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By Kotaro Ogura

"The electrolysis process in which CO2 is selectively reduced to C2H4 at a three-phase(gas/solution/metal) interface on a copper-mesh electrode has been developed in a concentrated solution of potassium halide. At open-circuit potential, CO2 is captured on the electrode by being inserted into the double-layer consisting of halide anions specifically adsorbed and potassium cations which are located in the Helmholtz inner and outer layers, respectively. CO2 thus activated is subjected to the electrochemical reduction. In the early stage of reduction, CO2 is converted to formate radicals that are adsorbed on the electrode by taking the place of halide anions. The reductive coupling of these radicals results in the formation of intermediates such as -CH2C(O)- and CH2=CH-, and C2H4 is finally produced. The catalytic activity of the electrode process involving the insertion of CO2 into the double layer is not deteriorated at all during the electrolysis, and the continuous reduction of CO2 to C2H4 is possible with the addition of inorganic acid under the assistance of natural energy.Carbon dioxide is a serious pollutant released from fossil fuel power station, internal combustion and many industrial operations. The easy release of CO2 to the air has caused the global warming, and the technique which intends to curtail CO2 by pushing it back into the ground has been suggested. However, this problem should be greatly mitigated if CO2 can be converted to innocuous substances. Especially, the reuse of CO2 as fuels and chemicals is extremely effective not only for the mitigation of the global warming but also against the depletion of the fossil fuel reserves. Several processes for converting CO2 to valuable compounds have been proposed including hydrogenation over heterogeneous catalyst at high temperature and electrochemical and photochemical reduction. In the conversion and cutback processes of CO2, however, it is of importance that the process is feasible under mild conditions, because the secondary generation of CO2 is feared if high energy is required and supplied with a fossil fuel. In this meaning, the electrochemical reduction of CO2 taking place at room temperature, which is similar to photosynthesis, is promising. From the practical point of view, it is further necessary that the conversion rate is high enough and the product is satisfactorily valuable."

Jan 1, 2008

By John E. Litz

Metal-bearing flue dusts are produced by some ferrous and non-ferrous industries. Many dusts are being or can be treated for recovery of metal values. Operating and proposed flowsheets for the most common dusts are reviewed. Advantages, disadvantages, product marketability, and cost implications are discussed for each flowsheet.

Jan 1, 1992

By Peter C. Hayes

"The high temperature reduction of solids through the use of reactive gas atmospheres has application in a wide range of industrially important processes. Whilst significant advances have been made in understanding and describing these processes, some key aspects of the chemical reactions and reaction mechanisms operating in these systems, for example, the transformation from metal oxide to metal, remain poorly understood. A number of different product morphologies have been identified in these reaction systems and the reaction rates have been shown to be critically dependent on the product structure.Theoretical examination of the elementary process steps taking place in the region of the gas/metal/metal oxide interface, combined with electron microscope studies of the resultant product microstructures, have enabled the key process and material variables responsible for the development of the various product morphologies to be identified. By considering i) established criteria for the stability of moving interfaces in a thermodynamic potential gradient, ii) the relative rates of chemical reactions on the oxide and metal surfaces, and iii) key process phenomena and physico-chemical properties of the solid phases, the mechanisms and conditions for the formation of various product morphologies are identified. Interestingly the analysis points to direct analogies between these phase transformations and, the phenomena and microstructures observed in metal solidification, and the potential to develop generic models of these fluid/solid reaction systems."

Jan 1, 2013

By William Petruk

The mineralogy of the primary and oxidized ores from the Malanjkhand porphyry copper deposit in India was studied to determine ore characteristics that affect metallurgy, and to assess applicable processes for recovering the copper. Three mineral assemblages were found. One occurs in primary ore, another in moderately oxidized ore, and a thir:d in intensely oxidized ore. Chalcopyrite, the main mineral in the primary ore, is relatively coarse-grained, with grain size increasing as the ore grade increases. High chalcopyrite liberations should be achieved at a relatively coarse grind, and good chalcopyrite recoveries should be obtained. The chalcopyrite, however, tarnishes readily and oXidizes to chalcocite in a relatively short time (several months). The presence of both the tarnished chalcopyrite and chalcocite may affect chalcopyrite flotation and reduce copper recoveries, The moderately oxidized ore occurs in an oxidized cap immediately above the primary ore, and stockpiled primary ore alters quickly to a moderately oxidized ore. Chalcocite is a major copper-bearing mineral in moderately OXidized ore. The concentrator processing this ore should be capable of handling a chalcocite-rich ore. The intensely OXidized ore contains a wide variety of acid-soluble copper-bearing minerals. Leaching may be required to recover the copper from them.

Jan 1, 1987

By Pedro A. Netto, Giulio R. Altoé, Sergio N. Monteiro, Ygor M. Moraes, Frederico M. Margem, Gabriel O. Glória

Since environmental issues are becoming more and more important Worldwide. Nowadays, Natural fibers are been used to substitute the synthetic ones. Although PALF fiber is an important natural fiber and its mechanical Properties surpass in various aspects some other lignocelluloses fibers, such few studies have been conducted with the fiber obtained from leaf of PALF plant. In order to better evaluate the mechanical properties and possible applications, this paper aims to improve the elastic modulus of the PALF fiber by Weibull statistics, by evaluating their mechanicals properties and possible applications. The fibers were divided in diameter intervals and the tensile strength and elasticity modulus were measured in each range. The fractured surface was examined using scanning electron microscopy. The results, interpreted by the Weibull statistical method, showed a correlation between the fiber elastic modulus and its diameter.

Jan 1, 2015

By R. G. Reddy

Industrial copper reverberatory furnace slags were treated by high temperature techniques (sulfide and carbothermic reduction) to recover copper in alloy or matte phase at 1473K. Recovery was investigated for the condi¬tions of varying amounts of metallic sulfide, carbon and CaO additions. The results showed that recovery of copper increased with increasing amounts of carbon addition, and also is strongly dependent on the initial concentration of copper in the slags. Copper recovery for both carbothermic reduction and sulfide treatment were modeled with linear relationships as follows: for carbothermic reduction (%Cu recovery) = 9.0 (%Cu in slag)initial 73.8 and for sulfide (%Cu recovery) = 7.1 (%Cu in slag)initial 82.2 Higher copper recovery was obtained with sulfide treatment than with carbothermic reduction of slags.

Jan 1, 1983

By Jürgen Antrekowitsch, Thomas Griessacher

"Heavy metal containing residues are typically hazardous wastes because on the one hand, a deposition gets more and more complicated and on the other hand, the large amounts of metals like Zn, Cu, Fe and Pb represent a significant value. Thus, a post-treatment of these materials with the recovery/recycling of the metals and stabilization of the waste is not only ecological but often also economical. The therefore typically applied recycling processes utilize pyrometallurgical steps, where carbon or carbon monoxide from fossil coal and coke is used as a reducing agent, which results in large amounts of CO2 emissions. An alternative option is the application of a hydrogen-rich gas emitted in biomass utilization processes as a carbon-neutral reducing agent. Investigations in a retort process which were done at different temperatures and times showed excellent results concerning the achievable reduction rates and final contents of the heavy metals for various residues.IntroductionNowadays heavy metal containing residues like electric arc furnace dust (EAFD), dust from cupola furnaces, waelz slag, etc. are declared as hazardous wastes in a growing number of countries due to the leachability of the heavy metals in these residues. For that reason it is no longer possible to landfill these materials or use them for road construction or disposal works. Some land filling activities, carried out until now, have only been realizable because of some process modifications or cost intensive post-treatment steps of these residues. But the disposal capacities for such materials are decreasing, therefore increasing the prices. The second point for the growing disposal limitations is the stringent environmental legislations and regulations, which restrict the number and amounts of materials which can be dumped [1 – 5].From the other point of view these heavy metal containing residues usually have high contents of zinc, lead, iron, etc., which represent a significant value and therefore a big potential to recover these metals. This is why in recent years the number of recycling processes and the amount of recycled heavy metal containing residues have continuously increased. These recycling processes have the target to recover the valuable metals from the residual materials in the form of a saleable product as well as the stabilization of the slag produced in these processes [5, 6]."

Jan 1, 2011

By Roberto Parra

The classic criteria of the preparation of the charge for the smelting of copper concentrates in a flash furnace considers the mass and energy balance from the chemical and mineralogy composition of the concentrates. The operation parameters fixed with this method don't assure the stability of the operation and the critical problems of the slag quality and dust formation occurs very often. This paper presents the results of a laboratory test that allows the predicition of the behavior of concentrates blends in the view of the minimization of the dust formation and the magnetite control in the slag. The combustion of different copper concentrates and blends were done in a drop tube furnace. The results show that the magnetite and dust formation don't have a linear behavior with the weight proportion of the blend and some optimal blends of 2 or 3 types of concentrates can be identified. From the reasonable hypothesis that the qualitative behavior of blends in the drop tube represents the real behavior in the burner, the preparation of the charge with this approach could help to solve those operational problems.

Jan 1, 2003

By Kazuteru Tozcwa

The oxidation of several sulfide minerals in aqueous ammoniacal solution is discussed thermodynamically. The region in which Cu(NH3)2 4+ is stable has been estimated as a function of pH and concentration of total ammonia, {[NH3) + [NH4)}. In ammonia leaching when copper in sulfides is assumed to be extracted in the form of Cu(NH3)2 which will be rapidly converted to cupric ammine, thermodynamic data predict that such minerals are oxidized readily in the following order, CuS, Cu2S, CuFeS2, ZnS, NiS, Ag2S. This agrees with investigations on ammonia leaching of sulfide minerals, reported previously. The leaching of copper sulfide concentrate has been examined experimentally. Copper in a copper sulfide concentrate, in which the main constituents were chalcopyrite and pyrite, was effective¬ly extracted. The copper extraction was affected by factors such as (1) agitation intensity, (2) oxygen partial pressure, (3) NH3/Cu molar ratio, (4) leaching temperature and (5) addition of ammonium sulfate. From the results obtained in this work, it is concluded that mass transfer of oxygen plays the most important role in ammonia leaching of copper sulfide minerals.

Jan 1, 1976

By André Laplante

The mineralogy of the Joe Mann mine differs from that of other deposits of the Chibougamau area that are exploited by Les Mines Camchib Inc.. It is characterized by very fine first generation gold and very coarse second generation electrurn. Successful milling required adjustments of the processing flowsheet, which includes gravity, flotation, and cyanidation. A study of coarse gold liberation in the gravity/grinding circuit is described. Modifications to the flotation circuit and the reconditioning of a small capacity cyanidation circuit are presented. As a result of the circuit modifications, gold recovery increased from 65 to 81% in flotation and cyanidation. Overall gold recovery increased from 77% to 88-89%. These improvements are mostly attibutable to the recovery of -10 urn gold, whose presence in the Joe Mann ore and original circuit tails had been identified by process mineralogy.

Jan 1, 1989

By G. G. Richards

"The slag fuming process has operated for close to 70 years to recover zinc from lead blast furnace slag. The process is normally carried out through the batch treatment of slag by submerged injection of coal and air. Within the bath the coal acts as both a reductant, to reduce Zno to zinc vapour, and a fuel, to maintain bath temperature during the endothermic reduction process. The partition of coal between the slag, combustion and bypass is dependent on factors such as bath depth and injection pressure. The option of continuous fuming has been pursued at the D. Blagoev smelter in Bulgaria using heavy fuel oil as reductant/fuel. There has, however, been little attempt at commercial continuous fuming with coal. This paper presents an analysis of a coal-based continuous slag fuming furnace. The data on the Plovdiv fumer is used as a reference point. Critical design criteria for continuous fuming include the slag feed rate, degree of coal combustion and furnace size. Mathematical modelling analysis suggests that continuous fuming with coal can achieve respectable zinc/coal ratios.IntroductionThe slag fuming process was developed in the early part of this century to recover zinc from non-ferrous smelting slags [1-3]. The majority of installed furnaces were put in place to fume zinc from lead blast furnace slag on a batch basis. In most cases coal is used to effect reduction of zinc oxide, but one furnace uses natural gas [4] and, in a curious twist, a continuous fumer was developed based on fuel oil [5].Given the general nature of blast furnace lead smelting, it is not surprising that slag fuming has remained a batch process, in spite of the advantages that could be gained by moving to continuous fuming. Blast furnaces are usually operated as relatively independent units, and tapping has traditionally been done into ladles. The presence of a crane aisle makes direct coupling of the blast furnace to a slag fumer difficult, especially in a retrofit situation. Furthermore, steady-state blast furnace operation is not easy to achieve. The size of these furnaces and the nature of their feed make it difficult to guarantee constant operation."

Jan 1, 1996

By Robert R. Grinstead

Two new ion exchange resins have been developed, which selectively absorb copper and nickel in preference to ferric iron from dilute sulfuric acid solutions of pH 1-3. The first absorbs copper and not nickel and can be readily eluted with 1-2N sulfuric acid. This resin is well adapted to the processing of copper leach liquors, including relatively low grade liquors obtained from dump leaching. The second resin absorbs nickel as well as copper in the same pH region, but only the nickel is eluted with 1-2N sulfuric acid. Elution of the copper requires much stronger (ca. ION) acid, altho both species are readily eluted with dilute (ca. lN) ammonium hydroxide. This resin, which should be useful in processing of certain types of copper-bearing solutions, may also be suitable for treating acidic nickel leach solutions of laterites and other non-sulfide ores.

Jan 1, 1976

By Batric Pesic

The interactions of mineral-pyrite with T. ferrooxidans were studied by using a cyclic voltametry technique. The interactions with bacteria were carefully examined during the entire growth stage of bacteria (fermentation). Several very important discoveries were made. For example, the pyrite surface invariably drastically changed its properties at the second day of fermentation. Beyond two days of fermentation, the cyclic voltamograms were insensitive to convective diffusion produced by stirring. The SEM study revealed that bacteria populated the pyrite surface at an extremely high density levels. The high density of bacteria, and the solid reaction products formed on the pyrite surface created conditions for pore diffusion which explained why the CVs became insensitive to convective diffusion in solution (stirring).

Jan 1, 1990

By C. Acuna

The standard procedure of fire refining consists of sulphur removal via air injected through tuyeres, arsenic slagging via soda-lime flux and oxygen reduction by air or oxygen deficient air or a steam fuel mixtures. The use of porous plugs to stir with an inert gas has been mainly considered as a surface renewing agent that increases the product quality and shorten the refining cycle. In the present study the effect of the bottom stirring by nitrogen gas injection through porous plugs for the treatment of the crude copper in the range of 400-150 ppm sulphur, 3,000?2,000 ppm arsenic and 14,000-7,000 ppm oxygen content was investigated. The combined effect stirring-reducing, by the use of air or a steam fuel mixtures through tuyeres for oxygen removal, follows a kinetics of first order where the constant, K, can be represented by the following polynomial expression: K = A .* R2 + B * R + C Where A, Band C are constants that depend on the nitrogen flow rate and R is the air-fuel ratio or the steam-fuel used in the reducing step. Depending on the optimization of the flow of nitrogen and the air-fuel or steam-fuel mixture and only if just the oxidation, complexing and reducing steps are considered, the process cycle might be shortened by 45%.

Jan 1, 2003

By John L. H. Patterson

Handheld XRF has become the favorite way of measuring the content and identity of alloys in the field. This is because of the very portable nature of the instrumentation and its simple operation. However, these analyzers have been unable to determine the concentration of the light elements like Mg and Si due to the very low energy of the x-rays produced by these elements. In the past accessories such as vacuum and He flush have given some analyzers the ability to determine these light elements with modest detection limits. The introduction of the Silicon Drift Detector (SDD) into this class of instrumentation has added a new level of analysis capability to portable XRF instrumentation. X-ray fluorescence is achieved by exciting a sample with a beam of x-rays, which in recent portable equipment are generated by a small tube. This results in the emission of characteristic x-rays from the sample under test. By measuring the energy of each x-ray it is possible to determine what element generated it. By counting the number of x-rays at each energy it is possible to determine the concentration of each element. The detection limit for each element is dependent upon the number of x-rays which reach the detector. As the number of x-rays increases the detection limit will improve. One of the major factors in an x-ray reaching the detector is the energy of the x-ray. As the energy of an x-ray increases the probability of that x-ray reaching the detector increases. The energy of an x-ray is inversely proportional to the atomic number (AN) of the element generating the x-ray. For example, an iron x-ray (AN=26) is 6.40 keV while an aluminum x-ray (AN=13) is 1.49 keV. As the energy decreases, the detection of the x-ray becomes less and less probable because the x-ray may be absorbed by the windows which are part of the instrument and detector or the air in the path between the sample and detector. In SiPIN based portable XRF analyzers, the lowest element which is detected with acceptable detection limits is normally considered to be Ti (AN=22). The detection limits for 60 second measurements on typical SiPIN XRF analyzer are given in Table I. Thus, portable analyzers have not been useful for measurement of aluminum and titanium alloys as major components of these alloys are Mg (AN=12), Al (AN=13) and Si (AN=14).

Jan 1, 2009

By Osamu Takai, Yoshiki Sato, Nobuhiro Tajima, Hiroyuki Sugimura

"Amorphous carbon thin films doped with nitrogen ( a-C:N) have been synthesized by means of shielded arc ion plating (SAIP). Their electron field emission properties, that is, threshold field strengths for electron emission and maximum emission current densities, were evaluated and compared with those of pure amorphous carbon (a-C) films prepared by the same SAIP apparatus. Among all of the fabricated a-C:N films, the a-C:N films with a N concentration of 23 %, which prepared using Nz arc plasm at a pressure of 1 Pa with applying a sample bias voltage of -100 V, showed the lowest threshold filed of 13.4 V/µm and the highest emission current density of 1.87 µAfcm2 at a field of20 V/µm. These field emission properties of the a-C:N film were much better than those of the a-C films. The best results obtained on the a-C film in this study were the lowest threshold filed of 15.5 V/µm and the highest emission current density of 0.052 µA/cm2 at a field of 20 V /µm. Nitrogen doping to aC was found to be effective for lowering threshold voltage for field emission and for increasing emission current density. The electron field emission characteristics of the a-C:N films depended not only on N concentration but also on chemical bonding state of nitrogen in the a-C:N films. The presence of the ~-C3N4-like phase, which contributes to improve wear resistance of a-C:N as well, distinguished by the NlsXPS peak at 400.5 eV is proved to be crucial in order to enhance field emission properties of a-C:N.IntroductionThere has been much interest in electron field emission from a cold cathode due to its potential applications in vacuum microelectronic devices including field emission displays which are expected as flat panel displays in next generation [l]. It is well known that efficient emission can be rather readily realized using tip-like shape cathodes, e.g., microfabricated three-dimensional electrodes [2], carbon nanotubes [3-5], etc. However, electron emission from planar surfaces is of particular importance since such a type of cathode is· simply fabricated and assembled into microelectronic circuits. Currently, amorphous carbon thin films doped with nitrogen (a-C:N) prepared by plasma processes have attracted attention because their threshold voltages of field emission are relatively low [6]. Among various methods for preparing a-C:N films, the process using arc plasma is of special interest since, in arc plasma, nitrogen is highly activated and new types of carbon nitride phase are expected to be synthesized. However, field emission properties of a-C:N prepared by arc plasma have been studied in less detail compared with that prepared by the other methods such as sputtering."

Jan 1, 2000

By Yotamu Stephen Rainford Hara

"The aim of our work is to investigate a low energy and clean route for the recovery of copper and cobalt from complex sulphide mineral concentrates. The mineral concentrates were roasted in air, in the presence of CaO (MS + CaO + 202 =MO+ CaS04) at temperatures below 973K. The roasted products containing CuO, CoO and Fe203 were carbothermically reduced at 1073K within an hour to preferentially reduce copper and cobalt. The kinetics of reactions were studied using the thermogravimetric technique and by characterisation ofreaction products using the XRDSEM-EDX techniques. The effects of MS:CaO ratio, roasting temperatures and physical nature of the mineral concentrates were analysed. The method for capturing S02 by forming CaS04 was analysed for reuse in the process. The energy balance for the above process is compared with that of conventional continuous smelting/converting process.1.0 IntroductionCopper sulphide mineral concentrates from Zambia contains substantial amouot of cobalt. The cobalt metal content in the concentrates ranges between 0.7 and 2 % weight, which corresponds to 3 and 9 % weight copper, based on the spot price of copper ($7 386/tone) and cobalt ($31 000/tone). Although the traditional approach using a combination of roasting-leaching-electrowining steps can be applied to recover copper and cobalt from sulphide mineral concentrates [1-4], there are two major draw backs of the traditional process: (i) the S02 emitted during roasting is too lean for economical conversion for sulphuric acid manufacture, which causes serious environmental pollution. (ii) silver and gold which are normally present in the sulphide concentrates are lost out [5] because they are not leachable by H2S04 or HCl which are the common leachants. The above two problems have been overcome by adopting flash smelting in which a rich S02 gas above 20% is produced [1, 5] and successfully converted into sulphuric acid. The precious metals tend to partition to blister copper and recovered during refming. However, nearly all cobalt is lost into the slag phase uoder oxidising condition which prevails during flash smelting. It is important to note that the cobalt content in the slag can be up to 2.6 % weight [6]. The recovery of cobalt from the slag is a process which requires huge amouot of energy since the slag is smelted above 1873K [6]. With a view of minimising the amouot of energy and S02 emission during metal recovery, our investigation involves roasting the sulphide concentrates in the presence of lime and reducing the roasted samples with carbon."

Jan 1, 2013

By D. J. Chaiko

Certain radionuclide ions (e.g., TcO4) exhibit unusually strong Affinities toward the polymer-rich phase in aqueous biphase systems generated by combinations of salt solutions with polymers such as poly(ethylene glycol) (PEG) and poly(propylene glycol) (PPG). Thus, aqueous. polymer ,phases could potentially be used to selectively extract these ions during pretreatment of radioactive tank wastes at Hanford. To help develop a fundamental understanding of the interactions between various ions and polymers in aqueous solution, interaction enthalpies between sodium -perrhenate and a random copolymer of PEG and PPG (UCON-50) were measured by microcalorimetric titration. An entropy compensation effect was observed in this system in which changes in enthalpic interactions were balanced by entropy changes such that the interaction free energy remained constant and approximately equal to zero.

Jan 1, 1999

By Jerry D. St. Clair

A multidisciplinary team of scientists and engineers at Wont has been working to understand heavy metal contamination of DuPont process waste streams and technologies for abatement of these metals. As part of this effort, an extensive study was made of a specific waste stream of importance in DuPont's environmental commitment. This 200 gpm stream contains 5-5000 ppm of nickel plus a variety of inorganic and organic constituents. The chemical complexity of the waste rendered conventional. alkaline precipitation ineffective, and only through the simultaneous application of analytical characterization, fundamental chemical understanding, and process engineering did effective technical approaches emerge. In this instance, ion exchange, sulfide precipitation, and caustic digestion ultimately proved successful in reducing the nickel to below the 1 ppm target. The results of this study will be presented, along with key learnings about the process of solving heavy metal contamination problems.

Jan 1, 1994

By E. O. Stensholt

The Hybinette electrorefining process for production of cathode nickel was in use at Falconbridge Nikkelverk A/S, Norway, until 1975 when conversion to the new chlorine leach process was started. In 1978 the conversion to electrowinning had been completed, but further major improvements to the process have been made up to 1987. After a major expansion program in 1985 - 87 the refinery has a nickel capacity of 54 000 mt Ni/year. The main feed materials to the process are converter matte from the Falconbridge smelter in Sudbury, Ontario, Canada, and from the BCL smelter in Selebi-Phikwe, Botswana. A typical composition of the mixed feed to the refinery is: 40 - 45% Ni, 25 - 30% Cu, 20 - 22% S, 2 - 3% Fe and 1.0 - 1.5% Co. The matte is chlorine-leached in the first process step, nickel being dissolved selectively in a train of leach-cementation tanks. Essentially all copper and sulphur that was present in matte appears in the leach residue as CuS. In 1986 an autoclave treatment stage was added to the process to improve nickel extraction from the leach residue. The resulting strong nickel chloride solution is purified by the process steps (1) precipitation of iron and arsenic, (2) solvent extraction of cobalt and other minor elements and (3) precipitation of lead and the remaining impurities. The nickel solution is then fed to the tankhouse, where various nickel products are produced by electrowinning. The chlorine gas that is produced during the electrolysis is returned directly to the chlorine leaching tanks to dissolve more matte. After stripping from the loaded organic phase and solution purification cobalt is also produced by electrowinning. The copper sulphide leach residue, which contains some nickel, is dead- roasted in fluidized-bed roasters. The sulphur is recovered and sold as sulphuric acid. The calcine is leached in spent copper electrolyte, from which cathode copper is produced by electrowinning. Precious metals and the remaining base metals are recovered from the copper leach residue. The Falconbridge chlorine process is very versatile. It can accept a wide range of impurities in the feed and still produce metals of exceptional purity.

Jan 1, 1988