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By William R. Webster

At the Richmond mecting in February, 1901, I presented for discussion the proposed rail-specifications of Committee No. 1 of the American Section of the International Association for Testing Materials, with a review of their work, and other matters relating to the heat-treatment and chemical composition of steel (Trans., xxxi., 455). In order to bring out the views of our members on the important points referred to, I offered for discussion the following questions and comments (trans., xxxi., 972): " 1. The advantages to be gained by using more metal in the flanges and web of the heavier sections of rails.

Jan 1, 1903

THE composition and quality of finished steel depend upon selection and proportioning of the raw materials of the charge as well as upon control of furnace practice. This chapter deals only with the raw materials of the basic open-hearth process that are important in determining the composition of the steel or slag. They are the metallic charge, oxygen-bearing materials, fluxes, alloying and deoxidizing additions, and certain refractory materials used for maintenance of bottoms. Other refractories, which may affect the slag composition, are discussed in Chapter 3. Wide variations are possible in the type and composition of charged materials but certain limiting relations among the elements of the charge must be observed. Since the process consists essentially of refining by the oxidation of undesired dements, a balance must be established between the sources of oxygen and the elements in the charge that are subject to oxidation (see Chapters 2 and 7). For example, if it is desired to use a high ratio of blast-furnace hot metal to scrap, it is necessary to add an oxygen-bearing material such as ore or mill scale to eliminate the excess carbon and silicon that are present in the hot metal. An example of the opposite extreme is the use of a metallic charge composed entirely of steel scrap. With this type of charge, it is common practice to substitute burnt lime for limestone as a flux and to charge some carbonaceous material such as coke to avoid an excess of oxygen in relation to the elements of the charge that are subject to oxidation. Elements such as copper and nickel, which are not oxidized or eliminated by, any other reaction, may be introduced into the charge only to the extent to which they are permissible in the finished steel. An example of adjustment of the charge for elements of this type is found in the use of steel scrap high in copper. In this case, metallic components of the charge other than the scrap should be low in copper, or a sufficiently high ratio of pig iron to scrap should be charged to dilute the copper from the

Jan 1, 1951

Jan 1, 1900

The President was authorized to appoint a committee comprising himself and five others, to draft an amendment to the Constitution for the purpose of bringing before the membership the suggested change in qualifications for members. The President thereupon appointed the following Committee: Edwin Ludlow, Chairman, B. B. Thayer, J. W. Richards, G. C. Stone, C. F. Rand, and P. N. Moore. The President was authorized to arrange with the Bureau of Mines for the payment of the necessary clerical assistance to copy the inventory of

Jan 8, 1917

By Nathaniel Herz

The use of zinc dust for precipitating the pecious metals from cyanide solutions is well established now in many places, and has many advantages over the shavings method of precipitation. Although much work has been done o,n methods of testing zinc dust, as yet. no absolutely positive test has been devised to determine the value of the material. Certain facts are known, but often it happens that results on a working scale are not as expected from the laboratory tests. The purpose of this paper is to record some obscrvations made while testing a large variety of zinc-dust samples in the laboratory. W. J. Sharwoodl has described standard analytical methods, which have been followed, with the changes noted. The regular determinations include zinc oxide, by solution in ammonia and ammonium chloride, lead, and precipitating efficiency. In some cases cadmium was determined by a method similar to that described by J E Clennell.2 I will discuss the precipitating-efficiency test in detail. The procedure is as follows: "A solution of potassium silver cyanide is prepared by dissolving 10 grams of silver cyanide (AgCN) and 5 grams of 99 %' potassium cyanide in a little water and diluting up to 1000 cc. It is then adjusted by addition of a little more XCN or AgCN until the solution indicates from 0.12% to 0.15% free KCN by titration with standard silver nitrate. The titration is best made by using a 10-cc. or 20-cc. sample, adding 1 CC. of 2 % potassium iodide, and a slight excess of ammonia, as the end point is then sharper. Or 15 grams of pure crystallized XAg(CN)2 may be dissolved in a liter of water and 1.5 grams XCN added. " Weigh out 0.5 gram zinc dust into a 300-cc. beaker. Add a few cubic centimeters of watcr and stir until zinc is well mixed, then pour in 250 cc. of the prepared solution, stirring vigorously. See that all lumps are broken up, and continue stirring for fully five minutes. Stir occasionally (at least every 10 minutes) until the end of two hours from the addition of the solution. Then filter upon an 11-cm. filter, wash precipitate thoroughly, sprinkle with test lead, wrap it carefully in the paper, place in a scarifier with about 20 grams test lead, burn paper cautiously in muffle, scorify five minutes, cupel at low temperature and weigh silver. Milligrams silver obtained from 0.5 gram zinc X 0.0606 = percentage precipitating efflciency."³

Jan 1, 1916

By Charles Catlett

My attention having been called several years ago to the possibility of increasing the yield of coke per ton of coal, as obtained in certain bee-hive ovens, I called the attention of the Institute to the matter at the New York meeting in 1899. I have had occasion since to witness the indifference with which this matter is ordinarily considered, and, on the other hand, the marked improvement which comes from even a most perfunctory effort in that direction; and I am almost tempted to say that nothing in connection with the coking of coal is at present so important. There are other factors, which are fundamental and necessary; but they have been considered already ; while the question of yield is, as a rule, absolutely ignored, or some figure is taken as the result of a special burning of one or two ovens, and the assumption is made that the whole battery is yielding at that rate. The uncertainty of this assumption I may illustrate by saying that, in my own observation, the burning of a single oven in a battery frequently gives, by actual weight, as much as 69 or 70 per cent. of merchantable coke, while the battery as a whole was yielding only an average of 63 per cent. Only from careful records, checked at least once a month, of the weight of the coal going to the ovens and the weight of coke produced, can any correct idea of the actual yield be gained, or methods be modified so as to produce good results; yet, as a rule, the crudest estimates are usually the only available data. In many cases there are reasons for this loose practice. The coal is mined by measurement; the payment for drawing the ovens is in proportion to the amount of cod which goes to them; and, not uncommonly, the royalty is so much a ton of coke, not of coal. The mine-manager is tempted to increase the volume of coal mined which is paid for as a ton, and to do the same thing in charging the ovens. Nor does he

Jan 1, 1903

By R. C. Ku, A. J. McEvily, T. L. Johnson

AS reported in a recent paper,' we attempted to measure the response to stress of as-quenched Fe-Ni-C martensites (Ms of -35°C) in both the micro-and macrostrain regions. To avoid effects associated with the diffusion of carbon, tensile specimens were quenched from room temperature at 78°K and tested after 15 min in situ. It was assumed that the transformation had terminated and that the retained austenite was essentially stable. In the tensile tests microplastic strains of the order of 10"* were measured at stresses below 20 ksi. It was concluded that the observed strains were due to the motion of dislocations in the martensite, the dislocations having been introduced during transformation. It was argued that transformation or plastic deformation of the retained austenite did not contribute to the non-elastic deformation measured in the microstrain region. In contradiction to the above argument, Magee and paxton2 have more recently shown that the strain due to isothermal transformation of retained austenite to martensite can contribute to plastic deformation at low stresses even at 78°K. Moreover we were unaware (nost)-a culpa) of a paper by Machlin and cohen3 in which it was clearly shown by resistance measurements that isothermal transformation at 78°K leads to the formation of an additional 1 pct or so of martensite after the initial athermal transformation, even in the absence of external stress. We have verified Machlin and Cohen's results in the following manner. A capacitance microstrain gage was placed on a tensile specimen before immersion in liquid nitrogen. After 15 min at 78°K detectable burst phenomena had ceased and it was then possible to obtain a continuous record of the additional extensional strain due to spontaneous isotherma1 transformation. The results for the Fe-Ni-C series studied are shown in Fig. 1, and are similar to those of Machlin and Cohen who investigated a low-

Jan 1, 1968

By A. S. Richardson

THE recent installation of a high-pressure propeller type fan at the Moose shaft of the Anaconda Copper Mining Co. at Butte, Mont., is of interest on account of novelty of design and also because an appreciable saving was made over the cost of a reversible centrifugal fan such as is ordinarily used where a high pressure is required. The lower cost is due solely to the fact that by means of controls 'on the power supplied to the three-phase, alternating-current, induction. motor, directly connected to the propeller it is possible to reverse the direction of rotation of the propeller and thus reverse the direction of air flow. The extra air ducts and reversing doors required for this purpose with centrifugal fans are not necessary, and their elimination greatly reduces these construction charges, which form a great part of the total expense. The Badger State mine for which the Moose shaft is used as the main outlet air course is now being-developed to the 4100-ft. level. The old centrifugal fan, formerly used at the collar of the shaft, was installed 15 years ago at a time when most of the stoping was being done above the 2400-ft. level, and when the temperature of the rock was much lower than it is now on the bottom levels recently opened. The old fan, therefore, became inadequate to maintain desirable ventilation conditions, on account of the increase in resistance to air flow incident to the greater depth of the mine workings and because a much larger volume of air is required to offset the higher rock temperatures. Propeller, or disk, fans commonly used in the ventilation of mines are not suited to high-pressure work, but economies in the cost of their installation have long been recognized. In South Africa use has been made of a number of propellers placed in series along a common shaft, the number of propellers used being varied with requirements for meeting different conditions of mine resistance, but the mechanical efficiency is described as being low. In Butte, experimental work was done by the writer along similar lines under somewhat different conditions, but with poor results as to both pressure capacity and mechanical efficiency. Tests were also made of two different types of propeller fans of moderate size, which were said by the manufacturers to be suited to high-pressure mine ventilation.

Jan 1, 1932

By G. W. Powell

ACCORDING to crank,' the accumulation equations for inter diffusion in a binary system whose molal volume is a function of concentration are

Jan 1, 1965

The curve of Fig. 3 for pyrite requires modification. There 11% a range of pH values from 6.2 to 7.8 for which no cyanide is required to prevent contact. From 7.8 to 11.3 a small amount of cyanide is required, with a sharp maximum of 20 mg. per liter at pH=9.6. The mistake arose from considering too few solution compositions (17 were considered) in constructing the curve. Subsequent work with other collectors indicates that the corrected curve is typical for such systems; it illustrates the further development of the dip in the pyrite curve of Fig. 5.

Jan 1, 1938

By Edward E. Hicke, Charles A. Stickels

The dihedral angle of liquid-lead inclusions in solid nickel has been measured as a function of temperature from 371 to 816 C at zero pressure. and as a function of pressure up to 50,000 psi at 317 and 593 C. Thermodynamic expressions are derived for the temperature and pressure coefficients of interfacial tensions in this system. A method is presented for obtaining relative tempmature and pressure coefficients from dihedral-angle data, and the resulting values are used in conjunction with the thermodynamic relations to calculate excess properties of the solid-liquid interface. Defining the position of the solid-liquid interface by the condition that the excess concentration of lead is zero, the excess concentration of nickel and the excess entropy at the solid-liquid interface are: where y(593) is the interfacial tension of the nickel grain boundary saturated with lead at 593C and zero pressure. These values are considered reliable to within a factor of two. While similar calculations are not possible for the nickel grain boundary, it is shown that the expwimental results imply that the excess concentration of nickel at the boundary and the excess entropy of the boundary are negative. THE temperature and composition dependencies of interfacial tensions in metal systems have been reported by several authors in the last 15 years.'-' No measurements of the effect of pressure on inter- facial tensions in metals have been reported, although measurements made on nonmetallic gas/liquid and liquid/liquid systems suggest that a measurable effect should exist.6-l2 The purpose of these experiments was to determine the influence of temperature and hydrostatic pressure on dihedral angles in the Pb-Ni system. The equilibrium dihedral angle is expressed as a ratio of interfacial tensions by2: where 8 is the dihedral angle, yGB is the Ni-Ni grain boundary tension, and SL is the solid Ni-liquid Pb interfacial tension. Three sets of ex- periments were run to determine: a) the effect of temperature from 371" to 816°C on the dihedral angle at zero pressure; b) the effect of pressure up to 50,000 psi on the dihedral angle at 371° and 593°C. THERMODYNAMICS The properties of interfaces of most direct concern are the interfacial tension, excess concentrations of various components at the interface and the excess entropy of the interface, S°. These quantities are defined following Gibbs. Consider an interface separating phases a and 0. Construct two surfaces C, and C such that all properties of phase a remain uniform up to C, and all properties of phase 0 remain uniform up to C. The region between C, and Cp is the interfacial region. Let a "dividing surface", D, be constructed in the interfacial region such that it passes through all points "similarly situated with respect to the condition of the adjacent matter."l3 Surface D divides the interfacial region into a portion a' adjacent to phase adjacent to phase . Let a closed curve, C, enclose an area A in D. Erect normal lines to D along C; these lines and the surfaces C,, Cp, and D then enclose volumes V and V' in the two halves of the portion of the

Jan 1, 1964

By Dwight K. Smith, Greg Carter

Studies have been conducted on The properties of many deep well cementing compositions to determine their Strength behavior over curing periods to 180 days at elevated tem-peratures and 3,000 psi pressure. This pressure results in essentially the .vat, compressive strength as that obtained with much higher pressures in ac-cordance with the findings of an API subcommittee ' These different compositions include API C1asses A, E, and F cements containig additives such as retarders, berrtorlite, heavy weight materials and pozzolans. All compositions except mixtures of Poz-zolrrrts and hydrated lime show from mild to severe degrees of strength lass over a temperature rang from -730 to 320" F after setting. Pozzolatl-time compositions actually gain in strength with time at these high temperatures. Other chemical find physical properties evaluated to observe their inter-relation.ship with Strength loss show very little correlation except in per-meability. As retrogression in strength increases, the permeability of set cement increases. X-ray difraction patterns on the set products indicate the formation of certain compounds having little or no strength value in those cementing compositions where strength loss was more severe. INTRODUCTION As a result of the growing trend toward deep well completions, a study has been made on the properties of the various cementing slurries presently in use at elevated temperatures and pressure. The strength of these compositions is of prime importance in selecting the most suitable material for use at high temperatures, to determine WOC time and the proper time to perforate with a minimum of shattering. Of primary interest in this investigation was the strength behavior of various compositions currently in use, and the effect of additives on cement after long periods of curing under severe conditions. Earlier investigators have pointed out that the strength of some cements will increase with increasing curing temperature to about 220 to 340" F, but at higher temperatures a loss in strength occurs at extended time intervals. Studies by the API Mid-Continent District Study Committee on Oil Well Cements' outlined a testing procedure whereby field conditions of temperature and pressure could be simulated in the laboratory.' It was observed that retarded cements undergo changes at elevated temperatures and some lose as much as 50 per cent of their early strength when cured at high temperatures. The scope of these tests was limited to curing periods of 1 to 28 days; additives were not covered in this study. Saunders and Walker' found that the use of additives influenced the strength behavior of cements at high temperatures, but studies were conducted only to a seven-day curing period. Ludwig and Pence' conducted an investigation of two types of cements under elevated pressures and temperatures in an effort to explain the causes of this loss in strength phenomenon. It was observed that with retrogression in strength there were other physical and chemical changes which took place as the cement aged. Today there are a number of cementing compositions available for use at well depths below 10,000 ft. Since all these earlier investigations were limited in curing time as well as the number and type of compositions studied, it was believed that a more extensive study should be conducted on the properties of cements at elevated temperatures, and this work should include those compositions actually in general field use at this time.

By Maurice B. Dusseault, Edo Nyland

Numerous consistent seismic signals are being generated in a pilot fireflood in a 750 m deep high permeability unconsolidated channel sand in Eastern Alberta. The pilot has a central air injection well, eight production wells on artificial lift, and two internally placed observation wells. Surface seismometers and a 12-hydrophone downhole string were deployed to detect seismics signals. Date were collected for 22 hours employing signal-triggered event detectors recording on cassette tapes. Monitoring during twelve hours of steady air injection at 625m3/s yielded a clear event frequency of about 50 events/h. The events were mostly clear compressional wave arrivals originating in the vicinity of the firefront. Stopping air injection caused a gradual drop in event frequency, and the rate was reestablished when air injection was reinitiated. Spectral frequency analysis and knowledge of material properties indicate that the events are shears of a stick-slip nature associated with the strain-weakening behavior of the over-compacted reservoir sands. The event amplitude indicates small-scale shearing, and different amplitudes suggest that planes re-shear with lower energy release levels. The triggering mechanism for shear rupture is high shear stress created by thermal expansion in the area of highest ther- mal gradient. Other enhanced recovery techniques may also produce useful signals for process control. In particular, steam flooding, hydraulic fracturing, and high-pressure injection operations likely generate mappable microseismic events which can be applied directly to production/ injection strategy.

Jan 1, 1982

By Richard A. Arterburn

For many years hydrocyclones, commonly referred to as cyclones, have been extensively utilized in the classification of particles in comminution circuits. The practical range of classification for cyclones is 40 microns to 400 microns, with some remote applications as fine as 5 microns or as coarse as 1000 microns. Cyclones are used in both primary and secondary grinding circuits as well as regrind circuits. The information given in this chapter is intended to provide a method, at least for estimating purposes, of selecting the proper number and size of cyclones and to determine the proper level of operating variables. Generally, it is recommended that cyclone suppliers be consulted for sizing confirmation. Sow cyclone suppliers employ digital computers to aid in the sizing and selection of cyclones. CYCLONE DESCRIPTION AND BASIC OPERATION Figure 1 shows a cutaway view of a typical cyclone. During operation, the feed slurry enters the cyclone under pressure through the feed pipe into the top of the cylindrical feed chamber. This tangential entrance is accomplished by two types of design, as shown in Figure 2. Since the majority of research has been done with the involuted type, the graphs and relationships shown may not be strictly applicable to other designs. As the feed enters the chamber, a rotation of the slurry inside of the cyclone begins, causing centrifugal forces to accelerate the movement of the particles towards the outer wall. The particles migrate downward in a spiral pattern through the cylindrical section and into the conical section. At this point the smaller mass particles migrate toward the center and spiral upward and out through the vortex finder, discharging through the overflow pipe. This product, which contains the finer particles and the majority of the water, is termed the overflow and should be discharged at or near atmospheric pressure. The higher mss particles remain in a downward spiral path along the walls of the conical section and gradually exit through the apex orifice. This product is termed the underflow and also should be discharged at or near atmospheric pressure.

Jan 1, 1982

By C. C. Miller, A. B. Dyes

The cost of finding and developing new reserves is continually rising. We must meet these rising costs with more economical operations. This can he accomplished if we revise our ideas of proper well spacing and well allowable to consider the concept of optimum well spacing. According to this concept, the optimum spacing is the one which leads to the maximum present worth for a reservoir when ail factors affecting total cost and total revenue are considered and when the wells are produced in the most eficient manner. Application of this principle efficiently utilizes available well potential and properly considers the recovery eficiency in addition to fixing the spacing on the basis of the amount and value of the oil to he recovered. This Study presents an analysis of one producing zone containing low gravity crude to illustrate the effect of these factors on the present worth and on the optimum economic spacing under two production drives—-evolved gas and water drive. The maximum present worth occurs when the optimum number of wells for open-flow operation is employed. Frequently, this optimum development cal1s for very wide spacing and the ideal field rates are not unreasonable. Under other circumstance. where proration is necessary, an optimum combination of well spacing and well allowable exists which permits production at relatively high rates. The optimum well density in a field depends on the recovery efficiency and the valule of the oil. In solution gas-driven reservoirs this optimum spacing for operation at high producing rates can vary from extremely wide spacing to handle viscous low gravity oil in thin formations to relatively close spacing in thick sands where good recoveries are expected. Because of the better recovery from water-driven fields, the optimum spacing in these fields is closer than in solution gas-driven fields. Also, the water encroachment pattern is dependent upon the well spacing, and an adequate numher of wells is needed to assure a good sweep eficiency. The economic optimum well density in a water-driven field is high enough for this purpose. INTRODUCTION From year to year domestic oil becomes more difficult to find. The fields we do locate are frequently smaller and deeper than older fields and the costs for men, material and equipment are continually rising. To replenish our reserves we must continue to search for and develop new fields, but experience has shown we cannot expect prices to rise in proportion to costs. Consequently, we must meet increasing costs by more economical operations. A vigorous effort is being made within the industry to improve exploration methods, to cope with the problems of deeper drilling, and to obtain a secondary yield from older fields. Many significant contributions have resulted from these efforts. The economic operation of new fields can be further improved by developing these fields on optimum spacing and producing the wells at higher rates. This would avoid the drilling of unnecessary wells and provide additional capital for seeking new oil. While the benefits of these practices are obvious, the problem of defining the optimum development of a field for natural depletion can become very complex. A study of the effect of well spacing and several reservoir variables on economic worth of a specific field is reported here to illustrate the problem and to show the magnitude of the benefits to be realized. This study is necessarily limited to the field conditions selected and is not intended as a general solution of the well spacing problem. It does, however, indicate factors to be considered, the trends to be expected, and the direction in which we should proceed in developing new fields. NO consideration is given to land and legal considerations which might arise. METHOD OF ANALYSIS The optimum method of developing and producing a field is to use the combination of spacing and prora-tion which gives the maximum return. In addition, we do not want to lose recovery. These considerations of maximum return and maximum recovery present no serious conflict. The value of each method of operation is conveniently expressed in terms of its present worth. According to the present worth method of evaluation,' an acceptable annual percentage return is assigned to the operation, and all incomes, capital costs, and expenses are discounted at this rate to the start of the operation. This net value is the present worth. If we apply the same discount rate to several alternate methods of operation, the one yielding the greatest present worth is the best method. If we express net income in terms of price per barrel of oil produced, drilling and equipment costs on a well basis, and expenses as cost per well year, this evalu-

By William Ide Pierce

It is often desirable to work an old mine that has not been in operation for some time arid that is filled with water. This is especially true in Nova Scotia, where no great depth has yet been reached in any of the mines. The following is a description of a self-dumping water-tank which was used by me at Tangier, for draining a mine, and which did the work of a large pump, while the original cost is merely nominal, in comparison with the price of a pump. The tank, A, Pig. 1, is 1 1/3 by 3 feet and 4 feet high, inside measurement, made of 2-inch stuff and securely bound with iron. There are two clacks in the bottom which open as the tank is lowered into the water, and which close and hold the water as the tank is raised. B is an iron rod running through the tank, below and back of the center, and projecting beyond the sides of the tank. C is one of two guides, and D, a movable iron rod in each guide. This rod, attached to an upright, E, is moved forward and close up

Jan 1, 1886

By J. B. Mackintosh

Some months ago I received a sample of a highly crystalline product occurring in the hearth of the shaft-furnace used in smelting the roasted niccoliferous pyrrhotite at Mr. Joseph Wharton's works near the Gap Mine, Lancaster County, Pa. Mr. Wharton first observed this product in cavities in the concretions in these furnaces about the year 1870, and published a description of it in that year.* Thinking that it might show some analogy to meteoric iron, he sent the present sample to Mr. George a F. Kunz, who turned it over to me, with the request that I should analyze it at my convenience. The results do not show the expected analogy, because the sulphur in meteoric iron is combined as FeS., while in this product there is only one-sixth the necessary amount of sulphur, which, however, seems to be combined with all the metallic elements present, forming a sub-sulphide of definite composition. I am informed by Mr. Wharton that he has had for a long time the sample which I have analyzed, and that it probably is about the same age as that which he first described. It is worthy of note that the material does not show any signs of oxidation, but that the crystals preserve a brilliant metallic lustre. The first two analyses, made by Mr. J. Voigt, are those given by

Jan 1, 1888

By A. Azis

The problem of expressing a nation's mineral resources in terms that convey a sense of economic reality poses a great challenge to those charged with keeping government policymakers informed. A model is presented that can be used to simulate and examine the effects of, for instance, differences in levels of output, transportation costs, mining costs or selling prices on the exploitability and expected order of development of new mineral deposits. The model in its present form can be used to screen, as a first cut, the economic from uneconomic deposits in cases where little or nothing is known about them in detail. To date, this has generally been done - reluctantly - by subjective judgments. This model provides an improvement on the "informed opinion" approach, as it forces those who use the model to be both systematic and explicit in their assumptions. Moreover, the procedure is repeat- able and each step can be defended and justified. Implications can be examined of the uncertainty associated with many of the variables. The model is entirely too general to be of use for actual feasibility studies. It is not useful, in the case of speculative or little-known deposits, to provide a model that has an input format more detailed than the information that is likely to be available. Should the user see a need for it, the model can easily be expanded to allow for the input of more detail or more variables.

Jan 1, 1977

By Roshan B. Bhappu, Ronald J. Roman, Dexter H. Reynolds

The reaction between manganese dioxide and molybdenite in a water- sulfuric acid medium was studied at atmospheric pressure and from 25° to 103°C. Both solids are dissolved to give, as final products in solution, Mo(VI), S(VI), and Mn(II). Stoichiornetric relationshifis are most simply represented by the equation MoSz + YMnO2 + 15H+ - HMoO-4 + 2HSO-4 + 9Mn++ + 6H20 The rate of this reaction was found to be dependent on temperature, manganese sulfate concentration, acid concentration, and, in a complex way, the surface areas of both manganese dioxide and molybdenite. Both the total amount of manganese dioxide and tnolybdenite and the ratio of manganese dioxide to molybdenite played a part in determining the over-all rate of the reaction. The effect of acid concentration on the rate was also dependent on the ratio of manganese dioxide to molybdenite. SEVERAL reports in the literature describe reactions using manganese dioxide in water-sulfuric acid media as an oxidizing agent. Nearly all previous work describes interactions between an ion and manganese dioxide, such as the oxidation of ferrous to ferric iron,' or the interaction between a molecule in solution and manganese dioxide, such as the oxidation of toluene to benzaldehyde.2 Only a few references describe the use of solid manganese dioxide to oxidize another solid in sulfuric acid. One report3 states, "Manganese dioxide in dilute sulfuric acid solutions had no beneficial effect (in leaching copper from chalcopyrite), but in more concentrated acid solutions the rate of solution was about the same as that for permanganate." In 1902 a German patent4 described a process which used manganese dioxide in strong (50°Be') sulfuric acid for oxidizing chromite ores to soluble iron and chromium salts. The process consisted of mixing the sulfuric acid with the finely ground ore and manganese dioxide. The pulp was then heated to about 120°C and an electric current passed through it. The manganese dioxide apparently dissolved in the strong, hot acid solution, oxidized the iron and chromium and itself was reduced to manganese 11! then was oxidized at the anode back to manganese dioxide, and the cycle repeated. An extensive study5 of the kinetics of the oxidation of pyrite with manganese dioxide indicated that in dilute sulfuric acid solutions (about 0.1 N) and at elevated pressures the dissolution of the pyrite was brought about by air oxidation of the iron to ferrous sulfate, followed by manganese dioxide oxidation of the ferrous sulfate to ferric sulfate. The mechanism proposed by the authors involved the oxidation of the iron at the surface of the manganese dioxide. Also! the oxidation of sulfide sulfur to sulfate was credited to the oxygen in the air, not to the manganese dioxide. Since the metallurgical literature is lacking in information concerning the use of one solid to oxidize another solid. the current investigation was under-

Jan 1, 1965

By D. C. Seidel, E. F. Fitzhugh

The Colorado School of Mines Research Foundation has developed a hydrometallurgical process for recovering nickel from oxidized ores, including both the iron-rich laterites and magnesium-rich, soft silicates. Known as the HSO-HTCP (Hydrothermal Sulfidization Oxidation-High Temperature Cementation in Pulp) Process, the system consists of feed preparation, sulfidization, oxidation, precipitation (cementation), and calcination and melting. This paper deals primarily with the sulfidization and oxidation phases of the process. Nickel sulfide ores lend themselves readily to concentration before smelting or pressure leaching, but neither of the major oxidized ore types — the iron-rich laterites and magnesium-rich, soft silicates-has been directly concentrated. Upgrading of crude ore in current practice is limited to cobbing lumps of the harder, lower grade rock (protore) from the softer, enriched silicate ore, because only a small percentage of the nickel in these ores occurs in discrete, contrasting mineral particles. There is no apparent mineralogical contrast in the superficial, iron-rich lateritic ores and, in fact, there is no firm assurance that the nickel atoms are within the lattices of the limonite minerals, or else irregularly adsorbed on the limonite. Within underlying, "rotten rock" silicates, occasional veinlets of gamierite and related nickeliferous silicates are found.' The gamierite veinlets, however, are only incidental, and the majority of the nickel atoms occur as erratic replacements of magnesium atoms in the micaceous chlorites of the ore mass. Pyrometallurgical processes account for nearly all the nickel currently being recovered from oxidized ores. Plants in New Caledonia, Oregon, Japan, Brazil and Greece smelt the ores to make ferronickels or a sulfide matte,2 and the ammoniacal leaching3 at Nicaro, Cuba, is preceded by a reducing roasL4 The only fully hydrometallurgical installation has been the politically ill-fated Freeport Nickel Co. enterprise, and this process was limited to lateritic ores.5p6 A hydrometallurgical technique which might handle both laterite and the typically richer silicate ores has been an enticing goal. The technique described here was developed at the Colorado School of Mines Research Foundation, Inc. on behalf of the Republic Steel Corp. It uses sulfur, heat, air and metallic iron to recover nickel from these ores. Inasmuch as the ores are treated as aqueous slurries, the cost of drying a plant feed that normally carried 30% or more moisture is eliminated, and there are no dust problems. Patent applications have been filed by Republic Steel Corp. on the procedures used for getting the metal into solution and on the subsequent recovery without liquids-so l ids separation of the slurry. It is referred to as the HSO-HTCP Process (Hydrothermal Sulfidization Oxidation — High Temperature Cementation in Pulp). THE PROCESS FLOWSHEET The results of various experimental studies have been combined to form the continuous flowsheet illustrated in Fig. 1. This flowsheet serves as a general pattern showing the sequence of the operations which include: (1) feed preparation; (2) sulfidization; (3) oxidation; (4) precipitation (cementation); and (5) calcination and melting. This paper deals primarily with the sulfidization and oxidation phases of the process. Feed preparation: In general, the silicate ores can be considered as earthy rather than hard, and preparation might be carried out before the addition of water in a trommel, or with water in a scrubber or log washer. This breaks up the earthy particles, allowing the hard lumps to be separated by screening. The oversize material from most ores is relatively barren and may be discarded. If there is occasion to control the iron-magnesium ratio in the plant feed, laterite, which normally breaks up readily into fine sized particles, and silicates are mixed in suitable proportions. The fine product slurry from the initial steps is mixed with elemental sulfur and fed to a conventional ball mill, although the amount of actual grinding that takes place is relatively small. The object of milling is to complete the disintegration to natural particle size and to produce an intimate mixture of the ore and elemental sulfur. This pulp, which is almost entirely -200 mesh, has a pH of about 7.0 and normally can

Jan 1, 1969