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By Vinay Jain, Dharmendr Kumar, Beena Rai, Venugopal Tammishetti

"Selective dispersion-flocculation is considered to be an effective process for the beneficiation of ultrafine particles. This process is based on the preferential adsorption of a flocculant on the mineral particles to be flocculated, leaving rest of the mineral suspended. It has been successfully implemented at plant scales for the beneficiation of ultrafine particles of iron ores, for which conventional methods such as gravity separation, magnetic separation and flotation do not work efficiently. However, the key element responsible for the success of any selective flocculation process is the appropriate choice of the flocculant used for achieving the desired selectivity. At our lab, we are working on design and development of such selective reagents for mineral processing applications, including the beneficiation of iron ore slimes, using a combined molecular modeling and experimental approach. In this study we have employed density functional theory (DFT) to calculate the interaction energies and explain the interaction mechanisms of chitosan with the main minerals present in iron ore slimes, namely, hematite [a-Fe2O3], goethite [a-FeO(OH)], gibbsite [a-Al(OH)3] and kaolinite [Al2Si2O5(OH)4]. The magnitudes of the computed interaction energies follow the trend: Hematite > Goethite > Gibbsite ~ Kaolinite Al-OH terminated > Kaolinite Si-O terminated Analysis of the optimized geometries and electronic structures reveals that the O & N atoms of chitosan molecule form coordinate bonds with surface Fe-atoms of hematite while only weak hydrogen bonds are formed in the case of goethite, gibbsite and kaolinite surfaces thus explaining reasons behind the stronger interactions with the hematite surface. The theoretical findings were validated by performing selective flocculation experiments using chitosan as a flocculant. The selective flocculation experimental results show that a final concentrate of ~60% Fe can be obtained from a feed containing 53.13% Fe with Fe recovery of 74%. The mineral estimation in the obtained concentrate indicated that hematite and goethite are recovered in concentrate while gibbsite and kaolinite are rejected in the tails. These observations were consistent with our theoretical findings. Our work highlights the promising role molecular modeling techniques such as DFT can play in the design and development of selective reagents for beneficiation of alumina-rich iron ore slimes."

Jan 1, 2018

At the present time, cyanide is the most widely used reagent to extract gold from its ores and concentrates. However, its use in mining has become the focus of intense attack by various groups throughout the world; as a consequence, a renewed effort has been launched to find suitable alternative lixiviants to recover gold. Chlorination was the most popular process to extract gold, before it was rendered obsolete with the advent of the cyanidation process at the turn of the last century, not least because it required the use of potentially hazardous and costly chlorine to oxidize/complex the gold. The PLASTOL® process, originally designed to recover the platinum group metals (PGM?s) from their ores and concentrates, provides an alternative to cyanide for gold ores. The process generates oxidizing conditions in the autoclave capable of forming the AuIII ion, and gold chloro-complexes result from the addition of small quantities (~5-10 g/L) of sodium chloride to the autoclave. The principles of the PLASTOL® process are briefly described, and several applications of the process to gold concentrates are presented. Various options available to recover gold from PLASTOL® leach solutions are also discussed.

Jan 1, 2003

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 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

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 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 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

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