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By Yuanyuan Zhang, Patrick J. Masset

"The reduction of FexO in slag is one of the fundamental reactions in iron and steelmaking technology, including the blast furnace process (BF). Experiments on the reduction reaction of iron oxide using CaO-SiO2-Al2O3-FexO-C mixtures were carried out using thermogravimetric analysis (TGA) under reducing conditions at temperatures up to 1100°C. The composition of the primary slag was chosen so that the FexO concentration varied between 0 and 75 wt % and the CaO/SiO2 ratio being kept constant to 0.90. From the TGA curves recorded isothermally at different temperatures the kinetic parameters of the iron oxide reduction were determined.IntroductionIn blast furnace the iron ores and coke are charged in layers from the top. The reduction of iron oxide by coke is one of the fundamental reactions in the blast furnace process. Although a great amount of work has been done on the topic of reduction of composites [1, 2, 3], gasification of carbon [4, 5] and reduction of iron oxides by CO [4, 5, 6], the mechanism of reduction in iron oxide - carbon powder mixtures is not fully understood. Fruehan [1] and Rao [2] studied the reaction rate of the reduction of iron oxide by different types of carbon and concluded that the reaction mechanism is controlled by the oxidation of carbon at temperatures up to 1200°C. Rao [2] studied the reaction of hematite with graphite as carbon source up to 1080°C. An activation energy close to 300 kJ/mol was calculated within the temperature range of 950°C to 1087°C. In his study, Fruehan [1] determined the rate of reduction of Fe2O3 and FeO by coal, coke and coconut charcoal as carbon sources within the 900°C to 1200°C temperature range. He found that the reduction of Fe2O3 by carbon occurs in two stages and that the reduction of Fe2O3 to FeO is faster than that of FeO to Fe. This is due to the fact that the CO2/CO equilibrium ratio is higher, and hence, the rate of oxidation of carbon is faster. Fortini and Fruehan [3] have studied the reduction reaction of wustite by graphite and wood charcoal. They found that the wustite reduction can have a significant effect on the overall rate of reduction in composites at high temperatures or in the presence of a large excess of carbon. The calculated activation energy of the reduction reaction by wood charcoal was close to 368 kJ/mol, while the activation energy of the reduction reaction by graphite was 444 kJ/mol."

Jan 1, 2011

By Yongzhong Xiao, Tiejun Chun, Jian Pan, Zhen He, Deqing Zhu

"In this paper, the reduction kinetics of low grade hematite ore was calculated. Mineralogy shows that the ROM (run of mine) ore is of low grade hematite ore type, assaying 27.2 wt% Fetotal and with main valuable minerals of hematite. The reduction kinetics shows that the reduction reaction rates of pellets with additive and without additive are all controlled by diffusion through the product layer. The calculated apparent activation energy of pellets with 12 wt% complex additive is 8.55 KJ/mol, dropping 62.23% compared to that of pellets without additive.IntroductionWith the rapid development of iron and steel industry in China, there has been a soaring demand for iron ores in the past decade. The imports of iron ores have increased from 148 million ton in 2003 to 620 million ton in 2010[1]. Therefore, large quantities of low grade iron resources are necessary to utilize in China at the moment. During the past years, extensive research has been carried out on the low grade hematite ores [2-6], such as reverse floatation, gravity separation, high-gradient magnetic separation and direct reduction-magnetic separation. Direct reduction-magnetic separation is an innovation way to treat the low grade hematite [7]. However, the research of reduction kinetics of low grade hematite is few. Some research about the reduction kinetics of reducing iron oxides by CO was studied [8]. The results indicated that the apparent activation energy is 8.0-28 KJ/mol when the reducing reaction is controlled by internal diffusion. The apparent activation energy is 50-75 KJ/mol when the reducing reaction is controlled by chemical reaction. In this paper, the reduction kinetics of pellets was also been studied."

Jan 1, 2012

By Shengqin Zhang, Jagannath Pal, Yousef Mohassab, Hong Yong Sohn, Mohamed Elzohiery

The kinetics of magnetite reduction with mixtures of hydrogen and CO of various compositions has been investigated as part of the development of a flash ironmaking process at the University of Utah. This new process bypasses the cokemaking and pelletization or sintering steps required for the blast furnace. The particle kinetics were studied using magnetite concentrate particles of different sizes. Reduction degree of 60% was achieved in a few seconds in at 1350 oC using CO reductant alone and over 90% when H2 + CO gas mixture was used. The effects of reductant partial pressures, temperature, and particle size on the reduction kinetics were studied.

Jan 1, 2016

By Shengqin Zhang, Yousef Mohassab, Feng Chen, Hong Yong Sohn, Mohamed Elzohiery, Amr Abdelghany

A novel ironmaking process is under development at the University of Utah aimed at producing iron directly from iron oxide concentrate in a flash reactor. This process will reduce hazardous emissions and save energy. The kinetics of magnetite reduction with hydrogen was previously investigated in our laboratory in the temperature range 1150 to 1400 oC at large temperature increments (~100 oC increments). Due to the significant melting that occurs above 1350 oC, the reduction kinetics was measured and analyzed in two distinct temperature ranges of 1150 to 1350 oC and 1350 to 1600 oC (~50 oC increments). Experiments were performed using magnetite concentrate particles of different sizes under various hydrogen partial pressures and residence times. Reduction degrees of more than 90 % were achieved in a few seconds at temperatures as low as 1250 ºC. Different rate expressions were needed to obtain reliable agreement with experimental data.

Jan 1, 2016

By M. Tangstad, D. Lu, G. Tranell, S. Gaal, J. Safarian

The kinetics of MnO reduction from high carbon ferromanganese slag was investigated using a sessile drop technique at 1600 ºC. The effects of reductant type, ambient atmosphere and slag composition on the MnO reduction were illuminated. Two different types of industrial reductants (ground to a particle size of 44 to 106micron and pressed to pellets) were used as substrates for small slag droplets of varying composition, which were reacted in a CO or Ar atmosphere with the reaction studied in-situ. The cross sections of the reacted slag-carbon samples were subsequently studied by EPMA to find the extent of MnO reduction as a function of reaction time. It was found that the rate of MnO reduction is affected by both the type of reductant, the ambient atmosphere and the presence of metallic components in the slag. Higher reduction rates were obtained for charcoal than for coke as reductant while a CO atmosphere unexpectedly yielded faster MnO reduction than an Ar atmosphere. It was also found that metal prills in the initial slag will increase the rate ofMnO reduction.

Jan 1, 2007

By Steven Wright

The extent and the rate of reduction of slags produced from the smelting of recycled lead batteries were investigated under laboratory conditions using graphite as reductant. Simultaneous reduction of PbO, Fe2O3, Sb2O3 and As2O3 occurred at temperatures of 1180 and 1200°C, with Sb and As reporting to the metal phase while the PbO content of the slag was above 2 wt%. Fuming of As from the metal occurred at lower concentrations of lead in the slag. Discard slags with low levels of As, Pb and Sb were produced. Arsenic levels were reduced to less than accurately measurable by ICP analysis, and Sb levels in the final slags were in the range of 0.1 to 0.2 wt%. The kinetic data obtained were analysed and compared with other measurements on lead oxide containing slags. The results showing a dependence of the reduction rate on the oxidation state and the basicity are consistent with other studies on well characterised industrial and. synthetic lead slags. These results indicate that when carbonaceous reductants are used, the rate of interfacial reactions play an important role in enabling the production of environmentally acceptable discard slags.

Jan 1, 1994

By A. B. Hazar-Yoruç

Ferrochromium produced by smelting chromite ores is an important alloying component in the steel industry. Ore, coke and fluxes are mixed and reacted in an arc furnace for a smelting process of ferrochromium. In ad-dition to this process, pre-reduction of chromite ore with carbon is an important industrial process. In all these processes, the mechanism and kinetics of reduction of chromite with carbon play an important role. In this study, the reduction of Turkish chromite ore with carbon was investigated. Chromite and carbon were ground to three different particle size groups. Chromite was mixed with carbon in stoichiometric and excess ratios. The samples were reduced under argon atmosphere at temperatures between 1,200° and 1,350°C. The formed phases and alloy compositions of reduced chromite samples were analyzed by optical microscopy, scanning electron microscope (SEM) with EDAX and X-ray diffraction analysis (XRD). Experimental results showed that the degree of reduction and the reduction rate increased with increasing temperature and decreasing particle size. The highest degree of reduction, 61.4%, was obtained at 1,350°C. The reduction took place in three stages: Stage 1: transformation of Fe3+ to Fe2+ and formation of metallic nuclei, Stage 2: formation of metallic crust around the particles and Stage 3: growth of the metallic crust and coalescence of the metallic phase.

Jan 1, 2007

By Yotamu Stephen Rainford Hara

"The study focuses on the reduction mechanisms of copper, cobalt and iron during carbothermic reduction of copper-cobalt mineral sulphide concentrates in the presence of lime, in the temperature range of 1073K and 1273K. We have used three types of mineral concentrates which were derived from froth flotation from the Copperbelt region in Zambia. The reduction mechanisms were studied using thermogravimetric analysis in which selected reactions were stopped at different times for characterising the reaction mechanism using optical microscopy, XRD and SEM-EDX analyses. Using SEM-EDX analysis, we have analysed in details the stages of metallic phase formation during reduction process. Metallic cobalt and iron were embedded into copper, thereby permitting magnetic separation of the reduced metals even though copper is diamagnetic. Methods of preferential reduction of metal values were investigated by analysing the metallic phase formation.IntroductionIn conventional smelting or converting of copper sulphide minerals, metallic copper forms by giving off S02 gas on. Although in terms of overall energy balance the selective oxidation for metal production has major advantages, the process suffers from drawbacks in smelting complex concentrates containing copper, cobalt and iron sulphides minerals and these are: (i) cobalt and iron are oxidised, and consequently cobalt is lost into the slag phase. (ii) The volume of S02 gas produced is in low concentrations, which is insufficient for extracting sulphur or manufacturing sulphuric acid. The release of dilute S02 causes serious environmental pollution. The major cause for the loss of cobalt and iron into the slag, is due to that fact that the oxides of these metals are more stable than their sulphides. Since cobalt and copper are more valuable than iron, reducing conditions are required in a separate slag treatment reactor using electric arc melting for recovering the lost metal oxides from slag. This energy-intensive step makes metal making expensive.During chemical beneficiation of mineral sulphides (Cu2S, CoS, FeS) in the presence oflime (CaO), two types of equilibrium conditions may be set up either by forming CaS under reducing conditions, or by stabilizing CaS04 under oxidising conditions [l]. By comparison in the presence of carbon, CaS and metallic phases form, enabling the recovery of metals from sulphide minerals, which have been investigated by a number of authors [2-9]. During reduction of metal sulphide in the presence of lime and with carbon, it has been proven that the overall reaction le proceeds via two main steps: [5, 8, 9] (i) the anion exchange reaction between metal sulphides (MS) and CaO as shown in equation la, followed by (ii) the reduction of metal oxide (MO) via reaction lb."

Jan 1, 2013

By A. Fyson, M. P. Smith, Margarete Kalin

"Drums containing 0.07 m3 of pyritic waste rock from a zinc/copper mine, with and without Natural Phosphate Rock (NPR) additions (40 kg/t waste rock) were set up outdoors. The effluent chemistry has been monitored over a period of 709 days. In the presence of NPR, the cumulative acidity discharged from 7 out of 8 drums was 80 % less than that discharged from drums without NPR. Mixing NPR throughout the drums was more effective in reducing acidity than placement of the NPR in a layer in the drum. NPR treatment was more effective for 'fresh' waste rock than for material which had weathered for more than 4 years. It is concluded that application of NPR to pyritic waste rock could greatly reduce acidity generated.IntroductionWaste rock dumps are significant sources of acid, generated by the oxidation of sulphides. Oxygen and water supply are oxidation rate-controlling factors, and oxygen supply is the reaction-limiting component. If secondary minerals can be formed on the surface of the rocks, pyrite oxidation and therefore acid generation may be reduced or inhibited. Neutralizing agents such as limestone do not prevent the oxidation of pyrite but treat the resultant acid mine drainage (AMD) or acid rock drainage (ARD).Meek et al. (1991) determined in pilot scale experiments that apatite mixed with tailings was more cost effective than liming or use of PVC liners to reduce oxygen and water penetration into the tailings. Phosphate is not acting as a neutralising agent but it creates a chemical condition on pyritic surfaces which prevents reactions of the oxidising agents. Precipitation of principally iron phosphates physically isolates the pyrite surfaces from further oxidation (Ziemkiewicz 1990; Evangelou 1994). The chemistry of the phosphate effects has been described by Spotts and Dollhopf (1990). Secondary mineral formation was evident in the leach pile at Gibraltar when leaching was impaired (Scott, 1991) indicating a link between oxidation and the mineral-formation process. This paper reports on effluent characteristics when waste rock is generating acid in the presence of NPR."

Jan 1, 1995

By Thomas Brynjulfsen, Merete Tangstad, Eli Ringdalen

Manganese ore fines cannot be added to the submerged arc furnace directly as they will prevent even gas flow through the burden. Low gas permeability in the burden will lower the degree of pre-reduction of ore subsequently increase the carbon and energy consumption of the process. In order to utilize manganese ore fines in the furnace, they are typically agglomerated into sinter. In this work, the melting and reduction properties of Gabonese sinter and Gabonese ore have been investigated in pilot scale experiments. Two experiments were conducted, one with 100% sinter as manganese source and one with 50/50 sinter and ore. Lime was used to achieve a charge basicity of 0.72 in both experiments. The composition of slag samples from the excavation of the furnace was established using EPMA(WDS), and the composition of the tapped slag and metal was found using XRF. It was found that while the coke-bed size would determine the tapped slag composition, the melting behavior of the Mn source would determine the mixing with lime.

Jan 1, 2014

By Don Rapp, Rufus Flinchum

Air blast and flyrock are two of the most critical concerns facing the blaster of today. This paper will provide the blaster with proven procedures for recognizing open face and bench surface problems, explain various surveying methods, and provide the mathematical formulas for calculating and designing proper hole placement and explosive load configuration. A concept called "Pattern Footage" is utilized in conjunction with a USBM study to develop blast designs aimed at minimizing air blast and flyrock. In addition to this main focus, this concept can be used in shot displacement and cast blasting design.

Jan 1, 1993

By Margaret E. Harris

The formation of nitrogen oxides, the decay of carbon monoxide, and the concentrations of residual hydrocarbons in the secondary combustion zones of propane-air and methane-air flames were studied in three enclosed burners designed to simulate gas appliances such as space and water heaters. The effect of thermally or chemically perturbing the combustion gases above these flames was determined theoretically and by means of factorial experiments. The concentrations of air pollutants and the flame temperatures were measured, and the effects of ingress of secondary air into the primary and secondary combustion zones, flame stability, burner port surface, and simulated recycling of combustion gases were noted. Based on this study, four principles were derived that, applied to gas appliance design, will insure minimal emissions of these air pollutants: 1. Oxides of nitrogen can best be kept low by depressing peak temperatures to about 3,050° F. 2. If this is not possible, then the secondary combustion zone should be cooled rapidly to this temperature. 3. Carbon monoxide concentrations can be limited by rapid induction of secondary air. 4. Hydrocarbon concentrations can be controlled by designing for well-seated, stable flames. In addition, empirical reaction rates were derived that predict the concentrations of nitrogen oxides and carbon monoxide in the primary and secondary combustion zones.

Jan 1, 1970

By Rufus Flinchum

Two of the most critical concerns a blaster faces today are airblast and flyrock. Airblast, sometimes called noise or overpressure, can cause damage to neighboring structures, especially windows. It also is the cause for many vibration complaints. The human sense of hearing is often more acute to identifying source than the sense of touch. When a blast occurs, the airblast is what identifies the event. The vibration that may be felt is then associated with the airblast. Vibrations of greater magnitude, such as passing trucks or construction work on the house, go unnoticed because their sounds are familiar or expected. Flyrock is the number one killer and cause of damage. Elasting laws provide limits for these two concerns. Failure to comply may result in fines, closing of the operation, and even prison. Airblast and flyrock originate from two distinct areas, the open face and the bench surface. Each of these areas is addressed in the detailed proven procedures that follow, and if used by the blaster in conjunction with his own blasting knowledge, a sound blasting plan can be developed to minimize the occurrence of airblast and flyrock.

Jan 1, 1992

By C Vejrazka, A Wyllie

A common problem faced by underground mining operations around the world is airborne dust sourced from production and auxiliary processes. In most underground mining methods, air is generally directed through a limited number of drives and is thus more effective at carrying dust away from operational areas quickly. In a block caving operation, there are a number of ways to set up ventilation systems. In its simplest form the air is entering the extraction level through access drives and then split over the number of extraction drives—based on the pressure differences—without being regulated. This is the case at Northparkes Mines. Larger operations and panel caves most often utilise designated ventilation levels and ventilation raises with some form of regulation to ensure adequate airflow to all work areas.Northparkes Mines utilise electric loaders as a productive means to transport ore to the run-of-mine (ROM) bin, which have the added advantage of allowing the mine to require less airflow through the extraction drives as dilution of exhaust gases is no longer required. Dust was controlled during the operational period of the previous two block caves by using water spray bars in each of the drawpoints, which were seen as the main source of dust. These drawpoint spray bars only wet the surface of muck piles and require a lot of water to achieve an effect on the overall air quality. The drawpoint sprays can be remotely operated from mine control, whenever a loader is sent to bog a particular drawpoint. A significant amount of airborne dust is also generated during loading as rilling of material occurs, with further dust being generated during tramming and dumping activities as only limited mixing of the water and ore occurs. The water sprays are ineffective at precipitating dust that has already become airborne.When built, the currently operational E48 cave was fitted with drawpoint water sprays. As the cave is in a different orebody with higher silica content, the water sprays were not able to keep airborne dust and thus silica quantities under control efficiently. It was therefore necessary to find more sustainable solutions. The problem was further intensified by the concurrent load-haul-dump (LHD) processes across multiple extraction drives and tipping points, as well as secondary breaking, using non-explosive blasting and development activities occurring nearby.This paper describes the practical approach taken at Northparkes Mines to reduce personal dust exposure on the E48 extraction level. As the extraction level is one of the main contributors to airborne dust at the mine, it is believed that much can be learnt by focusing improvement efforts initially on this part of the mining process and later applying the effective solutions in other parts of the mine.CITATION:Vejrazka, C and Wyllie, A, 2014. Reduction of airborne dust on the E48 extraction level at Northparkes mines, in Proceedings 12th AusIMM Underground Operators’ Conference 2014 , pp 227–232 (The Australasian Institute of Mining and Metallurgy: Melbourne).

Mar 24, 2014

By G. Tairova, J. Ioffe

Arsenic, selenium and mercury species are common contaminants in mining aqueous streams and present significant environmental and health problems. The objective of this project is to investigate methods to lower the concentrations of these elements in mining aqueous streams. A new composite media for removal of these elements of concern from mining effluents was developed. The results of bench scale and pilot plant experiments, using the media, indicated removal of arsenic, selenium, mercury and other elements of concern below detection limits.

Jan 1, 2014

By S. D. F. Rocha1, L. Katsarou, G. P. Demopoulos

"Crystalline scorodite (FeAsO4·2H2O) has been pointed out as the most stable compound to immobilize arsenic for disposal due to its good stability performance according to EPA’s TCLP test. However, in anaerobic conditions, arsenic releasing is increased to undesired levels due to scorodite reductive break down, in eh <100 mV at 5.5< pH <7 which causes contamination of groundwater. In this work, the concept of encapsulation by controlled deposition of mineral coatings immune to pH or redox potential variations is presented. Aluminum and calcium phosphates were evaluated as coatings and the release of arsenic from scorodite previously coated with phosphates was substantially decreased when compared to the VALUES (obtained from crude scorodite, both in oxic and anoxic conditions. INTRODUCTIONThe widely acknowledged hazardous properties of arsenic as a soil and natural water contaminant and its adverse health effects when present in drinking water have led to very strict environmental regulations (Mandal & Suzuki, 2002) aiming at the drastic reduction of the presence of arsenic in the effluents of the mining and metallurgical industries.In Canada, the Metal Mining Effluent Regulations (Government of Canada, 2002) dictate that the maximum monthly mean concentration in tailings for arsenic must be lower than 0.5 mg/L. At the same time the new Environmental Protection Agency’s (EPA) standard for drinking water foresees concentrations of arsenic less than 0.01 mg/L, which means that the leachability limit for the industrial waste is set at 1 mg/L arsenic (EPA, 1994; Le Berre et. al, 2007). One of the preoccupations of the mining and metallurgical industries is directed to the elimination of arsenic presence in all its effluents, especially since arsenic is commonly found in many ores mainly in the form of oxides and sulphides. After processing of arsenic-containing ores and concentrates, arsenic can be present either in solid residues and tailings, liquid effluents or in flue dusts. Several of these forms of arsenic waste materials are soluble and therefore may cause the contamination of ground water, if disposed of without further treatment."

Jan 1, 2012

By G. Gomathi, K. Asokan, K. Subramanian

An electrochemical reactor with anode and cathode chambers separated by a composite perfluoro polymer cation exchange membrane was designed, fabricated and used for the reduction of dissolved carbon dioxide under ambient conditions to formate. The flow reactor enhanced the mass transfer of carbon dioxide compared to the batch reactor. Experiments were conducted using two different perfluoro polymer membranes - Nafion 961. Efficacy of CO2 reduction on various cathode materials (Cd, Pb, Sn and Zn plated stainless steel woven mesh) were determined. Optimum values of flow rate and current density were evaluated for the energy efficient formation of formate in aqueous KHCO3 (pH 7.5-8.5) buffer solutions.

Jan 1, 2008

By Guohua Bai, Mingjun Rao, Jianchen Lim, Guanghui Li, Tao Jiang

"By using thermogravimetry, optical microscope and chemical phase analysis, the solid-state reduction of carbon-burdened chromite pellets in the absence and presence of additives were investigated. The effects of reduction temperature, reduction time and additives on the metallization of chromite pellet were studied. The results indicate that the pre-reduction ratio of carbon-burdened chromite pellets is improved with the increase of reduction temperature and the addition of additives. The metallization of chromium is increased from 63.9% to 92.8% at 1300 °C for 4h with the addition of 2 wt.% of sodium borate. Investigation suggests that the reduction of carbon-burdened chromite pellets is diffusion controlled. The apparent activation energy without additive is 192.1 kJ/mol, while it decreases to 170.4 kJ/mol in the present sodium borate.IntroductionFerrochrome is used to produce high strength, corrosion resistant, wear-resisting, high temperature resistant and oxidation resistant special steels, and it is becoming one of the most important alloy materials for the production of stainless and high alloying ferritic steels [1-5]. Demand for ferrochrome is steadily on the rise due to the growth of stainless steel industry. Nowadays, more than 80% of the world's ferrochrome is utilized in the production of stainless steel [6-7].Ferrochrome is mainly produced in submerged-arc furnaces (SAF) with chromite lump ore. However, lump ore merely accounts for 20% of the chromite ore output, while fine ore (< 8 mm) accounts for about 80% [8]. Therefore, agglomeration of chromite fine ore is necessary before charging into SAF."

Jan 1, 2011

By Dolly Chakraborty, S. Ranganathan, S. N. Sinha

Pre-reduction of chromite outside the submerged-arc furnace (SAF) can significantly lower the specific power consumption in the SAF process. Conventional processes for the pre-reduction of the ore operate at relatively high temperatures, at 1400-1500°C. It is possible to enhance the rate of reduction at low temperatures by optimizing the flow rate of inert gas over the reaction site. The influence of the flow rate of inert gas on the rate of reduction of chromite ore was investigated. The rate of reduction initially decreased wit the flow rate of the gas. It increased subsequently at higher flow rates to be followed by a decrease again. There was an optimum flow rate at which maximum reduction could be obtained. It was possible to achieve high levels of reduction at 1200°C by optimising the flow rate of the gas. The degree of reduction obtained was comparable to that obtained at 1400-1500°C, by conventional process routes.

Jan 1, 2007

By J. Björkvall, S. Ångström, L. Kallin

In this paper results from industrial trials of CaC2 injection during stainless steel production in an electric arc furnace at Sandvik Steel is presented. The main purpose of the investigation was to analyse the effect of the injection on slag foaming and final chromium oxide concentration in slag. The results show that both an increase in slag foaming and a decrease of the final chromium oxide could be obtained during the charges with CaC2injection. On the basis of the results, the economical requirements are also discussed. Both the technical and economical requirements could be achieved for steels alloyed with Mo. In order to secure the economical requirements for all steel grades of interest, the injection technology must be further developed. It would also be important to utilize the positive effect of the slag foaming on the electric energy consumption. The work has been performed as a part of MEFOS frame research programme with participants from Sandvik Steel, AKZO Nobel and Avesta Polarit. Keywords: stainless steel, EAF, slag foaming, injection, CaC2

Jan 1, 2004