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By G. Tapia, R. J. Kelley

Empresa Minera de Mantos Blancos S.A. successfully commissioned two copper SX-EW plants in late 1995. The design of these solvent extraction plants is such that chloride tenors of 30-35 g/l can be tolerated in the leach solution with no contamination of the electrolyte. The design was carried out in conjunction with Bechtel-ARA engineers and was based on the successful application of the available technology in the market; this mainly focused on decreasing the aqueous entrainment in the organic phase. This entrainment can reach 20,000 ppm in conventional plants.

Jan 1, 1998

By D. S. Flett

"The current state-of-the-art of chloride hydrometallurgy for treatment of complex sulphide bulk concentrates is reviewed. General considerations regarding the various flowsheet steps are examined and options discussed. Then, individual flowsheets are presented and discussed. Finally, the forward prospects for chloride hydrometallurgy for treatment of complex sulphide bulk concentrates is considered and conclusions drawn concerning the likely application of this technology in the future. IntroductionHydrometallurgical processes for treating sulphide concentrates, in general, have received considerable attention over the last three decades or more. Many flowsheets have been developed, many pilot-plant studies have been undertaken and several processes are now successfully operating. For example, direct ammoniacal pressure leaching has been used by Sherritt Gordon Mines since the 1950s to extract nickel from pentlandite concentrates, the roast-leach-electrowin route is widely used to recover zinc from sphalerite concentrates and direct sulphuric acid pressure leaching of sphalerite concentrates has been successfully commercialized. Also, Duval Corporation operated a direct cupric/ferric chloride leaching process (Schweitzer and Livingston, 1982) with electrowinning to recover copper from chalcopyrite concentrates, this process (now closed) being the only chloride process which has been commercialized for a sulphide flotation concentrate. Despite these developments, it has long been considered, particularly for copper sulphide concentrates, that direct hydrometallurgical processes are in the main unlikely to be able to compete successfully with smelting for large-scale operations of simple high-grade single metal concentrates. As long as such concentrates can be produced commercially, smelting is likely to remain the principal processing route (Flett, 1981). This view is being challenged nowadays through pressure leaching developments made by Dynatec and CESL in Canada and the recent start-up of the Western Metals Gunpowder plant at Mt. Gordon in Queensland (Flett, 2000). Complex sulphide ores offer even greater opportunities because of the ability to produce a bulk sulphide concentrate from the complex sulphide ore with considerably higher metal recovery than is often possible from the production of individual metal sulphide concentrates from differential flotation. Interest continues to focus on hydrometallurgical solutions to these processing problems, particularly with regard to chloride hydrometallurgy. This paper, therefore, reviews current state-of-theart with respect to chloride hydrometallurgy"

Jan 1, 2002

By H. I. Kim

The leaching of a complex matte in chlorine and chloride media was studied. The matte was prepared from manganese nodules by the reduction smelting-sulfidation route. From XRD analysis, the major phases of the matte were identified as CuFeS2, CuS2, (FeNi)9S8, (FeNi)S2, Ni9S8, Ni3S2, (CoFeNi)9S8 and Co metal. Investigated were the chlorine, hydrochloric acid, hydrochloric acid-oxygen, ferric chloride, ferric chloride-oxygen, cupric chloride and cupric chloride-oxygen systems. The results are discussed in terms of reagent concentration, retention time, leach temperature and gas sparging rate. The chlorination process resulted >99% metal extraction efficiency within a short retention time and at atmospheric temperature. However, there were no preferential extractions of Cu, Ni and Co with respect to Fe. The cupric chloride-oxygen system produced leach liquors with the lowest Fe content and with a high base-metal extraction. Sulfide sulfur was converted to mixtures of elemental sulfur and sulfate in all the studied systems.

Jan 1, 2009

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

By William E. Bedal, Richard S. Kunter

Artech Recovery Systems, Inc has developed a low pressure and temperature chloride leach process called the "Caslumu1 Process" to extract metals from arsenical flue dusts and residues and fix the arsenic in an environmentally stable form as ferric arsenate (scorodite). The process was pilot tested at Hazen Research in an integrated plant including continuous recycle from August 1989 to October 1989 during which several tons of flue dust were processed. Based on this pilot program, the process was deemed technically feasible and produced commercially salable products. Residues from this pilot program were subjected to a long-term stability test jointly designed by Prl environmental services and the USEPA. The process, its versatility, and the nature of the products ls discussed in some detail.

Jan 1, 1992

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

Economic and environmental pressures are shifting the world balance of titanium dioxide production away from sulphate based. manufacture towards the more cost effective and cleaner chloride route. In the chloride process for titanium dioxide pigment manufacture, TiOz and other metal oxides in the feed ore are reacted at high temperature with chlorine in the presence of carbon. These gases are cooled after they leave the reaction zone, upon which solid contaminants precipitate and are substantially removed. The liquid titanium tetrachloride is purified by distillation before again being vaporised and interacting with hot oxygen to form pigmentary titanium dioxide and regenerate chlorine for recycle. The base pigment is wet milled, surface treated (by coating with hydrous oxides of silica, alumina and others) and redispersed before packaging. Optical properties of TiO2 pigments are reviewed and the role of refractive index and particle size explained in brief. Pigment related factors affecting the opacity, colour, undertone, gloss and durability of coatings are examined with respect to manufacturing requirements. The superior performance of chloride based pigments is briefly reviewed.

Jan 1, 1991

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 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