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By Carl F. Floe, John Chipman

THE system molten copper-oxygen-sulphur is of interest from both the practical and theoretical standpoints; practically, because oxygen and sulphur play an important role in the commercial production of copper, and theoretically because it offers a chance to study the reaction between an oxide gas, SO2, and a molten metal. Reactions of this type, such as that between CO or C02 and molten iron, are important in many metallurgical operations. Again, the determination of any gas-metal equilibrium is of theoretical interest and value insofar as it contributes to the general development of the laws for solution of gases in metals. This problem is being given an increasing amount of attention in modem metallurgy. This paper is the first of a series and presents the results of a determination of the solubility of sulphur dioxide in molten copper at temperatures from 1100° to 1500°C., and pressures from about 20 mm. of mercury to somewhat above atmospheric. REVIEW OF PREVIOUS WORK The solubility of gases in most liquids has been found to obey Henry's law, which states that for a fixed temperature the amount of gas dissolved is directly proportional to the pressure. However this law does not hold for liquid metals. Instead, it appears that for many gases, particularly the simple diatomic ones such as 02, N2 and H2, the amount dissolved in liquid metals is directly proportional to the square root of the pressure. This is known as Sieverts' law. It may be recognized as a special case of Henry's law, which applies when the solute gas is dissociated into atoms or when it reacts with the solvent metal to form solute molecules containing single atoms of the gaseous elements, as, for example: [2M -}-G2 = 2MGK =G) IYf X[I]] which, if the solubility is not too high and the concentration of metal therefore nearly constant, can be simplified to: [MG = Ki Pa,[2]] Following the same reasoning, it would be expected that the solubility of SO2 in copper would be proportional to the cube root of the pressure, the reaction being as follows: [6Cu + S02 = Cu2S + 2Cu20[3] K Cu2S X (Cu20)2(Cu)e(Psm)[4]] or, neglecting the change in metal concentration and considering that the concentrations of sulphur and oxygen are both proportional to the volume V of gas absorbed: [K1 =or Vdo,= K2/PBO [5] PsO]

Jan 1, 1941

By M. D. Hassialis, Arthur F. Taggart

WARK1 observed some years ago that collector-coating reactions with xanthates and with fatty acids clearly follow paths parallel to those prescribed by the familiar mass-action law for reactions in dilute solutions. He proposed, therefore, the logical hypothesis that they are governed by the solubility=product principle. However, he went astray in the application of his proposal to collector coating by overlooking the fact that coating involves a heterogeneous reaction. A mistaken concept of the meaning of the word adsorption also entered. Wark thought that the concentration of metallic ion that must be used in setting up the solubility-product equation for the coating reaction was that which could be obtained by solution of the mineral. Since this is very low for sulphide ores, and since the amount of the collector ion necessary for coating produces an extremely low concentration, the resulting ion-concentration product, under conditions when coating occurs, is much lower than that which would indicate a saturated solution of the collector-coating compound. Hence he was forced to the position that the solubility product governing the coating is much smaller than the standard solubility product. To justify this position it was necessary to postulate a coating mechanism that did not obey the ordinary laws of chemical reaction. This Wark did by adopting the concept that adsorption is a property of matter, rather than merely a more or less ephemeral local concentration thereof. Thus he says (p. 142 of ref. I): "Adsorption is not a purely physical property of the solid surface, for the specific nature of the adsorbed molecule or ion is important." The result was that he destroyed the great potential utility of his postulate by tying it to this erroneous concept in the words (pp. 142, 143): "It will be obvious that the adsorption solubility product is less than the normal solubility product." The writers have found quantitatively in the case of galena and potassium ethyl xanthate, and semiquantitatively in the case of covellite and the same collector, that the coating reaction does follow the mass-action law to the extent that coating occurs when the ordinary solubility product of the coating compound is exceeded, and that coating does not take place under the reverse conditions. In the course of the investigation leading to the establishment of this fact it was necessary to work with xanthate concentrations so low (down to 0.0004 mg. per liter), that very long conditioning times, and bubble-contact times of as much as 16 hr. were necessary sometimes to follow the reactions. The results have led to some illuminating conclusions as to necessary collector concentrations in normal flotation operations, and the action of the frothing agent in connection therewith. The experimental work comprised. accurate determination of the standard solubility product of lead ethyl xanthate, development of a much less laborious

Jan 1, 1946

By R. Velkova, D. Bojinova

The objective of the present investigations is to establish the effect of the preliminary mechanical activation of phosphates on the degree of phosphorus extraction by bioconversion of Bulgarian and Tunisian phosphates using A. niger fungi and T: thiooxidans microorganisms. The influence of the phosphate concentrations, the type of the nutritive medium and the incubation times on the process of biological mobilization of the phosphates was studied. When the concentration of phosphates in the medium is twice as high, an equal and/or higher degree of phosphorus extraction can be achieved through the bioconversion of mechanically activated phosphates compared with non- activated phosphates under similar conditions. A maximum degree of 90+% phosphorus extraction in utilizable form was achieved at definite conditions.

Jan 1, 2002

By Felicia F. Peng

Using granular media for removal of soluble manganese from mine water and industry waste stream has the advantage of forming a compact surface layer of manganese oxide coating on the media. This process can avoid the step involving the separation of voluminous sludge of manganese hydroxide by the high-pH method for soluble manganese removal. The removal of soluble manganese is accomplished by adsorption and oxidation. The adsorption of Mn(II) on the manganese oxide-coated media was rapid through the specific adsorption and may be due to the ion exchange of hydroxyl ions on the manganese oxide by Mn(II). In the subsequent step, the adsorbed Mn(II) form the intermediate manganese complex on the manganese oxide product is oxidized with dissolved oxygen or other available oxidant source in the aqueous solution. This paper presents the efficiency of removal of soluble manganese from mine water by using a laboratory fluidized bed and the recovery of manganese oxide coating on the anthracite coal particles. In order to accelerate the formation of the manganese oxide layer on the surface of anthracite media, dilute potassium permanganate solution is used as an active oxidant. The effects of operation parameters on the manganese removal including pH, flow rate, concentration of feed and oxidant dosage are evaluated.

Jan 1, 1996

By S. Power Warren

Introduction It is generally conceded by flotation men that the condition at the surface of a particle of mineral or gangue is the most important factor controlling its behaviour in a flotation cell. Much research work has been devoted to the study of the forces that are active at the surface of the particle and of the effect of the surrounding solution upon these forces. Study of the relationship between mineral or gangue particles and gas bubbles indicates that, in the main at least, flotation is a physical phenomenon. The important factor, that of mineral-gas-bubble attachment, is unquestionably physical; however, modifications may be effected by chemical means, whereby the nature either of the surface of the particle or of the surrounding solution may be changed. For example, the coating of lead sulphide that forms on lead-carbonate ore particles when sodium sulphide is added greatly aids the flotation of the carbonate particles. Without going into the question as to why, under certain surface conditions, mineral particles will attach themselves to gas bubbles whereas under other conditions they will remain unaffected, it may be stated that there are three general conditions in a flotation pulp which control the attachment of the particle and the gas bubble.

Jan 1, 1933

By X. Zhou

"Hydrogen induced failure and degradation in structural metals, namely hydrogen embrittlement, has been a long-standing industrial problem for more than one century and remains unsolved. Despite the proposal of numerous models, no consensus has been reached, and considerable discrepancies in experimental observations and theoretical calculations exist. One aspect that is central to the understanding of hydrogen embrittlement is the interaction between hydrogen and grain boundaries. In this study, we investigated the influence of several solute elements (i.e., Cr, Mo and Nb) on hydrogen segregation at the representative 9 grain boundary using first-principles calculations. Our results showed that the presence of Mo and Nb can reduce the tendency of hydrogen segregation at grain boundaries, while meanwhile enhance the grain boundary strength. This indicates that Mo and Nb are salutary elements that can be used to increase the material’s resistance to hydrogen embrittlement, providing new insights in designing hydrogen embrittlement resistant Ni alloys. INTRODUCTION Hydrogen embrittlement (HE), a phenomenon of hydrogen triggering premature failures in structural metals, has been a headache for industries ever since its first discovery one century ago (Johnson, 1874; Zhou, Marchand, McDowell, Zhu, & Song, 2016; Zhou, Ouyang, Curtin, & Song, 2016). It is well accepted that the segregation of hydrogen at microstructures such as grain boundaries (GBs) plays a key role in determining the occurrence and severity of HE. GBs are two-dimensional defects where significant local lattice distortion exist, which leads to large free volume and thus locations for hydrogen trapping and segregation. Numerous works have clarified GBs as the energetically preferable places for hydrogen segregation. For instance, Geng et al. demonstrated the preferential segregation of hydrogen at the S5(120) GB in several metals, and suggested a decohesion-type of HE in light of Rice-Wang thermodynamic theory (Geng, Freeman, & Olson, 2001). Birnbaum et al. illustrated that complete intergranular crack of Ni GBs can be induced by hydrogen segregation when the hydrogen concentration is sufficiently high, evidencing the significant role of hydrogen accumulation on GB weakening (Lassila & Birnbaum, 1987). Yamaguchi et al. demonstrated strong segregation hydrogen also occurs at S3 GBs in alpha-iron, showing that local hydrogen clustering (i.e., multiple hydrogen atoms, up to six, per unit cell) can be trapped at the S3 GB (Yamaguchi, Kameda, Ebihara, Itakura, & Kaburaki, 2012)."

Jan 1, 2017

By Ragnhild Aune

In fire refining of copper, the affinities of various impurity elements on dissolved oxygen is of great significance. Further, in the design of oxygen probes in liquid copper, the influence of solute interactions on the activity of oxygen need to be considered in order to evaluate the oxygen concentration in molten copper. The present paper presents a series of measurements of the activities of oxygen in liquid Cu-M-o alloys (where M stands for Mn, Zn, As, Se or Te) carried out by the present group employing the solid electrolyte galvanic cell technique. Extreme care was taken to control the oxygen potentials in the inert gas atmosphere, and to keep the oxygen levels very low in the molten metal. The oxygen content was determined by analysis of the samples taken out from the melt. The results obtained showed that Mn has a strong negative influence on the activity coefficient of oxygen in liquid copper. A similar, but less prominent effect was observed in the case of Zn. Arsenic had no influence on the activity of oxygen in Cu (liq.). Se and Te had slight negative effect on oxygen activities in copper at XO > 10-5, while at lower oxygen levels the interaction coefficients were found to be positive. The results obtained were compared with empirical models for the calculation of interaction coefficients available in literature.

Jan 1, 2003

By Ragnhild Aune

In fire refining of copper, the affinities of various impurity elements on dissolved oxygen is of great significance. Further, in the design of oxygen probes in liquid copper, the influence of solute interactions on the activity of oxygen need to be considered in order to evaluate the oxygen concentration in molten copper. The present paper presents a series of measurements of the activities of oxygen in liquid Cu-M-o alloys (where M stands for Mn, Zn, As, Se or Te) carned out by the present group employing the solid electrolyte galvanic cell technique. Extreme care was taken to control the oxygen potentials in the inert gas atmosphere, and to keep the oxygen levels very low in the molten metal. The oxygen content was determined by analysis of the samples taken out from the melt. The results obtained showed that Mn has a strong negative influence on the activity coefficient of oxygen in liquid copper. A similar, but less prominent effect was observed in the case of Zn. Arsenic had no influence on the activity of oxygen in Cu (liq.). Se and Te had slight negative effect on oxygen activities in copper at XQ >10-5, while at lower oxygen levels the interaction coefficients were found to be positive. The results obtained were compared with empirical models for the calculation of interaction coefficients available in literature.

Jan 1, 2003

By Ronald J. Roman

Research pertaining to flow of solutions in leach dumps has generally been neglected. This technical note proposes a method for evaluating the flow patterns and incorporating the results into dump-leaching models. Three dump-leaching models1-3 have been proposed to scale up laboratory test data to expected field results. These models are based on the same physical picture in a dump and differ only in the importance of diffusion or surface chemical reaction rate. Selection of this rate-controlling phenomemon is based on type of ore (sulfide or oxide), physical dimensions of the particles being leached, and the leach heap itself. All three models are applicable to specific types of operations. The models are similar in the use of a size distribution analysis for the dump material and the assumption that the leach solution flows around each particle. Transport of the leaching agent to the interior of the particle takes place by diffusion [(Fig. 1)]. However, normal dumps are of a higher bulk density than the material in a laboratory column used to generate the scale up data. How does this difference in bulk density affect the scale up equations? Increasing the bulk density can be expected to give more particle-to-particle contact; therefore, individual particles will be blinded by each other. As blinding increases with bulk density increase, the particles will behave like larger particles with a coarser apparent size distribution. The extreme will occur when the bulk density reaches that of the undisturbed rock, the entire dump behaving as a single particle with the dimensions of the heap itself. Harris4 alluded to this phenomenon in his paper. An alternative method of describing the same phenomemon is to consider the flow paths of the solution. At high bulk densities leach solution no longer surrounds each particle, but flow paths are separated by several particles and channeling is said to take place. Instead of the particle radius being the maximum distance through which the leaching agent must diffuse, the maximum distance is half the separation distance of the solution flow path. Particle size distribution must then be replaced in the models by the concept of channel separation distribution. Like size distribution, channel separation distribution specifies the cumulative percentage of the rock in the dump situated less than a specified distance from a solution channel. Thus, [ ] Distribution of the solution channels is a function of how the dump was built (among other things), and therefore it cannot be determined in the laboratory. Accordingly, it becomes necessary to determine a range for d and a in existing operations or measuring these parameters before leaching starts. Howard5 gives a clue to one possible technique of measuring solution channel distributions. When his paper was published little was known about the phenomemon of leaching; the importance of this type of data was not recognized. [Fig. 2] is a Y-Y log for one hole drilled

Jan 1, 1978

By Vladimiros G. Papangelakis

During the past five years, chemical modelling work at the University of Toronto has elucidated the role of soluble magnesium on the autoclave acidity and has demonstrated why feeds rich in magnesium, and other divalent metals, require more than the stoichiometric requirements in acid to produce a leaching performance comparable to that of low magnesium feeds. This understanding has allowed the calculation of acid additions to the pressure acid leach (PAL) on a less empirical basis. Optimizing acid additions to the PAL confers savings in neutralization costs, ensures high productivity and minimises corrosion problems. Hence, our picture of the solution chemistry inside the autoclave during the PAL process has been substantially improved and is reviewed here. Experimental techniques based on solubility and direct acidity measurements that support the theoretical predictions are presented. Concepts of chemical modelling of electrolyte systems at high temperature and software issues are also discussed. Finally, a better understanding of the solution chemistry at temperature has led to better kinetics models because all metal dissolution and precipitation reactions are acid driven and controlled. . Therefore, reactor modelling efforts by our group are also presented and a reactor model with very good performance, as compared to pilot-plant data, is also made here. Finally, in spite of the above success in PAL solution chemistry and reactor modelling, significant challenges lie ahead in theoretical data gaps and instrumentation; these are also discussed in this paper. Keywords: Laterites, process modelling, pressure acid leach, solution chemistry, chemical modelling, reactor simulation

Jan 1, 2004

By P. Somasundaran

Three major types of solution chemical equilibria involving flotagents (Le. flotation reagents such as collectors, frothers and modifiers), minerals and solution play a crucial role in determining the behavior of complex flotation systems. Minerals of phosphates (apatite and francolite), tungsten (wolframite and scheelite) and associated carbonates (calcite and dolomite) are sparingly soluble in aqueous solution and form dissolved mineral species in bulk solution. Such dissolved species interact with mineral solids, often resulting in surface conversion of the minerals. In addition, they can interact with various flotagents and lead to surface or bulk precipitation and loss of selectivity in the flotation. Relevant solution equilibria of such sparingly soluble minerals and their interactions with oleic acid and structurally modified reagents were determined in this study using a multi-pronged experimental approach. Methods to manipulate and control the solution chemical equilibria and thus achieve selectivity in flotation systems are discussed.

Jan 1, 1990

By N. Ahern, D. B. Dreisinger, G. Van Weert

In the thiosulfate leaching of gold, degradation of the thiosulfate reagent is a major cost. One of the intermediary degradation products is trithionate, which also inhibits gold recovery from solution by ion exchange. Little attention has been given to this species in the context of gold leaching - the limited information on trithionate and its solution chemistry available in the literature is seldom directly related to gold leaching conditions. This review is a compilation of the published knowledge on trithionate, with a specific focus on identifying the relevance of this information to gold leaching and the shortcomings in the knowledge base.

Jan 1, 2005

Heap leaching has become one of the prime technologies used for the recovery of precious metals from low-grade ores over the past ten years. The recovery process involves mining and stacking the ore on engineered leach pads, with or without crushing and/or agglomeration, followed by leaching with a low concentration sodium cyanide solution. The metal-bearing, pregnant solution is then processed by zinc precipitation or activated carbon absorption to extract the precious metals. The leaching process continues until all economic metal values are removed at which time the spent heap leach pads, the leached materials and excess process solutions require decommissioning. The management of these solutions may present a potential challenge for successful and environmentally sound decommissioning due to their composition, volume or continuity of generation from the spent ore even though active leaching has been terminated. The principal objectives of solution management in decommissioning spent heap leach pads are to meet all operative environmental regulations in a cost-effective manner and to leave the pads in a condition where they do not present a long-term liability either to the operator or to the environment. This involves the reduction in volume of the residual process solutions and/or treatment of these solutions to where they meet applicable water quality criteria. In the past, the environmental and economic aspects of decommissioning and solution management have been overlooked or under-estimated during the planning of mining operations. As a result, there is a potential for long-term liabilities and costs to be recognized only at the end of active leaching, a time at which operating revenues and cash-flow are minimal. Therefore, the decommissioning process requires addressing at the mine planning stage and agencies now require that a plan for solution management after the cessation of operations be submitted prior to initiation of mining. This paper discusses aspects of process solution management during decommissioning, both in terms of quantity and quality, and how potential issues may be recognized and planned for in the initial stages of heap leach design.

Jan 1, 1992

By D. D. Rabb

Originally, the term solution mining applied to a dissolution, washing, or "brining" of soluble salts such as halite (common table salt), potash or trona. After the mid-sixties, however, the definition has been expanded to include heap and dump leaching, in-place (in situ) leaching, removal of oil from tar sands, extraction of sulfur from deep wells by the Frasch process and the recovery of metalliferous solutions from geothermal sources. Solution mining is also known as borehole, non-shaft, or chemical mining; the extraction of soluble mineral values from a variety of ores using appropriate solvents and chemicals. Solution mining frequently involves chemical changes; for example, copper usually goes into solution as copper sulfate, gold and silver as a cyanide compound, and uranium as a sulfate or uranyl tricarbonate. The valuable constituent is removed from the solid body of the ore by mass transfer to a aqueous solution.

Jan 1, 1986

By Paul H. Johnson

Chemical mining may be defined as the in-place extraction of metal values from ores located within the confines of a mine (that is, broken or fractured ore, stope fill, caved material, or ores in permeable zones) or ores located in dumps, prepared ore heaps, or tailing ponds. The term solution mining has, in general, been used to mean the in-place dissolution of water-soluble mineral salts with leach solutions. Chemical mining is presently in its embryonic stage. Basic research needs to be done to understand the influence of physical and chemical factors in chemical mining, and applied research needs to be done on both a small and a large scale to develop practical techniques of field practice. The areas of research include the following: (1) Leaching chemistry, the influence of physical, chemical, and biological factors in in-place leaching (2) Hydrodynamics of chemical mining systems (3) The development of new, as well as old, leaching agents for use under chemical mining leach conditions (4) The development of new means of contacting fine and coarse materials (with solutions) under static leach conditions (5) The development of new processes for generating and regenerating chemical mining leach solutions (6) The development of metal recovery processes

Jan 1, 1969

By Charles H. Jacoby

The solution mining of evaporites has a history of approximately 5,000 years. The insitu leaching of metalliferous ore will have many of the same characteristic problems which have confronted industry for years in the production of evaporite minerals. Basically we will be converting the less soluble forms of valuable metals into their more soluble salts and producing these in much the same manner as, for example, sodium chloride. There are a number of problems which we are faced with that are more complex and complicated and, therefore, will require a higher degree of sophistication than previously employed. One of our most important undertakings will be the clearcut definition of the problems involved. While a great deal of expertise can be drawn from the solution mining of evaporites and the oil industry, problems peculiar to the hydrometallurgical field will need to be solved. One of these is the introduction of permeability into an impermeable rock so as to expose the sought after values of metals which by volume are infinitesimal when compared with sodium chloride, potash or other type water soluble mineralization. After establishing this permeability which will be miniscule when compared to a solution cavity, there will be the maintenance of this permeability. In general, salt deposits are of a somewhat uniform chemical composition and thus their chemistry was relatively simple. Each metalliferous ore body is somewhat unique in its chemistry and will need to be treated accordingly.

Jan 1, 1974

By J. G. Davis

Continental Oil Company has spent over four years of research on the fundamentals of potash solution mining. This work included laboratory investigations of salt solution, brine flow, selective extraction of KC1 from sylvinite, and control of cavity geometry. Laboratory results were expanded by means of a series of field tests, and subjects such as well completion and hydraulic fracturing were added to the investigation. Both single-well and multi-well mining systems were studied in the field work. The current paper discusses one field test in which potash was solution mined from a thin sylvinite ore zone in the Carlsbad Potash Basin. A two-well mining system was used for this test. The potential economic value of solution mining has been recognized for many years, and applicable United States patents date back into the past century. Principal advantages of the process over conventional mining include (1) the use of drilled holes and solution techniques in- stead of excavated shafts and caverns and (2) the ability to mine both land and marine deposits through any type of overburden geology and below conventional mining depths.

Jan 1, 1969

By Robert C. Sutter

In 1958, it became obvious to some of us in the solution mining business that there were certain problems in connection with our sodium chloride brining operations which were industry- wide. These were the types of problems which, while they were important to the safe and economical operation of our salt brining operations, were not such that their solutions would give an individual company a great competitive advantage over his competitor; and since they involve the safe and efficient mining of a natural resource, it was obvious that the answers would, in any event, be shared industry-wide. Since we were dealing with underground solution mining and, consequently, unseen and remotely controlled operations, the problems are formidable and the solutions difficult. While all of us were doing work to improve our operations, none of us could justify the expenditures necessary for basic research in these areas. Consequently, the idea was conceived of research sponsored by many companies with the same problems. In 1960, 11 companies entered into a' formal agreement to jointly support research on a specific problem of sodium chloride solution mining. The project to be undertaken was the development of a method for measuring the size and extent of underground solution cavities in sedimentary salt beds. It was agreed that all research was to be performed by independent research organizations. A part-time consultant or administrator was retained to administer the research contracts and to provide technical advice.

Jan 1, 1966

By L. D. Boughton

Solution mining projects are conducted through one or more boreholes which penetrate en ore body. Proper drilling, completion and maintenance of the boreholes, therefore, is essential to the success of any solution mining operation. Wells drilled for solution mining encounter problems quite similar to problems encountered by the petroleum industry in drilling, completing and maintaining wells for the production of oil, gas or water. Many of the services developed and much of the experience gained by the petroleum industry is applicable to solution mining wells. As in the petroleum industry, each individual wellbore and ore body in a solution mining project provides its own problems. These vary greatly from well to well, and it is not possible to set down data or outline programs that will apply to all wells. Instead, the design of the drilling, completion, production and maintenance programs should be worked out for each individual well. The purpose of this paper, then, is to generally describe materials, equipment and techniques available for these programs and to discuss the purpose and sequence of their use.

Jan 1, 1971

By J. M. Keane

The Solution Mining review arrived too late to appear in the May issue. Solution mining, in its broadest definition, includes all forms of leaching where a lixiviant solution is brought into contact with a metalliferous or non-metallic ore and the resulting pregnant solution is processed for recovery of the valuable soluble material. Technologies such as dump leaching, heap leaching, stope washing and in situ lixiviant solution injection and recovery fit into this definition of solution mining. A publication entitled the US Gold Industry (Dobra and Thomas) reflects the major impact that solution mining techniques have had on precious metal recovery. In 1989 (the last year for which statistics are available), the United States passed Australia to become the third largest gold producing country in the world after South Africa and the Soviet Union. It is estimated that when the final figures are in for 1990, the US will probably pass the Soviet Union in gold output. If the state of Nevada is ranked as a separate country, it will rank fourth in the world in gold production for 1990. A good proportion of this increase in gold production over the past few years can be attributed to the application of solution mining technology to low-grade, precious-metal-bearing material. Solution mining techniques have also made inroads in copper production. Many operations located at former underground mine sites employ in situ leaching as an adjunct to conventional dump and heap leaching practices.

Jan 1, 1991