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By Hiroaki Kawamura, Takeshi Yoshikawa, Kazuki Morita, Yutaka Yanaba

"To develop an alternative metallurgical process for phosphorus removal in the production of solar-grade silicon (SOG-Si), slag treatment of metallurgical-grade silicon (MG-Si) was conducted, followed by acid leaching. Phosphorus-doped silicon alloy or MG-Si containing certain amounts of phosphorus and calcium was reacted at 1723 K and 1773 K with CaO--CaF2 of several compositions. Phosphorus removal from the molten silicon into the slag phase was confirmed by reduction to phosphide ions, P3-, and phosphate ions, P3-. These ions were separately determined using a wet chemical analysis method developed by ourselves. The highest phosphorus distribution ratio obtained was 2. 7 after reaction for 18 h with 17.5 mass% CaO--CaF2 slag. We then conducted acid leaching of the silicon and achieved removal of a large fraction (over 90 % ) of the phosphorus, which was much higher than that obtained by ordinary oxidizing slag treatment.IntroductionIn recent years, the production of solar cells has been increasing rapidly. Because of this, the demand for solar-grade silicon (SOG-Si) has also been growing rapidly. The development of lower-cost mass production processes is therefore needed to provide silicon feedstock. Phosphorus is one of the impurities in metallurgical-grade silicon (MG-Si). Because of its large segregation coefficient (kp = 0.35) [l ], it is difficult to remove phosphorus using a solidification refining process. Vacuum melting is considered to be a promising method for removing phosphorous from MG-Si [2], but the issues of high cost and large energy consumption have still to be resolved.Slag treatment is often used to remove impurity elements by oxidizing reactions during general oxidation refining processes. For example, phosphorus in molten steel is removed into a slag phase as phosphate ions, PO4 3-l-, by the following reaction:"

Jan 1, 2013

By Jeffrey W. Braithwaite

The laboratory characterization of the oxidation of chalcopyrite under conditions of deep solution mining is presented in this paper. A salient feature of this system is the pH buffering effect resulting from simultaneous acid producing and acid consuming oxidation reactions. The solution chemistry and related sulfur partitioning of the oxidation reactions are detailed. The contribution of temperature, acid concentration, oxygen pressure, particle size, and solution additions to the kinetics of copper extraction are presented. A mixed kinetic model was used to describe the kinetics of oxidation.

Jan 1, 1976

By E. Fockedey

he destruction of free cyanide on a Co3O4 doped carbon felt was studied. The experiments were done with an eiectrochemical filter press cell on dilute alkaline solutions containing 250 mg/l NaCN. No chloride ions were added to the solutions. The cobalt oxide protects the felt against corrosion and has a catalytic effect on the degradation of the cyanide. This kind of electrode allows working with current density as high as 1200 Aim without any visible degradation of the felt. The most interesting results were obtained with a current density of 400 Aim' at which the cyanide concentration can be lowered to 5 mg/l with a current efficiency of more than 70 % and a specific energy consumption of about 10 kWh/ kg CN.

Jan 1, 1998

By Akira Kaneda, Nozomu Hasegawa

"In the Mitsubishi Continuous Copper Smelting and Converting Process, slag/matte mixture overflowed from the smelting furnace is separated continuously in an electric furnace (slag cleaning furnace, CL-furnace). In order to improve the separation efficiency of slag and matte and to minimize power consumption, the design and the operating conditions of the CL-fumace should be optimized. In the previous study, the authors developed a mathematical model for simulating phenomena in the CL-furnace. The model consisted of 3 modules, electric field analysis, heat and fluid flow analysis and the particle tracking method. In this study, the model was partially modified: k -E. model was adopted, and the effects of various conditions, such as furnace shape (including accretion) and scale, electrodes configuration, immersion depth of electrodes, and thickness of slag layer, were evaluated. And the optimum design and operating conditions were discussed.IntroductionUnder the recent environmental restriction, advantageous features of the Mitsubishi process have attracted much attention. The process uses 3 furnaces connected by launders. Mixture of matte and slag formed in a smelting furnace flows continuously to a slag cleaning furnace (CL-furnace), where the matte is separated from the slag. The matte is continuously siphoned out to a converting furnace and converted to blister copper. The slag overflowed from the CL-furnace is discarded. Because the slag contains about 0.6 % copper, improving slag/matte separation efficiency and decreasing copper loss make a great profit. Moreover the process requires a large amount of electric energy, so reduction of electric power consumption brings in enormous benefit.The objective of this study is to optimize the design and the operating conditions of the process, especially the CL-furnace. This will be achieved by developing the mathematical model and clarifying relations between the design or the operating conditions and various phenomena in the furnace. Fig. 1 shows an outline of the CL-furnace. The mixture entering through an inlet is separated to slag layer and matte layer . In order to maintain the temperature of the melt at a predetermined level, 6 electrodes are immersed into the lag and Joule's heat is generated by 3-phase alternating current flowing."

Jan 1, 2000

By K. Nona C. Liddell

There is a significant amount of early work that has been largely forgotten that deals with the validity of the pseudo-steady approximation for liquid-solid reactions. Much of this was originally published in the chemical engineering literature but is highly relevant to hydrometallurgical processes. The purpose of this paper is to summarize some criteria that were been developed by various authors for determining the error associated with use of shrinking core models for liquid-solid systems.

Jan 1, 2002

By R. S. Tahautdinov, A. N. Posazhennikov, V. V. Bastrygin

"The Bakal (South Ural, Russia) deposit of iron ore bearing iron carbonate (siderite) with the capacity of more than 1 billion tones belongs to the MMK. This ore cannot be fully processed via blast furnace technology because of high content of MgO. According to the investigations carried out in the USA and Japan in 1999-2004 the ITmk3 (Ironmaking Technology mark three) RHF technology is a breakthrough in Ironmaking. Four iron ore types (hematite, magnetite, high and low Al2O3/SiO2) were tested. Reduction, melting and slag removal can be achieved in just 10 min. The main objective of the investigation is to establish optimum operation conditions for the production of iron nuggets from iron carbonate bearing ore via the ITmk3 by means of the lab scale testing. Samples of iron ore and carbon reductant were chemically and physically analyzed. Green pellets were processed via a lab tube furnace to simulate RHF conditions. The nuggets and slag were chemically analyzed. This preliminary test work provides valuable information which may be used for large-scale testing in a commercially sized RHF.IntroductionThe ITmk3 process upon which this paper focuses was developed by Kobe Steel in its research facilities in 1996 [1]. After pilot testing at Kobe Steel’s Kakogava Works in 1999-2004 the pilot demonstration plant was built and operations were successfully carried out by Mesabi Nugget joint venture in 2002-2004. Steel Dynamics has committed to building the commercial plant at the Mesabi Nugget site in Hoyt Lakes (Minnesota). Only 4 iron ore types (hematite, magnetite, high Al2O3/SiO2 and low Al2O3/SiO2), as well as 4 coal types with range of volatility, ash and fixed carbon were tested. Results were consistent with nugget characteristics confirming ITmk3’s flexibility with respect to raw material inputs. At the same time, no research in the field of nugget from iron carbonate bearing ore with high content of MgO has been done. Such kind of iron ore is restricted for charging into the blast furnace due to contamination of MgO. The reason for restriction is the limitation of load of MgO in the blast furnace. If a lot of MgO enters the blast furnace, slag becomes viscous. The viscous slag is obstacle for stable operation of the blast furnace."

Jan 1, 2011

By E. V. Redin

"The Bakal (South Ural, Russia) deposit of iron ore bearing iron carbonate (siderite) with the capacity of more than 1 billion tones belongs to the MMK. This ore cannot be fully processed via blast furnace technology because of high content of MgO. According to the investigations carried out in the USA and Japan in 1999-2004 the ITmk3 (Ironmaking Technology mark three) RHF technology is a breakthrough in Ironmaking. Four iron ore types (hematite, magnetite, high and low Al2O3/SiO2) were tested. Reduction, melting and slag removal can be achieved in just 10 min. The main objective of the investigation is to establish optimum operation conditions for the production of iron nuggets from iron carbonate bearing ore via the ITmk3 by means of the lab scale testing. Green pellets were processed via a lab tube (chamber) furnace to simulate RHF conditions. This preliminary test work provides valuable information which may be used for large-scale testing in a commercially sized RHF.IntroductionThe ITmk3 process upon which this paper focuses was developed by Kobe Steel in its research facilities in 1996 [1]. After pilot testing at Kobe Steel’s Kakogava Works in 1999-2004 the pilot demonstration plant was built and operations were successfully carried out by Mesabi Nugget joint venture in 2002-2004. Steel Dynamics has committed to building the commercial plant at the Mesabi Nugget site in Hoyt Lakes (Minnesota). Only 4 iron ore types (hematite, magnetite, high Al2O3/SiO2 and low Al2O3/SiO2), as well as 4 coal types with range of volatility, ash and fixed carbon were tested. Results were consistent with nugget characteristics confirming ITmk3’s flexibility with respect to raw material inputs. At the same time, no research in the field of nugget from iron carbonate bearing ore with high content of MgO has been done. Such kind of iron ore is restricted for charging into the blast furnace due to contamination of MgO. The reason for restriction is the limitation of load of MgO in the blast furnace. If a lot of MgO enters the blast furnace, slag becomes viscous. The viscous slag is obstacle for stable operation of the blast furnace."

Jan 1, 2012

By J. van Driel

NOx is a growing concern for acid plant operators due to recent legislation reducing the allowable stack limits, as well as continually more stringent requirements for product acid quality. NOx also causes a major problem during maintenance as NOx rich acid residues fume following exposure to moisture in the air. Until recently, the solution for NOx related issues was to treat the symptom, rather than the cause. NOx in product acid was treated using chemicals and the NOx in the plant stack was generally left untreated. As part of an environmentally driven change in concentrates, Budel Zink installed the first gas phase NOx destruction process to be incorporated into a commercial scale acid plant. Nitrogen oxides contained in the process gas are reduced selectively with ammonia over a catalyst to form nitrogen and water. As a result, the NOx reduction is in agreement with the permit requirements.

Jan 1, 2002

By G. Diáz

The PLACID process applied to the recycling of spent lead-acid batteries is being developed by an European Consortium within the Brite-Euram II programme. The status of the project entitled "Lead Recovery from Lead Oxide Secondaries" is described in this paper. The main laboratory and batch experimental results and the preliminary feasibility study are summarised. The description of the demonstration pilot plant and continuous campaigns programme for 1995 are also included. An interesting global approach is proposed, integrating the Placid process in the existing spent battery recycling pyrometallurgical facilities. This yields important improvements in the overall process. Grids would be easily treated by the conventional pyrometallurgical route, obtaining lead alloys,, while battery pastes, slags and fumes would be fed to the Placid process, obtaining pure electrolytic lead (>99.99 %), ideal for battery paste manufacturing. The implementation of the Placid process into the existing battery recycling pyrometallurgical facilities is analyzed from technical, environmental and economical viewpoints. Greater overall lead recovery, lower operating costs, reduced waste production, environmentally safer residues and much better lead product quality are the key advantages. The authors draw the following final conclusion : Integration of the Placid process with conventional pyrometallurgical treatment is a feasible and very attractive alternative route for spent lead-acid battery recycling.

Jan 1, 1995

By Brajendra Mishra, Mark L. Strauss, Gerard P. Martins

Nearly the entire worldwide production of europium is recovered, as a minor constituent, from mining bastnäsite, monazite ore, or ion absorbing clays. However, this research indicates a process to recycle europium from waste lamp phosphors as a strategy meet the demand for europium. In this process, waste fluorescent lamp powder is retorted, sieved, leached, and precipitated to produce a mixed europium/yttrium rare earth oxide (REO). Europium is separated from yttrium by selectively reducing Eu(III) to Eu(II) using zinc powder and precipitating europium (II) sulfate from solution using sulfuric acid. Screening experiments were conducted observe the effect of pulp density, precipitation time, entrance pH, and stoichiometric ratio sulfate upon the grade and recovery of europium (II) sulfate. The best conditions to maximize grade and recovery of europium (II) sulfate were a 1 h precipitation time, 10 the stoichiometric ratio of sulfate, 100 g/L mixed REO, and the entrance pH equal to 3. The maximum grade of europium sulfate was 95.93%, and the maximum recovery was 73.32%.

Mar 1, 2018

By Egil Krystad, Merete Tangstad, Kai Tang, Gabriella Trenell

"A new UMG-Si refining concept has been proposed in this paper. Liquid Si and another liquid metal phase (Me) were separated by the molten slag spontaneously based on their different physicochemical properties. Two metal/slag distribution reactions are able to occur in the system simultaneously. Experimental investigation on the B and P distribution equilibria among Si/slag/Me was carried out in the graphite resistance furnace under the inert atmosphere. The B and P doped silicon was in equilibrium with either the SiO2-CaO or SiO2-CaO-l0%CaF2 slags at 1600 and 1650°C, respectively. The pure Fe and Cu metals were used in order to ""capture"" B and P in the slag phases. B and P in samples were determined by the ICP-MS. B and P distribution coefficients for the Si/slag/Me equilibria were compared with the theoretical calculations. The possible kinetic barriers for the Si/slag/Me three-layer equilibria have been analyzed. The metal contaminations in the three-layer equilibria were also examined. The present study provides a new approach for the refining of MG-Si.IntroductionMost of the impurities in the metallurgical silicon (MG-Si) are rather ""dilute'', ranging from few to several thousand ppms. However, the target impurity levels for upgrade metallurgical silicon (UMG-Si) feedstock are often far below the level of ppm. In such extreme case, the conventional refining technologies face the great technical challenges. B removal by slagging has already been implemented industrially. Removal of Pis frequently carried out by the vacuum distillation. The separating treatments for B and P removals lead to increase refining cost, total CO2 emission and longer pay-back time of solar cell module.It is well known that the phosphate capacities of slags in equilibrium with liquid silicon are extremely lower. However, if we introduce another phase that possesses high ""phosphor capacity"" into the Si/slag system, one would expect to continuously remove P from Si through molten slag to the new ""phosphor capturer"". The so-called three-layer refming concept is thus proposed in the present study. Liquid Si and another liquid phase (Me) are separated by the molten slag spontaneously based on their different physicochemical properties. Two metal/slag distribution reactions are able to occur in the system simultaneously."

Jan 1, 2013

By Rodney T. Jones

DC arc furnaces were first used industrially for the reductive smelting of chromite fines to produce ferrochromium thirty years ago. Since then, they have been used for a variety of applications, including the smelting of ilmenite to produce titania slag and pig iron, the recovery of cobalt from non-ferrous smelter slags, and the smelting of nickel laterite ores to produce ferronickel. The power of these furnaces has increased from 12 MW to 72 MW for ferrochromium, and to 80 MW for ferronickel. The largest of these furnaces requires two electrodes to carry sufficient current to generate this much power. A review is presented of various DC arc furnaces in use, along with a discussion of the likely ways in which furnace power might be increased further in the future.

Jan 1, 2014

By Manju Gurung, Birendra Babu Adhikari, Keisuke Ohto, Hidetaka Kawakita, Katsutoshi Inoue, Shafiq Alam

Novel bio-adsorbent gel was prepared by immobilizing functional groups of glycidyltrimethyl ammonium chloride, a kind of quaternary ammonium chloride, onto polymer matrices of persimmon extract for the recovery of precious metals such as palladium(II) and platinum(IV) from chloride media. It was found that this adsorption gel exhibits high selectivity to gold(III), palladium(II) and platinum(IV) over base metals such as copper(II) and iron(III) while crude persimmon extract, the feed material, exhibits high selectivity only for gold(III). From the adsorption isotherms study, the maximum adsorption capacities for gold(III), palladium(II) and platinum(IV) were evaluated as 3.30, 1.67 and 1.00 mol/kg, respectively. Those for palladium(II) and platinum(IV) are higher than those of simple quaternary ammonium chloride type of chemically modified persimmon tannin gel and commercially available anion exchange resin.

Jan 1, 2016

By A. Erçin Ersundu

In the present work, three different domestic iron ores; Sivas Divrigi B Head high grade hematite lump ore, Malatya-Hekimhan-Hasançelebi medium and low grade magnetite lump ores reduced with Soma-Kisrakdere lignite coal to investigate their suitability for sponge iron production. A laboratory scale box furnace was used to carry out the reduction experiments. In the experimental studies different operation parameters were selected being Cfix/Fetot. ratio, temperature in the range of 1100 - 1250 oC and time, to determine their effects on metallization. Metallization degree up to 90 % was found in the reduction experiments realized by using Sivas Divrigi B Head high grade hematite lump ore, whereas for Malatya-Hekimhan-Hasançelebi medium and low grade magnetite lump ores 60 - 65 % metallization degrees were obtained.

Jan 1, 2008

By M. Vijayalakshmi, S. Saroja, C. Sudha, T. N. Prasanthi

"Ti-5Ta-2Nb alloy and 304L austenitic stainless steel were joined by explosive cladding process. Investigations on 'as received' explosive clad revealed high hardness very near the interface due to martensitic transformation of 304L steel base plate. To improve ductility, explosive clads were heat treated in the temperature range of 823 to 1073 K for 1 to 20 h. Consequent change in the microstructure and microchemistry of the clad interface was studied. No change in the interface microstructure was observed for heat treatment at 823 K. Increase in temperature lead to the formation of various reaction zones at the interface, their number and width increase with temperature and time of thermal exposure. Growth kinetics of the reaction zones was monitored and activation energy required for formation was calculated. From elemental redistribution profiles, effective inter-diffusivities of alloying elements were calculated as a function of concentration and activation energy required for inter-diffusion was evaluated.IntroductionFor engineering components exposed to highly oxidizing and corrosive environments, a titanium based alloy i.e Ti-5Ta-2Nb (Ti-Ta-Nb) is often chosen as a structural material [1,2]. For economic consideration, vessels and piping exposed to non-oxidizing conditions are fabricated from 304L austenitic stainless steel (304L SS). Hence, dissimilar joint of Ti-5Ta-2Nb alloy and austenitic stainless steel becomes unavoidable. Fusion welding processes are not suitable for joining Ti and Fe based alloys due to the propensity for the formation of intermetallic phases and subsequent reduction in the bond strength [3,4]. Hence, explosive cladding, a solid state welding technique, was used to achieve high integrity, corrosion resistant joints between the two alloys."

Jan 1, 2012

By Oscar Perales Perez, Atsuo Kasuya, Kazuyuki Tohji, Yoshiaki Umetsu

"The removal of iron and various heavy-metal ions by their incorporation into stable ferrite-type precipitates at 25°C is a promising alternative to clean up large volumes of polluted aqueous effluents. Our research work investigated the conditions to produce magnetite and various M-bearing ferrites (where M: Zn, Cu, Co, Ni, Cd, etc.) directly from aqueous solutions at 25°C by simultaneous control of the oxidizing conditions and pH. The formation of the solids was followed by monit9ring the oxidation-reduction potential (ORP) and rate of proton release during the aerial oxidation of the suspensions at constant pH (contact stage). Only mildly oxidizing conditions, represented by ORP values between -110 mV and -150 mV and a moderate oxidation rate of Fe(II) species were conducive to well-crystallized ferrites at ambient temperature.' It was also found that increasing the Fe/M mole ratio in starting· solutions enhanced the stability ·of the M-bearing ferrites at ambient temperature. When the formation of the ferrite was incomplete, aging of the sludges in their mother liquors at 25°C promoted the crystallinity of the precipitates. The mentioned conditions ·favored the suitable progress of the ferrite-forming reaction involving the oxidation of Fe(II) entities, subsequent hydrolysis of produced Fe(III) species and dehydration of the intermediate:· Furthermore,· the ferrite formation at· low temperature permits the elimination of iron and co-existing heavy metal ions to sufficiently low concentration.In tum, the characterization of the precipitates evidenced their magnetic nature (room-temperature saturation magnetization above 60 emu/g) as well as the effective incorporation of target metal ions into the ferrite structure."

Jan 1, 2000

By Tian Sugui

By means of the long-term aging treated, creep properties measuring and microstructure observation, an investigation has been made into the microstructure and creep behavior of the casting and rolling GH4169 superalloy after long-term aged. Results show that, after the casting and rolling GH4169 superalloy treated by long-term aged, significant amount of " phase are dispersedly precipitated within the grains of the alloy, and some of the NbC, Cr7C3 carbide are distributed along the grain boundaries. In the range of the applied stresses and temperatures, the creep activation energies and stress exponents of LTA GH4169 alloy during steady state creep are calculated to be Q=541.1kJ/mol and n=16.2, respectively. During creep, the deformation mechanism of LTA GH4169 is thought to be the twinning and dislocation slipping within the twinning regions, and the damaging mode of the alloy is the intergranular fracture, and the non-smooth crystal surface is displayed in the fracture regions of the alloy. Thereinto, the carbides film formed along the grain boundaies has a few effect on the strength between the boundaries, which is a main reason of resulting in the alloy possessing a longer creep lifetimes.

Jan 1, 2009

By Ivan Imris

The iron production has generated many tonnes of very fine residues with high concentration of iron. In addition, during the recycling of galvanised steel scrap in the steel making processes the zinc and lead are largely concentrated in the dust. These kinds of dusts are usually dumped beside the metallurgical plants and cause environmental problems. Therefore the metal recovery from the metallurgical residues has become a major interest not only from the viewpoint of metals recycling but mainly from the viewpoint of environmental land protection. The thermodynamic analyses and laboratory experiments suggested that the metals could be recovered from metallurgical wastes by reduction roasting and by plasma smelting processes. The iron rich pellets with very high metallization may be obtained from metallurgical wastes by the reduction roasting and the inert slag and pig iron could be produced by plasma smelting processes. In both cases the iron rich products are suitable for the steel production. During the reduction roasting or plasma smelting the high volatile zinc and lead metals were removed and enriched as a secondary dust, Zn-Pb concentrate, which is suitable for processing in zinc and lead smelters. Suggested processes are commercially feasible and environmentally friendly without any solid or liquid waste.

Jan 1, 2003

By J. V. Happ

The investigation reported in this paper was prompted by the belief that vacuum processing of copper mattes could provide significant advancement to present-day copper smelting and converting technology. Specifically, vacuum distillation of copper mattes in a unit such as the R.H. vessel used in vacuum degassing of steel, can lead to improvements in: converter flue-gas-cleaning system, purity of acid (or liquid SO2), aisle hygiene, purity of electrorefined copper and smelter flexibility. In the study conducted, removal of Volatile impurities (arsenic, antimony, bismuth, lead and zinc) from liquid mattes, by vacuum distillation in a laboratory-scale equipment was performed. The conditions investigated covered a temperature range of 1123-1223K, absolute pressure of 6.5-0.5kPa (50 - 3 mm Hg) and with bleed gas consisting either of pure oxygen or argon. Six matte samples (four U.S. and two foreign) were tested. Under the "best" conditions arsenic and antimony were reduced to << 0.01% in the product matte. The removal of bismuth, lead and zinc was variable and appeared to be influenced by the matte composition of the sample. As might be expected, the rates of distillation of the various species were increased at higher temperatures and lower absolute pressures. The influence of a small flow rate of gas (02 or Ar) over the melt did not have a signifi¬cant influence on the extent of impurity removal. The magnetite content of the matte was reduced by up to 30% during vacuum treatment and was favored by a low partial pressure of oxygen over the melt. Substantial amounts of sulfur were also evaporated and an, overall increase in copper grade of the matte was realized. The paper concludes with an evaluation of industrial aspects of the process as applied to conventional smelters.

Jan 1, 1983

Thallium is a very minor element found in lead ores. It&apos;s behaviour during lead smelting has recently become of much greater interest due to the effects it had on the health of waste heat boiler maintenance contractors at a Canadian smelter. In this paper the behaviour of thallium in both traditional and direct lead smelting processes will be examined using computational thermodynamics techniques. Yazawa and his coworkers have made extensive use of computational thermodynamics to examine and illustrate pyrometallurgical processes. It has been shown that thallium behaviour during smelting is strongly influenced by the extent of oxidation of the lead concentrate and by the presence or absence of chlorine in the charge. The condensation behaviour of thallium species in the waste gas handling system was also modelled and it has been confirmed thallium-rich deposits can form at the high temperatures prevailing in waste heat boilers.

Jan 1, 2003