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By Jack W. Carlson

Considering the magnitude of today's public concern with critical mineral and fuel materials, regarding both their midterm and long term availability, the Nation is fortunate to have in place and operating the coordinated data systems of the Geological Survey and the Bureau of Mines. Under the supervision and policy direction of the Assistant Secretary--Energy and Minerals, these Department of the Interior agencies have long been responsible for important mineral activities in the Federal Government. Aside from their highly respected mineral industry publications such as the monthly Mineral Industry Surveys, annual Commodity Data Summaries and topical Professional Papers and Reports of Investigation, the Bureau of Mines and Geological Survey data bases and expertise have been readily available for use in emergency situations. Policymakers and decisionmakers in government have placed major reliance upon this ready mineral data and analytical capability in World War II, the Korean War, the recent price control era, and the Arab oil embargo.

Jan 1, 1975

By I. L. Sills

Introduction So many minerals and mineral products are used in the glass industry that it would require an unduly long paper to deal adequately with all of them. Only those that go to make up the batch for the more common types of glass will be discussed here, and even with these only, the list is a lengthy one. It is true that for the body of the glass comparatively few materials are required-as silica sand, soda-ash, lime, and feldspar. The others are used mainly to colour or decolorize the glass, or to give it some other desired characteristic, such as high lustre, greater physical strength, or opalescence; but, although they may be present in very small quantities, they are just as in-dispensable to the glass industry as are the main constituents of the batch. Sand Sand is essentially quartz, the dioxide of silicon, Si02. Most glass contains from 71J to 75 per cent silica. Sand for use in the glass industry, or 'glass sand', is obtained both from deposits of unconsolidated material, commonly referred to as 'sand', and from solid rock-sandstone, quartz, or quartzite. For the manufacture of glass, the material must possess a high degree of purity, as noted below, so that, although sand is widespread in most parts of the world, and sandstone, quartz, and quartzite are not at all uncommon, it is only in certain places that suitable deposits are found. At the present time, most of the glass sand used in Canada is imported from France, Belgium, and the United States. The French material, from Fontainebleau, near Paris, is known the world over as a very high quality glass sand. That from Belgium is nearly as good and is lower is price.

Jan 1, 1934

By D. J. McCulla

Mineral development and utilization affect the health of the economy and the pattern of long-term development throughout Canada. There are many diverse opinions on the contribution of minerals to the economy, but there is a dearth of adequate quantitative information. This paper discusses some recent research and provides some new information.

Jan 1, 1977

By Joan Weinberg

Seasonally adjusted new factory orders for primary metals declined in January, February, and March, especially in the steel industry. The decline was part of an apparent slowdown for the entire manufacturing sector. Orders for all durable goods, including not only primary metals, but also clay, glass, and stone products, fabricated metal products, machinery, and transportation equipment, fell in January and February. In March, orders rose a slight 0.8%. According to the U.S. Department of Commerce, the downturns in durable goods orders in January and February were the first back-to-back declines in 3 years. They were largely attributed to a drop in orders for transportation equipment, mainly auto-mobiles and aircraft, while the small gain in March was due to a surge in aircraft orders. Higher interest rates may be partly responsible for the slowdown in durable goods orders over the past 3 months. The higher rates have also hit the construction industry--another major end-user of minerals. Construction of new homes and apartments fell by a seasonally adjusted annual rate of 5.4% in March, following a 12% decline in February.

Jan 1, 1989

By David S. Brown

What troubles me so often about debates over the environment, which I have heard since I entered government in the late 1960's, is that the issues are so often presented as a false dilemma--the either-or fallacy in logic. The either-or fallacy allows only two possible choices: Either protect the environment or exploit it. In reality, however, there may be a few more options. The diverse, often competing, values that the Earth offers require us to weigh and balance those options through a range of policy options. A quality environment and economic growth and opportunity are not mutually exclusive. First, let me acknowledge that I support a set of resource values recognized in U.S. laws and deemed important down through history for the success of free, progressive, and secure societies: the importance of access to raw materials. Increasingly, however, mineral raw materials have been viewed at best as not particularly relevant to a sophisticated, technologic society, and at worst monstrously destructive of our natural environment. Both perceptions, in my judgment, are wrong.

Jan 1, 1989

No noticeable international economic recovery occurred during the first half of 1982. Industrial production continued to fall in the United States, Canada and Italy and to hold steady in France. Modest increases in production occurred in Japan, England and Germany, although some decline took place from March to April. The U.S. mining industry has been more severely affected by the world recession than the U.S. economy. This is not immediately obvious when comparing the U.S. mining industrial production index from 1981 to 1982, which decreased 8.5 percent, as compared to a 7.1 percent decline for total domestic industries. However, "mining" industry statistics in the U.S. national economic accounting system include petroleum and natural gas as well as minerals. When metal mining is isolated, the decrease in production from 1981 to 1982 is 19.3 percent. If metal mining production continues to perform at the same rate during the third and fourth quarters of 1982 as during the first half of the year, declines from 1981 levels will be quite severe. Aluminum will have declined 22 percent, copper 18 percent, iron ore 24 percent, lead 3 percent, steel 29 percent, titanium 2 percent and zinc 25 percent.

Jan 1, 1982

By Frank F. Aplan

In looking into the crystal-ball scene of minerals beneficiation for 1970 and beyond, an impartial observer becomes con- fused as to what has been done and what is possible in the way of improvements. The mining official must balance the burden which is being shouldered by the mineral industry for maintaining our environment in its pristine state on one hand, with the solid advancements made in technology and cost savings on the other hand. Then the official wonders if this is really the criterion for judging overall performance today. As a prospective engineer, Dave Bolles sees it this way: "Specialization has caused many engineers to subordinate everything to doing their job the cheapest and fastest way. In the future this won't be enough. The engineer in the mineral industry will be responsible not only for mining, concentrating and smelting, but also for the resultant wastes- the mine dumps, the tailing dams and the slag piles." (See Drift on page 63).

Jan 1, 1971

By Burt C. Mariacher

To note that environmental considerations had a major im¬pact on the minerals processing industry in 1971 would be something less than a profound observation. The degree of its importance was demonstrated by MBD when it established the Environmental Committee as a new unit committee within the Division to achieve greater participation in exchange of information relating to the technologies and problems involved. It is appropriate and necessary to devote special attention to this timely aspect of minerals processing, as its influence penetrates the research, engineering and operations of almost all unit technologies that comprise minerals processing. The pollution abatement aspect of this industry has been such a dominant factor in recent years there is reason to wonder whether progress in unrelated technologies has been curtailed. Perhaps so, to some degree, but unit committee reviews presented in this article suggest rather that it would appear to have served as a catalyst for accelerated progress in development of new methods and improvement in more conventional ones. Present concepts regarding primary metal or mineral recovery and by-product potential may change considerably as a result of improved technology in waste product treatment.

Jan 2, 1972

By R. W. Smith, K. H. Lee

Bond type simulated closed-circuit grindability tests and batch grindability tests were run on six pure minerals plus a limestone and a taconite ore. The simulated closed-circuit tests were made at five different meshes of grind. The minerals tested varied widely in hardness and breakage pattern. For all simulated closed-circuit tests both Bond and Holmes work indices were calculated and compared. The Bond grindability testlm6 has been widely and quite successfully used for predictions of such items as ball mill power requirements and as an aid in plant comminution equipment selection. The test is interesting in that although run as a series of batch tests it is over-all a simulated closed-circuit test with a circulating load of 250%. The simulated closed-circuit feature is probably the primary reason for the notable success of the test. Perhaps the major criticism that can be brought against the test is that it is time consuming, since it normally takes a trained technician about an eight-hour shift to perform it.4 For many purposes this is an acceptable time requirement. However, if a grindability test is to be used for mill control purposes it should be performed in as short a time interval as possible, preferably under an hour. Sometimes in industry strictly batch tumbling mill tests are run and an attempt is made to correlate such batch tests with plant mill operation. Then an attempt is made to adjust operating tumbling mills based on data from the tests. The tests, however, frequently do not correlate well with operating data. The purpose of the present work was to explore some of the similarities and differences between a simulated closed-circui.t grindability test and a batch type test. Six different minerals plus a limestone and a taconite ore were tested in the experimentation. These materials varied widely in hardness, breakage characteristics, etc. Standard dry Bond grindability tests were mn on all materials at 48, 65, 100, 150 and 200 meshes of grind. Feed material was prepared by stage cmshing to -6 mesh. Initial feed volume was 700 cc. Care was taken to maintain the standard constant weight (about 20125 gm) and number of balls (283) during all the tests. Rotational speed was 70 rpm. Table I lists the materials studied along with pertinent data regarding the materials and Bond grindabilities obtained. In addition, dry batch tests were performed on all materials. These tests were made in the same mill as was used for the Bond tests. An identical ball charge and an identical feed volume were used. After rotating the mill for a predetermined number of revolutions at the same rotational speed as for the Bond test, the material was removed and separated from the ball charge. A screen analysis was performed on this product. Knowing the original size distribution of the feed and the size distribution of the product, it was possible to calculate the grindability or grams of a particular mesh produced per revolution of the mill. After the screen analysis of the product, the various fractions were recombined and placed back in the mill for further grinding. After grinding for additional revolutions of the mill the procedure was repeated. Thus, it was possible to obtain grindabilities for each material at a number of meshes of grind and for various revolutions of the mill. Grind-abilities obtained from batch tests are shown in Table 11. COMPARISON OF BOND AND BATCH GRINDABILITIES Figs. 1A through 1D show relationships between batch and Bond grindabilities. Figs. lA, lB, 1C and 1D show respectively graphs indicating the relationships for batch tests run for 100, 300, 500 and 700 revolutions of the mill. For a particular material on each graph, points are shown for 200, 150, 100, 65, and 48 meshes of grind except for several missing coarse meshes of grind for galena which did not fall conveniently on the figures. For each material and graph the point nearest the origin is for 200 mesh, the next for 150 mesh, the next for 100 mesh, etc. Considering Fig. lA, it is interesting to note that all relationships shown are essentially straight lines. There are, however, considerable differences

Jan 1, 1969

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 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 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