Search Documents

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

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

Mar 1, 2017

By Hideyuki Itou

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

Jan 1, 2006

By R. J. Nankee

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

Jan 1, 1985

By 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 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 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 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 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

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 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 Jesse Betterton

IN the Parkes process of lead refining, after desilverization has been completed by means of zinc additions, there will remain in the lead from 0.5 to 0.6 per cent zinc. At this stage in the refining practically all impurities are reduced to refined lead specifications except zinc and antimony. All excess of copper and nearly all the arsenic goes out with the silver. Silver remaining should not exceed 0.1 oz. per ton. It thus remains only to remove zinc and antimony to produce refined lead. The older practice was to complete refining by means of oxidation processes in reverberatory furnaces. Essentially this consisted of heating the lead to 1200° to 1300° F. and allowing it to come in contact with a considerable excess of air passing through the furnace, or accom-plish the same result by blowing the lead with steam by means of pipes introduced for that purpose, at the same time allowing air to enter the furnace. Usually some procedure involving alternate oxidation and reduction with fine coal or coke was employed in order to reduce the weight of dross or skim finally removed from the furnace. This practice had many elements of weakness in that the main flow of lead, after the preceding expensive operations had been performed, and the whole refining process nearly completed, was subjected to an operation at a comparatively high temperature, which involved much lead loss if the furnaces were not on bags, and the production of 3 to 5 per cent of the weight of the lead as dross or skim, which had to be resmelted and the lead either refined or produced as antimonial lead. In addition, the operating expense of the process was a considerable item. The, process of dezincing with chlorine was developed as a substitute for the foregoing described oxidation process, and finally resulted in such advantages as nearly equal operating costs, a practical elimination of the lead loss, and the direct production of a very valuable byproduct, zinc chloride, that may be sold as such or retreated for its zinc and chlorine contents, both of which can be reused in the refining processes.

Jan 1, 1933