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By O. Hyvärinen

Outokumpu has developed a new chloride leaching process called HydroCopper®. In this process copper sulfide concentrates are leached at atmospheric pressure in concentrated sodium chloride solution using cupric ions as the oxidant. Copper is recovered from the purified leach solution by precipitating cuprous oxide, which is then reduced to pure copper and further melted and cast directly into copper products. The key reactants: sodium hydroxide, hydrogen and chlorine are generated from the spent sodium chloride using chlor-alkali technology. An important feature in the HydroCopperTM process is that the gold contained in copper concentrates is leached as chloride complexes and recovered from solution by activated carbon. Conditions for the leaching of gold-bearing pyrite can also be achieved in the chloride system by optimizing the redox conditions. This paper deals with the basic factors affecting gold leaching from copper sulfide concentrates. Opportunities for the recovery of refractory gold associated with arsenopyrite and pyrite will also be discussed.

Jan 1, 2005

By C. R. Everly

"The purpose of this paper is to review the most effective methods of reducing chloride transfer and chloride removal in the solution extraction and electrowinning (SX/EW) process. Elevated chlorides in electrolyte have various negative effects including a reduction in current efficiency, increased handling costs at rod plants and smelters, increased anode corrosion, cobalt losses due to increased electrolyte bleed, degradation of HDPE piping, and increased corrosion in the SX/EW plants. Historical controls that Sierrita has used to control chloride transfer, in order of effectiveness, have been chloride gasification at the EW that is directly correlated to amperage and chloride concentration in electrolyte, wash stage bleed and efficiency, width and velocity of aqueous bands, and electrolyte bleeds. Maintaining high bleed rates and high amperage settings has been a challenge with decreasing pregnant leach solution (PLS) grades, so keeping chlorides out of the electrolyte has become imperative. The effectiveness of reducing aqueous entrainment, optimizing wash stage efficiencies, and improving organic quality to reduce the transfer of chlorides to the electrolyte are illustrated in this study. INTRODUCTION The transfer of impurities from PLS feed streams to electrolyte in the Copper Solution Extraction process is a very common problem and is the reason that the wash stage exists in most SX operations. The main impurities affecting the SX process are iron, chloride, nitrate, and manganese. Elevated chlorides in the electrolyte have various negative effects including reduced current efficiency, increased handling costs at rod plants and smelters, increased anode corrosion, increased cobalt losses due to increased electrolyte bleed, degradation of HDPE piping, and increased corrosion in the SX/EW plants. Freeport-McMoRan Sierrita Hydromet is unique in that a high-chloride byproduct stream from the molybdenum process is pumped into the SX raffinate solution pond. This byproduct steam accounts for the majority of chloride introduced to the circuit, and over the years has built up to a point where 4000ppm chloride is consistently in the PLS feed to the SX. Concentrations of chloride over 70 ppm in electrolyte will result in downgraded cathode, so it is important to limit chloride carryover from SX as much as possible. Historically, Sierrita has been able to manage chloride levels with reactive techniques including increasing electrolyte bleeds and rectifier amps. Decreasing copper in PLS has made high amps harder to maintain, and increasing bleed rates have a direct impact on production goals."

Jan 1, 2015

By Edgar Peek

"The two dominant metallurgical problems in treating most base metal sulphide concentrates in both the chloride and sulphate system are iron removal and sulphur elimination, respectively [1-3]. In this paper the opportunities, limitations and fundamentals of the chloride metallurgy system are described against this background. Only the treatment of oxide and sulphide ores is considered. Both hydrometallurgical and pyrometallurgical unit process operations are highlighted, since most successful base metal processes are based on a combination of the two. Hence, an overview of the technical and also some economical aspects of chloride metallurgy are presented.This overview summarizes the successful applications of chloride metallurgy, but it will not give exhaustive process and plant descriptions. It predominantly focuses on the essential technical features of the metallurgical unit process operations, while providing numerous references separately."

Jan 1, 2011

The physico-chemical principles of chloride hydrometallurgy are reviewed to rationalise the complex chemistry in chloride-based processes for metal sulphides in terms of the predicted Eh-log[Cl-] relationships, measured changes in activity of H+, Mz+, Cl- and solubility of Ag(I), Cu(I), Cu(II), Pb(II), Ni(II), Au(III), Sb(III) and Bi(III). These changes reflect the nature of chemical speciation, competing effect of hydration/hydrolysis and chloro-complexation,composite effect of increasing acid and/or salt concentration and decreasing water activity. Rate data for the dissolution of PbS and ZnS in HCl containing Fe(III) or Cu(II) are compared and contrasted to highlight the effect of acid and chloride concentration, water activity, and the nature of oxidant. It is shown that LiCl, NaCl and HCl influence the kinetics of oxidative PbS leaching based on their effect on solubility of PbCl2 co-precipitated with elemental sulphur on the mineral surface. Evidence for the beneficial effect of Cu(II) in sulphide leaching is discussed.

Jan 1, 2003

By William D. Riley

The U. S. Bureau of Mines has developed technology to recover by-product materials from aluminum scrap using engineered scavenger compounds (ESC). ESCs are structural oxides with a channel or tunnel structure that allows them to hold ions of a specitksizes and charges. The scavenging reaction is easily reversible allowing the ESC to be recharged for continued use and the ion is recovered as an electro deposit. Key features of this novel technology are; a) ESC ,systems are designed to have a high degree of selectivity for a desired ionic species. b) The recovered mater.ial requires little or no additional reprocessing prior to reuse. Two current uses for the ESC technology that are described in this paper are the removal and recycle oflithium (Li) from lithium aluminum (Li-AL) alloys; and, using ESCs as a replacement for the conventional demaging (magnesium removal) technology used by the secondary casting industry. Research indicates that the ESC technology proposed for both these applications has either 'distinct economic and/or environmental advantages over previously employed methods of recovering. metal values from aluminum scrap.

Jan 1, 1995

By C. W. Washburne

Professor Lane makes an interesting contribution to the study of cholride waters, in saying that calcium chloride waters occur not only in the greenstones of Lake Superior copper mines, but also in the interbedded felsitic conglomerated and…

Jan 1, 1915

Reply to discussion of the paper of C. W. Washburne, presented at the New York meeting, February, 1914 (Trans., xlviii, 687 to 694 (1914)). C. W. WASHBURNE, New York, N. Y. (communication to the Secretary*).-Professor Lane makes an interesting contribution to the study. of chloride waters, in saying that calcium chloride waters occur not only in the greenstones of the Lake Superior copper mines, but also in the interbedded -felsitic conglomerates and "in far-removed sandstones, e.g., near Whitefish lake, and Ontonagon, in the Michigan iron mines, and in the Storm King granite." Surely these are not connate waters preserved from the Algonkian sea, assuming that the Algonkian sediments are marine rather than continental. Finding the same type of water in the Storm King granite points rather toward an abyssal source. The possible connection of these waters with the magma of the greenstone is immaterial, although some basic calcic magma is the most probable source. It is to be expected that the ascending water of the region would be found not only in the greenstones, but in all the rocks which it could penetrate. The ascent of water of this kind along vertical passages, and the consequent addition of a common ion: to the circulating sedimentary salt solutions, would explain the precipitation and localization of the "giant, concretionary" salt plugs of the Gulf Coast, without making the ex-excessive demand for an improbable quantity of salt in the adjacent sediments that is required by the unmodified theory of Harris. With-out such a precipitating medium most of the dissolved sodium chloride would have been lost by passing on to the surface without precipitation. The base to which the chlorine ions were attached is immaterial, providing they were sufficiently concentrated, but the presence of the chlorides of calcium and magnesium in the solutions is indicated by the associated bodies of secondary dolomite.

Jan 4, 1915

By C. W. Washburne

THE waters of many oil fields have been regarded as buried sea water which has been retained in the sediments since the time of their deposition. The preservation of connate water through geological time has seemed improbable to only a few geologists, but there is room for doubt that buried sea water could remain in the strata during their periods of deformation and during the many subsequent epochs of. the circulation of meteoric ground-water. Some have even suggested that the calcium chloride water in the deep mines of the Lake Superior region is ancient sea water buried in the Algonkian lavas, but it is hard to understand how such water could be derived from the highly sodic and sulphatic water of the sea. It would seem more plausible to connect the calcium chloride with the highly calcic magmas of the greenstones in which it is found. Chemical analyses of waters associated with oil differ widely from the composition of sea water, requiring extensive alteration of the latter, if the former is truly its derivative. The first notable difference is the general absence of sulphates from oil-field waters, but this has been explained satisfactorily through reduction by hydrocarbons and organic matter. Oil reduces sulphates with the production of hydrogen sulphide (or sulphur), water, and carbonates (or carbon dioxide). The second striking difference is in the high ratio of chlorine to sodium. An examination of the analyses of chloride waters from oil fields shows that they contain a large relative excess of chlorine over that in sea water. Moreover, there is difficulty in finding chemical reactions that are probable in nature, by which sea water could be converted into anything like the chloride waters of oil fields. In the latter a large part of the chlorine occurs as calcium acid magnesium chloride. This condition might be produced by the removal of sodium carbonate, which; however, cannot be precipitated in the presence of much calcium or, magnesium.

Jan 3, 1914

By William E. Ford, Edward Salisbury Dana

I. Anhydrous Chlorides, Bromides, Iodides; Fluorides. II. OxycMorides ; Oxyfluorides. III. Hydrous Chlorides; Hydrous Fluorides. The Fourth Class includes the haloids, that is, the compounds with the halogen elements, chlorine, bromine, iodine, and also the less closely related fluorine.

Jan 1, 1922

By Van Weert G

Ferrous chloride solution pyrohydrolysis is a successful IICI regeneration process which is carried out in either a spray roaster or a fluid bed. Pyrohydrolysis is not restricted to ferrous chloride only, every metal chloride can theoretically be hydrolysed. In practice, however, the conditions for ferrous chloride pyrohydrolysis differ from those of many non-ferrous metal chlorides eg zinc, lead and cadmium. Hence, a pyrohydrolyser could function as a ferrous/non-ferrous separator, eg an iron oxide and zinc chloride separator. Most pyrohydrolysers operate on solutions, in which case more than 50 per cent of the process energy is needed for heating and evaporating water. However, this disadvantage would be diminished by feeding a slurry to the reactor. Against this background it was decided to investigate the chloridisation of zinc ferrite which is an iron bearing solid with a non-ferrous impurity, and subject to processing and disposal problems. Synthetic zinc ferrite was chloridised in a tube furnace. The gas atmosphere in the tube furnace resembled that of a fluid bed pyrohydrolyser and consisted of HCI, 1120 and nitrogen. Gas composition, temperature, residence time and sample mass were varied. The experiments showed that complete (99.6 per cent) zinc extraction from synthetic zinc ferrite was possible in a simplified pyrohydrolyser atmosphere at 1100 K in four hours. The zinc ferrite was converted into gaseous zinc chloride, and hematite and magnetite solids. It was also found that zinc removal from the zinc ferrite lattice caused not only rccrystallisation of the zinc ferrite into hematite, but also hematite crystal

Jan 1, 1993

By Theodore Holt

Outline of the Process THE Mines Operating Co.'s plant at Park City, Utah, was designed to treat the low-grade fillings in the old stopes of the Ontario mine. These fillings carry 6 to 14 oz. of silver, 1 to 2 lb. copper, 0.01 to 0.015 oz. of gold, and a small percentage of lead and zinc. The treatment consists in mixing the crushed ore with coal dust and salt and then roasting in a new type of furnace y combustion of the contained fuel. The roasted ore is leached with an acid salt solution to dissolve the silver, gold, copper, and lead. At present these metals are precipitated together on scrap iron and the product sold to a refinery. The only new feature of importance in this scheme of treatment is the roasting process, which makes possible the chloridizing of ores without any loss of the valuable metals, and at a very low cost. History of the Development of the Process The roasting process had its beginning in connection with research work at the Utah State School of Mines. N. C. Christensen, Jr., who held one of the School of Mines' fellowships, was engaged in some experimental work on blast roasting. At the same time I was doing some work on the insoluble gold in Mercur base ores. Mr. Christensen roasted some of this base gold ore in his pot furnace, and found that when he mixed a sufficiently low percentage of fuel with the ore, it did not sinter but roasted to a leachable product. We considered this a new application of blast roasting, and proceeded to test out a large number of ores in several different types of small roasters which we constructed. This experimental work continued well into the summer of 1911.

Jan 7, 1914

Discussion of the paper of THEODORE P. HOLT, presented at the Salt Lake meeting August, 1914, and printed in Bulletin No. 91, July, 1914, pp. 1699 to 1708. F. S. SCHMIDT, Salt Lake City, Utah.-Any furnace that can make a chloridizing roast to yield an extraction of 92 to 93 per cent. and do this at a cost of less than 24c. per ton in a 10-ton unit opens great possibilities for the treatment of certain classes of ores. This cost does not include the salt and will be reduced to about 16 1/2c. per ton in the 35-ton furnace which are now being designed. On a trial run the roaster treated 9.6 ton: of Ontario stope fillings crushed to pass a ¼ -in. opening. The ore is well adapted to chlorination with the exception of insufficient sulphur and occasional days of high lime, but is not adapted to any other process The following is an analysis of the crude ore: Ag, 9.52; Au, 0.029 oz. Pb, 0.71; Cu, 0.11; SiO, 79.4; Zn, 0.57; S, 1.00; Fe, 7.9; Mn, 0.89 CaO, 1.20 per cent. The composition of the mix was: Per Cent. Dry crude ore : 83.4 Moisture 4.4 Salt 8.3 Coal dust 2.3 Pyrite, 70 per cent. pure 1.6

Jan 11, 1914

By H. P. Allen

THE chloridizing mill of the Standard Reduction Co. is located about 75 miles south of Salt Lake City on the Tintic branch of the Denver & Rio Grande Western R. R. and 12 miles from the Tintic Standard mine. The daily capacity is 200 tons of a siliceous, low-grade, silver-lead ore from this property. It has operated continuously since it was started in January, 1921. The process consists essentially of a chloridizing roast followed by a percolating leach with a nearly saturated solution of common salt, acidified with sulfuric acid, the precipitation of silver on sponge copper and of copper and lead on tin-plate cuttings. The precipitates are shipped to a smelter. Some of the general ideas involved are said to have been used by Augustin in England, in 1840. A number of textbooks treat of the subject, especially the chloridizing roast followed by a leach with sodium hyposulfite or amalgamation. The process was revived in this district by Theo. P. Holt, N. C. Christensen, the Bureau of Mines, and others.

Jan 8, 1925

By R. Padilla, M. C. Ruiz, L. Salinas

Chloridizing roasting of bismuthinite (Bi2S3) with NaCl–O2 has been studied to remove the impurity Bi by volatilization from copper concentrates that contain bismuthinite. The study was conducted using mixtures of Bi2S3 and NaCl in a horizontal furnace and TGA apparatus. The variables were temperature, oxygen partial pressure, and NaCl concentration. The chlorination was analyzed by weight loss measurement method. XRD results of calcines reacted for short times in 21% O2, and 850–1000 °C showed the presence of Bi, BiOCl, and Na2SO4, while at longer times in the same conditions, Bi2O3 was identified as a stable phase. Thus, the chloridizing-volatilization of Bi2S3 proceeds through the formation of Bi and BiOCl. Temperature affected significantly the fraction of weight loss of samples. At 600 and 900 °C in 10.3% oxygen, the maximum weight loss was 4 and 20%, respectively. An increment in the partial pressure of oxygen in the range 1–21% affected negatively the Bi2S3 conversion. At normal roasting temperatures (550–700 °C), bismuth volatilization by NaCl roasting was found to be marginal.

Mar 1, 2017

By Hideyuki Itou

Municipal wastes are mainly incinerated in Japan. Both bottom ash and fly ash from the incineration treatment are smelted recently to decrease the volume. Direct smelting of municipal wastes is also becoming popular. The smelting treatment generates fly ash which contains concentrated heavy metals such as Zn, Pb and Cu, and the harmfulness is causing concern. The smelter fly ash is mainly landfilled after stabilization. An effective treatment process of the smelter fly ash is required to recover the metals. For the treatment process, an application of chloridizing volatilization technique is considered. Chloridizing volatilization experiments were carried out to determine the effects of various factors on the volatilization behaviors in this study. A pretreated ash was mixed with a main raw material which mainly consists of hematite. Calcium chloride water solution was added into the mixture. The mixture was pelletized, dried and used as samples for the volatilization experiments. The sample was placed in the reaction tube heated in an electric resistance furnace. 5%02-95%N2 gas with controlled humidity was introduced into the reaction tube. Effects of humidity in the carrier gas, addition of calcium chloride and mixed ratio of the ash to the main raw material were investigated on the volatilization of Zn, Cu and Pb. To determine the volatilization behavior, samples were taken from the furnace at specified temperatures on the heating stage. In addition, experiments at specified holding temperatures for 15 minutes with shortened heating time were conducted. The two series of experiments revealed the effect of heating temperature on the volatilization behavior of Zn, Cu, Pb and Cl.

Jan 1, 2006

By R. J. Nankee

Coal is our most abundant, low cost energy resource. Expansion of its use is being challenged due to "SO2 emission" regulation with even more restrictive legislation pending. High quality coal reserves are becoming more limited due to greater use in recent years. Aids to allow more use of coal in today's environment include beneficiation of coal before combustion and scrubbing the emissions from coal during combustion. Dow's efforts to help meet these challenges by beneficiating coal include true heavy media gravity separations with chlorinated solvents and liquid/liquid partitioning processes and "Dow Solvent Recovery Technology" to recover the solvent from product (or floats) and rejects (sinks), The objectives of the efforts to clean coal are to reduce sulfur and ash. In this paper, the solvents will be described; a general flow diagram presented; some of the results on upgrading various coals will be described, and projected costs of full-scale plants using chlorinated solvents will be compared to conventional cleaning plants.

Jan 1, 1985

By R. J. Nankee

Recent on-going efforts to develop commercial coal cleaning beneficiation processes using chlorinated solvents-as the separating media will be described. True heavy media separations were performed on raw coal feedstocks, including Pennsylvania anthracite; Western, Eastern, and Midwestern bituminous; and lignite coals. Separation techniques included bath-type devices, cyclones, and liquid/liquid partitioning. Details on separation devices, removal of solvent, and recovery and recycling of solvent will be discussed. Projected costs of full-scale plants will be given for various coal sizes. A number of the coals evaluated are good candidates for beneficiation using chlorinated solvents. Coal beneficiation is desirable to provide needed coal quality. These needs include low ash fuels for coal water slurries and low sulfur fuels to meet emission regulations. In October of 1985, a paper, "Chlorinated Solvents for Coal Beneficiating"' was presented at the fall meeting of SME-AIME at Albuquerque, New Mexico. It reported the results obtained from various coals as feedstocks and of the separations using chlorinated solvents. These beneficiation results depended on true heavy media gravity and liquid/liquid partitioning separations. This paper will include detailed descriptions of the liquid/liquid partitioning process used in "Dow's Advanced Coal Cleaning Technology?2 and of the "Dow Solvent Recovery Technology.?3

Jan 1, 1987

By I. Gaballah

High and low grade concentrates of tantalum and niobium oxides were obtained by leaching a medium grade tin slag. Chlorination and carbochlorinalion of these concentrates were studied between 200 and 1000 "C. Chlorination or carbochlorination of the low grade concentrate led, at 1000 OC, to the extraction of about 95 % of the tantalum and niobium oxides. However, the tantalum and niobium chlorinated compounds were contaminated by iron and manganese chlorides. Complete extraction of the niobium and tantalum pentoxide was achieved during the carbochlorination of the high grade concentrate at 300 and 500 "C, respectively. While chlorination of this concentrate at 1000 "C, allowed to the volatilization of about 60 and 80 % of Ta205 and Nb205. In both cases, condensates were composed of almost pure tantalum and niobium chlorinated compounds. The results demonstrate the advantages of the lixivialion based on the "pseudo- structure" of the raw tin slag to obtain the high grade concentrate. The conclusions of this work suggest that the carbochlorination of the high grade concentrate is an efficient process for the extraction of refractory elements from tin slag.

Jan 1, 1993

By Georgina De Micco

The National Commission of Atomic Energy is investigating a suitable physicochemical process for the conditioning of spent nuclear fuel and treatment of the scrap of research reactors of the Al-UxSiy type. A possible way of processing is through dry chlorination of the cladding with the purpose of selective separation of the aluminium from the remaining elements such as Fe, Ni, Zn, Cu, etc. transforming them into volatile chlorides. Some important advantages of this method are the thermal stability of the chlorides that allow the easy separation of the halides by physical methods and the low volume of radioactive waste generated. The interactions in the following systems were studied in the range of temperature between 150º-500°C: Al-Fe, Al-Ni, Al-Cu, Al-Zn, Cu-Zn and the pure metals. We found that the reactivity was different depending on if the elements were alloyed or separated. The separation factors of the systems under study were determined. Nickel is perfectly separated from aluminium for all temperatures, whereas good conditions for copper separation were achieved below 400ºC. In the case of iron, complete isolation was never attained. However, by decreasing temperature to 150ºC it is possible to obtain aluminium chloride with less iron content. The separation of zinc from the product was also difficult. It was detected that zinc chloride volatilization decreases when other chlorides were present, for example cooper chlorides. In the Cu-Zn alloy, zinc chlorides remained in the condensed product due to interactions with copper. The samples were characterized by scanning- electron microscopy (SEM), X ray diffraction (XRD) and atomic absorption.

Jan 1, 2006

By Raphael Titi-Manyaka, I. Iwasaki

Chlorination and chloridization behaviors of pyrite, pyrrhotite, chalcocite, covellite, chalcopyrite, bornite, heazlewoodite, millerite, and pentlandite in chlorine, gaseous ferric and sulfur chlorides were investigated by thermogravimetric analysis. The reaction mechanisms are discussed in terms of theoretical weight changes, thermodynamic calculations, and X-ray analyses of reaction products. The experimental findings are in direct application to the development of a scheme for producing nonferrous metal chlorides, elemental sulfur, and ferric oxide from complex sulfide flotation concentrates.

Jan 1, 1977