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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

By I. Iwasaki, K. A. Smith

A chlorination process for treating metal sulfide flotation concentrates is described. The process involves low temperature chlorination combined with sulfur chloride conversion and selective oxidation to produce nonferrous metal chlorides, elemental sulfur, and ferric oxide in a three-stage fluidized bed reactor. The nonferrous metal chlorides may then be water leached, separated, purified, and electrolyzed to recover copper and nickel metals and to regenerate chlorine for recycling.

Jan 1, 1986

By A. L. Sweetser

EXPERIENCE has shown how difficult it is to obtain information regarding laboratory-tests in connection with the chlorination-process for the extraction of gold from its ores, and I therefore present the following method, somewhat in detail, for the benefit of those who may desire to pursue research work in this field. The ore chosen was a partly-decomposed porphyry, extremely siliceous and comparatively soft, and of an average value per ton of from $25 to $26 in gold and $0.68 in silver. The chemical analysis gave : Fe2O3, 3.35; FeS, 1.5; MnO2, 0.75; ZnCO3, 4; Al2O3, 3.20; H2O, 0.7; SiO2 and insol., 83.50 per cent. The ore, first crushed to pass a 5-mesh screen, was coned and quartered until a 45-lb. sample was obtained. Samples for assay and analysis, taken from this lot by means of riffles, were crushed to pass a 100-mesh screen. The original sample was divided into 10-lb. lots, of which one was crushed to pass a 10-mesh screen; another through a 12-; the third through a 20-, .and the last through a 30-mesh screen. Because of the production of an excessive quantity of fine material it was deemed inexpedient to crush finer than 30-mesh size-a decision the wisdom of which is proved by the data in Table I., showing the increasing ratio of slimes, in proportion as the ore is crushed finer. In order to determine the percentage of fines in the sizes of mesh selected, a weighed sample of ore was taken from each mesh, and a sample from the 10-mesh lot was passed successively through 20-, 40- and 100-mesh screens, and the percentage remaining on each screen determined. This process was repeated with the 12-, 20- and 30-mesh lots, with the results given in Table I.

Sep 1, 1907

By Charles H. White

Discussion of the paper of A. L. Sweetser, Tress., xxxviii., 236. CHARLES H. WHITE, Harvard University, Cambridge, Mass. (communication to the Secretary*) :-Those interested in leaching-processes gladly welcome contributions on either laboratory-tests, such as are reported by Mr. Sweetser, or mill-tests made on larger quantities of ore; and especially valuable are such reports, even with negative results, if the methods adopted are the outgrowth of an intimate knowledge of the conditions to be met. It seems very desirable, therefore, that as complete details as possible be given in reporting on such tests, particularly with respect to the character of the ore under examination. The questions of prime importance in the sampling of ore and in the making up of charges for laboratory-tests are those respecting its grade and uniformity. In Mr. Sweetser's paper the first of these questions is answered definitely, but the answer to the second, although apparent on inspection of the results, might be more strongly emphasized with advantage, since it is only on account of the extreme uniformity of the ore that the satisfactory results obtained could have been expected. It seems advisable to call attention to the fact that for average ores, and more particularly for uneven, or 11 spotted ores, the quantities used by Mr. Sweetser are not usually regarded as sufficient to insure satisfactory results. Let us examine the method somewhat in detail. The ore was crushed to pass a 5-mesh screen, and a sample of 45 lb. was taken out for assay and tests. The diameter of the largest grain of this ore, according to Richards,1 was 2.67 mm.-assuming here, as in the following cases, that the wire of the screen was of the largest size used for the purpose, thereby giving any possible advantage in this respect in favor of the method. The table in Richards's book, p. 852, shows that 45 lb. is a sufficient quantity for a fair sample with uniform ores, but not sufficient

Jan 7, 1908

By Ana E. Bohé, Georgina De Micco, Gastón G. Fouga

"In this work the reaction between several manganese oxides and chlorine is investigated in the range of temperatures between 650 and 950ºC. The reaction path for the chlorination of MnO is established, which involves recrystallization of high valence manganese oxides (Mn3O4 and Mn2O3) followed by its chlorination. For this reason, to understand the reaction of MnO, the chlorination of Mn3O4 and Mn2O3 has also been studied. The starting temperature for the reaction of these oxides is determined by non isothermal thermogravimetric measurements. The effect of temperature is analyzed, under our experimental conditions the rate of reaction is mass transfer controlled. The activation energy for the volatilization of manganese chloride is obtained which is in good agreement with volatilization enthalpy of MnCl2.IntroductionMany oxide ores which have manganese in their composition undergo chlorination processes during the extraction of refractory metals such as Ti, Hf and Nb. Although several works related with chlorination of manganese oxides were reported, there is no information about the kinetics or mechanism of the manganese oxide chlorination reactions. Okahara et al. studied the chlorination of manganese oxides and established that they react easily above 250ºC. Furthermore, they observed that chlorination of high order oxides is more difficult when there is not a reducing agent [1]. Ivashentsev studied the chlorination of manganese oxides using Cl2(g), CO(g) + Cl2(g) and COCl2(g). He established that the reaction of MnO started at 130ºC with formation of MnCl2(s), he also observed recrystallization of manganese sexquioxide [2]. Finally, the chlorination of manganese nodules from the ocean was studied by Murthy and Reddy [3] with the aim of obtaining valuable metals such as Mn, Co, Ni and Cu. They studied the influence of several parameters like temperature, carbon percentage, particle size and chlorine flow rate in the extraction process."

Jan 1, 2008

By Samantha Moodley, Rauf Hurman Eric, Cevat Kucukkaragoz, Aditya Kale

"Two titania slags, rutile and synthetic rutile were chlorinated with petroleum coke and CO in a small bubbling fluidized bed reactor. The study aims to identify differences in chlorination mechanism, compare conversion rates, blowover and the chlorination of impurities for the various titania feedstocks at different temperatures.Chlorination rates were highest at 1000ºC; rutile chlorination significantly increases as temperature increases from 800ºC to 1000ºC. At 1000ºC, synthetic rutile had the highest chlorination conversion rate; this was followed by Slag B which in turn was more reactive than Slag A and rutile. The mechanism for slag, synthetic rutile (SR) and rutile chlorination differs. Synthetic rutile feed is porous, providing a larger surface area for the chlorination reaction, hence the highest conversion rates was attained. Titania slag becomes porous with the initial chlorination of FeO and MnO whilst rutile remains solid. As the porosity of slag particles increases so does its tendency to be elutriated. Ti2O3 is oxidized within the early stages of chlorination during the chlorination of FeO and MnO. Ti2O3 not oxidized is then rapidly chlorinated.IntroductionTitanium dioxide (TiO2) is the most common compound of titanium, about 95 - 98% of extracted titanium minerals is processed into TiO2 white pigment [1]. Two processing routes exist for the production of TiO2 pigments, i.e., sulphate and chloride based processes. In the chloride process, titania feedstock is fed to a fluidized bed reactor together with reductant and chlorine gas. A temperature of 1000 - 1300ºC is maintained in the reaction zone and apart from silica, zirconia, uranium and thorium, virtually all the metal oxides in the feed are converted to their respective chlorides [2]. Chlorine is recovered and recycled back to the reactor."

Jan 1, 2012

By H Aral, L Malishev

The carbothermic chlorination of titaniferous materials such as rutile, synthetic rutile (SR), upgraded slag and ilmenite in a fluidised bed is an established commercial process. In this work, ilmenite sourced from the Murray Basin area of South Eastern Australia was chlorinated and an assessment of the chlorination characteristics of the ilmenite, in terms of pre-treatment, type of reductant and reaction time was made. Selective chlorination of Murray Basin ilmenite to remove Fe and Mn was achieved in this work. A synthetic rutile sample containing around 93 per cent TiO2, one per cent Fe2O3 and 0.5 per cent MgO was produced at a chlorination temperature of 1000¦C with around 25 per cent loss of Ti as TiCl4. Raising the reductant to ilmenite ratio in the chlorination reactions increased the amount of Ti chlorinated. However, complete chlorination of Murray Basin ilmenite to produce FeCl3 and TiCl4, was not achieved under the conditions used in this work. Pre-oxidation of Murray Basin ilmenite before chlorination had little affect on its reactivity, compared with æas receivedÆ ilmenite. In contrast weathered West Coast ilmenite chlorinated appreciably better than West Coast primary ilmenite, in terms of bed residues remaining and amounts of elements removed. The presence of large amounts of Mg and chrome spinel grains in the Murray Basin ilmenite used in this study are likely to make it difficult to chlorinate directly in a commercial chlorinator. However, this is not to say these ilmenites will be unsuitable for chlorination applications. Further work is needed in the separation of Mg and chrome spinel grains from Murray Basin ilmenites and the products resulting from these tests could then be assessed in terms of chlorination performance, so that further processing options can be explored.

Jan 1, 2000

Zirconium chloride is of great commercial importance as starting materials for production of ZrO2, Zirconium metal and other Zirconium compounds from its main resources (Zircon Sands). The present study concerns with preparation of pure ZrO2 from Zircon by direct chlorination technique. Different parameters affecting the chlorination process are studied viz. carbon, chlorine flow rate temperature and time. The chlorination extent is determined from the loss in weight and chemical analysis of reaction products. The maximum chlorination extent -92% are achieved at 1100°C for 30 min. Zirconium oxide is produced from the collected zirconium tetrachloride either by calcination at 900°C or by hydrolysis in water in presence of RCI with a purity = 99%. Evaluations of the products of the process are investigated microscopically and by X-ray diffraction. The apparent activation energy of the chlorination of Zircon is determined to equal 36 kJ/mole.

Jan 1, 1997

By D. S. Barr

The Freeport McMoRan chlorination circuit is comprised of four related processes: ore chlorination, gas scrubbing, chlorine supply and excess hypochlorite removal ("hypo kill"). Each of these processes are described, and related to the pertinent mineralogic components in the carbonaceous ore feed to the plant. The chlorination system in use at Jerritt Canyon to passivate forms of preg-robbing organic carbon has proven to be a cost effective and efficient means to recover gold from low sulfide carbonaceous refractory ores, where gold may not be specifically associated with either the sulfides or the carbon.

Jan 1, 1987

By G. L. Hundley, R. E. Mussler, D. H. Yee, F. E. Block, R. S. Olsen

An anhydrous chlorination process for the recovery of copper from chalcopyrite was investigated. Pelletized concentrate was reacted continuously with gaseous chlorine in a vertical shaft reactor at 550° and 650°C. While the copper was withdrawn with the rest of the metals as molten chlorides from the bottom, 99-x% sulfur was distilled from the top of the reactor. The molten metal chlorides were pulverized and dropped continuously into an upward flowing stream of oxygen. Over 80% of the iron chlorides were converted to oxides in a vertical free-fall reactor at 800° and 900°C while the copper chlorides passed through unoxidized. Copper was recovered in powder form by electrowinning continuously from chloride solutions using a diaphragm cell. The product sloughed easily from a titanium cathode and showed no iron contamination. Current efficiencies and power consumptions averaged 77% and 1.24 kw-hr per lb.

Jan 1, 1974

By Larry G. Twidwell, Jannette L. Chorney, Bryce D. Ruffier, Katelyn M. Lyons, Daniel W. Gaede, Ryan J. Foy, Jerome P. Downey

The Army Research Laboratory (ARL) has an interest in the recovery and processing of rare earth elements. At Montana Tech, elevated temperature chlorination of rare earth oxides is presently being investigated as a potential methods leading to the selective separation and recovery of rare earth elements from mineral ores and concentrates. After preliminary evaluation, ytterbium oxide was selected as a representative surrogate material for more extensive chlorination studies. Methods used to determine the conversion and recovery include X-ray diffraction (XRD) and inductively coupled plasma (ICP) analysis. These data have been used to establish and confirm process conditions that consistently yield high conversion efficiencies. Based on the promising results, further experimentation is underway to ascertain the metallurgical response of other rare earth oxides and carbonates to the roasting process. The end goal is to create a robust process for industrial application that has greater efficiency and reduced costs as compared to current practice.

Jan 1, 2015

By John B. Wright

This paper describes laboratory techniques and subsequent results of Bureau of Mines research to produce chlorination-grade feedstock from an abundant, low-grade, domestic, rock ilmenite ore. The research is part of the Bureau-effort to devise technology that may help decrease U.S. dependence on imported raw materials. A rock ilmenite containing about 46 wt pct Ti02 was smelted in an electric arc furnace with coke, woodchips, and Na2C03 to separate most of the iron as pig iron and to form a low-iron, titanium-enriched slag. The slag was ground, pelletized, oxidized, and then sulfated with mixtures of SO2 and air in a continuous 4.5- to 9.1- kg/h apparatus at 1023 to 1223 K. The sulfated slag, containing 60 to 65 pct TiO2, was reground and leached in water at ambient temperature to decrease the combined levels of the troublesome Ca, Mg, and Mn impurities from 7.0 to 1.7 wt pct. At levels of more than 3 wt pct, these impurities contribute to operating and disposal problems, The final product was upgraded to about 84 wt pct TiO2. This material potentially is suitable for chlorination in a fluidized-bed reactor. The most favorable results were achieved with leached slag sulfated at a feedrate of 4.5 kg/h and at temperatures of 1073 to 1123 K.

Jan 1, 1984

By G. W. Elger, H. E. Bell, J. E. Tress, J. B. Wright

This paper describes laboratory techniques and subsequent results of US Bureau of Mines (USBM) research to produce chlorination-grade feed- stock from an abundant, low-grade, domestic, rock ilmenite ore. The research is part of the Bureau effort to devise technology that may help decrease US dependence on imported raw materials. A rock ilmenite containing about 46 wt % TiO2 was smelted in an electric arc furnace with coke, wood-chips, and Na2CO3 to separate most of the iron as pig iron and to form a low-iron, titanium-enriched slug. The slug was ground, pelletized, oxidized, and then sulfated with mixtures of SO2 and air in a continuous 4.5- to 9.1-kg/h (10- to 20-lb per hour) apparatus at 1023° to 122J0 K (1380° to 1740° F). The sulfated slug, containing 60% to 65% TiOb, was reground and leached in water at ambient temperature to decrease the combined levels of the troublesome calcium, magnesium, and manganese impurities from 7.0 to 1.7 wt 70. The final product was upgraded to about 8.4 wt % TiO2. This material is potentially suitable for chlorination in a fluidized bed reactor. The most favorable results were achieved with leached slug sulfated at a feed rate of 4.5 kg/h (10 lb per hour) and at temperatures of 1073° to 1123° K (1470° to 1560' F).

Jan 1, 1986

By N. Kanari

One of the criteria to define the market value of chromite concentrate is its chromium to iron ratio. Changing this ratio for a definite chromite mineral is impossible by physical processing. This study investigated the possibility of increasing this ratio through the carbochlorination and the oxychlorination of chromite concentrates. Experiments are carried out up to 1000 °C. The characteristics of samples and reaction products are determined by SEM, XRD and chemical analysis. The carbochlorination of a chromite concentrate at about 600 °C leads to the . selective partial elimination of iron allowing a higher Cr/Fe ratio of the treated concentrate. Selective extraction of iron could also be achieved at about 950 °C by oxychlorination. In this case, a part of chromium contained in the concentrate is recovered as chromium oxychloride. The obtained residue had high content of Cr, Mg and A1 oxides. Such material has probably better chemical and thermal properties that may. be useful for foundary and refractory applications. Two flow-sheets for the beneficiation of the chromite concentrates using carho- and oxychlorination are suggested.

Jan 1, 1997

By M. Suzuki, M. Dobashi, M. Kahata, T. Yoshida

Almost 30% of steel in Japan is produced by electric arc furnace (EAF) treatment of iron scrap. EAF dust includes approximately 20 wt % of Zn and 3- 5 wt % of CI and is treated by the pyrometallurgical processes to recover Zn as Zn oxide. Direct hydrometallurgical processing is one of the most effective methods to recover high purity Zn. In this case, CI in the EAF dust is dissolved in the liquid phase by leaching, and the CI anion in electrolyte attacks anodes which are commonly made of a lead base alloy. Several processes have been proposed to remove CI anions from acidic sulfate solution. In this study, an electrolytic process was examined to eliminate CI anions from Zn sulfate electrolyte. From our study it can be said that the elimination rate of CI anion depends on the anode material ( i.e., the elimination rate is Pb-Ag alloy == Pb > DSE== Pt). In industrial Zn electrowinning process, the electrolyte contains Mn, which means the influence of Mn should be considered in the elimination of Cl. Mn dioxide deposition on an anode plate reduces the efficiency of CI removal. A periodical reverse current electrolytic system was examined to prevent this efficiency decrease, and deposited Mn dioxide could be removed very rapidly when the current is reversed. More than 95% of CI anion could be removed by this method in a shorter period than direct current method.

Jan 1, 1997

Chlorine as a lixiviant for gold possesses a number of significant chemical and Idnetic advantages over cyanide but because of its corrosive and vaporous nature the method of implementation needs to be significantly modified. At comparable reagent concentrations the dissolution rate for gold in the C12/Cl- systems is some 10 - 100 times that achieved in the 02/CN system. The dissolution rate in the chlorine system is largely a function of the concentration of C12, Cl- and pH. Under conditions of low Cl', (less than 50 g/1), the dissolution rate begins to drop off dramatically over the pH range from 3 - 4. Increasing the level of dissolved chloride ions shifts the pH of this rate reduction to around pH 5 at 100 g/l NaCl, and to around pH 6 at 300 g/l NaCl.

Jan 1, 1991

The capacity of chlorine based solutions to rapidly and effectively dissolve coarse gold in oxide ores is well established. The inherent advantages of chlorine are high dissolution rates (10 - 100 times those of cyanide), and low cost. The high dissolution rates mean that coarse or poorly liberated gold may be dissolved over relatively short periods and hence ore particle size may cease to be such a critical factor. The cost of size reduction to allow adequate gold liberation in order to achieve an adequate gold recovery is less of a consideration when using chlorine than in traditional plant or heap leaching cyanide-based treatment systems.Because chlorine based solutions capable of dissolving gold evolve an unpleasant vapour phase with the potential for significant chlorine losses into the atmosphere, traditional heap leaching with active solutions being sprayed onto prepared heaps is not possible. The ore must be covered and the solution may be introduced beneath that cover through prepared injection `wells' and recovered through production 'wells'. The pit is flooded with active solution beneath an overburden or cover with the solution migrating from the injection 'wells' to the production 'wells' over a period of around five - ten days.

Jan 1, 1992

Alluvial mining even of shallow deposits is often economically a marginal proposition and causes significant disruption of the land surface through the need for large scale excavation. In-situ leaching using chlorine-based solutions eliminates the need for excavation, the disruption of surface activities, and may greatly reduce processing costs and improve recovery especially of fine gold. A spreadsheet model has been developed to design and analyse the economics of in-situ leaching of alluvial deposits. In-situ leaching of shallow deposits may be achieved in a number of ways including solution infiltration via perimeter ditches or the use of injection and production wells. In most instances deeper alluvials may only be processed using well systems. Two deposits are analysed in this paper. The first consists of one metre of payable wash beneath one metre of overburden. Some thirty fields per year are treated processing 450 000 BCM per year at a cut-off grade of around $4/tonne ($8/rn3 or the gold value equivalent of 0.26 gh or 0.52 g/m3). The principal costs are well drilling and labour. Sensitivity analysis indicates that doubling the throughput halves the cost. The economics of the project are relatively insensitive to reagent costs and consumptions, and halving the recovery doubles the cut-off grade. Shallow deposits treated using the infiltration ditch system may be marginally cheaper and more conveniently managed although this depends on the relative cost of digging the perimeter ditches. In a second example, deep leads with one metre of wash beneath 30 metres of overburden necessitate significant drilling and feature reduced throughputs as a consequence. In the example chosen 30 fields a year are processed for an annual throughput of 65 000 tonnes costed at around $20/tonne (1.4 g/t Au equivalent, $40 /m3). Sensitivity analysis indicates that throughput, and drilling cost per metre are not important but there is a high sensitivity to recovery and to the depth to payable wash.

Jan 1, 1992