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By R. G. Reddy

The Margules .equation is used for interpreting excess Gibbs energy of several ternary systems. In the present study activity coefficient of 'a dilute solute, 2, in a binary solvent 1-3 was derived. The derived expression is used to interpret logarithmic activity coefficient of oxygen and sulfur in several metallic systems. Self interaction parameter of the solute is derived from the partial function of solute using constant compositional path. An expression for logarithmic activity coefficient and self - interaction parameter of solute is also derived using Maclaurin infinite series. The derived equation is based on Maclaurin infinite series used successfully to deduce thermodynamics of self interaction of oxygen as a interstitial atom in two metallic systems. The predicted thermodynamic parameters values using Maclaurin infinite series and Margules. equations, are in excellent agreement with the experimental data and also our predictions are far more accurate than the predictions made by other models.

Jan 1, 1996

By C. A. Young

The remediation of cyanide (CN-) and nitrate (NO)-) anions in mine and agricultural waters by various photolytic methods has been reviewed and investigated. Photolytic methods such as direct photolysis, homogenous photolysis, and heterogeneous photocatalysis are briefly described and compared. Results and discussions show that each method has certain advantages and disadvantages. For each method, Eh-pH diagrams prove useful for determining reaction mechanisms. Preliminary results obtained for cyanide oxidation and nitrate reduction show that homogeneous photolysis can be superior due to faster kinetics than the other methods. The photolytic methods were individually, not simultaneously, tested and compared. Differences in concentrations of products were obtained and attributed to differences in photoconversion efficiencies and other inherent characteristics of .the photolytic methods. Various reaction mechanisms are proposed in accordance with the literature as well as measurements obtained from solution analysis using ion selective electrodes and ion chromatography .

Jan 1, 1995

By R. Hurman Eric

The dew-point technique of activity measurements take advantage of the volatility of a component in solution. The pressure of the volatile component over a sample is determined from observations of the temperature at which condensation of the vapor occurs. The method is applicable best when the vapor pressure of the components would differ by about two to three orders of magnitude. Experimentally, this is a closed system involving the use of evacuated and sealed transparent quartz sample probes. Furthermore reliable vapor pressure data of the volatile component is essential along with a specialized high temperature furnace capable of giving reproducible results. In this context, the vertical Dew-Point Furnace (DPF) was designed and built after elaborate trails until enough proficiency was gained for reprodueible results. Over the years the DPF was modified and improved. The DPF developed was versatile and could easily be used for activity measurements in the isopiestic mode (another method of measuring activities of a volatile component in a solution). The necessary ancillary systems; namely evacuation-flushing-evacuation followed by sealing of quartz sample probes under vacuum were also perfected over the years. As and when necessary the dew-point technique was supplemented by classical equilibration-quenching method employed on the sealed quartz sample probes to reveal necessary phase equilibrium information. The following were studied utilizing the above technique: (i) Activities in CuzS-PbS and FeS-PbS binaries and CU2S-FeS- PbS ternary at 1200°C; (ii) Activities in CuzS-SnS and FeS-SnS binaries and Cu2S-FeS-SnS ternary at 1200°C; (iii) Phase equilibria and thennodynamic in Cu-Pb-S, Fe-Pb-S, Fe-Sn-S, Cu-Sn-S and Ag-Sn-S systems. Most recently the following systems have been tackled: (i) Phase equilibria and thennodynamics in the Ag-Pb-S and Sn-Pb-S systems; and (ii) Activities in Ag2S-FeS-CuzS-PbS quaternary at 1200°C.

Jan 1, 2003

By B. Nowak

For sources with an iron-to-vanadium ratio of far above 1, it is proposed to leach in acid and to oxidize under autoclave conditions. During this oxidation process, it is experimentally shown that divalent iron contained in this solution will be oxidized to trivalent iron, whereas free acid contained will be consumed by this reaction. In case no acid is present or already fully consumed, a solid consisting of ferric compounds and an iron-vanadium-co-precipitate will form that can be filtered from the solution. If choosing the right reaction conditions, this filter cake has an iron-to-vanadium ratio of close to 1, whereas the liquid remainder is almost vanadium free. This precipitate, identified as FeVO4, 1.1 H2O, can be processed by conventional technologies such as caustic leaching, or probably salt roasting or reduction with aluminum, yielding common marketable products.

By Jeffrey W. Fergus, Shiqiang Hui

"Aluminum is an important alloying addition to the zinc used in the hot-dip galvanization of sheet steel to control the properties and appearance of the resulting coating. Optimization of the galvanization process requires control of the alloy concentration which can be improved through the use of chemical sensors. Aluminum sensors based on molten electrolytes are commercially available but are not widely used because of their high cost. One approach to reducing the cost is to use a solid electrolyte which can simplify the sensor design and thus reduce the cost of fabrication. In this paper, the development of an aluminum sensor based on a solid fluoride electrolyte, specifically magnesium fluoride, will be described.IntroductionThe concentration of the zinc bath used in hot-dip galvanization affects the galvanization process as well as the properties of the resulting coating. Thus, accurate in situ measurement of the alloy composition can be used to improve process control. This paper describes a solid-electrolyte-based aluminum sensor for monitoring the bath composition during hot-dip galvanization."

Jan 1, 1997

By I. Goy D. Gaballah

Decontamination of synthetic K2Cr2O 7 solutions containing 10 to 1000 ppm of hexavalent chromium using chemically treated barks have been studied at a laboratory scale. Metal removal from solutions depends on the pH, the initial concentration and the bark species. The use of a pulp density of 2 % in an agitated flask at the optimum pH for 2 hours leads to a percentage chromium removal of about 95 of the initial metallic ions content. Other trials conducted by column percolation permit the determination of the maximum retention capacity of the treated bark. Depending on the bark species, oak or pine, the rate of saturation is 110 and 215 mg of Cr per gram of bark respectively. The incineration of the metal charged barks gives recyclable, ashes containing 36 and 54 % of chromium metal for the oak and pine barks respectively. Experiments, of Cr6+ removal from industrial effluents containing up to 1800 ppm have been carried out on the semi-pilot plant scale. They have lead to the elimination of about 90 % of hexavalent chromium from this industrial waste solution. Further studies are conducted in order to define the hexavalent chromium binding mechanisms on bark constituents.

Jan 1, 1992

By R. Hurman Eric

The dew-point technique of activity measurements take advantage of the volatility of a component in solution. The pressure of the volatile component over a sample is determined from observations of the temperature at which condensation of the vapor occurs. The method is applicable best when the vapor pressure of the components would differ by about two to three orders of magnitude. Experimentally, this is a closed system involving the use of evacuated and sealed transparent quartz sample probes. Furthermore reliable vapor pressure data of the volatile component is essential along with a specialized high temperature furnace capable of giving reproducible results. In this context, the vertical Dew-Point Furnace (DPF) was designed and built after elaborate trails until enough proficiency was gained for reproducible results. Over the years the DPF was modified and improved. The DPF developed was versatile and could easily be used for activity measurements in the isopiestic mode (another method of measuring activities of a volatile component in a solution). The necessary ancillary systems; namely evacuation-flushing-evacuation followed by sealing of quartz sample probes under vacuum were also perfected over the years. As and when necessary the dew-point technique was supplemented by classical equilibration-quenching method employed on the sealed quartz sample probes to reveal necessary phase equilibrium information. The following were studied utilizing the above technique: (i) Activities in CU2S-PbS and FeS-PbS binaries and CU2S-FeS- PbS ternary at 1200°C; (ii) Activities in Cu2S-SnS and FeS-SnS binaries and Cu2S-FeS-SnS ternary at I200°C; (iii) Phase equilibria and thermodynamic in Cu-Pb-S, Fe-Pb-S, Fe-Sn-S, Cu-Sn-S and Ag-Sn-S systems. Most recently the following systems have been tackled: (i) Phase equilibria and thermodynamics in the Ag-Pb-S and Sn-Pb-S systems; and (ii) Activities in Ag2S-FeS-CuzS-PbS quaternary at 1200°C.

Jan 1, 2003

By Shengli Wu, Fengjie Zhang, Feng Chang, Hua Lu, Kaiping Du

In order to make a complete understanding of steel plant metallurgical dusts and to realize the goal of zero-waste, a study of their properties was undertaken. For these purposes, samples of two sintering dusts (SD), two blast furnace dusts (BFD), and one electric arc furnace dust (EAFD) taken from the regular production process were subjected to a series of tests. The tests were carried out by using granulometry analysis, chemical analysis, X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive spectroscopy via SEM (EDS), and Fourier transform infrared spectroscopy (FTIR). The dominant elements having an advantage of reuse are Fe, K, Cl, Zn, C. The dominant mineralogical phases identified in sintering dust are KCl, Fe2O3, CaCO3, CaMg(CO3)2, NaCl, SiO2. Mineralogical phases exist in blast furnace dust are Fe2O3, Fe3O4, with small amount of KCl and kaolinite coexist. While in electric arc furnace dust, Fe3O4, ZnFe2O4, CaCO3, CaO, Ca(OH)2 are detected.

Jan 1, 2015

By G. Gao

Flyash from municipal solid waste (MSW) incinerators is frequently classified as a characteristic hazardous waste due to its lead and cadmium content. Extensive investigation has therefore been carried out to detoxity the flyash by leaching and to recover lead, cadmium and zinc. Detoxification can be accomplished by leaching in HCI/NaCI solutions. Optimization of leaching conditions for effective detoxification and subsequent metal recovery can be achieved by controlling the acidity of the lixiviant and flyash to lixivaint ratio. Lead and cadmium In the leaching solution is recovered by cementation with zinc dust. Leaching and cementation experiments have shown that zinc concentrations suitable for electrowinning, > 15 g/liter, can be achieved. Experiments have also been performed to determine the effects of pH, particle size of the zinc dust used, quantity of zinc added and dissolved impurities on the cementation kinetics. After recovery of lead and cadmium, electrowinning or electrowinning coupled with solvent extraction can be used to recover zinc. A process flowsheet is presented.

Jan 1, 1991

By A. González

Arsenic is one of the main contaminants present in Chilean copper concentrates and its abatement represents a challenge for the process metallurgy, particularly under the strong environmental requirements in the global community. The possibility to form ferric arsenate directly from a gas phase by means of a heterogeneous reaction between an arsenic gas bearing and iron oxide was studied at laboratory scale. A thermodynamical analysis for the system Fe-As-O-S has been initially made, in order to obtain the stability conditions for the ferric arsenate or other FeAsyO2 type compounds. Experiments were made using an hematite sample suspended in a thermogravimetric device. AS4O6 gas generated from solid AS2O3 that was passed through the iron oxide sample and its instantaneous weight change was recorded directly. A kinetic study for the AS4O6 volatilization was made to control the gas composition. A chemical control between 300 and 600°C with an apparent activation energy of around 14 Kcal/mol As2O3 was determined. The samples after the reactions were chemically and XRD analysed. Arsenates detected corresponds to complex compounds. Results shows a dependence on temperature and oxygen content in the gas phase. The kinetics for iron arsenates formation is slow, reaching an arsenic capture of 6% after 80 minutes of reaction when an oxygen content of 50% is fed continuously at 800°C and 3,56% As in the gas. Experiences made at the same temperature but under higher oxygen content in a closed reactor, allowed arsenic capture close to 60%. For higher temperatures the capture is considerably lower.

Jan 1, 2003

By Martin Reyes, Juan Hernández, Julio Cesar Juárez, Isauro Rivera, Ma. de los Ángeles Hernández, Francisco Patiño

The dissolution of Ag contained in metallurgical tailings was studied by adding ions Cu2+ and Zn2+ in S2O3 2- medium. Chemical analysis of mine tailings by cupellation revealed a Ag concentration of 71 g/ton. The XRF and XRD analysis confirmed the preponderance of SiO2 in the mineral matrix. The experimental dissolution process was conducted in alkaline solution using six concentrations of NaOH and five of S2O3 2-, at different temperatures, also using five concentrations of Cu2+ and Zn2+ as a catalyst. The results showed similar values for both systems (96.8% and 97.13%). The ion Cu2+ and Zn2+ increases the dissolution of Ag, and decrease the reaction time of dissolution. Under the conditions used, pH and stirring rate did not affect the dissolution of Ag.

Jan 1, 2015

By Mitsutaka Hino

The contents of gangue minerals, such as Al2O3. P2O5, crystalline water and so forth in the iron ore imported to Japan tend to increase year by year. Though the increments of such gangue contents arc approximately 0.1-0.2 mass%, some problems for the blast furnace operation in ironmaking process have already been reported, In order to clarify the mechanism of harmful effect caused by the small increment of gangue minerals, mainly Al2O3. on the blast furnace operation, the dripping behavior of Fe,O-CaO-SiO2-Al2O3-MgO slag from the iron funnel, which simulated the micro-porosity in sinter ore, has been observed with the wide range of basicity, Al2O3, Fe2O and MgO contents. The effect of MgO on the dripping behavior of slag has been summarized in this paper. It was found that the addition of 2mass% MgO resulted in large increase of hold-up on the most of the conditions. When Fe2O content was less than 20mass% and the basicity was lower than 0.8, MgO lowered the hold-up even if the slag contained 10mass% Ah03. Every slag hold-up showed the minimum at the basicity of less than unity on the conditions of constant Fe2O and Al2O3 contents, This trend became remarkable when the slag contained 2 mass% MgO.

Jan 1, 2003

By Ludwig Hermann

"Phosphorus is required by every cell of living organisms and essential for plant growth. It is a non-renewable resource that must be mined from natural deposits, going gradually into depletion. Abundant secondary resources are available in sewage sludge and meat and bone meal, with the highest exploitable P concentrations in ashes that remain from their widely used combustion with energy recovery. ASH DEC has successfully removed heavy metals and transformed sewage sludge ash into a marketable P fertilizer by application of a thermo-chemical treatment process. Pilot scale investigations in which ash was treated proved that generally heavy metal limits required by fertilizer legislation can be attained. To achieve a high P availability for crops – an essential fertilizer quality feature – was a more challenging R&D task. Our presentation demonstrates the scientific approach and R&D results that lead from assessment of market requirements to licensed products.IntroductionPhosphorus (P) is required by every cell of living organisms. It is one of the major elements for plant nutrition and therefore essential for crop production. P supply in plant nutrition depends entirely on external inputs into soils [1]. This is achieved by P-fertilizers deriving from rock phosphate deposits that are gradually going into depletion. Serious prognoses anticipate that rock phosphate will be the first low running resource in the world [2]. In the EU, last year 2.530 kt of phosphorus (P2O5 in fertilizers) was consumed and only 313 kt (P2O5 in rock phosphate) was mined. Since 2007, rock phosphate prices have increased by 500% because of a tight supply situation [3].For these reasons, P recycling is becoming an increasingly important issue. Suitable secondary raw materials with regard to their high P-content and abundance are sewage sludge and meat and bone meal. In the EU 989 kt P2O5 are accumulated annually in theses materials, of which 632 kt P2O5 are permanently lost to landfills and other forms of disposal. The main reasons for their limited recycling are concerns on heavy metal contents and organic pollutants that may incite health hazards. As an additional shortcoming, the availability of P from these materials to plants is poor and storage and transportation are problematic issues [4, 5]."

Jan 1, 2008

By Gaballah I.

Elimination of arsenic, mercury and zinc from synthetic solutions containing H;\A.sD4. HgCI2 and ZnCI2 using modified barks was investigated. The pH range was varied from ?1 to 10. The initial concentrations of individual element were 10,100 and 1000 ppm. More than 99 % of mercury and 65 % of zinc cations were removed by the modified bark .. In this case, the modified bark reacts as a cation exchanger leading to the release of ' two protons for every HgII or ZnII fixed by this material. About 30 % of arsenic was eliminated from the solution. This 'low efficiency could be attributed to? the presence of arsenic ,as. anion. Decontamination of a treated industrial effluent containing 4 ppm of ion? metals was performed on a pilot plant scale by the modified bll(k. More than 70'% of these ion metals were eliminated.

Jan 1, 1995

By Jean P. Murray

The extractive metallurgical industry is a major consumer of high-temperature process heat. It is, consequently, a major contributor of C02 emissions and other greenhouse gases derived from the combustion of fossil fuels for heat and electricity generation, or from the process itself. These emissions can be substantially reduced by replacing fossil fuels with solar energy as the source of process heat. Concentrated solar radiation can supply a large amount of thermal energy to endothermic reactions at temperatures exceeding 2000 K. Another potential for C02 emission reduction exists as well. Thermodynamically, the total amount of energy required for metal production at any given temperature is the enthalpy change of the reaction, AH. Of this total, an amount equal to the Gibbs free energy AG must be supplied as high quality energy in the form of electrical work or by using a reducing agent. Many conventional metallurgical electrolytic processes and reducing furnaces are unable to add only the thermodynamically required electricaVchemical energy due to process inefficiencies. Electrical work in excess of AG for the reaction may be used to supply process heat, or excess chemical reducing agent burned to supply process heat. Besides the thermodynamic and economic drawback, this inefficiency results in excess C02 emissions derived from the combustion of fossil fuels. With these practices, energy becomes an important cost element of the metal produced. Highly-concentrated solar energy has the demonstrated potential to separate these two forms of process energies, allowing the addition of only the thermodynamically required high-quality energy while high-temperature solar process heat is provided to the reactor. Examples of metal oxide reduction processes that have been studied experimentally in solar furnaces include the production of Fe, Al, AI/Si alloy, Mg, Zn, Tic, Sic, CaC2, TIN, Si3N4, and AIN by carbothermic reduction of their oxides, and the high-temperature solar- electrothermal reduction of ZnO.

Jan 1, 1999

By Suchun Zhang

The alkaline oxidation of refractory gold concentrates containing arsenopyrite and pyrite at ambient temperatures and pressures has been found to be accompanied by the simultaneous dissolution of gold without the addition of cyanide. A detailed study has been made of the kinetics of the oxidation of the pure minerals and of several concentrates. The reaction products of the oxidation of arsenic and sulphur have been monitored using chromatographic techniques. In the case of arsenopyrite, thiosulfate, monothioarsenate, arsenate and sulfite are the principal products while thiosulfate has been confirmed to be the dominant product of pyrite oxidation. Gold, either as added powder or as a constituent of the concentrates has been found to dissolve simultaneously during the alkaline oxidation of both arsenopyrite and pyrite, and this appears to be associated with the in-situ formation of thiosulfate as a lixiviant. The effects of temperature, stirring speed, oxygen partial pressure, alkalinity and pulp density on the oxidation of arsenopyrite and the dissolution of gold have also been investigated. Keywords: Gold, dissolution, arsenopyrite, pyrite, alkaline, oxidation, thiosulfate, thioarsenate

Jan 1, 2005

By E. Allain

Extraction of basic metals from sulfides by conventional pyrometallurgical processing leads to the emission of SO2. To avoid this inconvenient, low temperature selective chlorination of sulfide concentrates could be an alternative. However, such process generates hazardous chlorides SxCly. A part of sulfur chlorides such as SCI2 can be recycled as a chlorinating agent of metal sulfides. Hydrolysis of sulfur chlorides, using a solution containing Na2S.9H2O, led to the recovery of more than 90 pct of elemental sulfur. Reduction of SxCly by hydrogen was investigated between 300 °C and 800 °C. About 70 and 90 pct of elemental sulfur were recovered from SC12 and S2C12, respectively. A flow sheet for the chlorination of metal sulfides and the treatment of sulfur chlorides was suggested.

Jan 1, 1998

By A. S. Rao

In the original roast-leach-electrowin (RLE) circuit at the Chambishi Cobalt Plant, commissioned in 1978, the separation of nickel and zinc from cobalt in aqueous streams was achieved by successive stages of precipitation using lime. However, this technique was not able to meet the increasingly stringent metal quality requirements of customers whilst maintaining acceptable process recoveries. Intensive process development work was carried out and, in July 1988, an ion exchange circuit for nickel removal was commissioned using DOW XFS 4195 resin and for the first time Z.C.C.M. produced high purity cobalt metal containing less than 0.10% nickel. Following further work, a solvent extraction circuit for zinc removal, using DZEHPA, was commissioned in February 1991 in order to enhance cobalt recovery by reducing co-precipitated cobalt losses. This paper outlines the process development, design, commissioning and subsequent operation of these nickel ion exchange and zinc solvent extraction circuits.

Jan 1, 1993

By S. Suzuki, Y. Maeda, N. Wakamatsu

"A new pyrometallugical technology, named KLS process, has been developed by Dowa Mining at its Kosaka Smelter to smelt various kinds of lead raw materials.The process consists of clearly separated two reaction steps, smelting and reduction. For this purpose, respective stationary furnaces are installed which are connected by a slag launder.Dry raw materials, together with pulverized coal and oxygen-enriched air, are injected through a lance pipe into the molten slag in the first furnace. It is kept under a high oxygen potential to remove sulfur completely. Resultant PbO rich slag overflows to the second furnace where pulverized coal and insufficient air are also injected through a lance pipe to reduce PbO to lead bullion and to compensate for thermal deficit. The entire operation is carried out continuously. The process development started back in 1981. In late 1986, a pilot plant with a capacity of 3.5t/H was constructed.Already nearly 20,000 tons of raw materials, mostly lead sulfate mixtures have been smelted successfully.IntroductionFor a long time, main raw materials for lead smelting at Kosaka smelter have been such secondary incombustibles as lead sulfate and lead-barium sulfate. The former is leach residue of the copper smelter flue dust and the latter originates from Iijima zinc refinery. While the most of lead concentrates produced locally has been smelted by an ISF of Hachinohe smelter in which Dowa Mining has a share.The surplus lead concentrates were processed at Kosaka by a hydrometallurgical method to convert PbS to PbSO 4 as pretreatment, and followed by simultaneous smelting together with the above secondary materials (1). Approximate output has been 1,5000 /M of lead bullion and slightly more than 2,000t/M of refined lead by adding lead bullion returned back from Hachinohe smelter (2)."

Jan 1, 1988

By V. M. Paretsky

Oxygen-flame converting of a solid ground matte containing heavy non-ferrous metals in a wide range of concentrations is one of the perspective trends meeting the demands of modern non-ferrous metallurgy. As. a result, of semicommercial tests on oxygen-flame smelting of nickel matte containing 13,5-17,5% Ni; 0,45-0,65% Co under continuous autogenous conditions a converter matte containing 68 8-75,0% Ni and 0,48-1-,0% Co and ferrite -calcium slag containing 1,4-8,4 Ni and 0,16-0,56 Co were pro¬duced. Nickel recovery in a converter-matte was 76,2%, copper - 58,'2% and cobalt recovery in. a slag was 90%. Slag cleaning in an electric furnace allowed to after-recover nickel and cobalt in an alloy to produce a dumpy slag containing 0,03% Ni and 0,02% Co. The development of modern' ecologically pure energy-saving autogenous technologies of the treatment of sulphide raw materials containing heavy non-ferrous metals makes certain demands of the perfection of a process of converting rich sulphide-metallic intermediate products obtained at autogenous smelting. These-demands were connected first of all with the fact that converting process stages because of process periodicity are more unfavourable from the point of ecology, power intensity and unit stability. Besides, during rich matte treatment the problems connected with heat shortage when using air blast and heat excess-when using top oxygen blast to treat luquid matte a-rise and when enriching air blast by oxygen up to 26% fast erosion of the brickwork of a tuyere zone takes place. The technology of Outokumpu and Kennecott companies-on solid- copper matte converting in a flash smelting furnace using air blast is not universal as its possibilities are limited by certain composition of mattes. Besides, flash smelting to produce highly basic or combined slags requires larger enrichment-of blast by oxygen or extra fuel feed. Naturally a flowsheet with continuous converting of matte of various composition up to white matte production is simple,

Jan 1, 1993