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By Olav Mellgren

Part I. The interaction between potassium ethyl xanthate and lead salts has been studied thermo-chemically. It is shown that ethyl xanthate reacts with lead carbonate, basic carbonate, thiosulfate and sulfate according to principles of simple chemistry, whereas reactions with lead sulfite, metasulfite, basic thiosulfate and hydroxide at high pH are associated with secondary reactions. A new compound "xanthogen thiosulfate" is postulated. Part 11. Adsorption of ethyl xanthate on galena has been studied quantitatively and thennochemi-cally. It is shown that an ion-exchange mechanism governs the adsorption process and that the heat of adsorption of xanthate on galena is equivalent to the heat of reaction of ethyl xanthate with bulk lead salts. It is concluded that the entropy content of the surface "compound" on galena is different from that of a corresponding bulk lead salt. Alkali depression is in part shown to be due to the instability of the xanthate-galena system at high pH and to the formation of basic lead salts. Sulfate and carbonate ions are shown to have a stabilizing effect on the xanthate-galena system. PARTI. THERMOCHEMISTRY OF ETHYL XANTHATE AND OF ITS REACTION WITH LEAD SALTS In the past little attention has been paid to the chemistry of lead xanthate. It is known that xan-thates form slightly soluble compounds with lead and that suspensions of lead xanthates in alkaline solution decompose rather readily.' The solubility of lead ethyl xanthate is of the order of 2.6 x 10-6 moles per 1. At increasing pH the xanthate concentration of a saturated solution contains more xanthate. Thus at pH 11 this xanthate content is about 100-fold larger than at pH 7.1 Xanthates are known to be consumed when added to a suspension of slightly soluble lead salts such as lead sulfate and lead carbonate. It is unknown to what extent this xanthate consumption is due to a simple chemical reaction because, frequently, observations are made which reveal secondary reaction products in such reactions. Thermochemical study of the reaction between xanthate and lead salts offers a means to clarify the significance of these reactions as the enthalpy changes can be accurately predicted from heat of formation of lead salts in pure solution reactions. In the present work the heats of formation of lead ethyl xanthate from potassium ethyl xanthate and lead salts are determined and some thermochemical aspects of xanthate in solution are studied. The results of these investigations are presented in Part I. In Part II the heat of adsorption of ethyl xanthate on galena surfaces is presented. All enthalpy changes were measured directly in a microcalorimeter. Calorimeter: The calorimeter used for measuring enthalpy changes was similar to that used by Redinha and Kitchener2 which was based on a description by Derbyshire and Marshall.3 Other useful references4,5 are listed. A sketch of the calorimeter

Jan 1, 1967

By R. B. Tippin, J. S. Browning

Inasmuch as the higher grade potash deposits are rapidly being depleted, it is important that economic beneficiation techniques be developed for recovering potassium compounds from lower grade sylvite ores and deposits containing clay materials. The Federal Bureau of Mines has conducted research to develop processes for heavy liquid concentration of potash ores, This method of concentration is discussed, and results of tests made on potash ores from New Mexico are presented. The tests demonstrated the technical feasibility of producing near commercial-grade potash concentrates, with a high recovery of the contained sylvite. The concentration of minerals based on their differences in specific gravity dates back to the very beginning of mineral dressing, and the use of heavy liquids in the laboratory to achieve optimum mineral separations has been utilized for many years. With the advent of froth flotation and its success, the incentive to develop new processes has remained relatively dormant. However, flotation refinements in the nonmetallic ores have not progressed as rapidly as in metallic (sulfide) ores because of the complexity of the deposits and the chemical similarities of the minerals.

Jan 1, 1967

By E. C. Tveter, R. B. Tippin

The separation of minerals by heavy liquids is a standard laboratory technique which goes back at least 50 years, but commercially economic application of this principal to ore concenfration has been prevented by problems of liquid recovery. Recent investigations which demonstrate the different types of liquid-solid systems on various ores using the two major heavy liquids - methylene bromide and tetra-bromoelhane — are discussed in this article. As a result of these studies, over-all liquid recovery, and especially desorption of heavy liquid from the mineral surface, was improved by the use of surfactants as well as both thermal and mechanical energy. The examples given in the article indicate that heavy liquids which should find major commercial use in ore concentration are now available. The sink-float process using a heavy liquid medium has long been recognized as a nearly perfect method of mineral separation based on the differences in density of the minerals. The use of heavy liquid separation (HLS) offers the potential of an ore dressing method that provides the maximum possible natural concentrate grade and high recovery. In addi- tion the process requires no water, causes no waste disposal problems, and is extremely simple — the crushed ore is merely introduced into a liquid whose density is between that of the minerals to be separated. The minerals lighter than the liquid float while those heavier than the liquid sink. As such, HLS has become a standard laboratory tool but major commercial application has been prevented by the requirement for complete recovery of the heavy liquid, imposed by economics and materials handling hazards. Investigations, both in the United States and abroad, have shown that improved liquid stability as well as improved chemical engineering techniques brighten the future for HLS in ore dressing. The available commercial heavy liquids suitable for mineral separation cost from $2.00 to $20.00 per gallon1 and on this basis alone their complete recovery is economically desirable. Possibly of even greater importance is the fact that any residual heavy liquid remaining on the products could create a serious toxicity hazard. Consequently, to make the process commercially attractive requires (1) essentially complete removal of the liquid from the ore products and (2) optimum recovery of the liquid for reuse. Until recently these two stipulations have remained as obstacles but laboratory and pilot plant research now in progress suggests that these may soon be overcome. Various heavy liquid recovery systems have been proposed to meet these requirements and might be classified into one or more of the following three general classes: Solvent Wash (Fig. 1): The dissolution of the heavy liquid from the ore with a less expensive solvent,

Jan 1, 1969

By W. B. Dancy, A. Adams

Laboratory test work on heavy liquid separation of sylvite from halite is reported. Numerous tests were run on sylvite ore sized in the ranges of 4x20 mesh, 10x65 mesh, 8x100 mesh, -8 mesh and -10 mesh with heavy liquids in the range of 2.05 to 2.15 sp gr. From the test results, it was concluded that, with the type of ore under study and a size in the range of -8 mesh, a recovery as high as 90% could be achieved with a product grade of 70% KCl. However, a final product at an acceptable recovery cannot be made with one pass, and the float must either be further processed with heavy liquids or dried and sent to a conventional froth flotation circuit. Potash ores occurring in this country consist essentially of sylvite and halite plus minor amounts of magnesium sulfate salts and montmoril-lonite-type clays. Recovery of potash minerals from evaporite ores in the North American potash fields is accomplished almost exclusively by use of amine flotation. European practice involves froth flotation as well as solution-crystallization processes. Laboratory and pilot plant test work has been reported in Europe and the U. S. on the application of heavy media separation to potash ore beneficiation. Work was probably discontinued because of lack of ore with the required very coarse liberation characteristics (1/8 to 1/2 in. liberation size). Sylvite, with a gravity of 1.99, and halite, with a gravity of 2.17, appear to be ideal for separation by heavy liquids, which are now available in gravities from 1.59 to 2.95. This paper reviews preliminary results obtained from laboratory test work on heavy liquid separation of sylvite from halite. TEST WORK The heavy liquids used in the tests under discussion were chlorobromethane, with a specific gravity of 1.923, and dibromethane, with a gravity of 2.490. These liquids, completely miscible, were combined in the proportions needed to give a mixture having the desired specific gravity. Feed for the laboratory tests was mine-run ore screened to the desired mesh sizes. In conducting the tests, the sample was fed at a constant rate into a stream of heavy liquid and the mixture directed into a small separatory vessel. The float overflowed into a collecting pan while the sink collected in the bottom of the separatory vessel and was removed at the end of the test. Approximately 500 g of feed constituted a charge. Pulp density of the feed was kept low to prevent particle to particle interference in separation. With feed in the range of 8x100 mesh, a pulp density of under 10% solids by weight was found advisable. With coarser feed the pulp density could be carried as high as 15% solids. Time of separation was very rapid. In the case of 4x20-mesh material, separation was effected in 15 to 30 sec; with -10-mesh feed, separation required about 1 to 2 min. SPECIAL EQUIPMENT Since heavy liquids are toxic to varying degrees, all separatory work was carried out in a standard laboratory fume hood. It was noted that complete removal of fumes was not being effected; therefore the hood construction was modified, resulting in a completely satisfactory arrangement for heavy liquid test work. In the interest of safety, details of this fume hood are reported here. Unlike most fumes, heavy liquid fumes tend to settle and flow like water, rather than to rise like a gas. Working on this assumption, a standard water drain was installed in the hood. Across the front of the hood a 1-in. barrier was constructed. In the rear of the hood a false back was installed, with an adjustable sliding door on both the bottom and top of this panel. As shown in Fig. 1, the exhaust fan pulled a vacuum behind the barrier, sucking the heavy fumes from the bottom of the hood. Another addition was the drying box, shown to the right of the hood. This is simply a box covered on top with hardware cloth and connected by a 6-in. inlet to the hood. Sample trays made of fine mesh wire filter screens were found ideal for drying samples. With this arrangement, air flowed completely through the sample and all fumes were drawn into the hood. In use, it was found effective to cover with a

Jan 1, 1963

By R. Wild, F. A. Wright

When a blast furnace has a certain defined burden and is operated under fixed conditions of blast temperature, etc., the fuel efficiency is determined by the extent to which the reducing gases can remove oxygen from the burden in the furnace stack. This is determined by two distinct factors: 1) The uniformity of gas-solid contact, and 2) The ease with which oxygen can be removed from individual pieces of burden. This latter is often called burden reducibility. When burdens were poorly prepared the first factor was by far the most important and a study of the reducibility of individual lumps was of rather academic interest. In recent years good burden preparation with emphasis on uniformly sized material has led to greatly improved gas distribution in the stack, and thus the second factor has become much more important and there has been a marked increase in interest in methods of measuring reducibility. This paper explores the Linder method of measuring such reducibility. The measurement of reducibility of burden materials must be carried out under conditions duplicating, as nearly as possible, those of the blast furnace stack. This is very difficult since the blast furnace process is a counter-current one, and thus the initial conditions encountered by the solid (gas temperature, composition, etc.) are the result of heat and mass transfer occurring lower down the stack. Any method of burden testing which does not take this into account is, at least to some extent, based on arbitrary assumptions. In an attempt to study blast furnace reactions under non-arbitrary conditions BISRA adopted the SCICE technique as a method of investigation. This technique has been used with a measure of success.' The SCICE technique, however, was found to be too slow for use as a routine test for burden materials and it was decided to construct additional equipment for burden testing. A test was required which would: 1) Be as realistic as possible. 2) Be quick and easy to operate. 3) Give some indication of the breakdown likely to take place during reduction in addition to a reducibility index. After a critical assessment of the reducibility tests which have been proposed it was decided to adopt the Linder test equipment and procedure as a basis for burden testing. THE LINDER TEST APPARATUS AND PROCEDURE The apparatus which was constructed (Fig. 1) was the same as that described by Linder2 except for minor changes in design. Linder also laid down a test procedure which he had derived from the results of investigations on Swedish blast furnaces. The variations of temperature and gas composition during the test were defined; these are shown diagram-matically in Fig. 2. BISRA's intention was to use the standard temperature and gas composition programmes for testing a variety of burden materials and also to investigate the influence of different programmes on standard burden materials, making use of information from the SCICE apparatus wherever this is possible. Up to the present, effort has been concentrated on the first part of the programme, and work on the second part has only just commenced. For each test 200 g of coke and 500 g of burden material were used. Linder had recommended that the coke and burden material should be between 1 and 1 1/2 in. and this was adhered to in early experiments on ores and sinters. Since the eventual aim of this work was to relate the test results to blast furnace operation, it was decided to carry out subsequent experiments using burden material in the size range used in the blast furnace, as far as this was possible. If the main interest was, for example, a comparison of the products resulting from different methods of agglomeration, then there would be advantages in using burden materials as close as possible to a standard size. After the charge had been placed in the reaction tube and this had been connected to the gas supply, rotation of the reaction tube at 30 rpm was started and the reduction programme was commenced, the gas temperature and composition being manually controlled according to the programme shown in Fig. 2. After the reduction test the charge was cooled in a nitrogen atmosphere. It was then removed from the reaction tube, the coke and burden separated, and the extent of burden breakdown assessed by screening it at 10 and 30 mesh. The extent of reduction was then

Jan 1, 1964

By R. J. Charles

PREVIOUS study' of simple impact systems indicated that energy required for fracture and size reduction of brittle materials is greatly dependent on the type of loading that is employed. In this regard it was postulated that fracture and size reduction of a brittle specimen might be accomplished by a high velocity impact at an energy level at which a low velocity impact would leave the specimen relatively undamaged. The finite time required to propagate energy away from the point of loading of an impacted object to other parts of the object and to its supports may permit a concentration of energy at the point of impact if the rate of loading is high. Localizing of energy at the point of impact could quickly initiate fractures that would propagate through the impacted material along with the traveling stress waves. As the cracks form, the initially absorbed strain energy would be released and portions of it travel ahead of the wack tips as stress waves. These secondary stress waves, combined with the initial stress waves derived from the impact, would produce high localized strain conditions in front of the fracture zone. The fracture zone would propagate and the specimen shatter. High rates of loading are brought about by short impact times, in turn obtained by employing high velocity projectiles that are of small mass compared to the impacted object. In the case of a low velocity impact, at an energy level equal to that of a high velocity impact that causes fracture, loading rate would be relatively

Jan 1, 1957

By O. E. Palasvirta

Close examination of most so-called n.eu processes in mineral dressing reveals that they were conceived and developed a long time ago. High-intensity magnetic separation is no exception. Although its application in iron ore beneficiation seems new, in Germany the process has been commercially successful for almost two decades. High-intensity separators have long been standard equipment in the glass sand industry; they have also been used in concentrating some of the more unusual para-magnetic minerals. The basic features of an induced-rotor, high-intensity magnetic separator were described by Desire Korda in Paris in 1905,' and many patents have since been issued for improvements on the original design. Fig. 1 shows the basic design of an induced-rotor separator. Several U. S. manufacturers have been supplying induced-rotor separators for many years, but these are all devices of relatively low capacity, not suitable for treating such low-cost commodities as iron ore. On the other hand, two German manufacturers are offering induced-rotor separators of high capacity, both proven in the field. The present investigation was prompted by the apparent success of the German installations and by the discovery of iron ores on this continent which may be amenable to high-intensity separation. The objective was to gain better insight into the underlying principles of separation in a high-intensity field and to use this knowledge in selecting or designing an optimum separator. THEORETICAL CONSIDERATIONS he well known low-intensity magnetic separators are. without exception, of the the magnet type with more or less similar field shapes. It is therefore permissible to speak of their comparative strengths in terms of field intensity alone. However, proper understanding of the high-intensity magnetic separation process requires somewhat deeper analysis of the relationship between the magnetic field and the attractive force. Contrary to a widely held belief, a magnetic field of parallel lines of flux exerts no attractive force on a magnetically susceptible particle, but merely aligns its poles parallel to the lines of flux. On the other hand, a non-uniform field attracts a magnetically susceptible particle in the direction of the converging lines of flux. Thus the force of magnetic attraction varies as the product of the field intensity and the field gradient: dH ds As the induced-rotor magnetic separator is primarily intended for separating feebly magnetic materials, it is important that maximum attraction be attained. For the designer, then, the relationship between the magnetic field and the attractive force has the following implications: 1) Insofar as possible, the separation gap must be saturated with flux. 2) The rotor surface must be shaped to insure maximum convergence of lines of flux toward the rotor. 3) The primary pole face (opposite the rotor, on the other side of the separation gap) must be shaped so that the lines of flux do not diverge from it at any location in the effective separation zone. The actual attractive force of the rotor, and its critical speed, can be calculated as shown by Runo-linna, provided that the true flux density, the field gradient, and the magnetic susceptibility of the mineral can be measured with sufficient accuracy. The irregular shape of the rotor surface makes flux measurements difficult, but it can be done if a suitable gaussmeter is available (see Fig. 2). Calculations by the author, and comparisons with the centrifugal force exerted by the rotor, indicate that the force pinning a hematite particle to the rotor is of the same order of magnitude as the force holding a

Jan 1, 1960

By M. E. Wadsworth, T. D. Chatwin

The kinetics of sulfidization of hematite (Fe203) by H2S gas at various partial pressures have been determined over the temperature range of 170° to 500°C. The process was controlled by thin films of pyrite (FeS2) and troilite (FeS) which were protective and formed diffusional layers. At higher temperatures the thermodynamic drive to form FeS2 decreased, and consequently the rate of formation of FeS, decreased. Conditions for the development of thin layers of FeSz consisting of 10 to 100 atomic diameters are presented. Laboratory flotation results on synethetic ores indicate floatability identical to that of pyrite of normal xanthate flotation. The prospect of high-temperature sulfidization of metal oxides using H2S, S, or other sulfur bearing compounds is intriguing as a potential activation process for flotation since the thermodynamics are very favorable for a large number of systems. If the kinetic parameters are sufficiently well understood it may be possible to provide surface sulfide layers a few angstroms thick, thus imparting normal sulfide floatability characteristics to the oxide. For thin layers the total sulfur pick-up would be small except for very high surface area materials but in most cases this sulfur could be readily removed by roasting if necessary. The general reactions for the sul-fidization of metal oxide MxO, to a metal sulfide MpSq using H2S may be written for the three conditions py > xq; py < xq; and py = xq: A large thermodynamic advantage is obtained in many systems because of the relatively large negative free energy of formation of H,O compared to H,S. For the temperature range 2S° to 1500°C &apos; where AFOis the standard free energy and T is absolute temperature. As is evident from Eqs. 4 and 5, the free energy of formation of H ,0 is approximately 35 to 37 kilocalories per mole greater than that for H,S over broad variations of temperature. For oxide-sulfide systems as outlined above, sulfidization may be expected to occur for the conditions: Groups I and 111: that is, if the terms on the right are more negative than those on the left the reaction is expected to occur thermodynamically. The value hFg,(,) is included in Eq. 6 since hFLzs is based upon gaseous S2 rather than the normal reference state, orthorhombic sulfur. The

Jan 1, 1969

By Whitman E. Brown, Louis J. Erck

The installation in 1948 of a Hum-phrey~ spiral concentrator section at the Hill-Trumbull plant of The Cleve-land-Cliffs Iron Co. is the latest commercial method on the Mesabi Range being used for the recovery of fine iron ore. In two stages of concentration 84 spirals treat approximately 120 long tons per hour of minus ? in. ore. These spirals augment the production of the heavy-density plant which recovers the plus 36 in. iron from the plant crude ore. Structure of the ore is such that, when crushed, about 50 pct of the plant crude is minus ? in. size. After de-sliming in a 66 in. Akins classifier, grinding the classifier product in a ball mill and again desliming in a 78 in. Akins classifier about 15 pct of the crude ore remains to be treated in the spiral plant. Overall recovery of the ball mill feed in the Hill-Trumbull spiral plant during the 1948 season was about 53 pct of the weight and 66 pct of the total iron content. Of the actual feed delivered to the spirals from the 78 in. classifier 64.9 pct of the weight was recovered containing 73.7 pct of the total iron. The average analysis of the spiral concentrate is 55.05 pct Fe and 14.83 pct SiO2. An average of mill assays during the 1948 season is given in Table 1. The Hill-Trumbull plants treat both wash ore and jig-type ore. During the 1948 season spirals were used only on the fine sizes of jig-type ore. At times the deslimed minus ? in. size is of sufficient grade to warrant bypassing the spirals but in the main the fine size is delivered to the 48 first stage spirals and thence to the 36 cleaner or second stage spirals. In the past several years numerous Mesabi Range ores in the fine size cate- gory have been tested by a wide variety of beneficiating equipment. The prodigious amount of research devoted to the recovery of values in the fine ore reflects the dire need of the iron industry to squeeze the last possible unit of iron from the mined ore and to develop suitable equipment and processes to satisfactorily concentrate the leaner horizons as they are encountered in the process of mining. Large governmental and private appropriations have been allotted, new laboratories built, research and technical staffs increased, and operator-manufacturer cooperative agreements applied to hasten the solution of the problem. The University of Minnesota, at its Eighth Annual Mining Symposium in January 1947, dedicated as its objective the bringing to light of technological developments in iron ore beneficiation. Papers were given at that time relating to processes being developed. Specifically, these papers reviewed flotation, Baum jig, selective media concentrator, Hardinge concentrator, Dorrco sizer, heavy media concentration, Hydrotator, and the Humphreys spiral. The Cleveland-Cliffs Iron Co., after encouraging results from tests in a small pilot plant using one full size spiral, made the first commercial installation of Humphreys spirals on the Mesabi Range at their Hill-Trumbull mine, Taconite, Minn. This company

Jan 1, 1950

By Whitman E. Brown, Louis J. Erck

L. A. ROE*—This paper is one of great value to the iron ore industry. The Humphreys spiral is a relatively new tool and gives promise of being quite useful in solving certain problems of iron ore beneficiation. Spirals have been tested on a martite ore at the Benson mine of Jones and Laughlin Steel Corp. in northern New York State. Our New York ore is considerably different, physically and mineralogically, than the one mentioned in this paper, and contains only 25 pct iron. This ore can be processed on spirals to give a concentrate containing 62 pct iron with an 85 pct recovery. On our particular ore we found operating difficulties when the spiral feed was coarser than 14 mesh. These were chiefly due to excessive "build-up" of locked middlings in the spiral circuit. In extreme cases these middling particles would accumulate to such an extent that the plant had to be shut down and the spiral surge tanks cleaned out. It is interesting to note that there exists a close relationship between the results of tabling a given iron ore and concentration of this same ore on Humphreys spirals. The size range of the ore must, of course, be within those limits acceptable to spiral concentration. Comparative tests on several of our mar-tite ores showed tabling results to be the same as spiral results. The authors make no mention of the use of a tailing stream splitter (now available from the spiral manufacturer) which is a useful tool in studying iron losses in the tailings stream. 011 our particular martite ore we found a considerable accumulation of fine-sized iron ore particles in the outside portion of the tailings stream. This fraction may be amenable to further treatment. E. H. ROSE*—The authors have concluded an interesting piece of work and this paper is an excellent factual account of a rapid and somewhat unusual transi-;ion in practice in the plant described. Perhaps it was modesty on their part which caused them so casually to limit to one sentence the fact that "several other methods of concentration on the fine ores representative of the Hill Trumbull group . . . failed to produce consistently an acceptable grade and recovery of finished product." The fact is that they were confronted by a difficult mineral-dressing problem and they are to be congratulated on their courage and persistence in staying with it until a satisfactory solution was evolved. A visitor to the plant might have been mildly astonished, as I was, to see one type of concentrator handling that part of the load early in the 1947 season, its experimental replacement by another a little later, and then in 1948 to see that both types had simply disappeared and their place taken by the spirals which were operating as placidly as though they had been there all the time. In working out economic methods of beneficiating Alabama red ore, most of which development is still ahead of us, it is likely that we also will pass through a period of successive disappointments, for we too have a problem where it is next to impossible either to "guess &apos;end right in the first place," or, because full-scale operating cost is such an important factor, to lay the ultimate answer on the line in advance by means of laboratory experimentation. Iron ore being what it is instead of what it used to be, it is encouraging to have the example the authors have given us today that a tough nut that will not crack on the first blow or the second is apt to do so on the third or fourth.

Jan 1, 1950

By L. R. Plitt, E. O. Lilge

Tests carried out with both kaolin and silica slurries show that flocculants of the polyacrylamide type can be used to improve the thickening performance of hydrocyclones. This thickening improvement demonstrates that contrary to previously held theories, flocs can be formed which are capable of resisting the shear forces in a hydrocyclone. For the 1.25-in.-diam cyclone used, optimum thickening occurs when the flocculant solution is injected into the slurry stream at or near the feed inlet. Hydrocyclones offer many distinct advantages over gravity thickeners. These advantages include simplicity, low initial and operating costs, small space requirements, and flexibility of operation. In spite of these advantages hydrocyclones have not been widely used as thickeners. The main reason for their lack of application is that hydrocyclones are unable to efficiently remove semicolloidal particles (less than 5 microns) from the suspending solution. In gravity thickeners, the fine particles can be induced to form particle aggregates, or flocs, which have the settling characteristics of large particles. In the hydrocyclone, however, it was always assumed that the existence of shear would prevent the formation of flocs.1-3 Thus, if no floc structure is retained, the thickening hydrocyclone must be designed so that its separation size is below the size of the smallest particle to be recovered. To obtain a very small separation size requires the formation of very high centrifugal forces, which necessitates the use of small-diameter cyclones. Small hydrocyclones have, in turn, very low throughput capacities which render them impractical for many industrial thickening applications. Thus, if the effects of flocculation cannot be utilized, the usefulness of hydrocyclones as thickeners remains limited to pulps which contain no very fine particles. It is well established that most substances acquire a surface electric charge when brought into contact with an aqueous medium. The repulsive interactions between similarly charged particles act to prevent flocculation. One method of flocculating a dispersion is to neutralize the repulsive surface charges by the addition of an electrolyte. The reduction of the electrostatic surface charge (Zeta potential) then permits the universal van der Waals attractive forces to operate between the atoms of the various particles and form particle aggregates. The lime additions used by thickener operators promotes flocculation by this mechanism. A second method of flocculating a dispersion is by the addition of long-chain macromolecules. In this case flocculation is brought about by a bridging mechanism in which the molecules are adsorbed with part of their length on two or more particles, thus forming a molecular bridge between the particles.4,5 The molecules also form bridges between themselves when a single particle is bonded to several polymer molecules. The type of bonding between the flocculant molecule and the particle may be hydrogen bonding, chemical bonding, or electrolytic attraction.6 The flour and glue which are used as thickener additives are believed to promote flocculation in this manner. In the past decade synthetic long-chain polymers with extremely high flocculating capabilities have been developed. The flocs formed by these new polymeric flocculants are larger and more shear-resistant than those formed by the presence of electrolytes.7 The advent of these flocculants raises the question: Are the flocs formed by these synthetic polymers stable enough to resist the liquid shearing forces in a hydrocyclone? The investigations reported in this paper were carried out in order to provide some answers to this question. EXPERIMENTAL WORK For the bulk of the test work a 5% slurry of commercially available kaolin with an average particle size of 5 microns was used. An initial evaluation of the available flocculants was carried out to determine which flocculant formed the most shear-resistant flocs. A combination of the techniques used by Healy7 and Booth8 was used for this purpose. This initial study revealed that the neutral high-molecular weight polyacrylamides produced the most shear-resistant flocs. One of these flocculants, Separan MGL*, was selected and then used for all the hydrocyclone tests. The flocculant was dissolved in water and added to the hydrocyclone as a dilute solution.

Jan 1, 1968

By R. F. Yap, N. Arbiter, C. C. Harris

A fully-instrumented driving mechanism has been constructed to study the power, aerating and solid suspension characteristics of several laboratory flotation machines. Machines operating over normal flotation speed ranges give substantially constant power numbers in liquid systems indicating that they operate close to fully baffled turbulent flow conditions. Owing to lack of geometrical scaling, power numbers for different sizes of cells of the same make are different. Even larger differences occur between cells of different manufacturers. For a given impeller, varying the tank size did not significantly affect the power consumption. Tank geometry and baffling has a slight effect on power consumption with shrouded impellers. For a given impeller speed, suspension height decreases while power increases with increasing mass of solids in suspension. While power consumption is hardly affected by particle size and clearance between the impeller and tank bottom, the suspension height significantly increases as clearance increases and as particle size decreases. Aeration was found to affect not only power but also the suspension characteristics of the machine. For closely sized particles, drastic sedimentation occurred when a critical value of the air flow number was exceeded. The critical air flow number decreased with increasing particle size. This effect was less marked with a wide particle size range. The self-aerating capacity of flotation machines increases with cell size at a given speed for the same impeller-shroud system, but decreases in the presence of frother and solids. Equations have been established for correlating all of the studied variables. Data taken from the literature were also correlated with these equations. The modern mechanical flotation machine has, over a period of 60 years, displaced other designs to become the dominant type. Once the correct chemical environmental conditions have been established, the major requirement, selective mineral-air adherence, is essentially a function of two operating variables — impeller speed and air rate. The special nature of this dependence is such that in the same apparatus, but under different operating conditions, adherence can be either prevented or destroyed. Another aspect of this observation is that flotation machines though differing in detail to a considerable extent can produce similar metallurgical results. It must be concluded that having determined the correct reagent levels, establishing the correct operating conditions are at least as important as machine design. Since about 1960, after 30 years of fairly stable circumstances, manufacturers have been developing new types of machines whose major feature is emphasis on pulp flow characteristics by virtue of new im-peller-stator designs. As far as can be ascertained, these new designs necessitate radical departures from accepted impeller speed-air rate values. Performance data are still awaited. Flotation machine development has been empirical, as is selection of operating conditions. The purpose of the work at Columbia University has been to elucidate the fundamentals of the subject so that the purely mechanical aspects of the flotation process can be understood in hydrodynamic terms.1-6 Hopefully, this might lead to intelligent selection of a particular machine and its operating conditions for a specific ore based on a minimum of testing, or even to new types of flotation machines. The present investigation is the most comprehensive to date.7,8 Earlier work, which was largely exploratory, has been repeated and extended and employes the most accurate measuring techniques available. Additionally, sufficient hydrodynamic data were obtained under flotation conditions to delineate the relevant operating ranges. Attention has been given to scaling in that several geometrically scaled tanks and impellers have been constructed and tested; it has been pointed out elsewhere that undistorted geometrical scaling rarely pertains in flotation machine design.5 This paper is divided into sections dealing with relevant combinations of the three phases: liquid, air and solid. Summaries of the literature have been given in previous publications2-4 and will not be repeated here. Recently, several reviews of mixing have appeared, which can be usefully referenced.9-11 It is of interest to note that flotation is not included

Jan 1, 1970

By M. A. Cook

Sutherland used an ion-pair adsorption model to derive the author&apos;s hy-drolytic pee-acid) adsorption equation for the contact bubble curves of Wark and Cox. To do so it was necessary to postulate that the sum of coverages of surface anion sites by the collector and depressant anions is practically unity. It is here shown that the free energy of Sutherland&apos;s postulated collector ion (x-)-depressant ion (OH-) exchange reaction (for no other than the OH- to compete with X-), namely EX + (OH-) Z SOH- + X-, is in some cases positive and X- should not even adsorb. Also, in many cases the (OH-) adsorption must be quite negligible even though the collector covers only about a sixth of the mineral surface at the threshold of air bubble contact. This, however, contradicts the postulate that permits one to derive the correct bubble contact eqwztion for the ion-pair model. Furthermore, the requirement for charge neutrality leads in the ion-pair model to the (impossible) constancy of the ratio @+)/(OH-) along a contact bubble curve in which pH may change by more than seven units. HYDROLYTIC ADSORPTION EQUATION Hydrolytic (free-acid or free-base) and ion-pair (H&apos;, X-, or R&apos;, OH-) adsorption models of the collector in metal sulfide and similar flotation systems are superficially alike and somewhat difficult to differentiate. This is because they yield, under seemingly valid assumptions, equivalent forms of the equations describing the distribution of the collector between the aqueous solution and the mineral surface. This has been discussed by the author and associates1-4 and more recently by Sutherland,&apos; both for simple collector-mineral and for more complicated collector-depressant-mineral systems. In the hydrolytic adsorption model the equations describing the contact bubble curves of Wark and coxeJ7 are as follows :2 Here X is the collector anion, D- the depressant anion, 9, and On are the fractions of the free-acid sites S on the surface of the mineral covered by collector and depressant free acids, respectively, and @ is the fraction of uncovered sites. Kx is the free-acid collector dissociation equilibrium con- stant, K1 that for the free-acid collector adsorption, KD that for the free-acid depressant dissociation, and K2 the equilibrium constant for the free-acid depressant adsorption. Eqs. 1 to 5 yield upon simultaneous solution the result is the critical free-acid concentration for bubble contact in the absence of depressant-free acid. Eq. 8 expresses the conditions along a simple collector-mineral contact bubble curve for the case HD = 0, or V = 0. Last and Cook showed that Eq. 6 applies generally and with good accuracy in the collector-depressant-metal sulfide mineral systems. Inci-dentally, it has been shown by infrared absorption studies that in some cases the free-acid adsorption process splits out water.&apos; In this case, Eq. 2 might be written SHOH + HX Z SHX + H20, with a similar equation replacing Eq. 4 for depressant-free acid-water exchange. This possibility does not change, however, the basic equations or considerations of the hydrolytic adsorption model. Indeed, this type of free acid-water exchange reaction was predicted for fluorite and iron ore flotation by oleic acid in the dry grinding and boiling processes.410

Jan 1, 1961

By R. W. Harper, M. C. Fuerstenau, J. D. Miller

Data were obtained with hematite with octyl hydroxamate and oleate as collectors to determine the mechanism of collector adsorption and also to establish the roles that conditioning time and temperature assume in this system. The presence of hydroxy complexes of iron are apparently necessary for chemisorption of collector to occur, and it appears as if extended conditioning times and elevated temperature promote greater dissolution of the mineral and hence greater concentrations of hydroxy complexes. Data were also collected with two natural hematitic ores. With one ore that was ground to 70% - 15u, an addition of 0.4 lb per ton hydrox-amate resulted in a final concentrate recovery of 86% at a grade of 64% iron. Satisfactory concentrate grade could not be obtained with fatty acid under these conditions. The effect of conditioning time prior to the addition of collector was also examined with another ore. When the ore was conditioned for 3 min, 19% of the iron was recovered in the concentrate at a grade of 67% Fe. With a conditioning time of 7 min, 73% of the iron reported to the concentrate at a grade of 62% Fe. These products were obtained with an addition of 0.2 lb per ton hydroxamate. This ore also responded well to flotation with fatty acid. The use of potassium octyl hydroxamate as a collector for iron oxide has been the subject of an earlier study.1 From this initial study, it was suspected that hydrolysis of surface ferric iron was involved in collector adsorption. More recent work in other systems has shown that slight mineral dissolution, followed by hydrolysis of cations common to the mineral lattice, is apparently necessary, and that adsorption of these hydroxy com- plexes probably occurs prior to the adsorption of collector. In view of these facts, work has been continued on the hydroxamate-hematite and oleate-hematite systems to gain better insight into the mechanisms of collector adsorption on iron oxide. Microflotation experiments in conjunction with infrared analysis were used in this regard. In addition it was felt necessary to establish more clearly the responses that can be obtained from natural ores when hydroxamate is used as collector as compared to those obtained when fatty acid is used. Experimental Materials and Techniques Pure potassium oleate, potassium octyl hydroxamate, synthesized from hydroxylamine hydrochloride and methyl octanoate, and a distilled Tall Oil were employed as collectors. Conductivity water was used in the

Jan 1, 1971

By A. F. Witt, A. M. Gaudin, A. K. Biswas

Finite contact angles in the rutile-water-organic liquid system are traceable to contamination or are due to addition of a surface-active agent. Finite contact angles are invariably accompanied by hysteresis.1-7 Besides surfactant concentration and pH, the nature of the organic liquid is found to be a factor influencing the magnitude of contact angle hysteresis. In a recent paper the authors have reviewed principles and applications of measurement methods for contact angles and their hysteresis.22 In this paper, these methods are applied to a system consisting of rutile, an organic liquid (benzene, decane, or dode-cane) and water. Surfactant (dodecylamine hydro-chloride) was used at various concentrations and various pH values. MATERIALS A synthetic rutile crystal supplied by the Linde Co. was used. It is a cylinder 1/2 in. diam, with faces cut perpendicular to the c-axis. The crystal is stated to be alumina-free and to be 99.9% pure. Rutile is a high surface energy solid, its calculated average field strength being 2.7 x 105 e.s.u.,9 its dielectric constant10 is 114. The zero point of charge of rutile was measured11 and found to be at pH 6.0. The atomic distances and bond angles of the tetragonal crystal of rutile have been precisely determined.l2 The organic liquids were specially purified. Reagent grade benzene was repeatedly shaken with concentrated sulfuric acid to remove thiophene, then neutralized with sodium hydroxide solution, rinsed with distilled water, dried overnight over anhydrous calcium chloride and filtered. The refractive index of this chemically purified benzene was 1.4977 (at 25°C) - very close to that of pure benzene (n25 1.4979).13 Both n-decane and n-dodecane were washed with aqueous sodium hydroxide, concentrated sulfuric acid (repeatedly, until the acid layer was colorless) and again with alkali, to free the organic hydrocarbon from fatty acids and unsaturated hydrocarbons. The organic phases were subsequently washed with distilled water and dried over anhydrous sodium sulfate. The filtered hydrocarbons were then distilled under vacuum (9-10 mm pressure). Decane, thus purified, showed traces of unsaturated and of carboxylic compounds. On gas chromatographic analysis the purified n-dodecane showed the presence of two impurities. However, the relative retention times of these components did not change substantially when measured on a polar or a nonpolar column. This indicates that the compounds were probably in the same polarity class, i.e. the components were nonpolar like dodecane. Conductivity water has always been one of the liquids. Conductivity of the water used was 10-6 ohm-&apos; cm". Dodecyl ammonium chloride was prepared from pure amine (supplied by Armour and Co., Chicago), by Li in the MIT Mineral Engineering Laboratory.14 The critical micelle concentration at 25°C is known, 0.0138 mol per liter15 or 3.06 gpl. All our experiments have been done at concentrations lower than the critical micelle concentration. The glass vessels, glass drop holder and the rutile crystal were all cleaned with hot chromic acid followed by distilled water, concentrated hydrochloric acid, and again distilled water, and conductivity water. During the experiments, a nitrogen atmosphere was maintained. For this purpose, commercially purified nitrogen was further purified by passing it over hot copper wire at 450°C, then through columns of acidic chromous chloride solution, concentrated alkali solution and distilled water. APPARATUS AND METHODS Hysteresis was produced by the "captive drop" or constant volume drop method as well as by the "expanding-contracting drop" or variable volume drop method. The image of the drop while it is expanding, contracting or moving is projected on a screen and photographed. The developed film is projected through an enlarger and the contact angles measured with a protractor.

Jan 1, 1964

By D. W. McGlashan, K. N. Mcleod

IN the use of free bubbles with precise temperature control and continuous pH measurement, the contact angle apparatus differs from all previous equipment. Experimental procedures differ sharply from the captive bubble method1,2 of introducing the gaseous phase in the three-phase system. When freed from the tube and captured by a solid surface, a bubble more closely conforms to the spherical ideal set up by the usual mathematical analysis of surface free energy or surface tensional relationships of the forces involved. The assembled equipment, Fig. 1, departs from the usual contact angle apparatus in providing: 1) water circulation for fixing temperature, 2) instruments to measure and record pH during testing, and 3) a system for producing and using free bubbles. The apparatus allows testing over a broad range of closely controlled conditions, and the use of free bubbles gives contact angles independent of operator manipulation, which was unavoidable in the older captive bubble method. A bubble released below the specimen rises through the liquid and contacts the mineral. If the mineral is gas-avid the bubble adheres, developing a finite contact angle. Reaction cells (1), 2x33/8x5 3/16 in. ID, are of pyrex glass 5 mm thick. To prevent optical distortion, the sides are optical flats and are planed parallel to within five wave lengths of light over the entire surface. Special cement is required to withstand chemical attack and thermal shock. The cell is placed in a thermal jacket (2) made of welded aluminum. A water seal for the optical ports is made by using O-rings tightened against the flats of the cell by fine-threaded and adjustable ports, Fig. 2. In-flow water is discharged downward from a manifold located near the bottom of the cell jacket. Water overflows the weirs at each end of the cell jacket, discharging from both sides to a collecting manifold (24). A hose (26) leads the overflow water to the thermal-conditioner well (4), which is recessed to accommodate a reaction cell and two beakers (150 ml). Both the thermal jacket and the thermal-conditioner well are insulated to minimize the effects of temperature differentials. Water, discharging from the thermal-conditioner well, returns to a thermostat bath and pump (3), from which it is pumped to the thermal jacket. The thermostat bath permits temperatures to be adjusted from 1" or 2°C to 80°C and will maintain the selected temperature within 0.2ºC. An electrode support (22) groups the four electrodes (8) so that they fit conveniently into the reaction cell, Fig. 2. This assembly holds the glass electrode, the calomel electrode, the temperature-

Jan 1, 1957

By E. F. Burch, R. W. Schoenberger

This paper deals with an investigation of the use of steam filtration for filter cake dewatering and shows that it may be applied on a practical scale. The advent of larger quantities of minus 1/4 in. coal in the raw feed to the preparation plant and the necessity of recovering this material has made the problem of meeting product moisture specifications more difficult. For a number of years thermal dryers have been used advantageously as a means of reducing fine coal moisture content where the over-all economics would justify such an installation. However, these units are not without their drawbacks because of high capital and operating costs, safety hazards and possible degradation of the product, and thus an alternative method of moisture reduction is highly desirable. After the various mechanical variables associated with filtration have been optimized, an examination of theory shows that surface tension and liquid viscosity are the only two remaining variables which might be altered to reduce moisture content. A lowering of the surface tension within the limits of normal wetting agent dosage results in a rather insignificant decrease in cake moisture content. Not until the dosage is increased to a point well beyond this limit is there an appreciable decrease in moisture. At these high dosage levels, interfacial tension is a major factor contributing to the appreciable moisture reduction obtained. Since no suitable method has been developed to recover and recycle this wetting agent, this phenomena is not of practical significance. On the other hand, a reduction in liquid viscosity has a pronounced effect on cake moisture. While it is readily apparent that one method of reducing liquid viscosity is to heat the entire feed slurry, it is equally apparent that this would not be an economic approach except, perhaps, in certain isolated cases. It does, however, suggest that water circuits should be designed to conserve heat as much as possible and to make use of any waste heat that may be available. The use of hot air as a heat carrying medium for drying porous materials on a filter has been practiced for many years. However, this method is restricted to materials with a high air rate in the order of 100 cfm/ ft2 because of the low heat release per unit weight of air passing through the cake. The normal fine coal filter cake has an air porosity far too low to make this a practical approach. Various types of radiant heating devices have been investigated and can significantly lower moisture content at reasonable thermal efficiency. However,

Jan 1, 1964

By C. E. Silverblatt, D. A. Dahlstrom

Previous bench-scale studies demonstrated that a substantial moisture reduction can be obtained by the application of steam to coal filter-cakes, particularly to those containing a limited amount of minus 200-mesh material. Consequently, U.S. Steel&apos;s Applied Research Laboratory conducted a study to determine the feasibility of steam filtration of 1/4 in. by 0 coal on a continuous pilot-scale installation in which an Eimco extractor is used. The test results showed that the moisture content of this coal could be reduced to 5.5% at a steam loading of about 175 lb of steam per ton of dry cake. In terms of steam consumption, this loading is calculated to be 1-1/2 lb of steam per lb of water removed. In some tests, only 1 lb of steam per lb of water removed was required. These levels of steam consumption are significantly less than the actual heat requirements of conventional thermal dryers. The satisfactory moisture reductions were obtained at filtration rates of 125 to 186 lb of dry solids per sq ft per hour. However, the proper design of commercial filters should improve the potential rates that can be attained. These results indicate that steam filtration has considerable economic potential for drying 1/4 in. by 0 coals and also has additional advantages over the conventional thermal drying of coal. The results of the previous bench-scale studies and those published by Burton&apos; demonstrated that a substantial moisture-content reduction can be effected by the application of slightly superheated steam to coal filter-cakes, particularly to those containing a limited amount of minus 200-mesh material. Consequently, US Steel&apos;s Applied Research Laboratory conducted a study to determine the feasibility of steam filtration of 1/4 in. by 0 coal on a continuous basis. In the continuous process, the dewatering operation on the filter is conducted in stages. In the first, the bulk of the water in the feed slurry is removed by conventional mechanical dewatering on a portion of the filter before the steam is applied. In the second stage, steam is applied to the cake. The steam condenses and releases its latent heat, thereby reducing the viscosity of the remaining cake water; this reduced viscosity then facilitates further drainage and produces a cake of lower moisture content. Because of the availability of feed coal on a continuous basis and since steam was readily available from a low-pressure boiler, the Applied Research Laboratory selected for the test site a coal-preparation plant that cleans Pittsburgh Seam coal. A slurry of table and flotation coal in percentages as they occur normally was used as feed stock. Typical analyses of this slurry are shown in Table I. DESCRIPTION OF FILTER AND EXPERIMENTAL PROCEDURES An Eimco Extractor was selected for the evaluation of steam filtration in a continuous process. This unit was chosen because of its availability and its design features that permit relatively simple hood construction, instrumentation, and operation. A photograph of the Extractor is shown in Fig. 1. In the filter a cloth medium is used that travels horizontally and continuously with a grooved, rubber drainage belt. The total effective filter area was 12.5 sq ft. As the feed slurry flows by gravity from the feed box onto the medium,

Jan 1, 1964

By R. B. Schluter, M. M. Fine

Processes for manufacturing prereduced pellets have heretofore required temperatures of 2100°F or higher. Sulfides will accelerate the liquid-phase sintering of metallic iron, yet do not deter the reduction of iron oxides. The sulfides may be introduced as gases to the kiln atmosphere or as solids in the re-ductants. The net result is that well metallized iron pellets with good crushing strength can now be produced at a little over 1800°F. One of the most persistent topics at technical gatherings and in the recent scientific press has been the reduction of iron ore. In May 1960, a symposium on the subject was sponsored by the Electrochemical Society. The proceedings, comprising two dozen papers, were later published.&apos; More recently, in November 1966, a similar gathering took place at Michigan Technological University, Houghton, Mich. The latest meeting was the International Congress on Production and Utilization of Reduced Materials at Evian, France, in May 1967. If the volume of literature, symposia and conferences is a measure of industry concern, then the current interest in reduction must be at a high level. Barrett,2 one of the early pioneers, stated some years ago that "The history of sponge iron has been so discouraging that many men in the iron and steel industry are violently opposed to giving it any further consideration." In spite of the "violent opposition" noted by Barrett, research people in and out of the industry continue to be attracted by the elusive prospect of uncovering a simple, viable means of direct reduction. Wild,3 one of the speakers at Evian, listed no less than 48 direct reduction processes (laboratory, pilot plant and commercial). Some of these were of historical interest only, but many others had resulted from developments within this decade. The previous big thrust into direct reduction occurred under the artificial impetus of a wartime economy (World War 11) and was largely an effort to provide more melting stock without coke ovens and blast furnaces. The present-day inquiry is proceeding at a more leisurely pace and the emphasis is different. For one thing, there is much less anxiety to circumvent the blast furnace. On the contrary, a whole new research endeavor has grown from the discovery that metallized burdens are exceptionally productive.4 Although the search for a melting stock

Jan 1, 1970

By Bernard Rachlin

IN the mineral industry measurement of density or specific gravity of slurries is often necessary or highly desirable. To date the most successful method of measuring the specific gravity of various media is to hand weigh a constant volume sample of the slurry. This method is time-consuming, however, and is intermittent rather than continuous. Most density measuring instruments in use today are variations of three basic systems: air bubble tube systems, radioactive methods, and displacer systems. The high cost of the radioactive cell, combined with the precision electronic measuring that is required, limits the practical utility of this procedure to a small percentage of critical processes. In the air bubble systems clogging of the bubble tubes with solids has rendered this type of measurement completely ineffectual for many applications. Continuous or intermittent purging of the bubble tubes with air or water to prevent tube clogging has been tried but has not been very successful, especially in the heavy media process. The displacer system, which presents the fewest complications of all the density measuring systems, consists only of a metal immersion unit and a means of weighing it. In the past, settling of the solid in the slurry has caused untrue samples and clogging of the media at the bottom of the chamber. It is also important to dampen excessive flow surges such as those caused by reciprocating pumps. The system described here successfully overcomes these difficulties. Description of the Process System: The process equipment, on which the field tests were run, was a

Jan 1, 1957