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Recovery of Rhenium from Mineral Raw Materials of Kazakhstan

Sep 13, 2010

By John B. Goddard

The discovery of rhenium on the ion exchange resin used at the uranium in-situ leach operations at Palangana (Texas) led to a laboratory study on the possible methods of recovery. Rhenium, present in small amounts in the ammonium carbonate leach liquors as the perrhenate anion, Re04-, concentrated on the anion exchange resin, which was a factor of ten more selective for rhenium than for uranium. Various elution systems were investigated for stripping the rhenium from the columns after the uranium had been eluted with chloride or nitrate solutions. Although the perchlorate ion was most efficient on a molar basis, nitrate ion combined the benefits of efficiency and low cost. A 3[N] or stronger concentration of nitrate containing up to 0.5[N] H+ was found to be the system of choice. A rhenium sulfide concentrate containing up to 14% Re was obtained from these effluents by hydrogen sulfide precipitation. Preliminary experiments were run to produce rhenium metal powder by oxidation of the concentrate to NH4Re04 followed by hydrogen reduction at elevated temperature.

Jan 1, 1982

By J. B. Goddard

The discovery of rhenium on the ion exchange resin used at the uraniun in-situ leach operations at Palangana, TX, led to a laborabory study of possible recovery methods. Rhenium was present in small amounts in the ammonium carbonate leach liquors as the perrhenate anion, ReO4-. It concentrated on the anion exchange resin, which was a factor of 10 more selective for rhenium than for uranium. Various elution systems were investigated for stripping the rhenium from the columns after the uranium had been eluted with chloride or nitrate solutions. Although the per-chlorate ion was most efficient on a molar basis, nitrate ion combined the benefits of efficiency and low cost. A 3N or stronger concentration of nitrate containing up to 0. 5N H + was found to be the system of choice. A rhenium sulfide concentrate containing up to 14010 Re was obtained from these effluents by hydrogen sulfide precipitation. Preliminary experiments were run to produce rhenium metal powder by oxidation of the concentrate to NH4ReO4 followed by hydrogen reduction at elevated temperature.

Jan 1, 1984

By Frédéric Bélanger, George P. Demopoulos, Pascal Coursol, Thomas Feldmann

"The use of scandium in industrial applications is expected to rise in the coming years, in large part due to the expected adoption of new, clean energy technologies such as solid oxide fuel cells or Sccontaining high strength aluminium alloys. Given that the supply of Sc is currently dominated by only a few countries (Russia and China) other sources for scandium extraction need to be investigated. This paper looks at different options for the recovery of scandium from waste solutions generated during the production of TiO2 pigments via the chloride process route. In particular, a direct solvent extraction (SX) approach and possible options for concentrating scandium before the SX step were investigated. It was found that the presence of Ti during solvent extraction causes severe formation of stable emulsions, which can complicate the successful application. This was particularly a problem after multiple contacts of the organic phase with fresh aqueous phase. On the other hand it was noticed that the presence of certain elements in the solution, e.g., iron, could possibly be utilized to concentrate scandium in a solid precipitate.INTRODUCTIONMany newly developed high-tech products depend on the use of chemical elements that are only produced in very small quantities. This can result in high and fluctuating prices, as can be seen from Figure 1, which may cause substitution with inferior alternatives, if possible at all (Reck & Rotter, 2012; US Dept. of Defense, 2013; Whittaker, 2011). One example is scandium (Sc) a member of the extended rare earth element family. There are only a few scandium ore deposits, but most Sc is produced from the processing of by-products of other metallurgical processes (Melcher & Wilken, 2013). Increasing demand for scandium metal and oxide (Sc2O3, scandia) is coming from its increased use in applications such as ceramic lasers (Li, Ikegami, & Mori, 2005; Rainer et al., 1982), high strength aluminium alloys (Lathabai & Lloyd, 2002) as well as solid oxide fuel cells (SOFC) (Thijssen, 2011). Especially, the spread of climate friendly SOFC’s, which are a commercial product today (Bloom Energy, 2014), is expected to be a main driver for future Sc2O3 demand. However, the rate of market penetration of this green technology depends on the availability of high purity Sc2O3 (>99.999%), since it specifically contributes to longer life-time and better safety of the SOFC’s (Bloom Energy, 2014; Irvine, Politova, & Kruth, 2005)."

Jan 1, 2016

By M. Kinnunen

Handling of municipal solid waste (MSW) and control of its potential resources is becoming increasingly important in modern society. The OECD (Organization for Economic Co-operation and Development) average on municipal waste produced in 2003 was that of around 570 kg per inhabitant. In European Union countries around half amount is of MSW landfilled. In Finland still 88% of MSW was landfilled in 2004. Since incineration reduces MSW volume significantly while producing heat energy, it has become one of the most common waste handling techniques. The shortcoming of incineration is however, that incinerated MSW is often not pre-sorted and it produces slags and ashes as side streams from which recovery of metals is difficult. This paper looks into possibilities of scrap metal recovery for recycling from municipal solid waste incineration (MSWI) bottom ash. In order to do that, a flow sheet of physical separation methods was developed and tested with Finnish rotary furnace MSWI bottom ash. In addition, an empirical model for estimation of the recoveries of scrap metals with physical separation methods for treatment of MSWI bottom ash was developed. According to the results of this study, for 1 Mt of incinerated MSW with 30% mass reduction, a minimum resource potential of 100 kt for magnetic metal scrap of roughly 24 % grade and about 19 kt of non-magnetic metal scrap of roughly 65 % grade. In other words, 57 kg magnetic scrap and 12 kg non-magnetic scrap per inhabitant at the mentioned grades, respectively. Although wide variations of parameters affect the MSWI bottom ash quality, it can be said that a considerable amount of metals is drained into MSWI bottom ash. Results of this study show that from MSWI bottom ash significant material streams metal scrap can be reintroduced into the resource cycle which would otherwise be lost.

Jan 1, 2014

By Parsons AE, Lewis IE

Selenium is a minor constituent of the raw materials processed by the Cockle Creek smelter of Sulphide Corporation Pty. Limited. Certain proposed raw materials contain higher levels of selenium, and these will create a problem with regard to the composition of liquid effluent discharged from the smelter. A method has been developed for removing selenium from the smelter circuit by the sulphation of the fume collected in the Acid Plant electrostatic-precipitators. It is planned that by treating 10-20% of the total dust arisings there will be a substantial reduction in the levels of selenium reporting in effluents when treating selenium-bearing raw materials. The selenium is recovered in elemental form.

Jan 1, 1978

By Frederic Benard

RECOVERY of selenium and tellurium at Copper Cliff by the Ontario Refining Co. has been previously described by the writer.1 During 1935 a new building was erected to house this operation and description of the new plant and process form the subject of this paper. The building, of modern steel and tile construction, covers an area of 5900 sq. ft. with a volume of approximately 165,000 cu. ft. The large monitored center bay is flanked by two smaller outside bays, one of which is devoted to the tellurium section. All equipment, ceilings and upper walls, are treated with aluminum paint, giving good illumination and facilitating good housekeeping, essential from a health standpoint in handling material of this nature. EQUIPMENT Layout and type of equipment conforms to the requirements of the process as described below. In the selenium section, storage tanks, neutralizing tanks and precipitators are of steel construction, lead-lined and. arranged for gravity flow (Fig. 1). The neutralizing tanks are equipped with water-cooled lead coils for controlling solution temperature, agitation being accomplished with compressed air. The precipitators are provided with mechanical agitators, and sulphur dioxide is introduced into the solution through 3-in. lead pipes leading from a manifold attached to the cover of the precipitator. Each precipitator has internal cooling coils and an air-jet exhauster to carry off fumes. Neutralized solutions are filtered in a 29-plate wooden filter press using heavy cotton duck as a filter medium, forced feed being maintained by a Welmet centrifugal pump. Dilute solutions are concentrated by evaporation in a vacuum evaporator, constructed of cast hard lead. Heat is supplied by an outside steam chest operating under 15 lb. steam pressure. The solution is circulated through the steam chest by a pump of antimonial lead at a rate approximating 400 cu. ft. per min. The evaporator is evacuated by a water-jet condenser that creates a vacuum of 26 in. of mercury under normal operating conditions. The capacity of the vessel is 60 cu. ft. and the rate of evaporation 25 cu. ft. per hour.

Jan 1, 1938

By Frederic Benard

RECOVERY of selenium and tellurium at Copper Cliff by the Ontario Refining Co. has been previously described by the writer.1 During 1935 a new building was erected to house this operation and description of the new plant and process form the subject of this paper. The building, of modern steel and tile construction, covers an area of 5900 sq. ft. with a volume of approximately 165,000 cu. ft. The large monitored center bay is flanked by two smaller outside bays, one of which is devoted to the tellurium section. All equipment, ceilings and upper walls, are treated with aluminum paint, giving good illumination and facilitating good housekeeping, essential from a health standpoint in handling material of this nature.

Jan 1, 1938

By Chandrakala Kari, Divyang Shah, Lakshmi Kanth Reddy, Kaushik Vakil, Sanjay Sarkar, Bhavin Desai

Gases rich in sulfur dioxide generated as a by-product of smelting and converting operations of copper concentrate contain selenium apart from zinc, lead, copper, cadmium, bismuth, antimony, and arsenic. The gaseous stream is heat exchanged in waste heat boiler, dust collected in electrostatic precipitator followed by cleaning in reverse jet scrubber to remove fumes, halogens and fine dust before passing to DCDA Monsanto catalytic converter to produce commercial grade sulfuric acid. The gas cleaning section of the acid plant uses water to scrub the smelting gases. During scrubbing, precipitated solids, known as sludge, settles at the bottom of the reverse jet scrubber containing 30 to 40 wt% copper and selenium up to 40 wt% selenium. In the existing process, the sludge collected during scrubber cleaning process is directly recycled to the smelter for copper recovery. However, the selenium is expected to again vaporize due to high oxidation potential during smelting and converting, causing accumulation of selenium in sludge. In present investigation, a roasting process has been developed to recover the selenium from acid plant sludge before charging it to smelter for copper recovery. Selenium is associated with copper in acid plant sludge as copper selenide, as determined by X-ray diffraction and electron microscopy. Thermodynamic and thermo-gravimetry study revealed that the copper selenide phase present in the sludge was amenable to oxidation at 600°C forming oxides of copper and selenium (Cu-Se-O). However, the dissociation of selenium from the copper oxide was made possible by sulfatation using sulfur dioxide between 450°C to 600°C, resulting into the formation of CuSO4(s) and SeO2(g). Lab scale experiments were carried out in vertical tubular furnace to determine the optimum roasting conditions with respect to roasting time, temperature and molar ratio of O2:SO2. Using these optimum conditions, selenium up to 90 wt. % in the form of SeO2 vapors could be recovered from the acid plant sludge in a large scale commercial roaster. Roasted sludge free from selenium and containing oxides and sulfates of copper could now be recycled in the smelter for copper recovery. INTRODUCTION There is an increasing demand for minor metals due to their use in innovative technologies. Similarly, the increase in demand for selenium is expected due to disruption in sectors related to renewable energy and photovoltaic battery. Selenium is a chalcogen and a non-metal with black or red crystalline appearance. Selenium is used in the glass industry to decolorize glass and to make red-colored glasses and enamels. It is also used in solar cells and as a photographic toner. Selenium is used as a brasses in stainless steel to improve its machinability. Selenium sulfide is used in anti-dandruff shampoos. In spite of the toxicity of its compounds, selenium is also an essential trace element for humans and animals. Selenium occasionally occurs free in nature, but more often occurs as selenides of iron, lead, silver and copper. There is an urgent need for the development of new methods for selenium recovery from the existing resources. Commercially, selenium is obtained only from anode mud produced during electrolytic refinery of copper.

Jan 1, 2019

By James E. Hoffmann

This paper reviews the chemistry of selenium and its compounds as it applies to the recovery of selenium from electrolytic copper refinery slimes. Based on this chemistry various processes for the extraction and recovery of selenium from refinery slimes are explained and developed. The optimum selenium technology processes is dependent upon many factors including copper refinery location, environmental and regulatory conditions, local markets for selenium or selenium chemicals, and other plant processes. For this reason there is no one best process but rather a variety of useful processes for winning selenium. Those which have demonstrated consistent utility in both ease of recovery and reliability are discussed in more detail. Recovery of selenium by Doré furnacing of slimes is the topic of a separate paper. The companies that have developed selenium extraction technology are not being cited in this paper for the following reasons: o Their current technology may be different o The actual inventor of a process is difficult to credit since many different organizations have pursued parallel inquiries in developing better processes. Finally, some selenium extraction processes have been omitted; not because they are unworthy of consideration but rather due to limitations of space.

Jan 1, 1984

By W. R. Smith

Introduction No commercial deposits of silica sand are known to occur in British Columbia, so all requirements for foundry and other uses must be imported. During the war, nearly 5,000 tons per year were used, all originating in Illinois and delivered to local consumers for about $12.00 per ton. Present requirements are somewhat less, but the cost is still of the same order. The relatively high cost of silica sand in British Columbia is not only a serious item for present consumers, but might be a deterrent to the establishment of a glass industry, should this be contemplated at any time. The present investigation was undertaken in an attempt to provide a cheaper source of silica sand within the Province. In 1936, a large number of beach and bank sand deposits in the lower coastal region of British Columbia were examined by the British Columbia Department of Mines, and samples were analyzed chemically and mineralogically. The deposits over the whole area proved remarkably uniform in mineral composition, consisting essentially of quartz, feldspar, ferromagnesian minerals, rock fragments, and various accessory minerals, and differing only in the relative proportions of the various constituents. In no case did the quartz content of any sand exceed about 40 percent and the average was of the order of 20 to 30 percent.

Jan 1, 1947

By C. V. G. K. Murty

Sillimanite, chemically named Aluminum silicate, 3Al2O3SiO2 is one of the three forms of alumino silicate polymorphs and commonly encountered in aluminous metamorphic, plutonic, and volcanic rocks and their weathering products. Most of the sillimanite deposits are granular and are of high grade available in coastal areas as associated mineral along with Titanium bearing minerals namely ilmenite, rutile etc. Sillimanite is one of the widely accepted raw materials for the manufacture of high alumina refractories (55-60 % alumina) or bricks. Sillimanite based refractory bricks are used for the lining of Blast furnaces, Arc furnaces, Soaking pits, Reheating furnaces of iron and steel, rotary kilns for cement manufacturing and general kilns for lime production. Considering the vast potential of unexploited sillimanite reserves in India, M/s Trimex Sands Pvt. Ltd., (TSPL)has set up a Mineral Sand Processing plant in 2010 at Andhra Pradesh with a capacity to produce about 50,000 tons of sillimanite per annum besides the production of various heavy minerals such as ilmenite, rutile, zircon and garnet. Traditionally in India, sillimanite is upgraded by froth flotation technique using Oleic acid as a collector cum frother, sodium silicate as depressant and soda ash as pH regulator. At TSPL, Conventional mechanical float cells are installed to float sillimanite. In addition to the usual problems associated with conventional cells, poor flow ability of the sillimanite concentrate is experienced in dry circuit due to the presence of sodium oleate. Fine garnet in the sillimanite concentrate contributes to high iron content in the final product, making sillimanite separation a nightmare for operators (lower recoveries coupled with inferior grades). Various efforts were made to improve the performance of the circuit such as introduction of additional frother like MIBC, optimizing the operating parameters such as pulp density, collector dosage, depressant dosage, air flow rate, pH etc., use of collector aids, stage wise addition of reagents etc. The challenges faced to produce a sillimanite product with stringent quality norms and the efforts made to improve the grade and recovery are described in this paper. Keywords: sillimanite, froth flotation, conventional mechanical cell

Sep 1, 2012

By B. Pesic

The recovery of silver and gallium from flue dust with acidified thiourea solutions was examined. The studied parameters were temperature, particle size, thiourea concentration, acid concentration, and the presence of oxidants. The study of the extraction of these two metals was undertaken in sulfuric acid medium. Silver dissolution was dependent on all examined parameters, whereas gallium extraction was only dependent on the initial acid concentration. The experimental results suggest a new very efficient method for recovery of both silver and gallium. Almost complete recovery of silver and gallium can be accomplished within 90 minutes. A technological scheme for recovery of both metals is also proposed.

Jan 1, 1986

Cyanidation tests by bottle agitation were conducted on an oxidized lead-silver ore containing approximately 12% Pb and 500 g/t Ag. Over 60% of the silver was leached when the ore was ground to 100% passing 0.15mm, whereas 50-60% of the silver was leached when the ore was only ground to 100% passing 0.5mm. Slurry handling and dewatering at the fine grind size were very difficult due to the high clay content of the ore, however this problem was greatly reduced at the coar- ser grind size. The silver recovery at the fine grind size was very dependent on cyanide solution strength with stronger cyanide sol- utions (containing more than 0.1% NaCN) re- sulting in lower solution silver contents. This was thought to be due to the precipi- tation of leached silver by zinc, which was also leached from the ore by the higher cyanide levels. There was a critical zinc level in solution of approximately 1000ppm, above which the silver recovery fell markedly. Cyanide and lime consumptions for this ore were high (typically 5 kg/t and 40 kg/t respectively), hence the processing of this particular ore by cyanide leaching is un- economic at current silver prices.

Jan 1, 1987

By T. G. Carnahan

The U.S. Department of the Interior, Bureau of Mines, performed a laboratory-scale investigation of technique for recovering silver from pregnant solutions generated in the hydrometallurgical treatment of complex base-metal sulfide concentrates with oxidizing chloride media. This provides a means for recovery and simplified reduction of accessory silver to metal from ions. The method consists of adding NaI or KI to the solution to precipitate AgI, which is then contacted with Na2S to produce Ag2S and to regenerate the iodide salt solution. Silver recoveries range from 99 pct with 20 pct excess iodide precipitant, to-92 pct when the theoretical stoichiometric amount of precipitant is employed. The Ag2S product can be reduced to silver metal by contact with aluminum chips in NaOH solution followed by purification with conventional fire refining techniques.

Jan 1, 1980

By Charles A. Rhoades

The Bureau of Mines is conducting research on a dual leaching method that offers the potential for the economic recovery of the silver as well as the manganese contained in some of the domestic manganiferous silver deposits. The method is an initial leach of the manganese with aqueous SO2 followed by a neutralization rinse, and then by a second leach for the extraction of silver with cyanide solution. Refractory silver in these ores is either bound by the high-valence manganese, chemically resistent to cyanide leaching, or is rendered inaccessible to cyanide leach solution by the surrounding manganese mineralization. Less than 10 pct of the silver was extracted when -1 in +1/2 in (-2.5 cm + 1.3 cm) ore pieces were leached directly with cyanide. However, extractions of 25 to 82 pct for silver and 65 to 96 pct for manganese were attained in laboratory column leach tests using the dual method on the same size ore pieces from six domestic deposits.

Jan 1, 1984

By C. Flores

It is well known that manganiferous silver ores containing manganese intimately associated with silver are not amenable to conventional extraction methods. The segregation process has been applied primarily for recovering copper from oxidized and oxide-sulfide ores. A new alternative process combining segregation roasting followed by flotation to recover silver from refractory manganiferous silver ores, was studied using a 23 factorial experimental design. Laboratory investigations have been conducted on a manganiferous silver ore analyzing 0.02% copper, 0.09% lead, 0.33% zinc, 12.55% manganese and 187 g/ton silver to study the effects of additives salt, coke and copper oxide on silver recovery. Results indicate that 79.3% silver recovery can be attained in the absence of copper oxide and 88.4% when the copper oxide content is 1.5% at '750°C, 2% salt and 1% coke and 30 minutes of roasting time. It was concluded that doping with copper oxide improves silver recovery.

Jan 1, 1994

By C. S. Ek

As a continuation of previous work, further tests have been carried out to recover silver from the residues obtained in a zinc jarosite process. Selective flotation has been performed with different reagents, and ?cleaning steps have been introduced to upgrade the silver concentrate. Leaching of crude residues, as well as flotation tailings, has been carried out with cyanide and thiourea. Finally, the different beneficiation methods are compared, and the industrial aspects? of their application are reviewed.

Jan 1, 1990

By W. Kunda

Silver nitrate solution is a very common product in hydrometallurgical processes involving the treatment of various silver bearing materials. Silver is recovered by electrolysis. The alternative method for the recovery of silver from aqueous solutions is the precipitation by hydrogen at elevated temperature and pressure. A previous study by the authors revealed the feasibility of this technique for the silver ammine sulfate system. Further study showed different behavior for silver in the silver ammine nitrate system and a systematic study was initiated to establish the optimum conditions for the process. The study showed that the process can be controlled by (1) composition of the feed solution, (2) temperature and (3) hydrogen pressure. The recovered silver product was in the form of very fine powder.

Jan 1, 1989

By William Romanoff

IN AN ARTICLE on "Recovering Smelter Dust and Oxide," published in the Engineering and Mining Journal (Vol. 131, No. 2), the authors briefly described some dust-recovery equipment and its operation at a secondary-metals brass-smelting and refining plant. A description of our experience in overcoming certain operating difficulties may prove of interest or value to those who are confronted with some of the same problems or who should equip their furnaces with dust-collecting equipment. The dust loss from reverberatory smelting and refining of brass con¬sists largely of zinc, with smaller percentages of lead, tin, and copper in the order named. At the Kramer plant, the fume discharge from the two stacks amounted to 3 to 4 tons of solids per day, making a dense smoke. With dust equipment in operation, the discharge from the stacks is invisible and approximately 2500 lb. of zinc and other metals is recovered daily thereby from each furnace operating.

Jan 1, 1933