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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

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

By Guolin Zheng, Tiejun Chun, Jian Pan, Deqing Zhu, Xianlin Zhou, Dong Chen

"The high temperature oxidizing-chloridizing roasting is one of useful methods to separate nonferrous metals from pyrite cinder and metallurgy slag. However, as one kind of main nonferrous metals in pyrite cinder and metallurgy slag, copper’s chlorination behavior is not demonstrated. In the present study, chlorination behaviors of CuO, Cu2O and CuS at the temperature range of 1025-1175 ? in air by simulating the chloridizing roasting process of pyrite cinder and metallurgy slag have been investigated. It is shown that Cu2O and CuS is much easier to remove, CuO is refractory to remove. In addition, the presence of SiO2 and CaO increases the Cu removal rate from CuO while the presence of SiO2, Al2O3, CaO and MgO decreases the Cu removal rate from Cu2O. Fe3O4 influences the Cu removal rate from CuO and Cu2O positively.IntroductionAs two kinds of significant secondary resources, pyrite cinder and metallurgy slag contain not only abundant iron but also considerable copper, lead, zinc etc. Millions of tons of pyrite cinder and metallurgy slag were discharged from nonferrous metal and chemical industries annually [1, 2] in China. The pyrite cinder and metallurgy slag are formed by roasting of minerals at a high temperature, so the properties of them are distinctly different from the natural iron ores, and the iron in them is closely associated with copper, lead, zinc and other nonferrous metals. High-quality pyrite cinder and metallurgy slag containing high iron and low impurities can hardly be obtained, leading to their low utilization degree [3]. Chlorination is characterized by the high reactivity of chloridion, the high volatility and low melting point of metal chlorides, and the big differences in the formation of metal chloride. Therefore, chlorination is widely applied in extraction metallurgy."

Jan 1, 2012

By I. Iwasaki, R. Titi-Manyaka

Chlorination and chloridization behaviors of pyrite, pyrrhotite, marcasite, chalcocite, covellite, galena, sphalerite, heazlewoodite, and elemental sulfur were investigated by thermogravimetric analysis. The possible reaction mechanisms are discussed on the basis of the theoretical weight changes and thermodynamic considerations. Chlorine is a more effective chloridizing agent than hydrogen chloride. In the light of the experimental results, a scheme for producing nonferrous metal chlorides, molten sulfur, and ferric oxide from complex sulfide flotation concentrates is discussed.

Jan 1, 1974

By M. A. Gimenes

The utilization of chlorination in extractive metallurgy and advanced ceramics areas has been widely investigated as a preparative route in order to obtain intermetallic compounds, which are used as precursors in the development of new materials and process. The major processes of decomposition of rare-earth ores use sulfuric acid and sodium hydroxide at high temperatures, however there is not much work concerning chlorination. In this work, a systematic study of the reaction between xenotime (REPO4), chlorine and carbon has been performed. Particular emphasis was on kinetic studies to establish optimized conditions for the reaction. The kinetics of chlorination of xenotime raw material by rare-earth elements/compounds has been studied over a temperature range from 600°C to 950°C. The influence on the rate of conversion of xenotime to RECl3 on temperature, partial pressure of chlorine, carbon content, and particle size were investigated. A global rate equation that includes these parameters has been developed. The results show that the process follows the unreacted core-shrinking model with a formation of a porous product layer. The powder X ray-diffraction technique corroborated this model showing clearly the patterns related to the formation of yttrium oxychloride (YOCl), indicating that the reaction mechanism involves the presence ofan intermediate step before the formation of lanthanide chloride.

Jan 1, 2000