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By J. L. Green

Virginia-Carolina Chemical Corp., in its Florida Operations, uses both roller mills and ball mills in dry grinding of phosphate rock. The roller mills have been in operation since 1954 in the Mining Department. The ball mills were installed and put in operation in 1960 in the Harding Concentrate Superphosphate Plant. The roller mills in the Mining Department are used to grind phosphate rock for outside customers. This involves short notice orders of varying grinds, grades and types of rock. The ball mills grind phosphate rock for use in V-C's own phosphoric acid and concentrated superphosphate plant. These mills grind generally two types of rock for one grind. In 1959, a 10% speed-up was made in the operating speed of the roller mills. This paper deals with the operational gains and resulting cost savings which evolved from this speed-up, and compares the present operations of the roller mills and of the ball mills in grinding phosphate rock. In January 1959 it was decided to determine the feasibility of reducing the grinding cost on the roller mills, per ton of rock ground, by speeding up the mill 10%. At this time, one mill was completely reconditioned so it would be in top condition. Extensive tests were then run both before and after the mill speed-up to determine the resultant cost savings. These tests showed that, due to this 10% speed-up, the mill capacity was increased approximately 20% and grinding power costs per ton were reduced approximately 10%. Table I shows the results of these tests. Each test run actually represents several of the same type rock and grind, averaged together. Each test run lasted approximately three hours. The validity of these runs has been confirmed by subsequent operation in grinding over 1,000,000 tons of phosphate rock. Accurate records have been kept on power consumption and repairs as well as tons produced. Two types of feed rock were used for the tests — pebble phosphate rock and flotation phosphate concentrate rock. The pebble phosphate rock size is approximately 80-90% plus 20 mesh. The flotation concentrate phosphate rock size is approximately 15% plus 20 mesh and 95% plus 100 mesh. The same two types of rock feed were used for all the test runs. Test Nos. 1, 2, and 3 were run at the original mill speed of 85.5 rpm on the vertical shaft. Test No. 1 was run with a feed of high grade flotation concentrates; the desired fineness attempted was 70% passing 200 mesh. Tests No. 2 and No. 3 were run with a feed of low grade pebble. Test No. 2 was run for a desired fineness of 70% passing 200 mesh. Test No. 3 was run for desired fineness of 50% passing 200 mesh.

Jan 1, 1963

By F. X. Tartaron

This article is a continuation of a previous paper by the writer in which Kick's Law was stated to be a part of comminution theory. ln the present paper, a broadening of ideas is attempted in order to state a general theory. The word "general" is employed because the new theory includes all previous laws and generalizations which are considered to be essentially correct. These ideas are combined into a coherent whole and the general theory can be expressed by the equation In the author's previous paper on comminution, ' the equations developed were based on Charles' equation of exponents a-n +1 = 0. 2 This paper is divided into two parts, designated as First Approach and Second Approach. In the First Approach, the equations of the previous paper are utilized, with Charles' equation of exponents being necessary. In the Second Approach, a separate and independent method is used to derive the same conclusions as in the First Approach, but without the use of Charles' equation of exponents. Holmes accepts the theoretical foundation of Kick's Law as sound but denies that the law as such operates in comminution. His idea is that Kick's Law requires homogenous matter whereas the presence of cracks, flaws and cleavage planes, which predominate in the coarser particles, makes matter unhomogene-ous. This explains why there is no experimental evidence to support Kick's Law. However, since the basis of the law is theoretically sound, all experimental evidence must be viewed as emanating from it. This requires modification of current comminution equations to fit this concept. Holmes makes the modification by changing the constant exponent n in the general energy equation used by Charles (E = - JCdx/xn) to a variable exponent r. The writer asserts that Kick's Law operates in comminution without modification but it does not

Jan 1, 1963

By H. W. Hitzrot

SEPARATING a mixture of particle sizes of material suspended in a liquid medium is by no means an exact science. Selecting machines for individual classifying operations is even more difficult. The plant operator's own background is of course invaluable, and considerable help may be obtained from technical articles, talks with sales engineers, and handbooks on ore dressing. These several sources of information, however, are difficult to marshal in proper perspective for the major decision on classification units that an operator may be called upon to make. To the present writer's knowledge this assembly of facts is not available in handbooks, and technical papers are scarce on classification equipment developed in the past five or six years. It is believed that this paper will be helpful to users of classification equipment at this particular period in the development of hydro-classification. For easy reference the following classification units now available and in use in metallurgical and industrial operations are listed below, with a brief description of each. Unit-type classifiers, bowl classifiers, and bowl desiltors are all rectangular tanks, slightly tilted, with reciprocating rakes or screws to remove settled sands. The unit-type classifier, Figs. 1 and 2, is available in widths from 14 in. to 20 ft and lengths up to 40 ft. The shallow bowl of the bowl classifier, Fig. 3, equipped with rotating rakes, is superimposed on the lower end of the tank. Reciprocating rake compartments for this design range from 18 in. to 20 ft wide. Bowl diameters vary from 4 to 28 ft. The flat-bottomed bowl of the desiltor, Fig. 4, of relatively large diameter, is equipped with rakes rotating outward and partly over a pit, which is created by extension of the rectangular tank into and under the bowl section. Bowl desiltors are available with reciprocating rake sections 4 to 20 ft wide and bowls from 20 to 50 ft in diam. The bowl desiltor is used for applications beyond the range of the bowl classifier. The hydroseparator, Figs. 5 and 6, is a circular tank equipped with slowly rotating rake arms, set on a slope, with interrupted rake or spiral blades to move the settled solids to a central discharge cone. Tank diameters vary from 4 to 250 ft. Tank depths at center are 2 to 3 ft for small units and up to 25 ft for larger units. Hydraulic classifiers of the sizer and super-sorter types, Figs. 7 and 8, are narrow, deep, rectangular tanks divided by vertical baffles into a series of pockets. Hydraulic water is added near the bottom of each pocket. Perforated constriction plates, spiral flow arrangements, or jets are used to disseminate the water under pressure (hydraulic water) throughout the bed of material in the pocket. Discharge valves on each pocket are operated automatically by a pneumatic mechanism, a pincer-type mechanism, or a pressure control and motor combination actuated by a hydrostatic tube within the pocket. Hydraulic classifiers are available in 4, 5, 6, and 8-pocket units of varying constriction plate areas to suit conditions. There is now a jet sizer of unit pocket design that can be made up in 1 to 25 sections or more to accommodate sizing requirements. The hydroscillator, Fig. 9, is a rectangular tank set on a slope of 3 to 4 in. per ft. A bowl is superimposed on the lower end. The bowl bottom is an oscillating rubber-covered disk, perforated to allow hydraulic water introduced beneath the disk to set up a teeter bed and thus produce an oversize or rake product exceptionally free of slimes, and material minus the mesh of separation. A shallow dam at the periphery of the bowl allows the coarse or oversize fraction to spill over and drop down into the tank compartment, where it is moved up the deck by reciprocating rakes. The material, minus the mesh of separation, overflows a circular and stationary weir which is several inches higher than the dam on the oscillating disk. It is carried off in a circular launder in the usual manner. These units are available in bowl diameters from 4 to 14 ft and with reciprocating rake compartment widths to suit the tons per hour to be handled. Centrifugal classifiers include the solid bowl centrifuge and the cyclone classifier. The solid bowl centrifuge, Fig. 10, consists of a truncated cone fixed to a horizontal shaft and rotating at high speed. An internal spiral rotating at slightly less speed continuously removes solids deposited on the inner surface of the cone, or bowl. Feed enters the cone by means of the hollow center shaft. Overflow leaves through ports at the large end of the cone, and oversize solids, moved by the spiral, exit through ports at the small end. Centrifugal classifiers of this type are available in cone diameters from 18 to 54 in. The cyclone classifier, Fig. 11, is a stationary cone having a cylindrical upper section and a lower cone section. Feed is introduced tangentially into the upper cylindrical section under pressure from a hydrostatic head or by means of a pump. Centrifugal force thus induced effects a classification within the cone, the fine sizes being carried off in the overflow through an opening at the top of the cylindrical section. Coarse solids at relatively high pulp density exit through a control valve at the apex of the lower cone section. Cyclone classifiers are available in 3, 6, 12, 14, 24, and 30-in. diam. The cone classifier, Fig. 12, is a steel-plate cone with sides usually about 60" from horizontal. It contains no rotating mechanism. Feed enters a feed-well at center and classification is effected by gravity and pulp density. Fines are carried off in the flow over a peripheral weir at the top of the cone. Settled solids exit through an opening at the apex. An apex valve actuated through levers and rods by the pulp density in the lower cone section is usually supplied. Diameters are usually maximum at 8 ft.

Jan 1, 1955

By A. Raja, C. C. Harris

Apparatus for maintaining constant — but adjustable — pulp level and rate of froth removal are described. The results of preliminary experiments into the effect of scraping speed on the rate of solid and liquid recovery with a semi-batch system are presented. Glass spheres restricted to a narrow size range is the solid under investigation. Graphical methods for estimating the mass of recoverable material and the zero error are given. The semi-batch procedure1 is extensively used in laboratory flotation testing, though the method is subject to variability of moderate severity. Raffinot2 concluded from a statistical study of the difference between replicate tests, that the ptincipal source of errot was the test itself and not sampling or chemical analysis. These differences can be ascribed principally to changes in pulp volume and reagent concentration, and uncontrolled rate and depth of scraping. Semi-batch testing has been criticized1 on these grounds as a means of investigating flotation kinetics. This paper discusses and describes modifications to laboratory flotation equipment which reduce the number of manual operations and lead to improved control. Kinetic studies were the primary reason for developing the apparatus described. It should, however be a useful aid in normal flotation testing. Some preliminary results of experiments are presented.

Jan 1, 1967

By E. O. Lilge, H. Siebert

A design of a multiple-bomb leaching unit particularly suited for the study of heterogeneous reactions, i.e. sol id-liquid-gas interfaces at high temperatures and pressures is presented. The component parts and overall design are described and illustrated in detail. The system has been tested by a limited number of experiments and found to work satisfactorily. Heterogeneous reactions at solid-liquid-gas interfaces, at high temperatures and pressures, are studied in either autoclaves1'4 or bombs5'9. Autoclaves are usually fairly large vessels which have a stirring arrangement incorporated in the design. Mechanical design limits the use of these vessels to relatively low temperatures and pressures. They are particularly well suited to rate or kinetic studies. Bombs can be designed to be operated at high temperatures and pressures, and are smaller vessels; because of this, stirring arrangements are not easily incorporated. In this paper a multiple-bomb system is described, that has been designed to incorporate the desirable features of both the autoclave and the bomb. The described unit has flexibility for an over all study of leaching. Most of the component units in this assemblage are standard equipment, designed and produced by well known manufacturers. No claim is made to the design of this equipment, and although described in some detail, this is done merely for clarity in the elucidation of the system presented. The general layout of the multiple-bomb assemblage is shown in Fig. 1A and 1B. The basic units in this system are: 1) 6 stainless steel 100 ml bombs (Fig. 4)

Jan 1, 1964

By Fred C. Bond, Jen-Tung Wang

Comminution energy is principally energy of deformation before breakage, which appears as heat An empirical equation is presented which covers the entire comminution range. The new strain-energy theory considers comminution from the known principles of mechanics and the reduction ratio. Energy requirements according to the different theories the romnnred. THE present status of the theory of comminution is extremely unsatisfactory. The amount of various ores and rock products crushed and ground annually approaches the staggering sum of perhaps one half billion tons. Yet the basic concepts underlying an operation of such magnitude are unknown, and actual knowledge of what takes place in comminution is almost entirely empirical. The responsibility for this situation cannot be charged to apathy or lack of appreciation of the importance of the problem. Many attempts have been made to evolve a workable hypothesis, but none has been completely successful. General Considerations In order to break rock, it must be subjected to a stress which strains the rock beyond its critical breaking point. The stress imparts energy to the rock, most of which is released in the form of heat when the stress and resulting strain are removed. If the strain induced exceeds the critical strain, the energy is released by breaking; if the induced strain does not reach the critical point, the energy is released with removal of the stress as energy of resilience. Rock is a brittle material and it is assumed that it breaks approximately at its yield point, so that no permanent deformation results from strains below the critical. When rock is broken the total energy input is accounted for by the heat liberated, and by the surface energy of the new surface produced. A small and probably negligible amount is released as noise. Rock is commonly broken under compression and the applied stress is ordinarily compressive. However, for breakage to occur, it is only necessary that the induced strain exceed the critical value, and this strain may represent the resultant of compressive, shearing, and tensile forces. The stress-strain diagram of rocks under compression, and the modulus of elasticity as determined therefrom, should be fundamental considerations in the development of any theories of rock breakage. Crushing in jaw or gyratory crushers results primarily from a squeezing action, and reduction in a hammer mill is the result of impact. The action in rod and ball mills is a combination of impacting, squeezing, and wearing away by attrition, or rubbing. In ordinary crushing and grinding, the forces are applied at protruding points and are not distributed evenly throughout the rock. This is one of the features of comminution which theoretical considerations have not covered adequately. Another feature is the effect of impact velocities, which may greatly influence the total energy required for breakage. Impact velocities may vary from 1 or 2 fps in crushers to 10 or 20 fps for ball mills, and as high as 100 or more for hammer mills. However, according to the findings of geophysicists, the velocity of sound and of compression waves in stone is many times greater; the primary longitudinal compression waves travel at perhaps 15,000 fps, and the secondary transverse waves, which may reach the surface and cause cracks to form thereon, travel at perhaps 5000 fps. When a crack tip forms, the total surrounding stresses are concentrated in this tip, which rapidly extends throughout the rock particle.1 It would seem that the energy required to deform the rock beyond its critical strain, resulting in the formation of a crack tip, represents practically all of the energy required. Most of the primary crack tips presumably form on the surface. A simple method of designating feed and product size is necessary for the evaluation of crushing and grinding results. Taggart's suggestion2 that the 80 pet passing size be used has been found very practical. In this paper, the square opening screen size which 80 pct of the feed passes is designated as the feed size F, and the size which 80 pct of the product passes, or the product size, is designated as P. The reduction ratio at the 80 pet passing size, or F/P is designated as n. The feed and prod-

Jan 1, 1951

By Fred C. Bond, Jen-Tung Wang

Comminution energy is principally energy of deformation before breakage, which appears as heat An empirical equation is presented which covers the entire comminution range. The new strain-energy theory considers comminution from the known principles of mechanics and the reduction ratio. Energy requirements according to the different theories the romnnred. THE present status of the theory of comminution is extremely unsatisfactory. The amount of various ores and rock products crushed and ground annually approaches the staggering sum of perhaps one half billion tons. Yet the basic concepts underlying an operation of such magnitude are unknown, and actual knowledge of what takes place in comminution is almost entirely empirical. The responsibility for this situation cannot be charged to apathy or lack of appreciation of the importance of the problem. Many attempts have been made to evolve a workable hypothesis, but none has been completely successful. General Considerations In order to break rock, it must be subjected to a stress which strains the rock beyond its critical breaking point. The stress imparts energy to the rock, most of which is released in the form of heat when the stress and resulting strain are removed. If the strain induced exceeds the critical strain, the energy is released by breaking; if the induced strain does not reach the critical point, the energy is released with removal of the stress as energy of resilience. Rock is a brittle material and it is assumed that it breaks approximately at its yield point, so that no permanent deformation results from strains below the critical. When rock is broken the total energy input is accounted for by the heat liberated, and by the surface energy of the new surface produced. A small and probably negligible amount is released as noise. Rock is commonly broken under compression and the applied stress is ordinarily compressive. However, for breakage to occur, it is only necessary that the induced strain exceed the critical value, and this strain may represent the resultant of compressive, shearing, and tensile forces. The stress-strain diagram of rocks under compression, and the modulus of elasticity as determined therefrom, should be fundamental considerations in the development of any theories of rock breakage. Crushing in jaw or gyratory crushers results primarily from a squeezing action, and reduction in a hammer mill is the result of impact. The action in rod and ball mills is a combination of impacting, squeezing, and wearing away by attrition, or rubbing. In ordinary crushing and grinding, the forces are applied at protruding points and are not distributed evenly throughout the rock. This is one of the features of comminution which theoretical considerations have not covered adequately. Another feature is the effect of impact velocities, which may greatly influence the total energy required for breakage. Impact velocities may vary from 1 or 2 fps in crushers to 10 or 20 fps for ball mills, and as high as 100 or more for hammer mills. However, according to the findings of geophysicists, the velocity of sound and of compression waves in stone is many times greater; the primary longitudinal compression waves travel at perhaps 15,000 fps, and the secondary transverse waves, which may reach the surface and cause cracks to form thereon, travel at perhaps 5000 fps. When a crack tip forms, the total surrounding stresses are concentrated in this tip, which rapidly extends throughout the rock particle.1 It would seem that the energy required to deform the rock beyond its critical strain, resulting in the formation of a crack tip, represents practically all of the energy required. Most of the primary crack tips presumably form on the surface. A simple method of designating feed and product size is necessary for the evaluation of crushing and grinding results. Taggart's suggestion2 that the 80 pet passing size be used has been found very practical. In this paper, the square opening screen size which 80 pct of the feed passes is designated as the feed size F, and the size which 80 pct of the product passes, or the product size, is designated as P. The reduction ratio at the 80 pet passing size, or F/P is designated as n. The feed and prod-

Jan 1, 1951

By D. R. Walker, M. C. Shaw

The laws of Kick and Rittinger are explained as functions of particle size with metal cutting theory. Comminution is shown to be basically the same process as metal grinding. The machine shop type of grinding operation is used to study mineral crushing. Evidence indicates that plastic flow occurs in comminution. THE laws of comminution of Kick and Rittinger have been debated for many years. Certain data obtained from ball mill and drop tests are found to be in approximate agreement with Rittinger's law while other data would seem to support Kick's law. In all these tests the energy required to produce a wide variety of particle sizes has been studied. Surface area has also been measured with considerable difficulty, at first because it was thought that the energy associated with crushing was that required to create new surface, later because of precedent and because a more fundamental variable was unknown. Tests made with the machine shop type of grinding process show that normally brittle materials that are usually crushed can behave like the more ductile metals. Brittleness is then a relative prop- erty largely dependent on specimen size and stress state. The machine grinding operation offers a convenient means for studying the comminution of materials in which the important size variable retains its identity. The energy required to grind a certain volume of material is shown to be strongly dependent on size. Kick's law is found to hold very well for particles below 1 micron in size, while Rittinger's law holds approximately in the comminution of larger particles. While a physical origin of Kick's law is established in terms of the theoretical strength of materials having a perfect lattice structure, there is found to be no physical basis for Rittinger's law. Because of its industrial importance, comminution has commanded considerable technical attention and has been the subject of continuous study for nearly a century. A number of empirical rules have been proposed to make it possible for grinding energies to be predicted. Of these so-called laws of comminution those bearing the names of Kick and Rittinger have been most widely applied and debated.

Jan 1, 1955

By O. B. Buchlen, J. W. Smith

The Coal Research Bureau of the School of Mines at West Virginia University, using an experimental flotation cell designated an airlift-cyclone was able to obtain a clean coal product containing 7.64% ash with 94% yield and 97% coal recovery. This favorable performance was obtained with the experimental flotation cell operating as a simulated three-stage unit on slurry taken from the fine coal circuit of a coal preparation plant. This experimental device, consisting of a sheet metal cyclone-like unit mounted on a U-shaped uplift pipe, uses a combined flotation and cyclone action to beneficiate the minus 14 mesh partially cleaned feed product. In addition to providing comparable analytical results, the airlift-cyclone possesses other attractive features among them being a low capital expenditure, utilization of moderate plant floor space, efficient operation on high density feed slurry, and absence of moving parts. The primary shortcoming of the experimental cell is its limited capacity. The Coal Research Bureau presently has under construction a larger unit which, it is hoped, will provide the capacity and quality to establish the airlift-cyclone as a commercially feasible unit. Froth flotation of fine coal is a practice which has only recently gained wide acceptance in this country. Various explanations can be put forth for this delayed acceptance of a very selective and efficient system of coal preparation. Among these reasons would be the advent of continuous mining machines resulting in the increased production of coal fines, the change in market patterns from domestic and rail consumers who did not want fines to a predominantly utility market which normally consumes fines, and also the imposition of legal restrictions in regard to stream pollution. However, the major detriment is probably the high cost involved both in installation and operation of the flo- tation unit and auxiliary systems. These facts assume greater emphasis when considering that froth flotation installations normally process a low quality feed product. A recent estimate' of installation costs including dryers, filters, and other auxiliary equipment for a flotation system was $5000 to $7000 per ton of capacity while the operating costs, exclusive of auxiliary equipment, were estimated at 10 to 306 per ton of feed. The Coal Research Bureau of the School of Mines at West Virginia University is currently developing a simplified froth flotation cell, designated an airlift-cyclone, which may provide considerable savings in capital and operating costs without sacrificing product quality or recovery. This experimental cell consists of three primary components: 1) a vertically mounted U-shaped pipe; 2) an air injector device; and 3) an integrally mounted cyclone-like unit (Fig. 1). A feed slurry is introduced at the top of one leg of the U-pipe while compressed air is injected near the base of the other leg. The air serves both to aerate the pulp and to cause it to flow upward into the base of the cyclone unit where the floated clean coal is separated from the reject material and unfloated coal which remains in slurry. The Coal Research Bureau's experimental airlift-cyclone is somewhat similar in principle to a flotation device developed by Russian engineers in the late 1950's. In tests upon a two-stage pilot-size device, the Russians obtained very favorable cleaning efficiencies.' However, later experience with production models demonstrated that rated capacities and acceptable product quality could not always be maintained.3 Because of these limitations, Russian engineers subsequently recommended that conventional, mechanical cells be used when cleaning difficult to float slurries. Engineers at the Coal Research Bureau felt that such a device utilizing the combined actions of a cyclone and a froth flotation machine offered numerous attractive features and merited investigation. Accordingly, a small capacity experimental airlift-cyclone was designed and, with the permission of the Christopher Coal Company Div. of Consolidation Coal Co., installed in Christopher's Humphrey preparation plant near Morgantown, West Virginia.

Jan 1, 1964

By S. M. Wu, R. L. Stone, T. D. Tiemann

The dissolution of silica from quartz in sodium hydroxide solutions was investigated by statistical methods. A second-order predicting equation was developed with 28 experiments expressing the dissolution of silica as a function of the variables quartz size, time, temperature and sodium hydroxide concentration. With this equation a comprehensive picture of the dissolution reaction was gained which included the effect on extraction of each variable and their interactions, fractional extractions, reaction rates and activation energies. A previous investigation of the extraction of silica from low grade siliceous iron ore by digestion in sodium hydroxide solutions presented the extraction as a function of time, temperature and sodium hydroxide concentration.' The present paper is an outgrowth of the previous work and develops by a mathematical analysis the functional relationship between the extraction of silica and time, temperature, sodium hydroxide concentration and particle size. Relatively pure quartz was used in this study in order that the basic quartz-sodium hydroxide reaction could be studied without the influence of other constituents that are commonly found in iron ores. The functional relationship between the dissolution

Jan 1, 1965

By F. W. Bowdish

Analysis of data on the equilibrium exchange of sodium ions from salt solutions for calcium ions, from various fractions of an oxidized calcareous iron ore from Lorraine, France, strongly suggests that the calcium may be attached to the solid by only one of its bonds. Nearly equal values were found for the equilibrium expression from data covering concentration ranges of 1000 fold for the salt and 235 fold for the ion-exchangeable calcium. Differences indicated between the exchangeable calcium contents of the slime and the sandy portions of the ore, as well as the equilibrium relationship itself, are of importance in the flotation of the ore. During an experimental program on the flotation of oxidized calcareous iron ores from Lorraine, France, ion-exchangeable calcium was found in the ore. Because this source of calcium ions, if not controlled, could thwart all efforts at flotation, an extensive study was made of the phenomenon. The part of that study reported here was to obtain data on the equilibrium established between ore solids and solutions of sodium chloride, and to analyze the data to try to understand better the physical chemistry of the exchange. The ore contains oolites of goethite and quartz grains embedded in a matrix consisting of calcite and a brown cement believed to be the residue from oxidation of the silicate minerals found in fresh unoxidized ore. When ground, a substantial fraction of the ore becomes a fine slime in which is concentrated more than half of the alumina content of the ore. It is believed that the alumina occurs as unidentified clay minerals with which most of the ion-exchange capacity of the ore is associated. A preliminary experiment on the exchange of ions from the ore for sodium ions from solutions of NaCl showed that calcium was about ten times as abundant as magnesium in the exchange solutions. Thus calcium was the predominant ion in causing difficulties with flotation, and it was the only one for which data was obtained in this study. It is believed that the omission of magnesium ion exchange from consideration does not invalidate the results. It is possible, however, that inclusion of magnesium in the analyses and calculations or its prior elimination from the samples would have improved the consistency of the results. EXPERIMENTAL Data about the equilibrium exchange of sodium from solutions for calcium from the solids were obtained using two different samples of material. The solids

Jan 1, 1963

By R. W. Smith

It is well known that certain silicates such as the feldspars and beryl can be readily floated from quartz at a low pH value using a long chain cationic collector in the presence of a fluoride.1-3 However, the mechanism whereby the fluoride activates feldspars and beryl is not known. Indeed, only a few authors have even speculated about possible mechanisms.1,3,4 As a first approach to the problem, it is perhaps best to look closely at the interesting character of hydrofluoric acid and how it dissolves silica and silicic acid. Hydrofluoric acid, unlike hydrochloric acid, is a weak acid with a dissociation constant of about 3.53 x 10-4 at 25°C.5 The reason for the weak acidic character of HF lies in the very small size of the fluoride ion.6 The pKa value is 3.45 which means that at pH 3.45 half the HF is present in molecular form and half in ionic form. The anion present is probably HF2.-6 At pH values below the pKa value, molecular concentration increases rapidly at the expense of the HF2- anion. It is known that HF readily attacks glass, silicates, quartz and silicic acid. The equation usually cited pertaining to the first step in HF attack of silica is6-'

Jan 1, 1965

By P. H. Metzger, D. W. Fuerstenau

The activation of sphalerite was found to occur at a much lower rate with Pb++ then with Cut++ or Ag+. To prevent activation with Pb++, the ratio [m in solution must approximate 103. An example is given illustrating how this condition is met in practice through the addition of zinc sulfate and soda ash. In selective lead-zinc flotation, the mill operator, especially the one who is concentrating a partially oxidized ore, often must add zinc sulfate and/or soda ash for effective depression of the sphalerite. In the present paper the authors show how this practice prevents the activation of sphalerite in the presence of Pb++. A number of years ago Gaudin (1) postulated that Zn++ might control the activation of sphalerite with Pb++ through competitive adsorption. However, recent experimentation has shown the activation of sphalerite with Ag+ and Cut++ to be a chemical reaction in which silver or copper ions replace zinc in the sphalerite lattice through the formation of a more insoluble sul-fide (2,3,4) Thus, if activation with Pb++ is similar to that with Ag+ or Cu t+, zinc salts should control the activation of sphalerite not through competitive adsorption but because the ratio of [zn++/Pb++] in solution regulates the extent of the chemical exchange between Zn++ and Pb++ in the solid phase. The objective of this investigation has been to study the kinetics and equilibrium conditions for the uptake of Pb++ by sphalerite and to investigate the prevention of lead activation with zinc salts. BASIC PRINCIPLES Sphalerite activation has been shown to be a replacement reaction wherein a less soluble compound is formed at the expense of the more soluble zinc sul-fide (2,3,4) For example, if sphalerite is placed in an aqueous silver nitrate solution, ZnS gives to the solution more S= than can exist together with Ag+, and hence the following reaction takes place: ZnS + 2 Ag+? Ag2 S + Zn ++; k = [zn ++]/[Ag ++]2 = 10 26 (1) Therefore, ZnS will dissolve in the presence of Ag+ and activation of sphalerite with Ag+ will proceed after monolayer coverage by solid state diffusion until equilibrium conditions are reached in the system (2, 4) Because of the large difference in the solubility of ZnS and Ag2S, zinc salts cannot affect the reaction unless a complexing agent, such as cyanide ions, is present to complex Ag+ more tightly than Zn++ . By complexing Ag+ and Zn++ in solution, the uptake of Ag+ by sphalerite can be regulated by controlling the ratio m. . Experimentally (2) it was found that the activation of sphalerite by Ag+ could be prevented through the addition of NaCN if this ratio reached a value of approximately 10 26. The mechanism of sphalerite activation with copper salts is given by the following reactions: ZnS + Cu ++ ? CuS + Zn + + ; (2) k = [Zn++]/[Cu++] = 10 11 ZnS + Cu + ? Cu2S+ Zn++; (3) Experimentally Mao (3) found that the activation of sphalerite with Cu++ or Cu + was prevented if the ratios expressed in Equations 2 and 3 were approximately l09 and l022, respectively, with cyanide ions as the deactivator. Although zinc salts do not affect the activation of sphalerite with silver or copper ions in the absence of a complexing agent, activation with lead ions theoretically can be controlled by the addition of zinc salts because of the relatively small differences between the solubility of ZnS and PbS (5). Equilibrium

Jan 1, 1961

By D. A. Elgillani, M. C. Fuerstenau, J. D. Miller

Adsorption of lead and ferric iron on quartz and alumina is presented as a function of pH. Only the hydrolyzed species of these metal ions, FeOH++ and PbOH+, adsorb significantly on each of these minerals. Zeta potentials of quartz were measured as a function of pH in the presence of various additions of aluminum, lead, and magnesium salts. Sign reversal occurs at the pH values where significant concentrations of hydroxy complexes are formed. Models of adsorption are presented in the absence and presence of collector. The mechanism of adsorption of metal and collector species in the activation of nonmetallic minerals is still the center of considerable discussion in spite of the extensive study given this system. Until recently, the view was widely held that hydrated metal ions were responsible for this phenomenon. This fact is surprising, since it had been shown that the pH range in which flotation is effected corresponds to that in which metal ion hydrolysis occurs.' Additional support of this concept was pro vided by the work of Wolstenholme and Schulman in another system.' Later work has shown that hydroxy complexes of metal ions are the active species. These studies have also indicated that basic aqueous complexes of metal-collector may be necessary for flotation.3-7 Depending on the molecular weight of the collector, formation of these complexes may occur before or after precipitation of the metal-collector salt has occurred. Ion pair formation can occur when low molecular weight collectors are involved because relatively high concentrations of metal hydroxy complex and collector can be present in solution before precipitation occurs. This is not the case when high molecular weight collectors are used. A model of aqueous complex adsorption has been presented6,7 in which it has been assumed that adsorption occurs by the formation of water from adsorbed hydroxyl and hydrogen of the hydroxyl contained in the complex. Other authors8 have suggested that hy-droxy complexes are involved in these systems but that collector adsorption occurs by replacement of the hydroxyl of the adsorbed metal hydroxy complex with a fatty acid anion. All of these investigations have involved mineral surfaces that were negatively charged so that it is not possible to state with certainty whether hydrated metal ions or hydroxy complexes are the active species in this system. Use of a positively charged mineral should be helpful, however, since the hydrated metal ion will be repelled from this surface. On the other hand, if the hydroxy complex adsorbs by splitting out water, surface charge should have no effect because of the free energy decrease that the system will experience when water is formed. In this regard, sapphire is well-suited for study, since its surface is positively charged until approximately pH 9. Electrokinetic studies of quartz in the presence of various metal ions should also be useful in establishing the mechanisms of adsorption in these systems. That is, if the hydroxy complexes adsorb by water formation, drastic changes in the zeta potential should occur in the pH range in which hydrolysis occurs. In this view, adsorption of ions of widely different hydrolysis characteristics on both sapphire and quartz was measured. In addition, zeta potentials of quartz were measured as a function of pH in the presence of various metal ions and compared with flotation responses obtained under similar conditions. Experimental Materials and Techniques Reagent-grade aluminum, ferric and magnesium chlorides, and lead nitrate were used in this investigation. Adjustments in pH were made with reagent-grade HCl or KOH. Conductivity water, made by passing distilled water through an ion exchange column, was used in all of the experiments.

Jan 1, 1971

By H. R. Spedden, A. M. Gaudin, M. P. Corriveau

A preliminary study of silver ion adsorption by sphalerite in ion exchange column with influent electrolyte marked with radiosilver is described. Rapid ion exchange occurs at first followed by slow reaction controlled perhaps by solid state diffusion. One experiment with radiocopper instead of radiosilver is reported briefly. IT has been known for many years that sphalerite is floated after it has been activated by a metallic cation, particularly copper.' The activation of sphalerite by copper is known to be an exchange of an atom of copper for an atom of zinc at the surface of the sphalerite.2,3 It has been estimated from various guesses of the available mineral surface that the depth of the copper-bearing coating is of the order of thickness of one atom. However, the exact mechanism of the activation process is unknown. A number of metals other than copper act in the same general manner."' " In particular, it has been known that silver replaces zinc at the surface of sphalerite. As copper is usually divalent, whereas silver is monovalent, it may well be assumed that there are differences, perhaps major differences, in the detailed scheme of activation by these two cations. Furthermore, since silver has unusual photoelectric properties and may be a contributor to the fluorescence of sphalerite, a study of its activating mechanism might open up some interesting avenues for exploring these other phenomena. The choice of silver as an activator of sphalerite was suggested also by the fact that its radioactive tracer, silver 110, is particularly convenient in that it has a long half-life and is energetic enough to permit counting through a counter window. The experimental technique selected, therefore, included the preparation of solutions of silver nitrate con- taining a proportion of active silver nitrate sufficient to give convenient counting data. In further considering the method to be used, a desirable choice seemed the use of batch experimentation in which a given solution was allowed to act on a certain lot of mineral for a given length of time at a given temperature, this period of mutual reaction being followed by analyses of the separated solid and solution. But an alternative method seemed more attractive. This is the method now so familiar to the users of ion-exchange resins, which was first made famous by the Russian chromatographer, Tswett.6-8 It consists in forming the mineral into a porous column through which the solution is allowed to flow at a constant rate. The usual method of allowing a batch of solid to react with solution is the equivalent of a single plate distillation operation while the chromatographic or ion-exchange column is a multiple-plate method—the multiplicity of the plates being represented by the reciprocal of the rate of flow of solution through the column. It seemed to us that the chromatographic method had such

Jan 1, 1952

By L. A. Roe

Magnetic separation of iron ores is one of the fastest-growing segments of the minerals beneficiation industry. The tonnage of taconite ores processed annually by magnetic separation will, in a few years, reach 100 million. Magnetic separation occupies an attractive position in the field of ore beneficiation. It is a simple yet effective method, used for some 150 years and steadily growing more important. This type of beneficiation orginated in 1792, when William Ful-larton was issued a British patent covering the separation of iron ore by magnetic attraction. What is magnetism, and why are some materials capable of being magnetized and others not The study involves many unknowns, and even a partial answer to these questions would be a dissertation in solid state physics and perhaps other fields of science. But the last two decades have revealed basic facts as to why certain materials are magnetic and what happens to them when they are magnetized. Some of the newer studies in solid state physics have developed a theory that can be applied to studies of magnetism. It is claimed that magnetism stems fundamentally from the spin of electrons in atoms that tend to go in pairs, spinning in opposite directions. The atom as a whole can act as a magnet only when there is an imbalance of electronic spin. Whenever an atom has an odd number of electrons, therefore, this imbalance exists. This neutralizing effect explains why a piece of material that contains atomic magnets is not necessarily magnetic. The physicists tell us that iron is composed of many small magnetized regions called domains, which consist individually of millions of atoms. The piece of iron becomes magnetized when an external force lines up these domains in the same direction. Fundamental data developed by physicists working in fields far removed from minerals beneficiation are now available for developing better magnetic separators for ore processing. More Data Needed on Magnetic Properties of Minerals: There is less information on magnetic properties of minerals than there is for certain aspects of magnetic separator design. When the data on magnetic properties is available, it is often directed toward the study of powders for tape recorders and other highly scientific endeavors that are of little use to the beneficiation engineer. W. R. Crane's table of tractive forces, published in 1902, is still a guide in the study of magnetic minerals. Bits of other information regarding electrostatic conductivity, dielectric constant values, and permeability of various minerals have also appeared but are of small practical value in magnetic separation of ore. It is extremely important to obtain pure mineral specimens for making investigations and to record results that may be of use in studies of magnetic processes. Reference to the large volume of data developed by those concerned with analysis and design of permanent magnets soon reveals that these people have extensively evaluated the effect of various impurities on magnetic properties. Much of the science of the ferrite industry is based upon spinel-type structures which are varied by substitution of selected elements or even subtraction of elements, leaving vacant sites in the space lattice. Magnetic separators are used to beneficiate a wide variety of industrial minerals. In this application the relatively large volumes of nonmagnetics are usually the commercial products. The amount of mag-

Jan 1, 1959

By W. F. Stowasser

downdraft traveling grate process to agglomerate pelletized iron ore concentrates has been successfully demonstrated in a pilot plant at Carrollville, Wis. Work there followed several years of development in the Allis-Chalmers Mfg. Co. laboratories, and the pilot plant phase was carried out in cooperation with Arthur G. McKee & Co., consultants and engineers to the iron and steel industry. End result of the process is conversion of iron ore concentrates into a form which can easily be transported and smelted in the blast furnace. Process Description The first of two process steps incorporates the art of balling and prepares the concentrates for burning. The second step consists of burning the green balls on the grate machine to the hardness required for shipping and handling purposes and for reduction in blast furnaces, see Fig. 1. Facilities are provided at the pilot plant to receive carload quantities of concentrate. The concentrates are loaded into a 50-ton bin direct from railroad cars. Because of the variable moisture content of the concentrates after shipment in an open railroad car it is necessary to repulp and refilter the concentrates to maintain a uniform and proper moisture content for the balling operation. Concentrates are conveyed to slurry tanks, and the slurry, at 50 to 60 pct solids, is pumped to a 4x4-ft drum filter. The filter provides feed of uniform moisture to the plant. Magnetite concentrates are normally filtered to produce a cake containing about 10 pct moisture, a necessary requirement for the following balling operation. The filtered concentrate is conveyed to a rotary bin table feeder which acts as a surge bin for the filter cake and delivers a steady flow of concentrates to the balling drum. It is often desirable to make additions to the concentrates as they are fed to the balling drum. These additives, such as bentonite, increase the strength of the finished green pellet and improve ballability of the concentrate. A vibrating feeder supplies additive to the feed belt, and the additive is mixed with the concentrate in the balling drum. The balling drum, shown in Fig. 3, is 8x3-ft diam. An oscillating cutting bar maintains the lining in the drum by trimming off the buildup of excess concentrate as it forms. The drum is operated in closed circuit with a lx4-ft rod-deck vibrating screen. Undersize pellets or seed pellets from the screen are returned to the balling drum until they grow to the desired size. Size of pellets is controlled by the opening in the screen deck. The formation of pellets in the balling drum is affected by many variables. Some of these are: the size distribution of the feed, the particle shape of the concentrate, the feed rate to the drum, the moisture in the concentrate, the speed of rotation of the drum, the slope of the drum, and the type of trimming obtained with the cutting bar. In this process, attempts are made to control the pellet size within the limits of % to 5/8 in. diam. The screened oversize pellets are conveyed under a coal feeder where sufficient powdered coal is added to the belt to produce desired results in the burning process. The top size of the coal successfully used has been 20 mesh, and anthracite was used in the test program. Fig. 4 illustrates the vibrating screen and the coal feeder. The pellets and free coal are conveyed together to the 5x3-ft diam- reroll drum that rolls the coal onto the surface of the pellets. This drum is also equipped with a cutting bar. The prepared pellets, containing bentonite, water, and surface coal, are elevated to the traveling grate, which consists of a continuous strand of 37 pallets. Each pallet, with a grate bar area 2 ft wide by 1 1/2 ft long, has 14-in. high side plates, Fig. 5. Feeding and distribution of the green balls to the grate is handled by a short conveyor which oscillates back and forth across the 2-ft width of the grate. An adjustable vertical plate located several inches in front of the head pulley of the oscillating conveyor controls the height of the bed and levels the moving bed of pellets. This method of feeding prevents segregation of various size pellets as well as fines and produces a uniform, permeable bed. The pallet train moves under the furnace and across four windboxes, located beneath the pallet frames, see Fig. 2. As the green pellets are deposited on the grate, partial drying of the pellets begins over a 2-ft long updraft windbox. The low temperature air reduces the moisture in the pellets in the lower level of the bed and this operation is essential to prevent sagging of the bed during later stages of the Process. The air used for this drying is recuperated from cooling the pellets on the grate, and supplemental heat, required for starting the Process, is obtained from an auxiliary burner. The pellets are then moved by the grate into the furnace and over an 8-ft windbox, designated as the downdraft waste windbox. Products of combustion are exhausted from this windbox to atmosphere. The furnace, shown in Fig. 6, is constructed with three chambers to provide downdraft drying, preheating, and ignition, respectively, to the pellet bed as it passes through. Overall length of the furnace is 5.57 ft; however, the exterior wall ends may be moved to reduce the length and also adjusted to Obtain the bed height desired, The drying, preheating, and ignition sections of the furnace are supplied with medium temperature

Jan 1, 1956

By H. Rush Spedden, Arvid Thunaes

R. R. Knobler and F. E. Albertson—Following the testwork done by Thunaes and Spedden, a Sullivan deck plant was built for the Colquiri mill. This plant started to operate in April 1945 and continues in successful operation. Since May 1950 the Colquiri mill has operated with a completely revamped flowsheet at a rate of 1000 tons per day. The old Sullivan deck section was retained with this new flowsheet. The "slime plant" in Colquiri consists of one 12-cell Denver No. 18-Sp. Sub-A flotation machine, one 16-ft and one 12-ft hydroseparator, six five-deck Sullivan-frames and six shaking tables for cleaning up the Sullivan deck concentrates, as well as 12 Deister plus three Plat-O tables on which the fine sands, which are not treated on the S-decks, are concentrated. Only —325-mesh fines are treated on the Sullivan decks. The combined hydroseparator overflows are fed to the S-decks. From 1946 to 1949, i.e. with the "old" flowsheet and an average mill feed of 800 tons per day an average of 45 tons per day was treated on four Sullivan rougher frames. The two additional frames were used as cleaners. At times, up to 90 and 120 tons of slimes were treated successfully on this Sullivan deck installation. The average operating data for the S-deck section in Colquiri for the year 1949 were as follows: The tests reported in this paper indicated a tin recovery of 42 pct. The actual plant results for 1949 show a 54 pct tin recovery from the Sullivan decks. The total average quantity of tin produced from the S-deck section in 1949 was 15 tons of tin per month. This corresponds to 3 pct of the total mill recovery. The difference between the 6 pct overall recovery-increase expected after the tests in 1943 and the actual plant results given for 1949 is explained as follows. According to the tests, a total of 170 tons was expected to be routed to the Sullivan decks, but because of certain changes in the flowsheet and mill amplifications,

Jan 1, 1951

By H. Rush Spedden, Arvid Thunaes

R. R. Knobler and F. E. Albertson—Following the testwork done by Thunaes and Spedden, a Sullivan deck plant was built for the Colquiri mill. This plant started to operate in April 1945 and continues in successful operation. Since May 1950 the Colquiri mill has operated with a completely revamped flowsheet at a rate of 1000 tons per day. The old Sullivan deck section was retained with this new flowsheet. The "slime plant" in Colquiri consists of one 12-cell Denver No. 18-Sp. Sub-A flotation machine, one 16-ft and one 12-ft hydroseparator, six five-deck Sullivan-frames and six shaking tables for cleaning up the Sullivan deck concentrates, as well as 12 Deister plus three Plat-O tables on which the fine sands, which are not treated on the S-decks, are concentrated. Only —325-mesh fines are treated on the Sullivan decks. The combined hydroseparator overflows are fed to the S-decks. From 1946 to 1949, i.e. with the "old" flowsheet and an average mill feed of 800 tons per day an average of 45 tons per day was treated on four Sullivan rougher frames. The two additional frames were used as cleaners. At times, up to 90 and 120 tons of slimes were treated successfully on this Sullivan deck installation. The average operating data for the S-deck section in Colquiri for the year 1949 were as follows: The tests reported in this paper indicated a tin recovery of 42 pct. The actual plant results for 1949 show a 54 pct tin recovery from the Sullivan decks. The total average quantity of tin produced from the S-deck section in 1949 was 15 tons of tin per month. This corresponds to 3 pct of the total mill recovery. The difference between the 6 pct overall recovery-increase expected after the tests in 1943 and the actual plant results given for 1949 is explained as follows. According to the tests, a total of 170 tons was expected to be routed to the Sullivan decks, but because of certain changes in the flowsheet and mill amplifications,

Jan 1, 1951

By M. E. Wadsworth, L. H. Raby, A. S. Peck

Infrared spec troscopy was used to study the adsorption of oleate collector on three varieties of hematite. Each of the minerals was found to react with either oleic acid or a solution of sodium oleate to form a mineral cation-collector anion chemisorbed layer at the solid-liquid interface. The chemisorption reaction displaced surface hydroxyls and was found to be pH dependent. The infrared band characteristic of the antisymmetrical C = 0 structural group of chemisorbed oleate appears between 1520 and 1540 cm-'. Evidence is presented which shows that molecular filming of the mineral surfaces with un-dissociated oleic acid precedes chemisorption. Infrared absorbance is correlated with the flotation behavior of the mineral. Adsorption processes are usually classified into two types which are distinguished and character- ized by the nature of the bond formed between the adsorbate and adsorbent. The process in which molecules chemically bond to solid surfaces is termed activated adsorption or chemisorption. If only weak van der Waals forces bind the molecules to the surface then the process is termed physical adsorption. Chemisorption is of primary interest in flotation systems since selectivity may be obtained if a single mineral is rendered air-avid by a specific collector mineral adsorption reaction. In previous studies infrared spectroscopy was used to define the mechanisms involved in the adsorption of oleic acid and sodium oleate on fluorite, barite, and calcite. Infrared techniques were particularly useful since adsorbed monolayers were identified in situ. Further, the infrared method permitted identification of reaction products in the solid, liquid, and vapor phases of the systems. The chemisorption reactions displaced F- from fluorite, SO4 from barite, and CO3 from calcite. This investigation was pursued in an effort to characterize and interpret the adsorption processes for synthetic hematite, compact red hematite, and specular hematite (crystalline hematite). Adsorption tests were performed using either oleic acid or

Jan 1, 1967