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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 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 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 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 M. E. Wadsworth, J. S. Cho

Colloidal silica dissolved in aqueous suspensions of high surface area thoria was permitted to adsorb on the thoria surface. Silica in three forms was identified by means of infrared spectroscopy and characterized by Si-O vibrational modes in the 9.0 to 10.5 region. A band at 9. 1 was attributed to free unad-sorbed silica, while adsorbed silica resulted in bands of greatest absorbency at 9.4 or 10.3p, depending upon the character of the surface bonding. Size considerations, the amount of silica adsorbed, and the character of the infrared spectrum for strongly adsorbed silica has been interpreted as evidence of formation of chain or layer silica linkages on the thoria surface. Infrared spectroscopy has been used successfully in recent years for the identification of minerals and synthetic inorganic substances. Unfortunately, infrared studies of silicate minerals have not proceeded to the point that unambiguous assignments may be made for Si-O vibrational modes as affected by lattice substitutions and structures. Several investigators have presented infrared spectra of silicate minerals, 1,7 and their work has pointed to the potential value of infrared to identify minerals as well as to note the sensitivity of various Si-O modes to structural and substitutional environments. The strong infrared absorption of various Si-O vibrational modes makes the infrared method a very useful tool for the study of silica adsorbed on the surface of solids of high surface area. Spaepen et a18 studied the adsorption of silica on thoria surfaces from aqueous solutions of silicic acid up to 300°C. A general review of the application of the infrared method to the study of surface adsorption has been presented by Pliskin and Eischens.9 EXPERIMENTAL Du Pont colloidal silica, Ludox SM (16.36% SiO2) and Ludox HS (30.25% SiO2) in aqueous suspensions were used as the sources of silica for the adsorption studies. The thoria used for this study was supplied by Union Carbide Nuclear Co.* under the preparation *Chemical Technology Div., Union Carbide Nuclear Co., Oak Ridge, Tenn. . number D-16-650. It was fired from the oxalate at 650°C and had a surface area of 32.4 ± 0.6 m2 per g measured by nitrogen adsorption. The chemical analysis of the D-16 thoria in ppm was: CO3= (5500), NO3- (< 4), so4±PO4 (100), and Si (20). The Ludox silica was placed in contact with the thoria in a two-liter autoclave10 between room temperature and 250°C. Slurries were made by placing 1 g of thoria in one liter of distilled water containing various additions of the silica sol. Samples were removed from the autoclave by opening a small stainless steel valve. Extracted samples were centrifuged for 10 min and excess solution was decanted. The sample was then dried for several hours at 80°C. Infrared samples were prepared by thoroughly mixing 10 mg of the thoria with 400 mg KBr in polystyrene vials on a "Wig-L-Bug" amalgamator. Pellets were pressed under vacuum and had final dimensions of 1.2 cm diam and 1.2 mm thick. Infrared spectra were

Jan 1, 1963

By S. R. Balajee, I. Iwasaki

The interaction between British gum 9084 and dode-cylammonium chloride (DAC) at quartz and hematite surfaces was established from coadsorption studies and streaming potential measurements. The cationic DAC interacts with the somewhat anionic British gum 9084, leading to the formation and adsorption of a binary complex of DAC-British Gum 9084 at the interface. The parallel ability to depress quartz along with hematite as a result of the interaction between DAC and British gum appears to be the main reason for the ineffective depressant action of starches and starch derivatives in the cationic flotation of iron ores. Amines are not particularly selective collectors for the flotation&apos; of siliceous gangue from iron ores and, therefore, a suitable iron oxide depressant is needed for a satisfactory separation. Various starches and their derivatives have been extensively tested with oxidized iron ores,&apos;-3 and it has been empirically established that British gums and dextrins are preferable. However, for the flotation upgrading of magnetite-taconite concentrates from 8 or 8.5% Si O2 to about 5% Si 02, British gums, which have been used so successfully on oxidized iron ores, have been found to have no effect and oftentimes are actually deleterious.4 In previous articles,5-7, starches were shown by adsorption measurements, flotation tests, and floccula-tion tests to interact with calcium ions in solution, and it was thought that a study on the interaction between starches and dodecylammonium ions would be able to shed some light on the anomalous flotation behavior described above. In fact, starches are known to interact markedly with paraffin-chain-type surface active agents and, thereby, to precipitate the starch or inhibit the iodine-starch reaction.8 From X-ray diffraction studies and viscosity measurements, the formation of a helical complex between mylose and a surface active agent has been postulated.9 The interaction with other types of hydrophilic colloids, such as synthetic polymers and proteins, has also been investigated and is usually explained in terms of van der Waals&apos; force interaction and/or ion-ion interaction. In the present investigation, the interaction of British gum and dode cylammonium chloride on quartz and hematite was studied by adsorption and streaming potential measurements in an attempt to establish the mutual adsorption behavior of British gum and dode-cylammonium chloride on mineral surfaces and to clarify the anomalous depressant activity of British gum in the cationic flotation of iron ores. All the measurements were carried out at a natural pH of near 7 because dodecylammonium chloride gives maximum selectivity of flotation separation at this pH2 and to avoid any third parameter in the system. EXPERIMENTAL MATERIALS AND METHODS Minerals: The quartz and hematite samples used for the adsorption tests were prepared as described in a previous paper,"J except that the specific surfaces of the samples were increased to 5,860 and 16,000 Sq cm per gm, respectively. For the streaming potential measurements, the 48165-mesh fractions screened out of the original samples were etched with hydrochloric acid, washed repeatedly with water, and stored under water in Pyrex bottles. Reagents:DodecyIammonium chloride (DAC) was prepared1 1 by bubbling dry hydrogen chloride gas through a benzene solution of high-purity dodecylamine supplied by Armour and Co. British gum 9084, received from Corn Products Co., was solubilized by first dispersing it in water to produce a 0.05% solution and then homogenizing it in a blender for 5 min. Distilled water was used in the preparation of the samples and the solutions and for all test work. Adsorption Measurements: The procedure for the adsorption density determinations was also the same as that described in the previous paper.1° The residual concentrations of the British gum and the DAC in the supernatant solution were analyzed colorimetrically by the phenol-sulf uric-acid and amine-picrate methods, respectively. The validity of the mine-picrate method for the colorimetric analysis of DAC in the presence of British gum and the analysis of British gum in presence of DAC were checked by establishing calibration curves between optical density and concentration. Streaming Potential Measurements: The cell assembly for the streaming potential measurements was similar to that described by Fuerstenau.&apos; The streaming potential

Jan 1, 1970

By H. L. Miaw, A. M. Gaudin, D. W. Fuerstenau

A quantitative method for evaluating density of slime coatings has been developed and applied to formation of iron oxide slime coatings on quartz and on corundum. Slime coating density is related to flotation recovery and to properties of the electrical double layer at mineral surfaces. IN spite of considerable study, the nature of slime coatings in flotation is still not completely understood. However, phenomena that control floc-culation and dispersion of colloidal systems are now interpreted in terms of electrical double layers.",&apos; Colloids will flocculate even though the particles carry the same charge, but when two dispersed colloids of opposite charge are mixed. flocculation ensues even more rapidly. Analogous phenomena seem responsible for slime coating on minerals in flotation systems. To shed new light on the issue it was considered desirable to devise a tool that would measure slime coatings. The usual method has been to examine photographs of presumably representative surfaces, after. an intervening washing in running water. But such an examination is non-quantitative, and the changes in chemical environment represented by the washing may have removed the slime coatings that existed during flotation. To provide the possibility for a correlation with electrical double layer phenomena, the experiments were made with quartz, corundum, and iron oxide, for which elec-trokinetic data are available.&apos;-" Since the properties of the electrical double layers of these oxides depend on the pH of the solution, pH will be the most important variable. Furthermore, because the zero point of charge for silica, iron oxide, and alumina occurs at pH 3.7, 8, and 9.5, respectively, the relative charge on the slime and mineral can be changed over wide ranges. Because of its practical importance in quartz flotation, iron oxide powder was chosen as the slime. Also, its uniform composition, contrasting color, and ease of analysis make experimentation simple. In this investigation, correlation was sought between the effect on flotation recovery of slime addition and slime coating density. Materials and Methods Details are available in a thesis by Miaw." The quartz was selected from pure Brazilian crystalline quartz, crushed, sized (65/150 mesh) acid-cleaned, washed, and stored in conductivity water. The corundum (synthetic alumina of high purity prepared by Linde Co., Chicago) was crushed, sized (65/100 mesh) deslimed, boiled in nitric acid, washed, and stored in conductivity water. The iron oxide slime, reagent-grade ferric oxide (—400 mesh) from Allied Chemical & Dye Corp., was heated to 160°C, cooled, and stored in a vacuum desiccator. In the electron microscope the slime particles appeared to be about 0.3µ in size, but their large specific surface (87,900 cm per g, by gas-adsorption method, using krypton) suggests that the actual particles are smaller than 0.3r. Had they been perfect nonporous spheres, they would have had a diameter of 0.13µ.

Jan 1, 1959

By S. R. B. Cooke, H. S. Choi, D. H. Harraway, I. Iwasaki

The mineralogy of natural iron ore samples and their slimes have been investigated and the nature of slime interference in iron ore flotation has been studied. The results have been correlated with the flotation behavior of a natural ore sample. Various conclusions have been reached as a result of these studies. In the flotation of iron oxide ores, desliming is generally considered to be an essential step to successful separation, irrespective of whether the iron oxide or siliceous gangue minerals are to be floated, although some workers have found empirically that certain collectors and reagent combinations are less sensitive to the presence of slime than others. The detrimental effect of slime is considered to be twofold. First, the presence of slime presupposes a high reagent consumption because of high specific surface. When clays are present and when cationic collectors are used abstraction by ionic exchange may augment this condition. Attempts to compensate by the addition of large amounts of reagent result in only partial correction. Second, slime coatings on granular particles tend to interfere with the bubble-mineral contact. The nature of slime coatings in flotation is quite complex and has been the subject of considerable study; an attempt was recently made by Fuerstenau et al.&apos; to relate the slime-coating density with flotation recovery and with the properties of the electrical double layer at the mineral surfaces. Although major constituent minerals in the oxidized iron ores of the Mesabi and Cuyuna ranges are hematite and goethite (limonite) as the iron oxides, and quartz and chert as the siliceous gangue, very little is known of the mineralogy and of the chemical and physical characteristics of the slimes, and still less of the interaction between slimes, collector, and the mineral surfaces. For pragmatic reasons iron ore slimes are defined as — 20p material, based upon the calculated settling velocity of a quartz sphere of the stated diameter, and of all other equal-settling mineral particles. Active slime interference with flotation is usually attributed to particles 5p in size or finer, the extent of such interference appearing to depend not only on the mineralogy but also on the size distribution of each mineral in the slime fraction. The objective of this work was to acquire a more specific knowledge of the constitution of iron ore slimes and of their role in flotation. The mineralogi-cal composition of natural slimes was obtained by differential thernal analysis (hereinafter referred to as DTA), electron microscopy, and chemical and X-ray analyses. Some flotation tests were made on natural ore samples. The surface properties of several constituent minerals were investigated by electrophoretic measurements and by determination of the adsorption of some typical flotation collectors. Finally, simplified flotation tests were made on granular goethite and quartz in the presence of various artifically prepared slimes; the results were compared with laboratory flotation tests made on natural ores. MATERIAL AND METHODS Mineralogy of Some Iron Ore Slimes: Samples of two wash-ore tailing::, hereinafter identified as A* and B, *Sample A of the present investigation 18 the same am ore A in ref. 3. of a wash ore C, and of a paint rock D, all from the Mesabi range, were selected for investigation on the basis of prior information concerning their flotation behavior. The two wash-ore tailings, when deslimed, were known to respond well to flotation, whereas the wash ore was high in goethite, tended to be slimy, and responded poorly to flotation. The paint rock also exhibited sliming tendencies, and was suspected to contain relatively large quantities of clay minerals because of its high A1203 content. Gruner states that the paint rock of the Mesabi frequently contains kaolinite. To ascertain the relative sliming tendencies of each sample a standardized desliming method was employed. All samples were ground through 65 mesh using jaw and rolls crushers. A 500-g sample of each

Jan 1, 1962

By D. H. Gieskieng

THE advent of curved jaw crusher wearing plates made an approach other than segmental layout analysis desirable for prediction of capacities. For some time it had been known that the drawing board capacities of crushers using these plates had to be considerably modified by complicated experience factors to achieve agreement with results. Because these apparent capacities could be readily increased severalfold by minor crushing chamber shape changes, it was necessary that the utmost precaution be taken in predicting capacities of jaw plates modified for nonchoking, special wear characteristics, or any other reason. To this end the laboratory and field tests outlined by the author in a previous paper1 were made on Blake-type jaw crushers. The results of these tests were summarized in a simple first degree equation applicable to crushers using either straight or curved jaw plates. This equation first outlines the maximum capacity potential of a given crusher, then reduces this figure in accordance with installation circumstances by means of a realization factor. It was found subsequently that this equation, with the addition of an eccentric throw factor, is applicable to standard types of single-toggle or overhead eccentric jaw crushers as far as maximum capacity potential is concerned. However, these crushers have realization factor curves somewhat different from those outlined for the Blake type. While this paper is concerned principally with standard type single-toggle crusher capacities, the evaluation of data obtained with these machines is simplified by comparative reduction to the 10 x 7 in. Blake-type equivalents upon which the summary of the preceding paper was made. Convertibility of data from one type of crusher to the other also tends towards confirmation of both. The agreement of these data is sufficient to be considered complimentary. Consequently the feed factors, f, previously reported for Blake crushers are slightly adjusted to an average with the single-toggle crusher results. Blake-type equation: C = f.d.w.y.t.n.a.r [I] Single-toggle type equation: C = f.d.w.y.t.n.a.e.r [21 where C is the capacity in short tons per hour through the crusher, f is a feed factor, dependent upon the presence of fines in the feed, and the surface character of the jaw plates used. Values of f : Smooth Plates Corrugated Plates With normal fines 0.0000414 0.0000319 Fines scalped out 0.0000368 0.0000252 Large pieces only . 0.0000312 0.0000215 d is the apparent density of the broken product in pounds per cubic foot. (If the true specific gravity of the feed is known, 40 pct voids may be assumed and d becomes 37.4 times sp gr). w is the width of crushing chamber in inches. y is the openside setting of the crusher, in inches. In the case of corrugated jaw plates it is measured from the tip of one corrugation to the bottom of the valley opposite. t is the length of jaw stroke in inches at the bottom of the crushing chamber. It is the difference between open and close-side settings. n is rpm, or crushing cycles per minute, a is the nip-angle factor. It is unity for 26" and 3 pct greater for each less nip-angle degree. A nip-angle of 20" has an a value of 1.18, and an angle of 30" has an a value of 0.88, see Fig. 1. r is the realization factor. It is unity for perfectly uniform choke feeding and usually less for actual operating conditions according to the method of feeding used and the probabilities of hang-ups involving the size of feed and crusher opening. Approximate values are given by the curves in Fig. 2. These values are further reduced by intermittent feeding, e is the throw or diameter of gyration of the single-toggle crusher eccentric in inches. As evident in Fig. 1A, variation of feed size will generally have little effect on nip-angle if both jaw plates have flat areas. Jaw plates having continuous curvature, as in Fig. 1B will have different nip-angles, depending upon the size of feed. For test work as described in this paper this effect was accounted. For general compilation of capacities for average feeds it is suggested that the nip-angle be taken at the various settings computed, at an arbitrary level, such as is indicated in Fig. 1C. Data Evaluation To bring the Blake and single-toggle type crusher capacity test results to common terms for evaluation, all data are converted to terms of 10 x 7 in. Blake-type performance at conditions of 100 lb per cu ft, 10 in. chamber width, 250 rpm, 0.65 in. stroke, 3-in. openside setting, and 18° nip-angle. (The nip-angle of the 10x7 in. Blake is 18° at 3-in. setting.) The single-toggle crusher performances are also divided by the eccentric throw to bring this effect to unity. As outlined,&apos; laboratory and field tests made on Blake-type crushers ranging from 10 x 7 in. to 60 x 48 in. were summarized along the foregoing conditions of speed, stroke, etc. This resulted in groups of data which correspond to feeds with fines, feeds

Jan 1, 1952

By B. H. Bergstram, C. L. Sollenberger

When glass spheres are crushed by slow compression loading, the outer lune-shaped fragments resulting from the fracture consistently fly outward at high velocity. About 45 pct of the strain energy fed into the sphere-platen system reappears in the form of the kinetic energy possessed by these fragments. These measurements were obtained from high-speed photographs. This kinetic energy can be utilized for addtional comminution if the fragments are allowed to impact against a suitable structure. Comminution theory has advanced considerably in recent years by the study of this unit operation under laboratory conditions. Some of the parameters have been isolated, but the experimental measurements of the pertinent quantities, such as energy, particle size, etc., are still only made prior to and after the conclusion of a fracture sequence. The catastrophic fracture process itself has not been adequately studied from a comminution point of view. It has recently been suggested by Gilvarry that the fragments which result from the free crushing of a single glass sphere by slow compression contain a considerable amount of kinetic energy after fracture. This kinetic energy, if properly directed, possibly can be partially utilized to cause additional fracture. In this paper a hypothesis will be presented which suggests that this kinetic energy is necessarily present and that its dissipation is the process by which a large part of the thermal energy imparted to the crushed product is generated. Evidence supporting the existence of kinetic energy and its utilization for secondary fracture will also be presented. THEORETICAL A previous paper4 has shown that the load-deformation curve of a system composed of an elastic sphere gripped by a pair of parallel platens, can be predicted by a consideration of the theories of Hertz as summarized by Timoshenko.&apos; The deformation A, of one half of the system is given by which states that the deformation is a function of the mutually applied load, P, the radius of the sphere, R; and the respective physical properties of Poisson&apos;s ratio, v, and Young&apos;s modulus of elasticity, Y. The shape of experimental load-deformation curves conform to this relationship. The energy input to the sphere-platen system, can be predicted from the integral of the load acting through the appropriate distance, dA. Since dA can be evaluated in terms of P from the derivative of Eq. 1, this integral can be integrated between limits of 0 and P. The test sphere, however, is loaded at not one but at two points of contact, i.e., at both ends of a diameter, and hence the total energy input, E, is twice the energy input at each end, or The energy input to the system calculated from this equation corresponds to the energy computed from the measured area under the load-deformation curve. Timoshenko, considering the impact of two perfectly elastic spheres, has shown that the inter-penetration distance A is given by - m f (D (^ * ^t w as modified for the special case where one sphere is of infinite radius, i.e., its surface is a plane; where M is the mass of the finite sphere of radius R, and V is the velocity of approach at the start of an impact and also equals the final velocity of separation for perfectly elastic bodies. Because A is also a function of the load and the elastic properties, as shown in Eq. 1, the velocity, V, can also be calculated in terms of the elastic properties and maximum load, P, or

Jan 1, 1961

By E. J. Haug, M. M. Fine

FOR several years work has been carried on by the U.S. Bureau of Mines at Rolla, Mo., to develop improved methods of concentrating the oxidized ores of lead and zinc. Various samples have been investigated, and results on some have been published 1,2 lished.l, 2 Details of the progress to date are given in a mineral dressing study now being conducted for an extensive oxidized lead-bearing tract in southeast Missouri, property of St. Joseph Lead Co. These oxidized ores present problems typical of many encountered in modern mineral dressing research in that recovery of very fine particles is of

Jan 1, 1956

By F. M. Hamilton, H. F. Ameen

Results of a laboratory investigation of some sintering variables are presented. The effect on physical properties of mix component variation and rate of cooling of the sinter is illustrated by crush and tumbler test results and data of reducibility tests and microscopic examination of sinters are shown. The results of using solid additions in the mix to improve bed permeability are given. SOME of the variables encountered in the sintering of iron ores and their effect on sinter properties have been investigated at the Jones and Laughlin Ore Research Laboratory in Michigan. Ores requiring agglomeration before blast furnace utilization may be classed as coarse, intermediate or fine. Coarse iron ore is considered similar to a — 1/4-in. Mesabi wash ore containing some 95 pct of its particles between 94 in. and 100-mesh. Intermediate iron ore is considered similar to our New York State magnetic concentrates in which all the particles are — 20-mesh and about 60 pct are +100-mesh. Fine ores are considered as being at least 100 pct —100-mesh. This paper will deal only with the two coarser classifications. Most of the work has been done in a small experimental batch unit previously described in an AIME1 paper. Results being obtained form a basis for present and future trials in production sinter plants. It is expected that new production units that may be added in the future will benefit from laboratory studies. In general, the results reported here are obtained by laboratory study, but it is Experimental Sinter Machine: The laboratory sinter machine employed in the work consists of a chamber with 1 sq ft of grate area. It is mounted on

Jan 1, 1951

By H. F. Ameen, F. M. Hamilton

Results of a laboratory investigation of some sintering variables are presented. The effect on physical properties of mix component variation and rate of cooling of the sinter is illustrated by crush and tumbler test results and data of reducibility tests and microscopic examination of sinters are shown. The results of using solid additions in the mix to improve bed permeability are given. SOME of the variables encountered in the sintering of iron ores and their effect on sinter properties have been investigated at the Jones and Laughlin Ore Research Laboratory in Michigan. Ores requiring agglomeration before blast furnace utilization may be classed as coarse, intermediate or fine. Coarse iron ore is considered similar to a — 1/4-in. Mesabi wash ore containing some 95 pct of its particles between 94 in. and 100-mesh. Intermediate iron ore is considered similar to our New York State magnetic concentrates in which all the particles are — 20-mesh and about 60 pct are +100-mesh. Fine ores are considered as being at least 100 pct —100-mesh. This paper will deal only with the two coarser classifications. Most of the work has been done in a small experimental batch unit previously described in an AIME1 paper. Results being obtained form a basis for present and future trials in production sinter plants. It is expected that new production units that may be added in the future will benefit from laboratory studies. In general, the results reported here are obtained by laboratory study, but it is Experimental Sinter Machine: The laboratory sinter machine employed in the work consists of a chamber with 1 sq ft of grate area. It is mounted on

Jan 1, 1951

By J. F. Shea, O. F. Tangel

Battelle Memorial Institute participated in a program for the General Services Administration aimed at developing a nickel-cobalt separation process that could be integrated in the Nicaro nickel plant. At the time the programwas being carried out, the Nicaro process was a straight-through operation, in which the ore was reduced and leached, after which the pregnant solution was boiled to produce a so-called "bulk precipitate" which contained virtually all of the nickel and cobalt which had been dissolved in the leaching step. The weight ratio of nickel to cobalt in Nicaro ore is approximately 15 to 20:l. The weight ratio of nickel to cobalt in the finished product had to be 100:l or higher to meet specifications. Because the Nicaro process embodied no nickel-cobalt separation step, the only way that a bulk precipitate of the specified nicke1:cobalt ratio could be produced was to so adjust roasting and leaching conditions that nickel would be selectively leached and most of the cobalt would be rejected with the tailings. The required selectivity, however, was achieved at the expense of nickel recovery, which was 5 or more per cent less than might have been obtained with the existing equipment, utilities, man power, etc., had selectivity been no object. The over-all purpose of the program was to develop a separation step that could be fitted into or onto the Nicaro facilities and which would permit the manufacture of a product that would meet the desired specifications and still permit the recovery of a maximum amount of nickel. Battelle suggested that this might be accomplished by reprocessing off-specification bulk precipitate and specifically suggested the process based on ammonium sulphate leaching followed by hydrogen reduction of the leach solution according to techniques developed commercially by Sherritt Gordon Mines Limited. Such a process would not only satisfy the objectives of the research but would present two additional advantages. (1) It would produce a separate cobalt product which could be further processed into metal, alloys, oxides, or salts. (2) It would yield nickel in metallic form which might be more generally marketable and command a slightly higher price per unit of nickel than the Nicaro oxide product. DESCRIPTION OF THE PROCESS Figure 1 is a flowsheet of the process. The essential features are: (1) Extraction of about 97 per cent of the nickel and about 85 per cent of the cobalt from bulk precipitate by a principal leach with ainmonium sulphate solution (Step A). Extraction of virtually all of

Jan 1, 1961

By W. J. Carlson, I. lwasaki

Manganese and silica in nonmagnetic tailings from the direct reduction-magnetic separation step were so closely associated that no physical concentration methods were effective. Dilute sulfuric acid dissolved manganese and iron rapidly; manganese in the form of silicates was virtually insoluble in sulfuric acid solutions, thereby governing the maximum extraction attained by leaching. Autoclave leaching at elevated temperatures and at high oxygen pressures reduced the iron extraction to less than one tenth without affecting the manganese extraction. There was an indication that autoclaving solubilized the manganese silicates appreciably. Elimination of iron from leach solutions was carried out by aerating the solution in the pH range of 6.5-7; a platinum-calomel electrode pair provided a reliable indicator for the end point of iron removal. The purified leach solutions were free of interfering impurities for the recovery of manganese as metal, dioxide, or carbonate. Manganiferous iron ores of the Cuyuna Range, Minn., are too low in iron content to be directly useful as iron ores, and too low in manganese content to be termed manganese ores. Common methods of physical beneficiation such as gravity concentration and flotation have not been successful in upgrading this material. The R-N process, when applied to manganiferous iron ores,1&apos;2 produces sponge iron by direct reduction of iron oxides, while leaving manganese as manganous oxide. From fine grinding and magnetic separation of the reduced ore, a tailing is produced which is relatively rich in manganese and low in iron content. The nonmagnetic tailing can readily be leached with acids and then further processed to recover manganese in various forms. In this way, two processes, neither of which would be an economic solution to the Cuyuna ore problem by itself, may be combined to produce two marketable products, thereby rendering the over-all process economically more attractive. This article reports on the results of a leaching study on the nonmagnetic tailings, both in a batch agitation vessel and in an autoclave; on the problems involved in the purification of leach liquors by aeration; and on the recovery techniques used to produce manganese metal by electrolysis, manganese dioxide either by electrolysis or by autoclaving, and

Jan 1, 1968

By E. O. Wagner, V. F. Parry, W. S. Landers

Development work has shown that the yield of primary tar from coal is proportional to the heat in the volatile matter of the coal and that the yield of tar from noncoking coals may vary from 10 to 45 gal per ton on the ash-free and moisture-free basis. Pilot plant operations have proved that 100 to 135 pct of the bench-scale carbonization-assay yield of tar can be obtained. FOLLOWING investigations by the Denver Bureau of Mines on drying fine coal in the entrained state,&apos;. &apos; Texas Power & Light Co. employed the fluidized technique to upgrade Texas lignite for use in power plants. Because of the rapidly rising cost of natural gas in Texas the company agreed to cooperate with the Bureau of Mines in studying further the upgrading of lignite by low-temperature carbonization, since potential value of the tar would help offset the cost of fuel. Considerable interest was aroused, therefore, when Aluminum Co. of America decided to use dried lignite in its 240,000-kw power plant at Rockdale, Texas, operated by Texas Power & Light. Carbonization of coal before burning in a power plant is not new. Plants in Germany have been operated for many years on carbonized brown coal and lignite briquets produced in large integrated plants. Large-scale experiments in carbonizing pulverized coal with hot flue gases were made 30 years ago at Milwaukee," and many inventors have proposed other processes. In the U. S., technical and economic problems have prevented successful operation of large plants on carbonized coal. but new techniques of handling solids in fluidized beds may overcome these difficulties, particularly if the higher volatile noncoking coals are used. Any bituminous material will decompose when heated to about 900°F to yield primary tar, gas, and char. The quantity of tar obtained from various coals depends on their rank and volatile content and to some extent on rate and method of heating. The liquid products derived from thermal decomposition of peat, brown coal. lignites, oil shale, and noncoking bituminous coals can be easily liberated by rapidly heating these materials in a fluidized bed at about 500°C (932°F). Since it takes only a few minutes to heat small particles of fuel to carbonizing temperature in a fluidized bed, processing plants can be built to handle up to 50 tph at relatively low cost. The pioneering development work being conducted at Rockdale, Texas, by Alcoa and Texas Power & Light will solve many engineering problems of such operations. The Bureau of Mines at Denver has studied the carbonizing properties of several hundred coals by small scale assay at 500°C, deriving a simple correlation between the potential yield of tar and the proximate analysis. This correlation, shown in Fig. 1, compares the heat in the volatile matter of the coal with the potential yield of primary tar. The yield of primary tar varies from 12 to 50 gal per ton of pure coal." About the same amount of heat is needed to * MAF equals moisture-and-ash-free basis. distil any dry coal at 500°C, and the time required to carbonize a given particle size is about the same for any coal. It is therefore obvious that coals rich in volatile matter will show the greatest profits when processed. Texas lignites are rich in volatile matter, which contributes some 5700 Btu per lb of MAF coal, and the potential primary tar and oil yield from this lignite averages 12 pct by weight or 27 gal per ton from the pure lignite. Texas lignites are considerably richer in potential tar than lignites of North Dakota and Montana. During 1950 the Bureau of Mines conducted many experiments on carbonizing fine dry coal in the entrained state, publishing a report4 n major features of pilot and commercial-size units required to carry out the process. Additional experimental work has been done at Denver and the pilot plant has been improved, particularly the facilities for studying removal of fine dusts from tar vapors and gases at high temperatures by electrostatic precipitation. A number of materials have been carbonized, including sawdust, peat, brown coal, Brazilian oil shale, lignites, and the lower rank bituminous coals having noncoking properties. Straight coking coals cannot

Jan 1, 1957