Search Documents

By D. H. NETLAND

DURING the year 1907 an investigation of the Clinton formation in New York has been carried out under the direction of the State Geologist, and a full account of the results has been prepared for publication.1 The more important economic features of the report are summarized in the present paper. Previous knowledge of this, the type, section of the Clinton has been contributed mostly by Hall and Vanuxem in their reports for the Natural History Survey of New York, which were issued in their final form in 1842-43. Brief accounts of the ore-occurrences have been given by B. T. Putnam,2 J. C. Smock,3 A. H. Chester,4 and E. C. Eckel.5 Prof. C. H. Smyth, Jr.,6has discussed the origin of the Clinton ores in two papers, which, so far as the local occurrences are concerned, have removed all doubt that may have existed on that subject. Distribution of the Clinton Formation. The Clinton strata in New York State are restricted to a single belt, Which extends from the eastern central part to the Niagara river, which it crosses, and thence continues for some distance into the province of Ontario. The New York

Mar 1, 1909

By Sherwin F. Kelly

Twenty five years of exploration has shown that the "geophysical dollar" is worth $1780 in the Orange Free State, $1488 on the Witwatersrand, $85 in Sweden, $28,000 in the Transvaal and $3500 or more in the U.S.

Jan 6, 1951

By H. J. de Haan, J. van Lookeren

In view of their size and favorable characteristics, Shell's heavy-oil fields on the eastern coast of Lake Maracaibo, Venezuela — known as the "Bolivar Coast" — are obvious candidates for the application of thermal recovery methods. During the last decade various methods have been tested, such as steam drive,', steam soak and in-situ combustion.3 Steam soak was discovered as a promising production method rather accidentally in 1969, during early steam drive testing in the Mene Grande Tar Sands1 When steam erupted at the surface due to breakdown of the overburden, the injection wells were back-flowed to relieve the reservoir pressure. This resulted in high oil production rates, all the more impressive because the reservoir is unproducible by primary means. It was concluded that injection of limited amounts of steam might be a very effective method for stimulation of heavy-oil wells. To obtain information that would be more widely applicable, testing of the process was continued in the eastern part of the Tia Juana field (Fig. 1). Here even more favorable results were obtained than in Mene Grande. This created sufficient confidence to prompt a large-scale project, which was considered essential for an adequate evaluation of ultimate recovery, steam requirements, mechanical problems and economic prospects. To obtain an early answer on the ultimate recovery a fairly depleted area was selected in the western part of the same field ("A" in Fig. 1). The first steam was injected in March, 1964. This paper describes the performance until the end of 1966. The production mechanism and well inflow performance are discussed in some detail. In view of the favorable results obtained so far, steam soak operations have expanded considerably since the start of this project. Presently, five other projects are under way, of which two are about the same size as the one under discussion, with further extensions being programmed. Description of the Project Reservoir Data Shell's part of the Main Tia Juana reservoir has a proven area of 8,800 acres and an average net oil sand thickness of 130 ft. It contained an initial quantity of 2,750 million bbl of stock tank oil (STOIIP), with an API gravity ranging from 10 to 15 API and a viscosity of 100 to 10,000 cp (at 122F). As a geological unit it is known locally as the Lower Lagun-illas member of the Lagunillas formation, which is early Miocene in age. The sand bodies are believed to be distributary channel sands deposited in a lower coastal plain. Most of the channel sands have lateral and some vertical communication. The field was developed mainly in the period from 1936 to 1950. The ultimate primary recovery is estimated at 18.1 percent of STOIIP, of which 12.5 percent STOIIP had been produced by the end of 1963 from some 540 wells. By then the average pressure had decreased from an initial value of 960 to 550

Jan 1, 1970

Jan 1, 1970

By H. C. H. Darley

The principal causes of unstable boreholes* have been known for many years. For example, in a paper published in 1938, Halbouty and Kaldenbachl listed nearly all the classes of troublesome shales that we know today. Much progress has been made since then, but we still have difficulty in identifying the cause of hole problems and consequently in selecting the right technique for combatting them. This subject was discussed at length by Kelly2 in a recent paper and much valuable information was provided. In the Shell Laboratory it was felt that there was a need for a better understanding of the basic mechanisms underlying the various forms of hole instability, and accordingly, a study was undertaken. This entailed reviewing the physics and chemistry of shales, developing tests for characterizing shales, and constructing a model to study borehole stability. Full simulation of underground conditions was not attempted; for example, we used reconstituted shale specimens, and often simple solutions or suspensions rather than practical drilling muds. Such procedures are necessary in order to establish mechanisms, but caution must be exercised in applying the results to the more complex conditions in the field. Part I — Compaction Swelling and Dispersion of Shales Compaction of Sediments Shales are formed by the compaction of sediments. Water is expressed as sediments are buried by subsequent layers, and the degree of compaction is proportional to the depth of burial, provided the water is able to escape easily to permeable formations. The younger sediments, when recovered at the surface, soften and disperse when mixed with water; the older shales have undergone diagenesis (alteration of the clay minerals, secondary cementation, etc.), and remain hard and unaffected by water. In this paper we shall apply the term "shale", as the drilling engineer does, to everything from clays, which are highly reactive to water, to completely lithified materials such as claystones and slates, which are completely inert. However, because these materials behave quite differently when encountered in the drilling well, it is desirable to develop a simple means of characterizing them. The feature that distinguishes the various shales is their dispersibility in water —soft clays disperse readily, harder shales disperse slowly when agitated, the lithified materials will not disperse at all unless milled. In the dispersibility test used in our study, a weighed amount of dry shale particles in the 12-to-100-mesh-size range was placed in a tube filled with distilled water and allowed to soak for 16 hours. The

Jan 1, 1970

By A. B. Cook, C. J. Walker, G. B. Spencer

Although water will displace oil from a petroleum reservoir to a greater extent than gas will, there are some reservoirs in which gas rather than water should be used for pressure maintenance. This is indicated by the high-percentage oil recovery in the case history reports on the Pickton field1 in East Texas and the Raleigh field2 in Mississippi. In gas cycling, total oil recovery includes vaporized products from the immobile oil in addition to oil produced by displacement. If a large part of the immobile oil is vaporized, total oil recovery may be higher than that obtainable from pressure maintenance by water injection. However, the amount of immobile oil vaporized may range from almost 0 to 100 percent, and no simple and reliable method has been presented in the literature for calculating oil vaporization. Development of such a method was the purpose of this study. Several papers concerning the calculation of oil vaporization have been published,3 6 and each is based on the concept dealing with K values — equilibrium constants for the various components in reservoir oils. (K for a component in a system of vapor and liquid in equilibrium is the mole fraction in the vapor phase divided by the mole fraction in the liquid phase.) This appears to be the most logical approach. Yet, the problem is too great for a perfect solution, even with modem laboratories to analyze oils and high-speed digital computers to perform calculations; the number of components in reservoir oils is too large. Because of their complexity no two reservoir oils are exactly alike. Also, K values change not only with variations in pressure and temperature but also with composition of the reservoir oil. In addition, during gas cycling, the lighter hydrocarbons tend to vaporize first. Thus, the reservoir oil becomes more dense and less volatile as gas cycling continues. Furthermore, the greatest amount of oil vaporization occurs near the injection well. Therefore, a simplified method is required for calculating oil vaporization because a rigorous method is not practical. The present methods of calculating vaporization generally require knowledge of the reservoir oil composition in which the mole fractions of the lighter components through hexanes are given; the remaining oil is described as C, + (heptanes and others of greater molecular weights). Assigning one K value for the C,+ system provides the simplest solution, but this incorrectly assumes that K for C, + does not change as gas cycling continues. This assumption can cause large errors because the K value may become less than a thousandth of the original after a large amount of oil vaporization. Another way to solve the problem is to determine changing K values for C, + according to how much of the C, + has been vaporized. To determine these values a sample of the reservoir oil is injected into a pressure-volume cell, and dry gas is batched in and out of the cell. Appropriate measurements and tests are made to determine K

Jan 1, 1970

By H. H. Wade, N. F. Schulz

The large quantities of iron-bearing materials, including taconite, semi-taconite,* and other low-grade ferruginous materials occurring in Minnesota and elsewhere, constitute an important potential source of iron. Satisfactory grade and recovery of iron ore concentrate cannot ordinarily be obtained from these ferruginous materials by simple methods of beneficiation. Iron is distinctive in that the free metal and two of its oxides [magnetite (Fe2O3) and maghemite (gamma-Fe2O3) ] are strongly ferromagnetic. The successful magnetic separation of natural magnetite from taconite has already been established on a commercial scale. The iron in semi-taconite, however, occurs largely as goethite (Fe2O3-H4O) and hematite (Fe2O3) which do not respond to ordinary magnetic separation methods. Magnetic roasting converts these iron oxides to magnetite, which can, after liberation, be magnetically concentrated. MAGNETIC ROASTING Hematite undergoes a stepwise reduction when exposed at moderately elevated temperatures to a reducing atmosphere containing hydrogen or carbon monoxide: Fe2O3? Fe3O4 ? FeO ? Fe Since the desirable product in magnetic roasting is Fe3O4, the conversion is halted after the first stage by controlling the reduction potential of the gas mixture with water vapor or carbon dioxide. The reducing gas mixture must be such that the oxygen partial pressure at the solid-gas reaction interface will be maintained intermediately between the oxygen partial pressures in equilibrium with Fe2O3 and Fe3O4 at the prevailing temperature. Because of the rapid increase in decomposition pressure of Fe3O4 with increase in temperature, the practical upper limit of useful reaction temperature is about 1400°F, above which over-reduction usually occurs in atmospheres containing hydrogen or carbon monoxide. On the other hand, useful reaction rates usually occur only above 800°F. Goethite reacts similarly except that the combined water probably has to be driven off thermally before the reduction to magnetite occurs. Iron carbonate must also be decomposed thermally to an oxide before conversion to magnetite. Iron silicates are apparently not amenable to magnetic roasting. The rate of penetration of the reaction toward the interior of a given ore fragment is dependent on the chemical composition and physical structure of the solid. Most ore fragments tested here reduced satisfactorily to 1/4-in. depth in less than 14 min at 1200°F. Some very dense fragments, however, were reduced to less than 1/32-in. depth under the same conditions. Determination of the optimum temperature, gas composition, ore fragment size, or time of exposure

Jan 1, 1961

By L. E. Lynd

Ilmenite concentrates prepared from beach and dune sands of Florida, India, Australia, and other localities deviate to varying degrees from the theoretical composition of pure ilmenite, and generally contain more TiO2 than the formula FeTi03 would indicate, and some Fe2O3. This variation in composition is due to different amounts of altered ilmenite in the concentrates. (') The alteration has been shown to take place by oxidation and leaching of the iron in ilmenite, to yield residual products consisting of amaphous or very finely crystalline titanium dioxide and ferric oxide. Other studies(2) have stressed that ilmenite may alter first to an amorphous titanium-iron oxide, or to an amorphous mixture of titanium and iron oxides, with later alteration to crystalline titanium dioxide. There has been some speculation as to whether alteration of ilmenite is usually caused by weathering or by hydrothermal pr0cesses.(3,4,5 Three main methods of approach were used to study the mechanism and rate of ilmenite weathering. (1) Etch tests were used to learn the relationship between crystallographic orientation and the rate of chemical attack on ilmenite. (2) Altered ilmenites in New Jersey sands were compared with ilmenite in rocks of the area from which the sands were probably derived. (3) Experiments were carried out to determine at what rate, and by what agents, originally fresh ilmenite could be altered in the laboratory under simulated weathering conditions. ETCH FIGURES ON ILMENITE CRYSTAL PLANES A rather large ilmenite crystal from Sannidal, Norway, about 11/2 x 11/2 x 2 inches, bearing a few natural faces with imperfect surfaces, was prepared for etching by grinding and polishing crystal planes whose Bravais-Miller indices (referred to hexagonal axes) had been determined by X-ray methods to be 00.1, 10.0, and 10.2. Metallographic examination showed that the crystal was homogeneous, and uniform in orientation, except for the presence of twin lamellae which were oriented with their broadest surfaces parallel to the 00.1 planes of the large crystal. Since ilmenite is rather inert to standard etch reagents, strong solutions of hot sulfuric acid and cold hydrofluoric acid were used. Preliminary tests established that better etch figures were obtained using HF than with H2So4 solutions. The etch figures produced on 00.1 and 01.0 planes of ilmenite by etching 3 to 5 minutes in cold concentrated HF solution are shown in Figures 1, 2, and 3. The figures on 00.1 are "etch hillocks", rather than pits, and according to Honess(6), this phenomenon

Jan 1, 1961

By Ivan B. Cutler, Milton E. Wadsworth

Coprecipitation of anionic and cationic polyelectrolytes has been applied to floccula-tion of several mineral systems. Results obtained in a study of the flocculation of kaolinite and hematite suspensions of polycationic and polyanionic electrolytes are presented. Greatly increased settling rates were observed following precipitation of positive and negative polyelectrolytes on the surface of finely divided minerals in aqueous suspension. The ratios of polycationic to polyanionic electrolytes required to produce maximum sedimentation have been shown to correspond closely with the equivalence points obtained by light scattering studies of systems containing the positive and negative polyelectrolytes by themselves. DISPERSION of colloids has been of interest to surface chemists for many years. Flocculation studies have been employed to evaluate the limits of colloid stability. In water suspensions, colloids become unstable and flocculate when the 5 potential, the potential of the kinetic solvation sheath, falls to a value at which van der Waals forces may act to draw the particles together. This may happen through an adjustment of the pH of the suspension or by addition of a salt. Optimum conditions for rapid formation of large flocs are found in the region of minimum < potential. In addition to these well known considerations, colloids in water suspensions are known to be flocculated by certain large organic macromolecules. These polyelectrolytes in some cases minimize the 5 potential and in other instances increase the attractive forces by supplying sites for hydrogen bonding.&apos; Use of organic polyelectrolytes in flocculation of mineral colloids has increased rapidly in recent years. These materials are now recognized as indispensable aids to fluid-solid separations in many extractive metallurgical operations. They have been found to increase both the settling rate in thickeners and the filtration rate of filters. In the elucidation of the characteristics of these organic reagents as floc-culants in this laboratory, it was discovered that interaction of certain polyelectrolytes had a surprisingly good effect on flocculation of mineral colloids. Experimental Procedure: The anionic flocculants used in this study were Lytron 886 and 887, produced by Monsanto Chemical Co. Both reagents are copolymers of vinyl acetate and maleic anhydride. Lime is added to Lytron 886, whereas Lytron 887 is all organic. These reagents possess two carboxyl groups for each acetate group and are therefore anionic in character. The cationic reagents used were the Peter Cooper Co. 1-X and 2-X glues. The structures are not definitely known, but the re- agents are amines and are cationic in character. The glues were prepared in the chrome-alum form. Both types of reagents may be classified as polyelectrolytes in that they are high molecular weight polymers and ionize in water. All data presented are in terms of sedimentation rate, measured in 250-ml glass-stoppered graduated cylinders. With suitable precautions such measurements are fairly reproducible and provide a sensitive means for selecting important parameters such as PH, reagent concentration, and floc size and density. Agitation was standardized with five complete end over end cycles of the suspensions in the stoppered graduated cylinders.

Jan 1, 1957

COUNCIL OF EDUCATION OF AIME (Formerly Mineral Industry Education Division) Established as a Division January 15, 1932 Established as a Council February 26, 1957 John C Calhoun, Jr, Chairman 0 Cutler Shepard, Vice-Chairman Thomas A Read, Secretary-Treasurer Dept of Mining & Metallurgical Engrg University of Illinois Urbana, Illinois COUNCIL OF ECONOMICS OF AIME (Formerly Mineral Economics Division) Established as a Division December 15, 1948 Established as a Council February 26, 1957 Louis C Raymond, Chairman Lorin A Cranson, Vice-Chairman Henry T Mudd, Vice-Chairman Adam K Stricker, Jr, Vice-Chairman Paul F Yopes, Secretary-Treasurer U S Bureau of Mines Albany, Oregon

Jan 1, 1957

By Cyril Wells, Paul E. Busby, Donald P. Hart

EARLY workers in the field have established that the diffusion of nitrogen follows normal diffusion laws. Concentration-penetration data from layer analyses of reasonably pure iron specimens nitrided in an atmosphere of CO-NH, are given in the literature,&apos; and were utilized to calculate diffusion constants for nitrogen. The diffusion of nitrogen in y-iron may be represented approximately by the equation D - 1.07x10-&apos; e-:".&apos;m&apos;"&apos;r The diflusion coefficients, D, given by this relation represent mean values, since carburization occurred simultaneously with nitriding. The rate of diffusion in a-iron has been determined from calculations based on data obtained by measuring the internal friction of samples at each of several frequencies and temperatures.&apos; The expression for the diffusion of nitrogen in a-iron derived from these experiments is D= 1.4x10-1 e-it tudent Increasing carbon content decreases the diffusion of nitrogen in a-iron.3 Oxygen, either dissolved or combined, has been shown&apos; to exert a marked influence on the diffusion of nitrogen from a nitriding atmosphere. D values increase rapidly with increasing amount of dissolved oxide in the metal, but diffusion is completely inhibited if preliminary oxidation has produced the slightest trace of iron oxide on the surface. Diffusion coefficients have also been calculated from permeability and solubility data,&apos; but these values are of questionable accuracy since the boundary conditions assumed may not actually exist. Experimental Method The method selected for determining the diffusion coefficient of nitrogen in a-iron in the present investigation was the so-called fractional saturation method. This method consists of heating the specimen in an atmosphere of H2-NH8 mixtures of known composition for a predetermined time. Following this treatment, the specimen is analyzed for nitrogen; and the diffusion coefficient is calculated from a known relationship of the fractional saturation, time of diffusion, and dimensions of the specimen. This relation is based on a solution of Fick&apos;s second law and assumes that the surface of the specimen immediately reaches a given concentration which remains constant during the diffusion anneal. Tabular solutions are available4-5 and provide the relationship between fractional saturation and the quantity \/Dt /a, where D is the diffusion coefficient in cm2 per sec, t is the time of the diffusion anneal in seconds, and a, in the present experiments, is the half-thickness of the slab specimen in cm. The method is adequately discussed elsewhere.9-10 Material The material for this study consisted of 3/32 in. thick (0.24 cm) carbonyl iron plate. The major impurities in this iron are oxygen and carbon, which are readily removed by long time high temperature treatment in an atmosphere of purified hydrogen. In order to reduce the diffusion anneal time for saturation runs, some of this material was rolled to a thickness of 0.015 in. (0.038 cm) prior to the hydrogen treatment. Hydrogen treatments were carried out in a hydrogen-purified Armco iron tube heated in a global

Jan 1, 1957

By S. Ramachandran, N. J. Grant, T. B. King

MANY investigations of the rate of the sulfur transfer reaction between carbon-saturated iron and blast furnace type slags have been made." It is evident that the reaction is complex, the rate being affected by the presence of elements dissolved in the metal that are readily oxidized and therefore capable of existing in the slag phase. Thus Goldman, Derge, and Philbrook- have shown that carbon, silicon, manganese, and aluminum, in order of increasing effectiveness, accelerate sulfur transfer from iron containing these elements to blast furnace type slags. Quantitative information is still, however, not available on the relation between what have been termed side reactions, such as silicon transfer and CO evolution, and the sulfur transfer reaction itself. In other words, the stoichiometry of the reaction has not been investigated. In the present investigation, the transfer of all reacting elements and the evolution of CO have been measured simultaneously in order to establish the mechanism of the reaction which occurs in practice. Information of this nature cannot be deduced from equilibrium studies. It should be pointed out that in kinetic studies of this type quantitative conclusions are applicable only to the system studied. This restriction should be borne in mind when attempts are made to compare results from different investigations. Apparatus The apparatus used enables slag and metal samples to be taken at frequent intervals and also provides a continuous record of the amount of gas evolved. A sketch of the apparatus is given in Fig. 1. It may be considered in three sections: 1) furnace section, 2) blank volume section, and 3) pressure measuring section. The furnace section is shown in detail in Fig. 2. It consists of two graphite crucibles, C and D, super-

Jan 1, 1957

By W. F. Boericke

WORLD production of silver in 1929 totaled 256 million ounces. In 1928 production was 258 million ounces, and in 1927, 254 million ounces. With an actual decrease in the amount of silver produced last year, as compared with 1928, and an increase over 1927 of less than one per cent, obviously there has been no overproduction of the metal in the popular sense. But the price of silver tells a different story. For 1927, the average quotation was 56.37 cents; it was 58.17 in 1928, and 53.0 in 1929. During the last year it reached a high point of 57 cents in January, and fell steadily, without interruption to the downward trend, to a low of 47 cents in December. Since then it has dropped to an all time low of 43 cents on February 6.

Jan 1, 1930

By Gerald Greene

Tan various lead producers have given the subject of lead drosses much attention in recent years but the problem of their economical treatment is yet to be solved. Formerly the copper in the furnace feed was removed from the furnace in the form of matte. The speiss at that time consisted principally of the iron arsenide. The practice today is to roast off most of the sulfur and the copper in the feed forms a dross in the furnace, which is removed from the furnace with the lead. This material is poured into the drossing kettles and allowed to cool down to but slightly above the freezing point of lead. The copper dross, containing almost all of the arsenic and part of the antimony, is skimmed off and treated in a small reverberatory furnace at most plants. This is essentially a liquation process. The skimmed dross contains from 70 to 80 per cent lead, and much of this lead is liquated out. The products from this treatment are: (1) impure lead, (2) speiss and (3) matte. The speiss from the reverberatory furnace was studied in this research. The literature on the subject is of very little assistance, as almost no work has been done on the problem of establishing the exact identity of the various phases present. One author(1) states that speiss consists of a series of isomorphous compounds of the general formula FexAsy in which the Fe may be replaced by Ni, Co, Cu, Pb, Ag, Au, Pt, Zn, Cd and the As replaced by Sb, S and Bi. Hofman(2) states that the iron arsenide present is Fe5As.

Jan 1, 1935

By Donald H. McLaughlin

PRICES paid for goods and services in paper currencies are undoubtedly determined by many interrelated factors, but among them none is more specific in pushing prices toward higher and higher levels than the vast increase in debts and monetary obligations of our own and practically all major governments. There is nothing unorthodox in the situation in which the gold miners find themselves today. With wages and the prices of all materials required in the production of gold at the high levels characteristic of a period of prosperity, phony or otherwise, and with shortages of both men and machinery to contend with as well, the spread between the returns in paper dollars that must be accepted for gold in the United States and the cost of producing it is rather painfully small for most producers. Technical

Jan 1, 1948

By Homer S. Frankhouser

Materials may be dredged, processed, stored and loaded for shipment at a single site in water depths ranging from 250 to 1200 ft. Solution mining may also be accomplished in deep sea situations. And, open air subsea mines with direct surface access may be developed and worked under the ocean floor. These concepts for deep sea mining are the results of extensive testing of individual components of the proposed systems by Dravo Ocean Structures, Inc., a subsidiary of Dravo Corp. A basic structure in these systems is the articulated platform. The platform consists of a gravity- type base and a buoyant cylindrical column which is constructed at an onshore location, towed to the offshore site and installed in a matter of days without use of heavy equipment. The base is also buoyant for towing purposes. This allows for gradual flooding to the point of negative buoyancy for positioning and anchoring to the ocean floor.

Jan 1, 1971

By Richard Rice

TURBO blowers for blast-furnace blowing have now been in use for some years, and a review of the experience gained and the present state of progress may be interesting. FIG. 1.-STEAM TURBINE DIRECT CONNECTED TO AIR COMPRESSOR. The first blast-furnace blowing engine of this type to be installed in America was built by the General Electric Co. and is installed at the oxford Furnace of the Empire Iron & Steel Co. This machine was put into operation March 8, 191.0. A duplicate unit is situated at the furnace of the Northern Iron Co. at Port Henry, N. Y., which unit was put into opera ion June 30, 1910 (Fig. 1).

Jan 5, 1914

By H. S. Price, J. C. Cavendish, R. S. Varga

A numerical formulation of bigh-order accuracy, based on variational methods, is proposed for the solution of multidimensional diffusion-convection-type equations. Accurate solutions are obtained without the difficulties that standard finite difference approximations present. In addition, tests show that accurate solutions of a one-dimensional problem can be obtained in the neighborhood of a sharp front without the need for a large number of calculations for the entire region of interest. Results using these variational methods are compared with several standard finite difference approximations and with a technique based on the method of characteristics. The variational methods are shown to yield higher accuracies in less computer time. Finally, it is indicated how one can use these attractive features of the variational methods for solving miscible displacement problems in two dimensions. INTRODUCTION The problem of finding suitable numerical approximations for equations describing the transport of heat or mass by diffusion and convection simultaneously has been of interest for some time. Equations of this type, which will be called diffusionconvection equations, arise in describing many diverse physical processes. Of particular interest here is the equation describing the process by which one miscible liquid displaces another liquid in a one-dimensional porous medium. The behavior of such a system is described by the following parabolic partial differential equation:

Jan 1, 1969

By T. R. A. Davey

The fundamental principles by which bismuth may be removed from lead by pyrometallurgical processes are enumerated. Qualitative discussion of the phase diagrams concerned is followed by presentation of quantitative diagrams. Brief mention is made of the practical aspects. Data presented show how chemical lead (<0.005 pct Bi) may be produced by the Jollivet, Dittmer, and Kroll-Betterton processes. BISMUTH is an element whose properties are very similar to those of lead, and its minerals are associated to a greater or lesser extent with nearly all the major lead ore deposits of the world. In consequence, the lead produced contains bismuth unless a special debismuthizing process is practiced. There does not appear to be any published comprehensive review of the effect of bismuth as an impurity on the properties of lead, and there is some uncertainty as to the beneficial or detrimental effects of small amounts of bismuth in lead used for particular applications. Standard specifications of most countries stipulate a maximum bismuth content of 0.005 pct for chemical lead. With one exception, this specification is met only by lead producers whose ores are relatively bismuth-free, or whose refineries are electrolytic. In lead for certain applications a higher bismuth content is preferred by some fabricators.&apos; In contrast to the refining for silver, copper, and antimony, the refining for bismuth does not usually result in a large overalil economic gain from the sale of byproduct. Thus, debismuthizing is customarily practiced only if market conditions demand a lead with a bismuth content lower than that produced by classical refining; i.e., softening, desilverizing, and zinc refining. Until this century, debismuthizing was carried out only a:; an incidental result of desilverizing, as later described. This century has seen the development of the Betts electrolytic process—the only successful one of many electrolytic processes proposed and patented —and a number of precipitation processes based on the pioneering work of Kroll,&apos; although only one of these, the Kroll-Better ton process,&apos; is in wide commercial use today. It is proposed in this paper to deal only with the pyrometallurgical processes, excluding those based on aqueous electrolysis. Historical Background Prior to 1833 silver (and incidentally bismuth) could not be removed from lead. To recover silver from rich bullion, the only course available to lead refineries was to cupel the bullion, forming a slag of litharge. The first slag tappings or skimmings, on reduction, yielded soft lead of very low silver and bismuth contents. Intermediate skimmings yielded a lead of somewhat higher silver and bismuth contents, which could if desired be recupelled. The last skimmings yielded a litharge very high in bismuth, which could by successive oxidation and reduction cycles be separated into high purity bismuth, and lead returns. This oxidation reduction process, with modern operating techniques, can still be used today to produce a portion of a lead refinery&apos;s output of very low bismuth content, as discussed later. In 1833 Pattinsone discovered that lead bullion could be purified of silver and bismuth by fractional crystallization, the primary lead crystals formed by partial freezing being purer than the melt. Repeated processing in pans produced a lead containing as little as 0.02 pct Bi. The simple explanation of this

Jan 1, 1957

Jan 1, 1966