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By Huayi Yin, Wang. Dihua, Wei Xiao, Xuhui Mao, Diyong Tang

"The world production of crude steel reached 1.55 billion tons in 2012,which generated ~2.5 billion tons of CO2. Electrochemical metallurgy especially through high temperature molten salt electrolysis with renewable electricity stands for a great opportunity for producing “green” metals. In recent years, electrolytic production of iron without emission of CO2 in different molten salt systems has been reported. A cost-affordable inert anode is the key to produce acceptable eco-friendly iron by the novel molten salt electrolysis processes. Based on the authors’ research, this paper will discuss iron production by molten salt electrolysis using a nickel alloy inert anode. On the other hand, the paper also covers a novel molten salt CO2 capture and electrochemical transformation (MSCC-ET) process, in which CO2 is effectively converted to value-added carbon and oxygen in a molten bath using a cost-affordable nonconsumable SnO2 anode.1. IntroductionEnergy and materials are cornerstones to support the development of human society. The traditional primary metal production, especially iron and steel, and electricity production are mainly based on the reactions between carbon (coal) and oxygen (represented by equations (1) and (2) respectively), which produce huge amount of CO2.MxOy + 0.5y C = x M + 0.5y CO2 (g) + Q1 ( 1 )C + O2 (g) = CO2 (g) + Q2 ( 2 )In 2012, the world production of crude steel reached 1.55 billion tons, of which 46.3 %, ~0.7165 billion tons were produced in China. Based on the average level of 1.7t CO2 emission per ton steel, more than 1 billion tons of CO2 generated from steel industry in China in the year. Besides the iron and steel industry, thermal power plant leads the CO2 emission in both USA and China. The total consumed electricity in China increased to 4959 billion kWh in 2012, ~70% of it was from coal fired power plant. The average CO2 emission for electricity production in the typical thermal power plant in China is around 0.78 kg kWh-1. It accounts for ~ 3.868 billion tons of CO2 emission from thermal power plant in 2012 in China."

Jan 1, 2014

By E. Oshima

The only one reverberatory furnace smelting in Japan has been alive in Onahama Smelter, Onahama Smelting and Refining Company. The fuel for the reverberatory furnaces had been changed from bunker C-oil to mainly coal and partially waste tires to reduce the energy cost. The steam, recovered by the waste heat boilers of the reverberatory furnaces, has been utilized fully for the power generation to save the purchase power. Copper concentrate has been smelted also by injection through tuyeres in the P.S. converters since 1983. The amount of concentrate, treated in the converters, was increased by the construction of small oxygen plant in December, 1990. In the paper, the current practice and improvements in the reverberatory and converter operations are described.

Jan 1, 1993

By R. G. Reddy

Reduction of different chromite ores with carbon was studied as a function of C/FeO ratio and temperature in the range 700 °C to 1100 °C by thermogravimetry (TGA) analysis. Powders of chromite ore(-150 mesh) and carbon(-150 mesh) were thoroughly mixed in a desired proportions and were placed in the reaction crucible. The reduction rates of reactions were determined by continuously monitoring the weight loss as a function of time at constant temperature using TGA set up. The analysis of results suggest that FeO present in the chromite ores is reduced to Fe involving gaseous intermediates CO and CO2. The overall rate of FeO reduction is controlled by the oxidation of carbon. A kinetic equation, that of random nucleation, was proposed. The activation energies for the reduction of FeO, present in Roast Movat and Transvaal ores, with carbon were determined to be 55800 and 23000 J/mole, respectively. The results of the present study are compared with the data available in literature. The low activation energy values as determined in this study suggest that the carbon oxidation reaction is catalyzed. It is concluded from the present investigation that the low grade chromite ores can be significantly upgraded to higher value added chromite that can be used as a feed source for economical smelting.

Jan 1, 1998

By Won C. Park

Experiments showed changes in the mineral content of dolomitic oil shale at temperatures and exposure times which bracket conditions encountered during in situ retorting. Laboratory results correlate with cores from a spent in situ retort at Occidental's Logan Wash test site at Garfield County, Colorado. Dolomite, CaMg(CO3)2, decomposes rapidly to form periclase, MgO, calcite, CaCO3, and CO . Both calcite and periclase are intermediate products that can be stabilized by CO atmosphere at lower temperatures, while steam accelerates the formation 2 of silicates. The decarbonation of calcite appears to involve a direct reaction with both quartz and periclase in forming these silicates. Decarbonation preceeds the formation of akermanite, Ca2 MgSi 207, and diopside, CaMgSi 206, within several hours of heating and is followed by the nucleation of forsterite Mg2SiO4, and monticellite, CaMgSiO4. Under in situ retorting conditions, akermanite and diposide are the major minerals above 800°C. Equilibrium is not attained within 200-300 hours. In situ retorting temperatures above 800°C for extended periods of time should reduce potential ground water leaching by the formation of silicate minerals. These silicates are less soluble than free lime, magnesium or alkali oxides. There is a corresponding decrease in the natural pH of these silicates from approximately 12 down to 7.5 to 9:

Jan 1, 1981

By J. G. Eacott

This paper reviews the role of oxygen potential and the advances that have been made in the application of tonnage oxygen in copper smelting. Brief reference is made to reaction kinetics before attention is turned to the thermodynamic considerations in copper melting to illustrate the importance of oxygen and. oxygen potential in the component parts of the overall smelting process. The chemical potential diagram for the Cu-Fe-S-O-Si02 system is used to elucidate the difference b etween the conventional matte smelting process and the modern continuous processes. A progressive oxidation scale' is constructed to show the common elements which exist, and the matte grades produced, during the smelting of concentrates to blister copper in commercially available copper smelting processes and those under development. The common route in producing blister copper from molten mattes, regardless of process, is illustrated on the Cu-Fe-S equilibrium phase diagram. The essential features of oxygen enrichment, in terms of its effect on combustion conditions (i.e. oxidation of fuel and sulphide minerals) and the heat balance are outlined. The benefits of oxygen enrichment are listed. The influence of tonnage oxygen and its effect on productivity, fuel savings, gas volume and strength in various copper melting processes are examined as a state-of-the-art review. Reference is made to the economics of tonnage oxygen utilization.

Jan 1, 1983

By Stavros A. Argyropoulos

Exothermic mass transfer takes place in various areas involving metallic systems, ranging from liquid metal processing operations to the growth of thin films in microelectronics. The formation of intermetallic compounds plays an important role in the exothermic mass transfer of metallic systems. Two types of exothermicity are identified , namely , Microexothermicity and Macroexothermicity. The former is encountered when small amounts of metals are mixed, while the latter is exhibited when a solid metal in a lump form is added into liquid metal. In this paper two types of exothermic mass transfer in metallic systems will be presented and reviewed. Mathematical modelling work for these types of exothermic mass transfer will be analyzed.

Jan 1, 1993

By N. Coone

By exploiting the results of solidification modelling foundries can enhance the quality and reduce the cost of their casting processes. However not enough information exists on the thermal boundary conditions, which control the transfer of thermal energy stored in liquid metal to the mould via the metal/mould interface during solidification. This is quantified by the heat transfer coefficient (h.t.c.). An experimental and numerical study was carried out to find the magnitude and variation of the h.t.c. in cylindrical castings during the solidification of grey cast iron in green sand moulds. The h.t.c. values were calculated using a time marching solution to the inverse heat conduction problem. The variation of h.t.c. with metallostatic head was analysed. There is a wide scatter in green sand thermal properties due to the large number of variables involved in mould manufacture including green sand compaction and water content. The sensitivity of the calculation to uncertainties in the thermophysical properties of the green sand was evaluated. Keywords: Heat transfer coefficient, grey cast iron, sand moulds. inverse technique

Jan 1, 2003

By Kimiaki Utsunomiya, Yasumasa Hattori, Yoshiaki Mori, Toyokazu Okubo

"The effect of various operating conditions on splashing behavior in a Peirce-Smith converter has been investigated with a 1/5.7 scale cold model. Dynamic similarity between the model and a commercial converter was attained by setting the modified Froude number in the model experiments in· the range for normal converter operation. It is known that for a given modified Froude number the dimensionless penetration length of gas into the liquid phase increases as the liquid density decreases. Moreover, penetration· length has a large effect on splashing behavior. Therefore, a heavy liquid, a mixture of water and lead concentrate was used as the liquid phase. It was concluded that the amount of splash dramatically decreases with a reduction in the buoyancy energy per, unit liquid mass and an increase in the horizontal distance between the tuyere tip and the edge of the mouth.IntroductionSubmerged gas injection is widely used in practice in ferrous and nonferrous pyrometallurgical operations to achieve large gas-liquid contact areas and good agitation of liquid for rapid chemical reaction. The common application in ·nonferrous industry is the Peirce-Smith converter with multi-tuyere for copper and nickel matte converting. This process has been used for over 100 years because of its effectiveness in mixing of the molten bath, as well as its merits of the engineering simplicity. However, the mechanisms which · determine the blowing performance is poorly understood, and the design and operating conditions of the Peirce-Smith converter varies widely from plant to plant, such as by diameter, length, mouth angle, tuyere position and level of molten matte. Smelters have continuously made an effort to increase converter productivity, implying maximum tuyere blowing rate. Above a certain critical blowing rate, splash of molten matte from the converter mouth becomes unacceptable because of dangerous ejection and accretion buildup around the converter mouth, which results in interference with effective hood sealing. In fact, a 1993 converter survey[!] reported that splash was a major limiting factor for blowing rate and 54% of responding plants from around the world regard it as a limiting condition[2]. In order to increase tuyere blowing rate a study of the effect of various operating conditions on splashing behavior is expected."

Jan 1, 2000

By Jewel A. Gomes

Keywords: Electrocoagulation, arsenic removal, fuel cell, windmill, energy simulation, combined Fe-Al electrode assembly Arsenic contamination of well-water in different countries has caused signs and symptoms of arsenic poisoning. Although several physicochemical treatments are presently used for the removal of arsenic compounds from drinking water, an electrochemical treatment, electrocoagulation, is a promising processing technology and currently is the most efficient (above 99% removal) and environmentally friendly technique, particularly if combined with alternative energy sources. Wind and fuel cell technologies can be considered the most promising developmental clean power sources. We will discuss new insights into the materials processing mechanisms and show the coupling of electrocoagulation with fuel cells and simulated wind energy sources. Different electrocoagulation plate materials were considered, along varied currents from the fuel cell to produce maximum arsenic removal. Coupling these technologies will remove carcinogenic arsenic from water sources, and will exhibit efficient usage of these energy sources by producing pure water for human and agricultural consumption.

Jan 1, 2005

By Gus Van Weert

Solvent extraction of iron from zinc refinery liquors has been investigated before, mainly on the MEHPA / HC1 stripping combination. Leakage of chloride into the zinc electrolyte and the costs of handling the ferric chloride eluate have prevented this option from being adopted. This work explores the stripping of the ferric loaded organic phase with nitric acid to take advantage of the possibility of regenerating up to 6N nitric acid, and clean spheroidal hematite production by autoclave treatment of ferric nitrate solution. The work was carried out with DEHPA (di 2-ethyl-hexyl phosphoric acid) in kerosine. Degradation testing proved the DEHPA to be very stable, when exposed to nitric acid solutions up to 6N and temperatures up to 70" C over a period of five days. Ferric iron was removed completely froma synthetic hot acid leach liquor, irrespective of the DEHPA concentration. Stripping the ferric turned out to be the problematic step. Although the stripping efficiency was considerable better at 50 than at 20° C, it decreased with increasing DEHPA/Fe ration in the organic phase. Eluates of no more than 5-10 g/l ferric nitrate were produced. surprisingly, nitric acid was found to be a less efficient stripping agent than sulphuric at equivalent normality and its efficacy levelled off above 4N. It was concluded that DEHPA does not appear to be the S.X. reagent to take advantage of the low cost autoclave decomposition of ferric nitrate opportunity in zinc hydrometallurgy and that another S.X. reagent, also resistant to nitric acid, but based on weaker compound formation is needed.

Jan 1, 1998

By Hong Yong Sohn, Miguel Olivas-Martinez, Zhixue Yuan

A novel flash ironmaking process that directly reduces iron oxide concentrate particles by gas is under development. The goal of this work was to study the possibility of reoxidation of iron particles in various gas mixtures. As the product iron cools down in the lower part of the flash reactor, conditions may become favorable for reoxidation because of equilibrium and high reactivity of iron particles. The effects of temperature (823 – 973 K) and H2O partial pressure (40 – 100 pct., Ptotal = 86.1 kPa) on the reoxidation rate were examined. The pressure dependence was first order with respect to water vapor, and the activation energy was 146 kJ/mol. A complete rate equation that adequately represents the experimental data was developed. For oxidation in O2-N2 mixtures, the effects of temperature (673 – 873 K) and O2 partial pressure (5 – 21 pct., Ptotal = 86.1 kPa) were determined. Reoxidation in pure CO2 was also investigated at 873 – 1073 K for comparison.

Jan 1, 2014

By Senlin Xie, Wanlin Wang, Lejun Zhou

"The innovative development of multiphase slag in hot-metal treatment has attracted considerable attention due to the reduction of CaO consumption and minimal environmental emission. In order to improve the efficiency of dephosphorization and to reutilize the waste-slag as an alternative source of phosphate ores, it is important to increase the distribution ratio of P2Os between the solid solution (2CaO· SiO2-3CaO· P2O 5) and liquid slag. An investigation was carried out to study the effects ofNa2O and B2O3 on the distribution ratio of P2Os, the results indicated that the increase ofNa2O would enhance the distribution ratio of P2Os with the formation of solid solution (2CaO·SiO2-Na2O·2CaO·P2Os), while B2O3 has the opposite function, and changes the morphology of solid solution. The study would provide an instructive way for the design of multiphase slag and re-utilization of waste-slag.IntroductionIn order to meet the increasing demand for high quality low-phosphorus steel, it requires a high efficient hot metal dephosphorization process. The current slag system for hot metal treatment contains large amount of solid CaO dispersed in liquid slag, which introduced a large amount of CaO consumption due to its low solubility, especially when CaF2 was restricted due to the environmental concerns. Therefore, new refming method to improve the utilization efficiency of CaO by using a solid/liquid coexisting multiphase slag was proposed, and the studies regarding to solid solution formation mechanism, mass transfer behavior of phosphorus and the phase relationship for multi-phase slag have been conducted. [1-6]Normally, hot metal dephosphorization slag consists of CaO--SiOz-FeO--P2O 5, and it has been approved that 2CaO·SiO2 forms a solid solution with 3CaO·P2Os at the hot metal treatment temperature over a wide range of compositions. [7] Kitamura et al [8] pointed out that the (2CaO·SiO2-3CaO·P2O 5) solid solution plays an important role in dephosphorization, and it has been regarded as an absorbents for phosphorus to lower the phosphorus content in liquid phase, which makes it more capable for future dephosphorization. l Besides, the multiphase slag has the potential to be recycled as a source of phosphorus, if the (2CaO· SiO2-3CaO· P2O 5) solid solution could contain high phosphorus content, and it can be separated from FeiO matrix 8hase due to the large difference of their magnetic properties under the strong magnetic field. [10, 11]"

Jan 1, 2014

By E. Oshilna

The Mitsubishi process has many advantages pertaining to economical and environmental matters. These advantages have led to the installations of the Mitsubishi process in constructing new smelters: The Mitsubishi process utilizes highly oxygen enriched blast air and uses a special lime slag in the C?furnace. These characteristics change the . distribution of Impurities from other processes which use P.S. converters, Recently an Increased amount of secondary materials which contain impurities Is being treated at Naoshima Smelter. In order to cope with an Increment of the Impurities load and maintain the cathode quality, many Improvements have been Implemented. This paper discusses the impurities behavior In the Mitsubishi process and describes the measures taken to treat an Increased ?amount of secondary materials:

Jan 1, 1998

By Bora Derin

The partial pressure ratios of sulfur and oxygen for several copper flash smelting plants were derived using the Reddy-Blander (RB) model and predicted dissolved sulfur contents available in the literature. The sulfide capacities (Cs) of six different flash smelting plants (FeO-CuO0.5- CaO-MgO-FeOwAIOl.s?SiO2) slags were calculated. The log (Po2/PS2) versus matte grades of various industrial processes was determined. The PoiPS2 ratio increased with an increase of copper grade. The calculated partial pressure ratios for the copper flash smelting are in good agreement with those of the experimental data.

Jan 1, 2003

By Bora Derin

The partial pressure ratios of sulfur and oxygen for several copper flash smelting plants were derived using the Reddy-Blander (RB) model and predicted dissolved sulfur contents available in the literature. The sulfide capacities (Cs) of six different flash smelting plants (FeO-CuOo.5- CaO-MgO-FeOu-AlO15-SiO2) slags were calculated. The log (PO2/PS2) versus matte grades of various industrial processes was determined. The PO2/PS2 ratio increased with an increase of copper grade. The calculated partial pressure ratios for the copper flash smelting are in good agreement with those of the experimental data.

Jan 1, 2003

By Bernd-Arno Behrens, Klaus-Georg Kosch

"In times of increasing energy costs automotive lightweight construction is gaining in importance. This paper deals with the production of hybrid steel-aluminum compounds by forging. The compound forging process is a promising method to successfully manufacture functional parts by applying resource-saving process steps. Nevertheless, challenges resulting from different material properties must be solved.The heating of hybrid material work pieces made of steel and aluminum is a great challenge. Steel is forged at a temperature of at least TSt =900 °C, while aluminum should not exceed a temperature of TA1= 500 °C. For achieving the required temperature gradient extensive experimental investigations have been carried out. Intermetallic phases form during the manufacturing process and can influence the bonding and the global part quality. In addition, methods for the characterization of the joining zone between the materials steel and aluminum are analyzed and the factors influencing the formation of intermetallic phases are determined experimentally.IntroductionIn times of increasing energy costs and stricter conditions relating to environmental protection, automotive lightweight construction is gaining in importance. The production of hybrid compounds by forging is a promising method to manufacture functional parts by applying resource-saving process steps. In compound forging a hybrid raw part consisting of a solid core, which is enclosed by a hollow casing, is joint in the forming process. This results in a graded material structure in the part in which the mechanical properties can be specifically adapted to the requirements. Compound forging is the form joining and/or firmly bonded joining of at least two different materials while plastic shape forming occurs (Figure 1)."

Jan 1, 2012

By Dong Hoon Han

The sulfation rates of magnesium oxide and calcium oxide (molar ratio 7:3) contained in calcined CMA ( calcium magnesium acetate) by SO2 were measured. The experiments were carried out in the temperature range 700 to 1100 °C and under the SO2 concentrations of 0.3 to I mol % (5 % 02). In the low-temperature range below 830 °C the reaction produced CaSO4.3MgSO4 and unreacted MgO, but no MgSO4 phase. The formation of CaSO4.3MgSO4 phase has a significant implication in that it allows the utilization of MgO for SO2 removal whereas the sulfation of MgO from conventional sources is so slow that it is of no practical interest. Thus, the calcined CMA can remove SO2 at lower temperatures than conventional SO2 absorbents and at a greater capacity. Above 950 °C only CaO reacts with SO2, but at a much greater rate than the calcined Ca(OH)2, which is one of the most reactive SO2 absorbents.

Jan 1, 1998

By Dale T. Peters

Conductivity, both electrical and thermal, are attributes accounting for about 70% of the applications of copper and its alloys. This paper presents results of on-going research into two new applications that depend on copper's excellent conductivity. The Copper Development Association (CDA), together with materials and motor company partners, is working toward a solution to the key problem preventing pressure die casting copper for the conductor bar/end ring structure of the induction motor rotor, i.e., lack of a durable high-temperature mold material. Work is showing that a combination of high- temperature materials and elevated temperature processing gives much improved mold life compared to die steels. Substitution of copper for aluminum in the rotor can result in a 20% decrease in electrical losses in motors consuming 35% of electrical power generated in the U.S. The second development uses the excellent thermal conductivity of several high-strength high-copper alloys to simultaneously improve productivity and part quality in the injection molding of plastic parts.

Jan 1, 1999

By Adam Powell, Salvador Barriga, Matthew Earlam

"The inert anode is a key enabling technology for dramatic energy and emissions reduction in extractive metallurgy. In molten salts, the materials challenge is nearly insurmountable: the anode must conduct electrons at high temperature in a pure oxygen and molten salt environment. A solid electrolyte, e.g. zirconia, between the salt and anode removes the molten salt stability constraint, and can act as a container for a liquid metal anode. This can be liquid silver for oxygen-generating inert anodes, or several metals for natural gas-fueled anodes; it is possible to switch between these modes. The solid electrolyte brings several other benefits: it eliminates molten salt contamination of the anode gas, creates a reducing environment enabling low-cost steel vessels, increases current efficiency, and eliminates carbon contamination of the product. New developments presented here, including current collector and low-cost anode designs, amplify these benefits for producing aluminum, magnesium, rare-earths, and other metals.IntroductionReactive metals such as magnesium, aluminum and rare-earths play increasing roles in efficient transportation and clean energy. In response to new fuel economy standards, automotive OEMs are planning large increases in use of aluminum and magnesium to reduce vehicle weight. Rareearth permanent magnet motors and generators exhibit better power-to-weight and efficiency than induction motors and other designs, making this today's primary motor technology for hybrid and electric vehicles, and for wind turbines. Nickel metal hydride (NiMH) batteries with lanthanum are dominant in hybrids. In 2011, transportation comprised 28.6 out of 103.1 EJ of US energy consumption [1] and 1,845 out of 5,471 million metric tonnes (MMT = 109 kg) CO2e of US greenhouse gas (GHG) emissions [1], creating big targets for economy-wide reductions.Unfortunately processes for making reactive metals for these applications are very inefficient and heavily-polluting. In primary aluminum production, Hall-Heroult cell electricity use [2] is more than double the reaction enthalpy due to heat losses through frozen cryolite side-walls and anode gases, graphite anode plants add significant energy use and GHG emissions [2] (see Table 1). Magnesium is even worse: silicothermic reduction by the Pidgeon process in China produces about 85% of the world's magnesium using coal or coke gas [3]. Chloride electrolysis begins with high-purity MgO and requires carbochlorination or hydrochlorination and costly chloride dehydration [4]—rendered unnecessary for aluminum by the Hall-Heroult cell. Production of neodymium and lanthanum with graphite anodes leads to inconsistent carbon content: small cells make 1 kg batches for analysis, sorting and sale by carbon content, with very high labor and analysis costs. And vertical electrodes give no incentive to reduce anode effect: some reports indicate that China's rare-earth metal industry emits more CF4 and C2F6—with global warming potential (GWP) 6500 and 9200 times CO2 respectively—than China's aluminum industry [5]."

Jan 1, 2014

By Ramana G. Reddy

Thermodynamic modeling and experimental study on impurity capacities and their distribution between mattes or metal and slags in smelting, converting and refining of non-ferrous metals was discussed. A brief review on the recent developments in copper smelting and converting is presented. The analysis showed that, copper smelting capacity increased by a factor of 10 since 60's, smelting rate increased by a factor of more than 5 and process fuel equivalent decreased by a factor of 2. A thermodynamic model for prediction of impurities capacities in slags and their distribution in mattes and slags was developed. The impurities capacities (i.e. sulfur and arsenic) of slags were calculated a priori with no adjustable parameters using the Reddy-Blander model. The capacities predictions were made in a wide range of matte and slag compositions, PSo, and temperatures in conditions pertaining to copper and lead industrial slags. The calculated results for sulfide and arsenate capacities are in good agreement with the available experimental and industrial copper and lead industrial slags data. The sulfide and arsenate capacities in copper slags (fayalite, ferrite and olivine) and lead slags are reviewed. The application of RB model predicted ratios of O2 and S2 partial pressures in industrial copper smelting processes are discussed. Application of this model for the prediction of Sb, Bi and other impurity capacities and their distribution ratios in mattes or metal and slags, in industrial smelting and refining processes is discussed.

Jan 1, 2003