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By D. Majuste

This paper describes an experimental approach to evaluate the effect of organic impurities or even additives on metal electrowinning and product quality. In addition to electrowinning tests and electrochemical measurements, the approach includes organic analysis by Fourier Transform Infrared spectroscopy and gas chromatography; video monitoring of the reaction interface; and product characterization by using scanning electron microscopy, crystallographic texture and bending tests. The mechanical behavior of metal cathodes was assessed with a customized bending device that is able to bend the cathodes up to angles similar to that of the stripping machine. In this work, the effect of a potential organic impurity, lubricating oil, on the production of electrolytic zinc is taken as a case study. The findings of the investigation allowed a better understanding on the role of this organic on energy consumption and product quality and a qualitative prediction for the behavior of Zn cathodes during the stripping operation. Simple control and optimization procedures resulted in significant energy savings.

By Djona M. Gaballah I.

Selective chlorination of unroasted and roasted spent hydrorefming catalysts was studied between 300 and 600°C using the following gas mixtures : C12+CO, C12+N2 and CI2+air. Such materials contain Co, Ni and Mo compounds supported by alumina and/ or silica. They also contain variable amounts of V compounds, C, S, etc., accumulated during the life time of the catalyst. Direct oxychlorination of the C+S rich sample allows higher extraction rates than those obtained by the carbochlorination of the same roasted one. It seems that the roasting step doesn't favor the economic metals' recovery. Results of the chlorination of C+S poor spent catalysts, in the presence of CO, in the chlorinating gas mixture, or of carbon added to the sample, were comparable. Cobalt and nickel chlorides were .extracted from the chlorination residues by their dissolution with acidified water, whereas molybdenum and vanadium chlorinated compounds were recovered by selective condensation from the vapor phase. The recovery rates of valuable metals as well as the selectivity were higher for the chlorination of spent catalysts than results obtained by the hydrometallurgical processing of the same sample. Results of the scale-up of the oxychlorination of the unroasted sample confirmed those of the laboratory scale. The global recovery rates were about 88 pct of cobalt, 93 pct of molybdenum and 76 pct of vanadium. The carbochlorination was applied to the recovery of W and Ti from Denox catalyst that is a carbon and sulfur free one. Recovery rates higher than 99 pct at temperatures lower than 500 °C could be obtained. This may indicate that the chlorination process can be applied to the treatment of various industrial wastes or by-product containing transition and/or refractory metal compounds A flow - sheet for the pretreatment of these materials is proposed.

Jan 1, 1995

By N. Kanari

The kinetics of oxychlorination of MgO by Cl2+O2 was studied in the temperature range of 850 °C - 1025 °C, using thermogravimetric analysis. The effects of C12/02 ratio, gas velocity, temperature and partial pressure of reactive gases on the reaction rate were investigated. The oxychlorination process was characterized by an apparent activation energy of about 214 kJ/mol. The reaction orders with respect to C12+O2. C12 and O2 at 950 °C were about 0.65.0.98, and -0.37, respectively. Some data about oxychlorination kinetics of MgO, Cr2O3, and MgCr2O4 contained in chromite were compared. Efficiency of using oxychlorination for the removal of iron oxides contained in magnesia was demonstrated.

Jan 1, 1999

By H. Y. Sohn, S. PalDey

"A new chemical synthesis process for the preparation of intermetallic compounds has been developed. It involves the vapor-phase reduction of mixtures of constituent metal chlorides by magnesium vapor to produce intermetallic compounds in the form of fine powder. The advantages of the process include (a) the use of inexpensive raw materials, (b) low reaction temperatures, and (c) products in the form of fine particles. Titanium and nickel aluminides were prepared by this method. The effect of AlCl/TiCl3 partial pressure ratio on the formation of different titanium aluminides was studied. A two-phase mixture containing 80 mol % of TiAl and 20 mol % of TiA13 formed at an AlC13/TiC13 ratio of 10. The amount of TiA13 was maximized to 72 mol% at an AlC13/TiC13 ratio of 16. The maximum conversion of the limiting chloride TiCl3 was 94 % . In the case of nickel aluminides, NiAI, NiAl3, and Ni2Al3 were formed by reducing mixtures of NiC12 and A1Cl3 vapors. The effect of the partial pressure ratios AlCl3/NiC12 and Mg/NiC12 on the formation of nickel aluminides was studied. The maximum content of NiAl obtained was 98 mol % . At the AlC13/NiC12 ratio of 19, a two-phase mixture of 17 mol% of NiAl and 83 mol% of NiA13 was produced. The product particles were very fine in the size range of 0.05 to 0.2 µm.A. IntroductionIntermetallic compounds are attracting much attention [1]. Titanium and nickel aluminides have attracted a great deal of attention from the aerospace as well as automobile industries because of their potential for high-temperature application (e.g., low density, good oxidation resistance, and high-temperature strength retention [2, 3]). Gamma TiAl and two-phase (TiAl and Ti3Al) alloys [4] are used for gas turbine engine rotational components as well as automobile exhaust valves. TiAl3 is one of the most extensively investigated aluminum-rich intermetallics. Nickel aluminides are attractive because of their low densities, relatively high melting point and good high-temperature strength properties. For example, Ni3Al shows increasing rather than decreasing yield strength with increasing temperature [5]."

Jan 1, 1998

By Mikhail Mikhaylenko

Natural and technogenic sources of rare earth elements (REE) and other rare and scattered metals are remarkable for their chemical diversity. The pregnant solutions going to processing for the valuable metals have very complex compositions. Both targeted elements and competing impurities are present in the solutions in different chemical forms. Thus processing of such materials demands application of different technological tools addressing numerous specific tasks on the way to the final product. Screening work was undertaken to identify the best resins among developmental and commercial products addressing typical cases in the hydrometallurgy of scandium and REE. The cases outline typical sources of scandium and REE, such as streams of TiO2 production, extracted phosphoric acid, barren uranium solutions and others. Specially designed ion exchange resins can be effective tools.

By Sven Eck, Andreas Ludwig, Menghuai Wu

"Phase separation is a frequently occurring phenomenon during solidification accompanied by melt convection, sedimentation or, in the case of two unmixable liquids, a Marangoni driven motion. In order to describe these phase separation phenomena a two-phase volume-averaging model was employed for globular equiaxed solidification of binary alloys and decomposition and solidification of hypermonotectic alloys. The model considers nucleation and growth of equiaxed grains or second phase droplets, motion and sedimentation of grains or droplets, feeding flow and solute transport by diffusion and convection. It allows the prediction of macro segregations and the distributions of grain size or droplet size. Evaluations were made by comparing the numerical predictions with experimental results. For example it is shown that the numerically predicted grain size distribution in a plate casting (Al-4wt%Cu) agrees reasonably well with the experimental analyses.IntroductionModeling of metallurgical processes is a rapidly expanding field and the research activities in the last decades cover a wide range of areas including melt pre-treatment, solidification and subsequent manufacturing routes. Among those activities solidification stands in the central position, because the primary structure of the materials, and even many defects such as porosity, (macro or micro) segregation and inclusions form during solidification. Those primarily formed structures or defects once existing are difficult to be removed or modified by the subsequent material processing.Solidification is a multi-disciplinary field involving thermodynamics, fluid dynamics and solid mechanics, heat and mass transfer, and other disciplinesr1 -31• One of the most challenging problems in solidification modeling is the complex interactions between physical phenomena occurring on different length scales ranging from atomic rearrangement over single crystal-melt interactions to heat extraction, momentum and species transport at the system level. Modeling an industry process on atomic scale is umealistic, even on grain scale (e.g. phase field method) it would need another 40 years to be able to model the exact grain morphology in a casting space envelope of 10x10x10 cm3 [ 4]. Therefore, the realistic models for industry process are based on the solution of the macro transport equations (mass, momentum, enthalpy and species) on system scale. The microscopic phenomena such as thermodynamics, nucleation law, crystal growth kinetics and interactions at the liquid-solid interface are considered with simplified models, which are coupled with the macroscopic transport equations."

Jan 1, 2004

By Kimio Itagaki

The distribution ratios of Ag, Pb, As, Sb and Bi for the Cu2S-FeS or Ni3S2-FeS matte / FeOx SiO2, FeOx-SiO2-CaO or FeOx-CaO slag equilibration in a MgO crucible were determined experimentally at 1523~1573K under controlled partial pressures of S2 and O2 at given PSO2 of 10.1, 50.7 and 101.3 kPa (0.1, 0.5 and 1 atm) and be observed dependency of distribution ratio on the matte grade, SO2 pressure and slag basicity were analyzed on the basis of thermodynamics,

Jan 1, 2003

By Tetsuya Uda

Our recent achievements of rare earth separation technique[1,2] and new process idea for rare earth magnet recycling[3] are reviewed, (1) Binary chloride mixtures of rare earths were separated by a new selective reduction-vacuum distillation process. According to our experimental results, apparent separation factors were 8.1 for the Pr-Nd chloride mixture and 570 for the Nd-Sm chloride mixture. These values are much higher than conventional solvent extraction methods. (2) A study of recycling process of magnet sludge was carried out. The rare earths in the neodymium magnet sludge were extracted by chlorination with FeCI2, An activated carbon was used as a de-oxidation reagent Metallic iron in the sludge was not chlorinated because the iron monochloride is not stable, The extracted rare earth chlorides were easily separated from Fe-alloy and the excess of FeCh by vacuum distillation, 96 % of neodymium and 94 % of dysprosium in the sludge were extraeted into chloride phase, By the vacuum distillation, a mixture of neodymium and dysprosium trichlorides of 99.2 % purity was recovered, On the other hand, the rare earth chlorides can be converted to the corresponding oxides by a pyrohydrolysis reaction accompanied by a formation of HCl gas, The HCI gas can chlorinate metallic iron to FeCh, Therefore, a new recycling process for rare earth magnet waste can be realized as a chlorine circulation type process. During the process, only carbon and water are consumed and there are no toxic pollutants, Moreover, the obtained rare earth oxide can be directly used as raw material in the conventional oxide electrolysis process,

Jan 1, 2003

By Mitsutaka Hino

The contents of gangue minerals, such as A1203, P205, 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 are 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 A1203, on the blast furnace operation, the dripping behavior of FetO-CaO-SiO2-AI2O3-MgO slag from the iron funnel, which simulated the micro-porosity in sinter ore, has been observed with the wide range of basicity, Al2O3, FetO 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 FetO content was less than 20mass% and the basicity was lower than 0.8, MgO lowered the hold-up even if the slag contained 10mass% Al2O3. Every slag hold-up showed the minimum at the basicity of less than unity on the conditions of constant FetO and A1203 contents. This trend became remarkable when the slag contained 2 mass% MgO.

Jan 1, 2003

By Peter Woodall, Paul Telford, Pengfu Tan

"Arsenic enters the Mount Isa copper circuit in the form of arsenic rich minerals in concentrates from both the Mount Isa and Ernest Henry copper mines. Arsenic is a volatile metal, and will partition in the copper smelter between smelter off gases, slag and anode. Most of the volatile arsenic will report to Isasmelt Electrostatic Precipitator (ESP) or Waste Heat Boiler dusts where it will form a re-circulating load within the smelter. ESP dust is produced at a rate of 15,000 - 20,000 t/y and is currently removed from the precipitator and leached in the new ESP Dust Recovery Plant to separate copper and arsenic from the ESP dust. This paper describes the laboratory test works of ESP dust leaching, neutralisation and cementation processes. The planttrial, commissioning and operation have been presented as well.1. IntroductionThe flue dusts generated in the process of copper smelting contain appreciable amounts of copper and other valuable metals including precious metals. These flue dusts also contain appreciable amounts of arsenic trioxide where arsenic occurs in the ore body. The copper smelters processing concentrates generate residuals, such as ESP dust, containing arsenic trioxide. ESP dust contains impurities such as arsenic and bismuth which are harmful to the copper refining process if they report to anode. These impurities are fumed off in the smelting process and report to the dust as arsenic and bismuth oxides.The content of arsenic in the feed of Mount Isa copper smelter is about 0.1 % to 0.4%. Arsenic is a volatile metal, and will partition in the copper smelter between off gases and anode. Most of the volatile arsenic reports to Electrostatic Precipitator (ESP) and Waste Heat Boiler dusts where it will form a re-circulating load within Mount Isa Copper Smelter. Unless arsenic is bled from the smelter circuit, it will build up to a point where both anode quality and smelter hygiene are adversely impacted."

Jan 1, 2011

By Leiting Shen

The thermodynamics of tungsten ore decomposition in mineral acid and alkaline solutions were studied. The published thermodynamic data of tungsten minerals were collected and assessed. The Gibbs energies of CaWO4 (−1538.43 kJ/mol), FeWO4 (−1053.91 kJ/mol), MnWO4 (−1206.08 kJ/mol), H2WO4 (−1003.92 kJ/ mol), and Na2WO4 (−1455.58 kJ/mol, aq) at 25 °C were adopted in the calculation using HSC software. The results show that CaWO4 is decomposed more readily in Na2CO3 solution than in NaOH,while FeWO4 andMnWO4 aremore reactive inNaOH solutions. Froma thermodynamic point of view, tungsten ore decomposes easily in acid solutions despite most ΔGo T increasing slightly with temperature. Oxidizing Fe2+ to Fe3+ in acidic solutions facilitates decomposition of FeWO4, and the reaction of CaWO4 in H2SO4 solution occurs more easily than in other mineral acids, due to the formation of sparsely soluble CaSO4. The results fit well with the experimental data and industrial experience previously reported in the literature.

By I. Gaballah

The kinetics of oxychlorination of pure CI-2O3 with C12+02 gas mixtures is studied by ThermoGravimetric Analysis (TGA) in non and isothermal conditions up to 1000 °C. The reaction of Cr2O3 with C12+O2 chlorination gas mixtures starts at about 550 °C and the reaction product is CrO2Cl2. The oxychlorination rate of Cr2O3 is almost proportional to the chlorine partial pressure and to the fourth root of the oxygen partial pressure in the chlorinating gas mixtures. At 800 °C, the maximum chlorination rate is obtained using a gas mixture having a C12/O2 ratio equal to 4. The apparent activation energy of the oxychlorination reaction of Cr2O3 is 87 and 46 kJ/mol at temperatures lower and higher than 650 °C, respectively. By varying the chlorine and the oxygen partial pressures of the oxychlorinating gas mixtures at temperatures higher than 550 °C, it is possible to extract selectively the chromium chlorinated compounds from the chromium bearing materials. a. Laboratoire Environnemem et Minéralurgie, BP 40, 54501 Vandceuvre, France, b. École Nationale Supérieure de Géologie, Rue du Doyen Marcel Rouhault, 54501 Vandoeuvre Cedex, France, c. Centre National de la Recherche Scientifique, 3 rue Michel - Ange, 75794 Paris Cedex, France, d. Insritut National Polytechnigne do Lorraine, Rue de la Font de Haye. 54501 Vandceuvre Cedex, France.

Jan 1, 1997

By I. Gaballah

Jarosite contains up to 15 % of heavy metal compounds 'HMC'. The current waste disposal methods will not be allowed in the near future due to new environmental regulations and pollution risks. For these reasons, thermal treatments of raw or decomposed jarosite, in controlled atmospheres, were investigated. The aim of these treatments is to decontaminate the jarosite and/ or to recover the HMC for recycling. According to physico-chemical characteristics of the samples, the thermal treatments in controlled atmospheres N2, CO+N2 and C12+air lead to the extraction rate that vary from 93 to 98 %. Heavy metal compounds were separated by cooling the gaseous phase. The treatments' residue was almost free from HMC. Between 700 "C and 800 "C, the chlorinating treatment was successful of eliminating more than 97 % of HMC contained in four different samples.

Jan 1, 1999

By P. F. Kerr

This is not a conventional professional paper. It deals mostly with personal experiences. These concern a background in applied mineralogy. Your committee asked me to do this. I accepted with a California enthusiasm which has since diminished with the approach of a Chicago winter. Nevertheless, I wish to thank your committee and also to apologize in advance for omissions and inadequate statements, as such a paper must possess. My introduction to applied mineralogy took place in 1922 at Stanford University. Physicists had recently demonstrated that crystalline powders would reflect x-rays in a systematic manner. Professor A.F. Rogers sug¬gested that significant x-ray reflections might be obtained from powdered opaque minerals. With the aid of Professor D.L. Webster in the Physics Department, I constructed an x-ray diffraction outfit. It was a crude affair, but it worked. Starting with 1924, we secured recognizable patterns of a goodly number of ore minerals (1,2,3). Today x-ray diffraction outfits are common, and a card system of mineral identification is constantly used.

Jan 1, 1981

By Alicia Esther Ares

This study was conducted to investigate the directional solidification of Zn-20%A1 and Zn20% A1-1O%Si-3o/oCu alloys under different conditions of heat transfer at the metal/mould interface. The type of structure obtained in both cases was analyzed and related to the solidification thermal parameters such as cooling rate, growth rate, thermal gradient and recalescence which were determined from the temperature versus time curves. These parameters were correlated with the structure-like length of columnar grains and size of equiaxed grains. The metallographic analyses were done performing quantitative metallography and composition analysis of the different alloying elements along the cast samples by SEM (Scanning Electron Microscopy) and EDXA (Energy Dispersive X-Ray Analysis). Correlations between properties, structures and thermal parameters were found.

Jan 1, 2008

Cuspidine (3CaO?2SiO2?CaF2) is one of the most important compounds crystallized in mold flux films during casting in the continuous casting process of steel. The primary crystallization field of cuspidine has been experimentally developed in the CaO-SiOrCaF2-SiF4 system. The cuspidine-NaF binary and cuspidine-CaF2-NaF ternary systems have been also experimentally determined to study effects of addition of NaF on the primary field of cuspidine. In order to discuss its thermodynamic stability the standard Gibbs energy of formation of cuspidine has been determined by an electromotive force method using CaF2 as solid electrolyte and a transpiration method as follows: The chemical potential diagram and constituent activities for the CaO-Si02-CaF2 system have been evaluated based on the obtained thermodynamic data.

Jan 1, 2003

By Tina Maniatis

Applied Biosciences has developed a biological technology for removal of arsenic, nitrate, selenium, and other metals from mining and industrial waste waters.The ABMet® technology was implemented at a closed gold mine site in Canada for removing arsenic from tailings pond water. The system included six bioreactors that began treating water in the spring of 2004. Design criteria incorporated a maximum flow of 567 L/min (150 gallons per minute) and water temperatures ranging from 10°C to 15°C. Influent arsenic concentrations range from 0.5 mg/L to 1.5 mg/L. The ABMet® technology consistently removes arsenic to below detection limits (0.02 mg/L). Data from the full scale system will be presented, as well as regulatory requirements and site specific challenges. Keywords: Arsenic, Sulfate Reduction, Metal Sulfide Precipitate, Biological Water Treatment

Jan 1, 2005

By George E. Cook, Peter C. Levick, Francis M. Wells

"Relationships are established between the peak current of a pulsed, rectangular current waveform and the pulse current duty cycle under conditions of constant arc power. By appropriate choice of these interrelated parameters, it is shown that the arc pressure may be varied over a wide range even though the arc power is held constant. The methodology is suggested as a means of countering the effect of gravity in 5-G welding, while maintaining constant heat input to the weld. Combined with appropriate penetration sensors, the methodology is additionally suggested as a means of controlling penetration. IntroductionBoth low frequency pulsation (typically 0.1 - 20 Hz) and high frequency pulsation (> 100 Hz) are often used with GTA welding. Benefits derived from pulsing include improved weld quality and better process control.Advantages cited for low frequency pulsation include claims that the total heat input to the weld is reduced, the weld bead size is reduced, weld penetration is increased, grain size is reduced, porosity is reduced, weld distortion is reduced, thinner materials can be welded successfully, and the tolerance of the welding process to material and production variations is improved (1-16). With respect to the latter, pulsing aids control of weld bead penetration by increasing the tolerance to component dimensions and joint fit-up. It also reduces the sensitivity to disparities in heat sink, and it helps to reduce distortion in thin section material or distortion attributable to poor clamping. In certain materials it can reduce the sensitivity to surface oxides and to cast to cast compositional variations (16). Low frequency pulsation is also useful in welding thick materials mated by a prepared groove. In these applications the low frequency pulsation is used to obtain proper sidewall fusion as the tungsten electrode is weaved from one side of the groove to the other. In this case the weld current pulsation is synchronized with the cross seam weave pattern, such that the high current pulses occur at each sidewall. This type of low frequency pulsation has proven particularly useful in welding with narrow width groove designs (17-21). Finally, Ecer (22) has shown that the pulsed current arc is more stable against magnetic disturbances than an equivalent constant current arc."

Jan 1, 1986

By L. R. Verney

A number of interrelated factors influence the economics of the sulphide smelting of copper, lead, zinc and nickel. This paper discusses these factors, mainly from a US point of view, and shows how they affect the cost of construction and operation of new and existing plants. The paper shows how metallurgical plant construction costs and the consumer price index have increased at a much faster rate than metal prices thereby making some metal mining and production operations within the USA, Canada and the EEC less profitable than operations elsewhere. This in turn inhibits new "grass roots" metallurgical developments. It is explained how retrofit of existing pyrometallurgical plants can be a more viable development than the construction of "green field" plants, especially if such retrofit improves, energy efficiencies, overall operating costs and reduces emissions of sulphur and other toxic wastes. Some aspects of metallurgical plant operation are examined, especially for copper and nickel, to show how changes in operating practices may develop in order to improve overall smelting economies, especially when developed in conjunction with objective retrofit. The paper also examines some financial aspects, especially insofar as the disparity between terms for loans offered to third world countries and the USA and the EEC are concerned and also comments upon the need, especially within the USA, for legislation to permit rapid depreciation of capital. Specific comments are made about environmental aspects, including the lack of uniformity of pollution control legislation and how environmental considerations may have some bearing of the location of future smelting operations.

Jan 1, 1983

By J. N. Hartley

Samples of ash from the May 18, 1980, eruption of Mt. St. Helens Were collected from several locations in eastern Washington and Montana. The optical microscope and the combined scanning electron microscope with energy dispersive x-ray microprobe were used to determine the composition and mineralogical characteristics of the samples. In addition, a quantitative image analyzer was used to examine the particle size distribution, and x-ray diffraction was used to identify major minerals. Both polished sections and ultra thin sections (less than 5 ~m in thickness) were prepared to study the mineralogical characteristics. The use of ultra thin sections provided access to microstructural detail. Mineralogically, the samples ranged from almost totally glassy to almost totally crystalline. Crystal-line samples were dominated by plagioclase feldspar (andesine) and ortho-pyroxene (hypersthene) with smaller amounts of titaniferous magnetite and hornblende. Nearly all the samples contained from less than 1 to 3 wt% free crystalline silica (quartz, trydimite, or cristobalite).

Jan 1, 1981