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By F. J. Chernosky

Most previous studies of coal flotation utilized chemically pure reagents. Since such reagents are not available in quantity, a study of various wmmercially available reagents as frothers was undertaken. Flotation procedures similar to those used in a large number of commercial coal flotation plants were employed. The reagents used were compared on yield-selectivity-wst basis. The selectivity was found to be relatively constant with yields above 70% but the reagent cost varied greatly. The types of reagents available were compared. In the past, a number of papers have been written on the use of various reagents as coal flotation frothers. For the most part, these have been an attempt to correlate the intrinsic chemical and physical proper- ties of the reagents or reagent groups to the floata-bility of various fine coals. Because of the type or nature of evaluations made, chemically pure reagents were normally used. Generally, these reagents are unavailable in commercial quantities. Therefore, the results obtained with these reagents were usually limited in usefulness to the plant operator or metallurgist. This paper presents the results of a study in which commercially available forms of various reagents were used as flotation frothers. Flotation procedures which would conform in general to those employed in a large number of commercial coal flotation plants were utilized. The objective of the test was to compare these reagents on yield-selectivity-cost basis, that is, 1) the yields obtained, 2) the ash levels obtained and 3) the reagent cost relating to these results. REAGENTS The reagents employed have been grouped into the following chemical classes: 1) aliphatic alcohols, 2) terpines, 3) glycols (synthetic water-soluble

Jan 1, 1963

By C. C. Harris, A. Jowett, S. K. Ghosh

An equation derived from first-order kinetics and accounting for return from froth to pulp has correlated continuous flotation data. The concentration of floatable material in the pulp can be altered either by changing the feed concentration or the feed rate. The latter does not affect the flotation rate constant, the froth to pulp return constant, and the concentration of non-floatable material in both the pulp and concentrate. Both the return constant and the concentration of non-floatable material in the pulp are directly proportional to the feed concentration, while the concentration of non-floatable material in the concentrate is related to the feed concentration. The investigation of the froth flotation process by continuous test methods, previously used by Brown and smith,1 Jowett and Safvi2 and Jowett and West,3 is being continued. Recent tests, primarily concerned with flotation cell design, have yielded kinetic data suitable for testing an equation proposed by Arbiter and Harris4 which postulates that a flotation process is defined by two rate constants: 1) the rate constant for mass transfer from pulp to froth. Previous workers have regarded this as the flotation rate constant. 2) the rate constant for mass transfer from froth to pulp, which has previously been ignored. THEORY Under continuous flow conditions at the steady state in Fig. 1 the equation developed4 is Symbols are defined in Table I. The air-liquid ratio terms4 have been omitted, since they are substantially constant for a given set of conditions. Also, for a system operating at the steady state Vf and V, remain constant and Eq. 1 can be written: Cp/Cc=b'/a,+Qc/a' [2]

Jan 1, 1963

By G. R. St. Pierre, A. J. Wilhelem

In connection with the reduction of hematite or magnetite to metallic iron, it appeared desirable to study the rate of reduction of each oxide to the next lower oxide under conditions which excluded all other condensed phases. For this purpose, pellets of Fe,O,, Fe,O,, and oFeOo were prepared. A gas train for the preparation of Ar-Hz-H20 mixtures was employed to establish a continuous flow of a controlled atmosphere over a pellet suspended on a balance. In this manner the following individual reduction steps could be studied: For example, pellets of hematite were reduced solely to magnetite by adjusting the gas atmosphere such that it was oxidizing to wustite. In other words, the reaction was complete when the hematite pellet had been totally converted to magnetite. The pellets were prepared from Baker Chemical ferric oxide. The ferric oxide powder was moistened and handrolled. Air sintering at 950°C produced Fe,0, pellets with a density of 3.65 g per cm3. The pellets ranged in size from 0.6 to 1.2 cm diam. The magnetite and

Jan 1, 1962

By M. A. Elliott

The technology of gasifying coal to produce synthesis and pipeline gas has advanced significantly in the Past 20 to 30 years. This period has seen the extensive use of oxygen in coal gasification, the development of suspension gasification processes and fluidized-bed gasifiers, the operation of various gasification processes at elevated pressures, and operation of gasifiers under slagging conditions. These developments are discussed, and their application to commercial and pilot plant gasifiers is reviewed. Typical processes for synthesis gas production are described, and operating results are compared. Pipeline or high-Btu gas may be produced from coal either by catalytic conversion of synthesis gas to methane, or by the direct reaction of coal with hydrogen (hydrogasification) to produce a methane-rich gas. Neither of these methods has been applied commercially, but developments pertaining to each of them are reviewed, and general processing schemes are discussed. The use of coal as a raw material for manufacturing gas has a long and distinguished history. In fact, the gas industry began in the early 1800's when William Murdock demonstrated that it was feasible to produce and distribute gas made by retorting coal. Coal was used exclusively for gas manufacture until the middle of the 19th centruy, when Lowe invented the carbureted water gas process. In that process, coke was one of the raw materials used, so coal was still an important factor in gas manufacture. However the availability and relatively low cost of natural gas in the United States, and its widespread distribution by long-distance pipelines in recent years, has virtually eliminated the use of coal as a raw material for gas manufacture in this country. It should not be inferred from the foregoing that the technology of coal gasification has remained static in the United States and abroad. In fact, in the past two decades many new concepts have been developed in both the science and the technology of gasification. This progress has been a result of the considerable expansion in research on the fundamental chemistry and physics of gasification reactions, and in development work on gasification processes. This expansion in effort stems in part from increased interest in the use of gas as a raw material for the synthesis of chemicals and liquid fuels, and in part from the need to develop methods for gasifying coal and other solid fossil fuels to ensure a long-range supply of energy in the form of gaseous fuel. In these uses of gas, synthesis gas, a mixture of hydrogen and carbon monoxide in various proportions, is the starting material. It may be converted catalytically to gaseous and liquid hydrocarbons and other chemicals, or to hydrogen for use in hydrogenation or reduction reactions. Since coal is our most abundant fossil fuel, it is inevitable that one day it will regain its prominence as a raw material for gas manufacture. It is of interest, therefore, to consider the present status of gasification technology, directing attention particularly to advances made in recent years. Inasmuch as many comprehensive treatises l-3 and review4-7 of gasification technology are available, no attempt will be made in the present review to cover all processes in detail. Instead, the discussion will be concerned chiefly with typical processes embodying the advances that are most likely to be generally applied. ADVANCES IN GASIFICATION TECHNOLOGY For purposes of this discussion the starting point will be the conventional processes that were used for many years for the complete gasification of coal. These were: 1) carbonization in coke ovens followed by gasification of coke with air and steam in cyclic water-gas generators, and 2) fixed-bed air-blown producers. Both of these methods have obvious deficiencies when we consider that the ideal complete gasification process would be a single-stage, continuous

Jan 1, 1961

By A. Alonso, J. Daubenspeck

In the nickel extraction process at Nicaro, Cuba, dried and ground nickel bearing laterites are reduced at 1300-1400F in multiple-hearth furnaces. Nickel is leached from the reduced ore by aeration in an aqueous solution of ammonium carbonate. Nickel carbonate is precipitated from the liquor and calcined to yield nickel oxide. The following are the more important modifications of the Nicaro process since plant rehabilitation and expansion. Ten percent increase in tonnage was achieved without decreasing the fineness of the ore by minor mechanical modifications of the grinding plant. Another five percent increase in tonnage was attained by intentionally overloading the ore prepration and leaching circuits in an effort to control cobalt extraction. Modifications at the sintering plant allowed it to handle the entire output of the expanded plant. A fifty percent increase in leach liquor cooling facilities alone provided an increase in nickel production of five percent. Stronger fresh leach liquor for increased nickel washing efficiency was obtained through improved distribution of water to the ammonia absorption towers. Advantage was taken of the reduced calcine's capability to precipitate cobalt, and modifications in the leach liquor circulation provided controlled cobalt solubility with minimum harm to nickel extraction. Several process changes at the drying plant brought about a ten percent reduction in the fuel oil consumption at this pint. Controlled air addition to the reduction furnaces' upper hearths burned formerly wasted combustibles thereby reducing oil consumption by twenty percent. The nickel extraction process successfully emplayed on the extensive but lowgrade lateritic ores of Eastern Cuba at the U. S. Government owned Nicaro plant, has been previously described in various publications. The large mine and plant operated by the Nickel Processing Corporation, located on the northeastern shore of Oriente Province, have been recently expanded to a yearly capacity of about 50 million pounds of nickel. Essentially, the operation involves open pit mining of a limonite-serpentine ore mixture containing 1.3 to 1.4 percent nickel and 34 to 38 percent iron. The comparatively lumpy, wet (25 to 30 percent moisture) ore is first dried and ground prior to chemical treatment, to which the entire 7,000 tons per day feed must be subjected. In the initial chemical action the dried and ground ore is reduced with carbon manoxide and hydrogen at 1300-1400° in multiple-hearth furnaces. The resulting metallic nickel is selectively leached from the reduced calcine by aeration in an

Jan 1, 1961

By J. E. Forciea, O. E. Palasvirta, L. G. Hendrickson

AH pilot and commercial plants working with Mesabi Range taconite employ wet magnetic separation. Progress is being made with a dry magnetic process, but this has not yet been applied to taconite except in the laboratory and pilot plants. Flowsheets in all five plants are similar, including multiple stages of grinding, each followed by magnetic separation, which rejects a finished tailing. The flowsheet in Fig. 1 is used in the preliminary and commercial plants of the Erie and Reserve mining companies and in Unit C of Oliver's Pilotac plant. At Erie the desliming operation is omitted. In the Reserve plants two ball mills are used with each rod mill. Pilotac uses flowsheet 2 in Unit A-B and has also tested flowsheet 3. Principal differences in the three flowsheets are the number of grinding stages and the type of roughing. The terms open-circuit roughing and closed-circuit roughing are best defined by the diagrams. Special Test Data Given in Table I: For the Erie and Reserve commercial plants, Table I reflects routine conditions. Pilotac, the experimental plant, has been run with several flowsheets, including those followed at Erie and Reserve's commercial operations. Pilotac data for these last two flowsheets are similar to commercial plant results and are not repeated in Table I; statistics are given, however, for special test conditions. using other flowsheets. when the objective was to 'to extra-grade concentrate, Variations Among Taconites: Although crude ore tributary to these plants is generally classified as taconite, there are important differences in mineralogy and fineness of dissemination.

Jan 1, 1959

By B. S. Gottfried

This paper is concerned with possible transport mechanisms which occur during segregated burning (i.e., burning in an oil reservoir in which the oil-bearing formation is overlain by a "clean" porous zone containing only gas). ,Two analytical models are presented. In the first, burning is assumed to occur at the gas-oil interface, and the dominant mechanism is taken to be the rate at which oxygen diffuses to the interface. The second model assumes that combustion occurs within the clean zone, with the dominant mechanism being the mechanism of fuel deposition from the oil-bearing formation to the clean zone. ,Comparison of the results of the analyses with limited experimental data indicates that the latter mechanism is much more plausible. Both models are idealized representations of the actual process and are somewhat conjectural, however, owing to the lack of more definitive laboratory or field data. INTRODUCTION In recent years there has been considerable theoretical and experimental research directed toward understanding the recovery of crude oil by underground combustion. Although two different recovery schemes have been proposed, known as forward and reverse combustion, it is only forward combustion that shows promise of becoming a practical recovery technique.17 Most of the analyses of the forward combustion process have considered it to be pistonlike; i.e., oil is displaced by a vertical combustion zone which, with its ensuing gases, pushes die oil forward as the flame front is propagated through the reservoir.l-8,ll,l2,14-16 However, information gained in field pilot studies indicates that, at least to a certain extent, forward combustion proceeds in a segregated manner in oil reservoirs.10 An ideal segregated system is one in which the oil-bearing formation is overlain by a "clean" porous zone containing only gas. The location of the combustion zone in such a system is not immediately evident, although combustion is believed to occur either at the gas-oil interface or within the clean zone. In either case, the combustion zone may be horizontal and it moves in parallel rather than in series with the produced oil. The purpose of this paper is to explore the likely mechanisms by which segregated burning can occur, and to determine the sensitivity of the resulting models to changes in various physical parameters. Two governing mechanisms are considered: the case of a horizontal combustion zone at the gas-oil interface with the rate of combustion governed by the rate at which oxygen diffuses to the interface, and the case of combustion within the clean zone with the combustion process controlled by the transport of fuel from the oil-bearing formation to the clean zone. Both models are somewhat hypothetical and involve considerable simplification of the actual process. However, the results allow some preliminary understanding of segregated burning which is useful in the absence of more definitive laboratory or field pilot data.

Jan 1, 1967

By S. G. Gibbs, A. B. Neely

Jan 1, 1967

Jan 1, 1963

By D. A. Elgillani, M. C. Fuerstenau, J. D. Miller

Adsorption of lead and ferric iron on quartz and alumina is presented as a function of pH. Only the hydrolyzed species of these metal ions, FeOH++ and PbOH+, adsorb significantly on each of these minerals. Zeta potentials of quartz were measured as a function of pH in the presence of various additions of aluminum, lead, and magnesium salts. Sign reversal occurs at the pH values where significant concentrations of hydroxy complexes are formed. Models of adsorption are presented in the absence and presence of collector. The mechanism of adsorption of metal and collector species in the activation of nonmetallic minerals is still the center of considerable discussion in spite of the extensive study given this system. Until recently, the view was widely held that hydrated metal ions were responsible for this phenomenon. This fact is surprising, since it had been shown that the pH range in which flotation is effected corresponds to that in which metal ion hydrolysis occurs.' Additional support of this concept was pro vided by the work of Wolstenholme and Schulman in another system.' Later work has shown that hydroxy complexes of metal ions are the active species. These studies have also indicated that basic aqueous complexes of metal-collector may be necessary for flotation.3-7 Depending on the molecular weight of the collector, formation of these complexes may occur before or after precipitation of the metal-collector salt has occurred. Ion pair formation can occur when low molecular weight collectors are involved because relatively high concentrations of metal hydroxy complex and collector can be present in solution before precipitation occurs. This is not the case when high molecular weight collectors are used. A model of aqueous complex adsorption has been presented6,7 in which it has been assumed that adsorption occurs by the formation of water from adsorbed hydroxyl and hydrogen of the hydroxyl contained in the complex. Other authors8 have suggested that hy-droxy complexes are involved in these systems but that collector adsorption occurs by replacement of the hydroxyl of the adsorbed metal hydroxy complex with a fatty acid anion. All of these investigations have involved mineral surfaces that were negatively charged so that it is not possible to state with certainty whether hydrated metal ions or hydroxy complexes are the active species in this system. Use of a positively charged mineral should be helpful, however, since the hydrated metal ion will be repelled from this surface. On the other hand, if the hydroxy complex adsorbs by splitting out water, surface charge should have no effect because of the free energy decrease that the system will experience when water is formed. In this regard, sapphire is well-suited for study, since its surface is positively charged until approximately pH 9. Electrokinetic studies of quartz in the presence of various metal ions should also be useful in establishing the mechanisms of adsorption in these systems. That is, if the hydroxy complexes adsorb by water formation, drastic changes in the zeta potential should occur in the pH range in which hydrolysis occurs. In this view, adsorption of ions of widely different hydrolysis characteristics on both sapphire and quartz was measured. In addition, zeta potentials of quartz were measured as a function of pH in the presence of various metal ions and compared with flotation responses obtained under similar conditions. Experimental Materials and Techniques Reagent-grade aluminum, ferric and magnesium chlorides, and lead nitrate were used in this investigation. Adjustments in pH were made with reagent-grade HCl or KOH. Conductivity water, made by passing distilled water through an ion exchange column, was used in all of the experiments.

Jan 1, 1971

By G. Beghi, G. Piatti

THE authors examined the problem of the gradual transformation of Al2O3 from the transition phases normally encountered in SAP (r -x-n)1-3 to the stable a phase. This phenomenon is well-known at temperatures above the melting point of aluminum,3"6 whereas in this paper the transformation was studied at temperatures lower than the melting point of the aluminum matrix.

Jan 1, 1967

By R. N. Edmondson, L. Mair, M. Tenenbaum

It is the policy of The Metallurgical Society to provide, in the TRANSACTIONS OF THE METALLURGICAL SOCIETY OF AIME, a prompt and accurate medium for publication of reports of significant new research in both the scientific and engineering aspects of metallurgy. Papers submitted to the Society are judged by competent reviewers according to established criteria for technical merit, accuracy, originality, and presentation. STAFF: Editor, Dr. Gerhord Derge; Editorial Assistant, M. A. Redmyrski; Staff Coordinator, James J. Burke. THE METALLURGICAL SOCIETY: W. R. Hibbard, Jr., President; J. C. Kinnear, Jr., Past-President; John Chipmon, Vice President; T. D. Jones, Treosurer; R. W. Shearman, Secretary. PUBLICATIONS COMMITTEE OF THE METALLURGICAL SOCIETY: A. w. Thornton, Chairman; Dennis Carney, John Chipman, J. C. Fulton I. H. Hollomon H. H. Kellogg, A. E. Lee, R. Maddin, J. D. Sullivan, and D. Swan. Review and selection of manuscripts is under the supenision of the following Publications Committees: Extractive Metallurgy Division: T. 0. King Chairman; S. J. Dickenson, R. P. Hermsdorf R. Schuhmann. Jr.. and P. T. Stroup. Institute of Metals Division: Robert Maddin, Chairman F. Lincoln Vogel Jr., Vice-chairman, W. A. Baikofen, R. W. Boliuffi J. H. Bechtold M. B. Beyer. R S. Busk, C. G. Gaetzel, Paul Gordon C. D. Groham, Jr., Robert F. Hehe-mann,' R. I. Joffee, F. c. Joumot Jr lrving R. Kramer A. J. Lena Harold Morglin, C. J. McHargue, Russell A: Meussner, J. B. Newkirk H. W. Paxton, G. E. Pellissier, I. S, Servi, Alon U. Seybolt, A. J. Shaler, and Jack Washburn. Iron and Steel Division: J. C. Fulton, Chairman; T. B King, F. C. Langenberg, W. 0.. Philbrook, and T. 0. Winkler. Published bimonthly by the American Institute of Mining Metallurgical and Petroleum Engineers Inc., 29 West 39th Street, New York 18, N. Y. Telephon: pEnnsvlvanio 6-9220. Subscription 522 Per year for non-AIME members in United States and North South and Central America; $25 foreign;, $5 for AIME members. Single copies, 54.00, single copies foreign, $5.00. The AIME is not responsible for any statement made or opinion expressed In its publications . . . Copyright 1958 by the American lnstltute of Mining Metallurgical and Petroleum Engineers Inc. . . . Registered cable address AIME New York , . . lndexed in Engineering Index Industrial Arts Index and Chemical Abstrats . . . Application for second class mail privileges ii pending at New York, N. Y. Volume 212, Number 4.

Jan 1, 1959

By John Nunes, Frank R. Larson

Temperature-dependent functions of various ten-sile flour stress and fracture parameters were investigated on iron and low composition alloys of Fe-C, Fe-Cr, Fe-Mn, and Fe-Ni. Data were obtained over a range of test temperatures from 200" to -196"C at an initial strain rate of 0.01 min". It was found that the strain-hardening exponent, n, for the Fe-Ni alloys increased significantly at very low testing temperatures with increased alloy addition. Also, the stress and strain at fracture followed a predictable transitional type of behavior. The flour stress-temperature dependence was evaluated employing the relation: M where it is shown that composition can strongly influence the constant M. An empirical formula describing this effect is as follows: M = MI (equivalent at. pct Ni)-'" Some preliminay, tests were run on several commercial steels to test the generality of this relationship. One of the phenomenological explanations of the ductile-to-brittle transition encountered in bcc metals is based upon the difference in the temperature dependence of the flow and fracture stresses.' It states simply that the fracture stress is relatively insensitive to temperature and that the yield or flow stress rises rapidly with decreasing temperature so that, when the flow stress reaches the fracture stress, brittle fracture occurs without appreciable plastic deformation. This behavior is illustrated schematically in Fig. 1 where the ductile-to-brittle transition is shown to occur at two possible temperatures. The lowest temperature, TB, represents essentially completely brittle behavior while the higher temperature, TN, represents "notch" brittle behavior. Support for this theory is obtained when it is observed that fcc metals, which do not commonly have a ductile-to-brittle transition, also do not commonly exhibit any strong temperature de- pendence of the yield stress. This relationship of yield or flow stress behavior with the ductile-to-brittle transition has been generally observed for most metals representative of these two crystallo-graphic structures. One exception to this generalization appears in the case of tantalum where no apparent ductile-to-brittle transition has been observed. However, this may simply be an indication that this type of behavior is not directly related to the flow stress and that some other mechanism such as twinning must also be operative. A comparison of the typical temperature dependence of the yield stress of some representative metals is shown in Fig. 2. In the study of the temperature dependence of the strength of metallic materials, considerable ef-

Jan 1, 1963

By G. Thodos, D. E. Matschke

Cansiderable time and effort frequently are expended to establish, with a degree of confidence, the PVT behavior of pure substances. In particular, a great deal of experimental information contributed by a number of investigators is available in the literature. The data of each investigator, although significant in themselves, cannot be used with a high degree of confidence until they are compared with the continuum of information presented by others. Current interest in thermodynamic and transport properties, for not only the gaseous state but the con-densed state as well, requires that PVT infarmation be presented for both regions. The density dependence on temperature and pressure, when presented as a continuum, is of considerable value in itself, especially since the available equations of state fail to properly account for the PVT behavior in the condensed state. For this reason and to incorporate PVT data recently presented in the literature, this investigation was carried out. In their studies concerned with the thermodynamic properties of methane, Matthews and Hurd in 1946 utilized the data of Kvalnes and Gaddy and Olds, Reamer, Sage and Lacey to establish the PVT behavim of methane in the superheated region and the saturated liquid densities of Keyes, Taylor and Smithl in conjunction with the Clapeyron equation to develop the densities for the saturated envelope. Current activity sponsored by API Project No. 44 under the direction of F. D. Rossini has led to a tabular presentation of compressibility factors for gaseous methane in the superheated region.la These values were obtained by using smoothed residuals, developed from experimental data and the Ben edict-Webb-Rubin equation,' to establish internally consistent compressibility factors for the real gas. This approach offers probably the most precise presentation of PVT information for gaseous methane to date. The PVT behavior of methane also can be represented accurately by equations of state such as the Benedict-Webb-Rubin equation or the Martin-Hoa equation.' These equations, although valuable for analytically representing the PVT behavior, lack precision in the compressed-liquid region. The PVT data available in the literature for methane were utilized to obtain reduced densities that are presented in Figs. 1 and 2 as functions of reduced temperature with parameters of reduced pressure. The critical constants utilized for methane are those reported by Kobe and Lynn." These critical values, T, = 191.1°K, PC = 45.8 atm and p, = 0.162 gm/cc, produce a critical compressibility factor, z, = 0.289. The PVT information, as obtained from the literature, in many instances was not presented in an immediately

By George C. Coupland

Ecstall Mining Limited, a wholly owned subsidiary of Texas Gulf Sulphur Company, is the owner and operator of the Kidd Creek Mine including the concentrator complex located near Timmins, Ontario. Canada, approximately 450 miles north of Toronto. The mine, concentrator and Timmins form a triangular arrangement with a 17-mile rail link connecting the mine and concentrator and both of these facilities 18 and 14 miles respectively by road from Timmins. A core drilling program in the spring of 1964 established the presence of a large massive sulphide orebody which was to become the Kidd Creek Mine. Texas Gulf Sulphur had been conducting an intensive search for base metal in various parts of Northern Ontario and Quebec since 1957. Of several thousand anomalies detected in airborne electromagnetic surveys, several hundred warranted ground inspection, but only one of more than sixty drilled became a commercial orebody, the Kidd Creek Mine. The geophysical exploration work has been well covered in a paper written and presented by Van Donohoo, presently a Vice-President of T.G.S., at the American Mining Congress in San Francisco in October 1969. GEOLOGY The orebody lies within a series of overturned rhyolitic flows and pyroelastics with a major peridotite intrusive to the east. The hangingwall and footwall are composed chiefly of intermediate volcanics, andesite and dacite. The southern end of the orebody appears to terminate abruptly against greywacke while the north end is bifurcated and the structure obscured.

Jan 1, 1970

By F. Petkovich, M. P. Sudbury

Development of a new method of treating flotation concentrates for the preparation of feed suitable for direct charging to blast furnaces or converters is described. The method takes advantage of the fact that pyrrhotite contained in the concentrates can be made to undergo exothermic reactions which, under properly controlled conditions, result information of oxidation products that serve to cement the concentrate particles together. Thus green concentrates either in the form of pellets or briquettes containing 5 to 8 pct moisture not only were hardened, but also completely dried autogenously by continuous countercu,vrent shaft treatment with air. The process was developed through pilot plant operations ranging from 35 1b per hr to 2.5 tph, culminating in products evaluation tests on a railway-car scale. Falconbridge Nickel Mines Ltd., Falconbridge, Ont., have practised sintering, on a travelling grate machine, for many years to prepare a pyr-rhotite-bearing Cu-Ni sulfide flotation concentrate for blast furnace smelting. In recent years the development of new mines, and the construction of concentration plants some 40 miles from the smelter has increased the quantity of concentrate shipped, and encouraged the search for a method of producing dry, hard pellets or briquettes suitable for direct charging to a blast furnace or converter, and capable of withstanding considerable handling. The cementing properties of pyrrhotite oxidation products were discovered during a search for a suitable agglomeration method for sulfide concentrates, and were exploited in a process subsequently developed for autogenously drying and hardening pellets and briquettes of pyrrhotite-bearing Cu-Ni sulfide flotation concentrate. EARLY TEST WORK The production of hard, dry pellets of concentrate filter cake was attempted in the drying plant of one of the new concentrators. While soft pellets were produced containing 5 pct moisture, attempts at further drying resulted in disintegration of the pellets and intolerable dusting. The plant therefore was controlled to produce a concentrate containing about 6 pct moisture. The partially dried concentrate, which was shipped to Falconbridge for sintering, tended to heat spontaneously in transit. An at- tempt to briquette the moist concentrate at Falconbridge, in a plant incorporating a muller, a 20-in. roll briquetting press, and a steam-heated travelling grate oven, was more successful, although the equipment corroded rapidly due to the acid nature of the concentrate after spontaneous heating had occurred. LABORATORY STUDIES OF SPONTANEOUS HEATING OF CONCENTRATE The spontaneous heating of partially dried concentrate was studied in the laboratory. Moist concen-

Jan 1, 1961

By E. T. Turkdogan

Jan 1, 1962

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 Karl A. Bauer, Cornelis Bezemer

The deposition of calcium carbonate scale on surface and subsurface production equipment creates an operation problem in many oil fields. The formation water in which the carbonate-scale-forming components are initially dissolved becomes supersaturated with calcium carbonate as a result of the drop in pressure during production. The continuous flow of a supersaturated solution through the production equipment results in the growth of a dense layer of calcium-carbonate crystals. For a scale layer to be built up, the supersaturated formation water should contact the walls of the production equipment. The tendency for scale to be deposited, therefore, will be low, if the crude has a low water cut and if the water is finely dispersed in the oil. A scale problem will occur, if at a high water cut part of the water is present as free water. The rate of scale deposition will then be approximately proportional to the rate of free water production. Depending upon where the formation water becomes supersaturated, scale may be deposited in the flow line only, in both flow line and tubing, and in some cases even in the perforations and in the formation near the wellbore. In the South Sumatran fields (Indonesia) the main difficulties encountered due to the deposition of calcium-carbonate scale have been restriction of flow through tubings and flow lines, wear and abrasion of plungers and liners, and stuck plungers or wellhead valves. So far, the only methods of combating the *Presently associated with Brunei Shell Petroleum Co., Ltd.. Seria. scale problem have been routine acidizing and additional well pulling. As for the pumping wells, it was estimated that some 50 percent of the total well-pulling effort was directly attributable to scale deposition. The most promising alternative was to prevent the deposition of calcium carbonate scale by means of chemicals. Inorganic polyphosphates such as sodium hexametaphosphate and trisodium polyphosphate are known to retard the formation of scale by the "threshold action". They are adsorbed on specific faces of the crystal nuclei and thus prevent crystal growth, thereby stabilizing supersaturation. Polyphosphates are effective at very low concentrations ( a few ppm), and far less than stoichiometric quantities are required to keep the scaling ions in solution. Recent investigations on barium sulfate scale1 have confirmed this mechanism. The types of polyphosphate mentioned can be applied as concentrated aqueous solutions either squeezed into the formation, lubricated down the annulus or injected via macaroni string. Several squeeze jobs with polyphosphate solutions have been carried out in the South Sumatran fields, however, with disappointing results. Lubrication down the annulus and injection through a macaroni string were not considered attractive in this area because of the kind of equipment and the degree of supervision these techniques require. Polyphosphates are also available in a granular, glassy form, which, in contrast with the readily soluble types already mentioned, show an extremely low

Jan 1, 1970

By A. E. Chute

The shortage of sulfur is not only continuing but appears to be worsening, attended by steadily rising prices. At the same time emphasis on air-pollution abatement is also increasing. These two factors, a rising market and the growth of environmental attention, have encouraged producers to carefully review all possible sulfur sources. As a result, production of sulfur from hydrogen sulfide occurring in petroleum is receiving greater attention than ever before. Until about a decade ago, the practice of recovering sulfur from hydrogen sulfide separated from gases (either found naturally or generated in desulfurization of liquid petroleum) was wide1y recognized but contributed little to total free-world sulfur production. However, during the past ten years, the production of sulfur from this source has increased so rapidly that it now accounts for a substantial portion of total production. This trend shows no signs of slackening, and current forecasts predict that recovered sulfur may become the dominant source of supply within ten years, exceeding mined sulfur production. This paper is intended to list sulfur sources and relationships, and to discuss the potential of producing sulfur from petroleum. The processing involved, in addition to product storage and transportation will also be discussed along with important economic aspects of sulfur recovered from hydrogen sulfide. For many years, most of the world's elemental sulfur has been produced from salt domes, predominantly by the Frasch process. During the past decade, however, another production source has developed so quickly that it is expected to surpass the Frasch production sources within a short time. This new source lies in the petroleum gases and liquids from which dramatically increasing quantities of elemental sulfur are being recovered. In the phraseology of the trade, the sulfur so obtained is know as "recovered sulfur," a term which does not, as one might expect, include sulfur recovered from other sources such as smelter gases. The growth rate of recovered sulfur compared to that of Frasch sulfur, total elemental sulfur, and total Free World sulfur in all forms is shown in Fig. 1 Since 1963, sulfur consumption has exceeded production,with the natural result that the price of sulfurhas continually increased. The posted price reported for f.o.b. Port Sulphur, La., has risen from as low as $18 per ton in 1962 to $32.50 per ton in mid-1967. With freight and other charges, delivered prices have of course run much higher, amounting to $45 or $46 per ton on the east and west coasts. In some cases, spot sales for as much as $60 have been reported. Although it is playing an ever-increasing role in the sulfur market, recovered sulfur was originally a by-product of the removal of hydrogen sulfide from natural and petroleum refinery gases. Today, however, it is often the most valuable product of a multi-product processing facility. Since there are two major sources of recovered sulfur—production and refining processes —natural gas is included with liquid petroleum for purposes of this discussion. Sulfur from these sources is produced in the form of gaseous hydrogen sulfide which is removed from a gas stream and converted to elemental sulfur. Gases in which hydrogen sulfide occurs naturally are natural gas and the gas produced from a high=pres-sure crude=oil or condensate field.

Jan 1, 1969