mechanisms" in the bath. Quantitative data on reaction rates would perhaps not be of much practical importance even if they were available; however, what few approximate data there are can be used in combination with data given in Chapters 16 and 17 to sketch a picture of the "chemical mechanics" of the open-hearth process that is consistent with essentially all the present available evidence. The result may later be found incorrect in many details but even so it will illustrate certain useful methods for obtaining a clearer understanding of the process. Consistent with the treatment in Chapter 15, but in simpler terms, we may say that chemical reactions in general involve the following elements or steps: 1. The reacting molecules are mixed together in space in such fashion as to favor collisions among them. 2. Units of what is usually an intermediate molecular arrangement called an activated complex are formed at a certain rate, depending on temperature and concentrations. 3. These activated complex units decompose into the reaction products (this step usually assumed to be so rapid as never to limit the over-all process). 4. In any of these steps, heat energy may have to flow into, or away from, the reaction zone to permit the reaction to proceed. 5. The products of reaction will usually have to move out of the way to permit further reaction. The temperature factor enters mainly through step 2, and its effect is very marked. (What is called temperature is really the mean energy content of all the molecules of the substance involved; at any one temperature a certain proportion of the moleculea will have much higher energy content than the mean value.) Various reaction rates measured at around room tem-

Jan 1, 1951

By L. E. Shiffman

W. J. Parton—Those operators faced with the problem of treating fine coal whether in bituminous or anthracite will find this paper most timely. I would like to take this opportunity of discussing Mr. Schiffman's paper and at the same time express certain views relating to our Tamaqua plant. I would like to ask the author what type of impeller and diffuser is used in the Denver cells? Screen analysis of products from individual cells indicate that coarser material resists flotation and only floats after greater retention time in the last few cells. Also, the need for a scavenger screen to reclaim non-floated coal particles further stresses this point. I have always felt that more efficient means of cleaning coal between 10-mesh and 28-mesh existed than flotation. Reagent and power costs are high for the flotation process. When floating +28-mesh particles, cell capacity is lowered and some of the particles are lost with the refuse. The Tamaqua plant of the Lehigh Navigation Coal Co. floats —28-mesh coal and capacity of recoverable coal is 40 tph for 1800 cu ft of Denver cells; or 0.05 tons per cu ft of cell. At Kimberly 7.75 tph for 600 cu ft of cell gives 0.013 ton per cu ft of cell. At Bessie 14 tph for 800 cu ft of cell gives 0.017 tons per cu ft of cell. It would be appreciated if the author would comment on what he feels is the upper size limit of particle to attain most efficient utilization of the flotation process. The dewatering screw is a very interesting development since it offers a simple way to prepare coal sludge for more complete clewatering by drainage or mechanical dewatering on screen or filters. In other words it could be used to accomplish the same thing as a thickener tank. I would appreciate having the author's comment on how he thinks such a screw dewaterer would work on a froth.* The process as used in floating coal at the Bessie and Kimberly plants may be referred to as more of a bulk oil float in contrast to a froth flotation process. Experiments on increasing capacity of cells is most interesting since we are going through such an experi- mental period at the present time. Recently a double overflow was installed on our No. 30 Denver cells. So far results are not conclusive. In reviewing this paper the following comments are made pertaining to investigation of methods for increasing capacity: Supercharging: Supercharged air in matte flotation or for that matter the use of the normal amount of air drawn in by the impeller would in all probability cause such an aeration in the cell as to destroy the buoyant effect given to the coal particles by the excessive amount of kerosine used. In other words, air creates an agitation zone throughout the cell, creating a boiling and thereby giving a lower recovery in the cell. It would be interesting to know whether the 7 pct increase in recovery was with no air being admitted to the stand pipe. Changing Impeller Speed: The speed of a receded disc impeller for a No. 30 cell as recommended by the Denver Equipment Co. is, I believe, approximately 250 rpm. At this speed and using supercharged air in excess of 8-oz pressure, we have observed a boiling action in the cells. In our flotation we endeavor to obtain some degree of froth flotation using pine oil as a frother. The boiling action as caused by increasing the amount of air added to the cells is detrimental to recovery in froth flotation. It is our belief that to obtain increased recovery from a cell in froth flotation, additional air must be introduced but at the same time this air must be dispersed throughout the pulp in the form of small bubbles and this can only be done by increasing the speed of the impeller. Therefore, if Mr. Schiffman decreased the speed of the No. 30 impellers and at the same time continued to use supercharged air, the boiling action may have been increased because larger bubbles developed. The lower recovery as reported could be due to this factor. Decreasing the impeller speed will definitely decrease the power consumed but may have other disadvantages. First, we believe it will permit "sanding" in the cell and this in our opinion will increase the wear on the impeller and diffuser, especially so, if there is pyrite and/or sand present in the feed. "Sanding" in the cell when air is used, as in froth flotation, will effect the dispersion of this air and cause boiling.

Jan 1, 1951

By R. A. Morse, C. R. Holmgren

The production of oil by water flooding can be substantially increased by the maintenance of free gas saturation in the reservoir during the flooding operation. This effect is accomplished by the alteration of oil relative permeability characteristics and the occupation by gas of pore space that would otherwise be filled with residual oil. The amount of reduction In residual oil can be calculated from appropriate water-oil relative permeability characteristics. This paper presents experimental data in support of the foregoing conclusions and an example of the calculations. The microscopic pore saturation concepts of the mechanism are discussed. A method of practical application to field floods is presented together with discussion of certain limitations. INTRODUCTION The presence of free gas has been reported by a number of investigators to significantly affect the oil recovery which can be obtained from sandstone flow systems by water flooding.1,2,3,4,5 The effect of gas, noted in every instance, has been to cause lower residual oil saturations than could be obtained by water flooding the same systems in the absence of free gas. The degree of improvement in recovery has been observed to vary widely, depending on the systems used and the conditions of the tests. The increased oil recovery obtained because of the presence of gas during a water flood has been variously attributed to changes in physical characteristics of the oil, selective plugging action of the gas, inclusion of oil mist in the free gas phase, and the additional sweeping or driving action of the free gas. All but the first of these suggestions imply changes in the displacement mechanism. The change in viscosity and inter-facial tension of the oil phase, within the pressure range used for all the experimental work, is certainly not sufficient to account for the differences in residual oil saturation noted dess there is a drastic change in the displacement process. One other effect which logically seems capable of causing differences in residual oil saturation of the magnitude noted in the experimental work is that of simple replacement. In a water-wet system containing oil, water, and gas, it is to be expected that the gas will exist inside the oil. This is the position of minimum free surface energy, since the gas-oil interfacial tension will be less than the gas-water interfacial tension. There is no apparent reason to expect that the existence of free gas within the oil phase should alter the saturation at which the non-wetting phase (now oil and gas) should become discontinuous and hence trapped so as to be unrecoverable by direct displacement by water. If this is the situation, then trapping of a certain percentage of gas saturation during water flood should result, at infinite water-oil ratio, in a like reduction of oil saturation below that attainable by flooding in the absence of free gas. It is visualized that the gas will exist as bubbles inside the discontinuous residual oil as illustrated in Fig. 1, with the size of the oil bubbles being substantially unchanged due to the presence of the gas. As a practical matter, it can be anticipated that the presence of a free gas saturation inside the oil phase will reduce the relative permeability to oil which will exist at any particular water saturation. This reduction will be caused by two factors — -the addition of the gas-oil interface, and the reduction of area available for oil flow in the pores containing gas. This reduction in oil permeability at any particular water saturation will result in water breakthrough at a lower water satu-

Jan 1, 1951