Search Documents

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 Baozhong Ma, Yonggang Wei, Shiwei Zhou, Bo Li, Chengyan Wang, Hua Wang

The effects of additives with Na2S, Na2SO4 and CaSO4 on phase transformation of nickel laterite ore in low-temperature reduction roasting process using carbon monoxide were investigated. The results showed that diffraction peaks of forsterite increased with increasing reduction temperature for 30min with the addition of 10wt% Na2SO4 and 50vol% CO, and diffraction peaks of forsterite increased with increasing the content of Na2SO4 at 900°C for 30min. Comparing the above three additives, phase transformation of nickel laterite ore were strongly influenced with the addition of 10 wt% Na2SO4 and 10 wt% Na2S. Calcium sulphide from the thermal decomposition of CaSO4 was carried out in the reaction product. SEM-EDS analysis result deduced that increasing the dosage of Na2SO4 from 10wt% to 15wt% could promote the polymerization of ferronickel and improve the grade of nickel in ferronickel.

Jan 1, 2015

By Bradley C. Bockrath

Some thirty coals were evaluated for liquefaction activity under a mixture of CO and H2 at 425° C. The viscosity of the liquid products was taken as an indicator of the degree of liquefaction. It was found that the direct liquefaction of a particular coal may be beneficially influenced by the presence of pyrite. Active pyrites are often found in the native mineral matter of the coal itself. For example, subbituminous and bituminous coals and lignites of relatively high pyrite content were found to liquefy more readily than similar coals or lignites which were poor in pyrite. The reactivity of inactive coals could be improved by using blends with active, pyrite-rich coals. In addition, pyrite was effective when added separately as pyrite concentrates obtained from coal beneficiation operations. Various other iron- and sulfur-bearing additives were also effective when used in combination as added slurry-phase catalysts, including iron oxides and mineral residues derived from liquefaction of active coals. Under liquefaction conditions, pyrrhotite ( Fe I- x5) is formed from pyrite or from the iron oxides and many sulfur containing species. Pyrrhotite was shown to be a hydrogenation/dehydrogenation catalyst for tetralin but is not active for initiating a variety of free radical reactions that do occur when pyrite is heated with tetralin. The role of pyrite in coal liquefaction is complex and still not well understood.

Jan 1, 1981

By Takashi Ikeda, Masafumi Maeda

"Demand for solar cells is increasing linearly throughout the world. Last year production totaled 3000 tons worldwide. The market size of solar silicon is expected to increase further because of international ""political"" demand to reduce carbonaceous emission from energy consumed. Most elemental silicon is produced by the carbon reduction of Silica in an electric arc furnace. Purity of silicon at this stage is 90-99%. Major impurities are Fe, Ti, Ca· and Al, and minor ones are P, B and carbon. The oxidizing metallurgical process is no longer effective to remove transitfon metals because those are less noble to silicon. Nonmetallic impurities such as phosphorus and boron must be reduced to 0.001ppm for semiconductor use. The most common process for high purity silicon is the Siemens C process, which is basically distillation of hydro-chlorinated silicon followed by CVD of SiHCl3. The cost of such silicon is expensive to allow its popular use in solar cells. Currently scrap silicon -of semiconductors is used for this; however, the supply-of that scrap is limited to just a portion of semiconductor production.In this paper world demand for silicon will be reviewed and some of the processes proposed summarized.IntroductionSilicon is element 14 in atomic number and has an atomic weight of 28.0855. Little elemental silicon is found in the earth, and it is mostly found as oxides or silicate. The Clark number of silicon is very large and the second in its number. If we were discussing the volatility of silicon element on the globe, we would never worry about it. However, it is very difficult to obtain pure elemental silicon because a high purity silicon compound is very rare. In most cases these are silica (silicon oxide SiO2). As shown in Table 1, there are many grades of silica ore classified mainly by their content of iron and alumina."

Jan 1, 2000

By Faustino G. Prado

In the, quest for an economical and environmentally friendly reclamation of metallurgical dusts generated during pyrometallurgical operations, our goal has been the separation and recovery of most of the components, as well as the complete recycle of all the reagents. Effluents have been avoided, within acceptable economic parameters. This presentation, which can be applied to a large spectrum of dusts and other residual-materials-, has focused on the dusts generated by the operation of Secondary Copper Smelters. Those dusts show a wide range of components, including zinc, lead-, copper, cadmium, tin, chlorine and-alkalies. Our present work deals with the use of ammonium salts in the separation and recovery of-the above mentioned elements in a marketable form. Most of the chemistry and techniques involved have teen already confirmed in commercial scale operations. Others have gone through pilot scale tests or bench scale tests. The recycle of reagents has also been- confirmed at the same operating levels. A preliminary evaluation indicates that the chosen route, in addition to a viable economy, offers a complete and safe reclamation within the most strict environmental regulations.

Jan 1, 1995

By Michael A. Lllga

Electrically Switched Ion Exchange (ESIX) is an approach for ion separation that combines Ion exchange (IX) and electrochemistry by utilizing electro active IX films to provide a selective, reversible, and economical separation method that greatly reduces secondary waste generation compared with conventional ion exchange. Studies on the development of films with improved stability and capacity and their use in continuous flow systems for ion separations will be. reported. Both technical and economic evaluations demonstrate ,the viability of once-through or batch recycle waste processing with ESIX.

Jan 1, 1999

By Kuniaki Murase, Tetsuji Hirato, Koji Nitta, Yasuhiro Awakura

"The redox behavior of copper species in an ""ammonium imide"" room temperature molten salt was examined in order to clarify the applicability of the salt to the electroplating media of various metals. Trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)- amide (TMHA-Tf2N), having an electrochemical window of 5.6 V (50 °C), and corresponding copper(II) salt were synthesized. In TMHA-Tf2N media monovalent copper ion, Cu(I), was stable and Cu metal was oxidized, or corroded, in the presence of Cu(II) species. Cathodic electrodeposition of copper metal and anodic dissolution of it were, thus, one-electron reaction and their current efficiencies were almost 100%.IntroductionElectrodeposition of metals from aqueous solutions is an important soft process for manufacturing thin-film materials, surface finishing, and extractive metallurgy. However, the electrodeposition of base metals, such as zinc, chromium, and nickel, from aqueous media inevitably accompanies hydrogen evolution, which lowers the cathodic current efficiency of metal deposition. Since the electrodeposition of aluminium, titanium, and rare earths from aqueous media is actually impossible due to their largely negative redox potentials, nonaqueous media such as aprotic organic solvent and high-temperature molten salts have been employed for the electrodeposition of these metals. Room temperature molten salts (RTMS),1, 2) or room temperature ionic liquids, have also been developed as a promising electrolytes for the electrodeposition of base metals. In this field, chloroaluminates of alkylpyridinium or alkylimidazolium cation have been well investigated for aluminium3) or alluminium-alloy4-5) electroplating media. On the other hand, in order to avoid high hygroscopicity arising from the use of aluminium chloride, attempts have been made to combine the alkylimidazolium cations with fluorine-containing hydrophobic anions, e.g. BF4-,6) CF3SO3- (TfO-),7) (CF3SO2)2N- (Tf2N-),8) and H(HF)n-ions,9) and investigated for electrodeposition media.'°) Recently, a new series of RTMS consisting of tetraalkylammonium cations and Tf2N- anion, sometimes abbreviated as TFSI- anion, was found independently by MacFarlane et al.11, 12) and Matsumoto et al. 13) This type of RTMS, which is commonly named ""ammoniumimide"" salt, has a wide electrochemical window of ca. 5 V and, thus, the RTMS seems to be suited for practical application as a solvent for the electrodeposition process. In this paper, we report the electrochemical behavior of copper species in an ammoniumimide RTMS, trimethyl-n-hexylammonium bis(trifluoromethanesulfonyl)amide (TMHA-Tf2N)."

Jan 1, 2000

By Shuqiang Guo, Xionggang Lu, Yuyang Bian, Weizhong Ding, Lan Jiang, Kai Tang, Changyuan Lu

For recovery of rare earth elements from the NdFeB based permanent magnet scraps, a high temperature process was used. Permanent magnets scraps were firstly oxidized in air. The optimal oxidation conditions under air are at temperature of 700oC holding for 30min. After the oxidation process, the oxides were reduced by graphite crucible at 1500oC under Ar atmosphere. By this way, the rare earth elements were recovered in the form of oxides, and Fe was separated to the metal phase. Boron distributed in both the rare earth oxides (REO) containing slag and the metal phase. In order to reduce the boron contents in the rare earth oxides, the carbon saturated iron bath and NdFeB added carbon saturated iron bath were used to refine the slag. By this process, the rare earth oxides with a comparatively high purity of 98.2% were gotten.

Jan 1, 2015

By Jiang Feng, Zhang Libo, Peng Jinhui, Guo Zhanyong, Ju Shaohua, Lei Ting

The clean utilization of the residue containing chloride, CuCl residue, produced from zinc hydrometallurgy is very important for the recycle of valuable metals. And drying is the main process in recycling. In this study, response surface methodology was used to optimize operating conditions of the drying of CuCl residue in a convection oven and desirability function used as the methodology for the optimization. Optimization factors were air temperature (80–100°C), material thickness (10–25mm) and process time (80–120min) while investigated responses was final moisture content. The optimum conditions were found to be the temperature of 95.48°C with the material thickness of 13.47mm for the process time of 89.48 min. Under optimum conditions, the predicted moisture content of CuCl residue was 4.11% while the experimental date was 4.13%. The experimental value after process optimization was found to agree satisfactory with the predicted value. After drying, XRD was used to analyze the main phases of CuCl residue. The CuCl residue is made up of CuCl,Cu2O, ZnS and other compounds.

Jan 1, 2015

By R. E. Burleigh

'Gold-telluride mineralization was deposited in quartz veins which cut a Late Cretaceous tonalite pluton emplaced near the southern margin of the Peninsular tectono-stratigraphic terrane in south-central Alaska. The gold-bearing veins formed shortly after the development of a widespread Cu-Mo sheeted quartz vein system. Early mineral assemblages consist of quartz, white mica, pyrite, and arsenopyrite (wall rock only). Subsequently, pyrite. sphalerite, chalcopyrite, zoned tetrahedrite and gold precipitated within multiply fractured veins. Late stage galena, tellurides (altaite, nagyagite, coloradoite), and Pb-Sb or Pb-Cu-Bi sulfosalta with gold constitute bonanza ore assemblages that are variably associated with quartz, white mica, ankerite, and calcite. Fluid inclusion evidence coupled with mineral assemblage paragenesis suggests the depletion of volatiles (C02, H2S) and cooling resulted in the precipitation of high grade gold mineral assemblages.

Jan 1, 1988

By J. A. Gonzalez-Dominguez

During the electrorefining of lead by the Betts process, ionic concentration gradients become established within the slimes layer. These gradients contribute to precipitation of secondary products and to gradients in electrode potential applied to slimes filaments, and thereby affect the dissolution of noble impurities. This paper describes the experimental results obtained when a typical lead anode was dissolved under galvanostatic conditions with concurrent interruption of current at preset slimes thicknesses. Reference electrodes were incorporated within the lead anode to follow the potential gradients across the slimes electrolyte. Samples of the slimes electrolyte were withdrawn in-situ and their compositional changes were related to transport processes across the slimes layer. Upon current interruption the anodic overpotential decays, first abruptly (as the uncompensated ohmic drop disappears), and then slowly (due to the presence of a back E.M.F. created by ionic concentration gradients that decay slowly). Current interruption measurements showed that: (A) concentration gradients exist across the slimes layer, (B) inner solution potentials within the slimes layer can be larger than those measured from reference electrodes located in the bulk electrolyte, (C) secondary products can shift the inner solution potential to negative values that reverse upon re-dissolution and (D) ionic diffusion is seen upon current interruption but it is complex and difficult to model due to the presence of processes that can support the passage of internal currents. SEM and X-ray diffraction analysis of the slimes filaments indicated that secondary reactions leading to the formation of Si02 and PbF2 take place (mainly at the anodelslimes interface). The onset of these reactions and their relationship to the Pb-F-Si-H20 Eh-pH diagram are linked to the industrial operation of the Betts process.

Jan 1, 1994

By W. Petruk

A study was performed to determine whether mineral textures affect are breakage during grinding, and to establish a correlation between are breakage and mineral liberation. A base metal are from the Brunswick No. 12 deposit in New Brunswick, Canada was ground for different periods of time in a laboratory ball mill, and both the unbroken are and the ground products were studied by image analysis. Similar size distributions were obtained for material from the 15-minute grind in a laboratory ball mill (K. 0 67 pm), for the grinding circuit discharge from a commercial mill (K. 0 = 59-72 pm), and for pyrite grains in unbroken are (K,. = 74 pm). This similarity indicates that the 1S-minute grind separated weakly adhering pyrite grains along grain boundaries, and represents the limit of easy breakage for the are. At this grind (15 minutes) large discrete are mineral grains and weakly adhering interstitial fillings aIrong pyrite were liberated. On the other hand, the 15-minute grind neither separated rooderately bonded pyrite grains nor released rooderate1y bonded interstitial minerals from pyritei a 45-minute grind (K.. 31 pm) in a laboratory ball mill was required. For Brunswick No. 12 are, a 45-minute grind in a laboratory ball mill (Keo = 31 pm) is equivalent to regrinding in a commercial mill (K ?? Fl:$ 30 pm). Grinding beyond 45 minutes in the laboratory ball mill broke the are by fracturing pyrite across grain boundaries and by Chipping grain edges. Such intense grinding (longer than 45 minutes) did not markedly increase sphalerite liberation. In contrast, the intense grinding increased galena liberation because a significant proportion of the galena occurs as minute inclusions in pyrite. These findings show that ore breakage and coincident liberation depend upon size distributions, intergrowths, and mode of occurrence of the minerals in an ore.

Jan 1, 1988

By G. L. Peralta

Geothermal energy is an important source of power in more than 12 countries and is a potential source in 50 countries. However, the exploration and use of geothermal resources generate residues such as scale and sludge. The scale is from the steam distribution pipes while the sludge is from cooling ponds. These solids contain significant levels of elements which are of environmental importance notably, arsenic, sulfur, copper, zinc and lead that require safe treatment and disposal. The compositions, phases, textures, morphologies and size of scale and sludge particles have been studied by laser particle size analysis, light microscopy, scanning electron microscopy, X-ray microanalysis, and X-ray diffraction. In addition, their leachability was tested with protocol leaching procedures and sequential extractions. The detailed spatial relationships and speciation of the environmentally significant constituents have received particular emphasis. The information obtained is useful in understanding how the scale and sludge are formed, their leaching behavior if disposed of in a landfill and in developing appropriate treatment strategies.

Jan 1, 1994

By Joseph Goodwill

1. PURPOSE The objective of this paper is to summarize a study undertaken by the EPRI Center for Metals Production (CMP). The overall purpose of the study was to identify electrolytic opportunities that might merit consideration for joint development by industry and EPRI. 2. SCOPE The electrolytic technologies of interest to this study include: Electrorefining, Electrowinning, and Fused-salt electrolysis. Recovery from primary, secondary, and waste materials were included in this effort; however, we excluded from consideration: Plating and coating operations, such as electrogalvanizing; Mining and milling operations in which electric energy is predominantly used for comminution; Electrothermal processes in which submerged-arc, open electric-arc, and plasma-based smelting processes use electric energy largely to provide a melting or refining ("heating") capability; and Aluminum electrotechnologies since these were the subject of a separate study (CMP 86-2). We recognize that there may be some "gray areas" between these excluded areas and the electrolytic sectors of interest. For this reason, a secondary criterium was used, namely, if the major use of electric energy was to extract or refine the

Jan 1, 1990

By Z. W. Zhang, Songsong Xu, Jinhui Li, Yun Zou, Yu Zhao

High strength low alloy (HSLA) steels with high strength, high toughness, good corrosion resistance and weldability, can be widely used in shipbuilding, automobile, construction, bridging industry, etc. The microstructure evolution and mechanical properties can be influenced by thermomechanical processing. In this study, themomechanical processing is optimized to control the matrix microstructure and nano-scale precipitates in the matrix simultaneously. It is found that the low-temperature toughness and ductility of the steels are significantly the matrix microstructure during enhancing the strength by introducing the nano-scale precipitates. The effects of alloying elements on the microstructure evolution and nano-scale precipitation are also discussed.

Jan 1, 2016

The high pressure acid leach process (HPAL) is being commercially used in four plants around the world to treat limonitic laterites. The two major operating costs of the HPAL process are the sulphuric acid and the energy required to heat the pulp to the desired temperature (>240°C). As an alternative to acid injection and steam heating, the in-situ generation of sulphuric acid and heat, produced during the high temperature pressure oxidation of sulphur-bearing materials blended with laterites, has been investigated at the laboratory scale. Various sources of sulphur have been examined, in particular, elemental sulphur, pyrrhotite and a Cu-Ni low-grade bulk concentrate. Under the proper blend ratios, all sulphur sources tested generated sufficient acid to result in equivalent nickel and cobalt dissolutions. A significant improvement to the process economics can result from the addition of sulphur sources containing valuable by-products, such as nickellcobalt andlor precious metals (gold and PGMs). This is especially true in the latter case, when the HPAL can be operated under Platsol conditions (i.e. with the addition of 5-10g/L of chloride), to dissolve the base metals and precious metals simultaneously in the autoclave. Various examples of the application of this concept are presented, together with a brief discussion of its implication on the autoclave design and the downstream processes to recover the values from the leach solutions. Keywords: limonite, co-treatment, acid consumption, sulphur, sulphur compounds, pressure acid leach (HPAL, PAL), Platsol process

Jan 1, 2004

By Augusto Viana Leandro Teixeira

Rare Earth Elements (REE) are fundamental for modern life products and green technologies. Supply constraints and the price peak of 2011 boosted intensive research for alternatives for processing and separation. Complex monazite- type, rare earth ores usually contain high acid consumption impurities, such as iron and aluminum, and radioactive thorium in their composition. These impurities are not removed by conventional concentration processes due to fine, micro-level association between the REE carrying minerals and the gangue minerals. This work presents a selective process route for REE extraction from iron-rich, monazite ores. The process involves sulfation by addition of concentrated sulfuric acid and pyrohydrolysis at temperatures of approximately 700–750 °C. Experimental results show REE extraction higher than 70% and low iron (below 5%) and thorium extraction (below 10%). A method based on thermogravimetric analyses was shown to be adequate to predict the behavior of a given ore sample in the sulfationselective pyrolysis-leaching process.

By Makoto Ohlsuka

The ternary Ni2MnGa intermetallic compound is an intelligent material which has both a ferromagnetic property and a shape memory effect (SME). The use of the shape memory alloy films for an actuator of micro-machines is very attractive because of its large recovery force. The purpose of the present study is to investigate the effects of fabrication conditions and to clarify the relationships between these properties and fabrication conditions of the Ni-Mn-Ga films. The Ni-Mn-Ga films with a thickness of nearly 5 um were deposited with a radio-frequency magnetron sputtering apparatus using a Ni50Mn25Ga25 or Ni52Mn24Ga24 target. They were heat-treated at various temperatures between 873 and 1273 K for homogenization and ordering and then cooled in a furnace. The composition of the films depended on the sputtering power. The as-deposited films were crystalline and had columnar grains. After the heat treatment the grains widened and the grain boundary became indistinct with the increasing heat treatment temperature. The martensitic transformation temperature of the heat-treated films increased with increasing nickel content. Furthermore the effect of plastic deformation and constraint aging on SME is also investigated. After plastic deformation, the two-way SME was shown through the martensitie transformation and its reversion, The intensity of X-ray diffraction peaks from stress-induced martensitie phase was found. The constraint-aged films also showed the two-way 3ME by thermal cycling.

Jan 1, 2003

By Jiang Feng, Li Chuanhua, Zhang Libo, Peng Jinhui, Ju Shaohua

Solvent extraction of Cu2+ from the leaching liquor contain Cu and Fe use a microfluidic technology. Currently, the conventional copper extraction process has many problems such as long distance and small driving force of mass transfer. In order to solve the problems, studies are carried out on the extraction process of low grade copper leaching liquid using Lix984N as an extractant with a new microfluidic solvent extraction technology. The effects of flow rate on the separation and extraction efficiency between Cu and Fe are studied, and the results show that a steady liquid-liquid interface of laminar flow is form in the micro-extractor, and extraction efficiency is 78 % and 2.5 % for Cu and Fe at the contact times of 0.84s respectively. Besides, the separation coefficient between Cu and Fe is as high as 140.04. The studied microfluidic technology has the advantages like improving extraction efficiency and reducing reaction time and providing the potential application in the hydrometallurgy extraction of Cu.

Jan 1, 2015

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