Influence of CaO-SiO2-Al2O3 Ternary Oxide System on the Reduction Behavior of Carbon Composite Pellet: Part II. Morphological Properties

Carbon composite pellets composed of hematite, synthetic graphite, and oxide system were reduced at 1773 K (1500 °C) in a laboratory-scale horizontal tube furnace. The morphological properties of produced pellets after reduction were examined using light optical microscopy and a scanning electron microscope. Microscopic observation confirmed the correlation between morphological change of pellets and compositional difference of CaO-SiO₂-Al₂O₃ ternary oxide systems. Samples were also analyzed by X-ray diffraction to investigate phase change during the reduction process. The impact of oxide chemistry was established as each pellet illustrated different states of iron oxide as a function of time. In addition, the surface area was measured by the BET-N₂ absorption method to clarify the reaction mechanism which is significantly affected by physical contact.     

The reduction of iron oxides by volatiles in a rotary hearth furnace process: Part II. The reduction of iron oxide/carbon composites

The reduction of iron oxide/carbon composite pellets with hydrogen at 900 °C to 1000 °C was studied. Compared to hydrogen, the reduction by carbon was negligible at 900 °C and below. However, significant carbon oxidation of the iron oxide/graphite pellets by H₂O generated from the reduction of Fe₂O₃ by H₂ was observed. At higher temperatures, reduction by carbon complicates the overall reduction mechanism, with the iron oxide/graphite composite pellet found to be more reactive than the iron oxide/char composite pellet. From the scanning electron micrographs, partially reduced composite pellets showed a typical topochemical interface with an intermediate region between an oxygen-rich unreacted core and an iron-rich outer shell. To determine the possibility of reduction by volatiles, a layer of iron oxide powders was spread on top of a high volatile containing bituminous coal and heated inside a reactor using infra-red radiation. By separating the individual reactions involved for an iron oxide/coal mixture where a complex set of reactions occur simultaneously, it was possible to determine the sole effect of volatile reduction. It was found that the light reducing gases evolve initially and react with the iron oxide, with complex hydrocarbons evolving at the later stages. The volatiles caused about 20 to 50 pct reduction of the iron oxide.     

Reduction Behavior of Panzhihua Titanomagnetite Concentrates with Coal

The reduction behavior of the Panzhihua titanomagnetite concentrates (PTC) briquette with coal was investigated by temperature-programmed heating under argon atmosphere in a vertical tube electric furnace. The mass loss behavior of the PTC-coal mixture was checked by thermogravimetric analysis method in argon with a heating rate of 5 K (5 °C)/ min. It was found that there are five stages during the carbothermic reduction process of the PTC. The devolatilization of coal occurred in the first stage, and reductions of iron oxides mainly occurred in the second and third stages. The reduction rate of iron oxide in the third stage was much higher than that in the second stage because of the significant rate of carbon gasification reaction. The iron in the ilmenite was reduced in the fourth stage. In the final stage, the rutile was partially reduced to lower valence oxides. The phase transformation of the briquette reduced at different temperatures was investigated by X-ray diffraction (XRD). The main phases of sample reduced at 1173 K (900 °C) are metallic iron, ilmenite (FeTiO₃), and titanomagnetite (Fe_3–x Ti _x O₄). The traces of rutile (TiO₂) were observed at 1273 K (1000 °C). The iron carbide (Fe₃C) and ferrous-pseudobrookite (FeTi₂O₅) appeared at 1473 K (1200 °C). The titanium carbide was found in the sample reduced at 1623 K (1350 °C). The shrinkages of reduced briquettes, which increased with increase in the temperature, were found to depend greatly on the temperature. With increasing the reduction temperature to 1573 K (1300 °C), the iron nuggets were observed outside of the samples reduced. The nugget formation can indicate a new process of ironmaking with titanomagnetite similar to ITmk3 (Ironmaking Technology Mark 3).     

Effect of Metal Additions to the Reduction of Iron Oxide Composite Pellets with Hydrogen at Moderate Temperatures

The hydrogen reduction behavior of iron oxide composite pellets containing Ni, Fe, and Mn from 973 K to 1173 K was compared with iron oxide and Al₂O₃ containing reference composite pellets to determine the effect of metallic species on the kinetics of iron oxide reduction. The Mn and Ni containing pellets showed slightly faster initial reduction rates compared to the Fe and Al₂O₃ containing pellets. The effect of the metal phases was found to be more significant at lower temperatures when chemical reaction at the interface is a slower and more controlling factor. From the SEM of partially reduced pellets, a wide intermediate region between an O rich unreacted core and an Fe rich outer shell was observed. Although an initially short topochemical receding interface controlled region exists, the mixed control between the topochemical receding interface and pore diffusion was prevalent. For Fe₂O₃/Mn composite pellets, the thermodynamic stability of the MnO is higher and Mn can act as a reductant for iron oxide. Thus, the overall metallization of the Fe₂O₃/Mn composite pellets decreased compared to the other Fe₂O₃/metal composite pellets. From the temperature dependence of the iron‐oxide/metal composite pellets, the apparent activation energy was calculated to be approximately between 15 to 20 kJ/mol, which is typical of a mixed control reduction mechanism of gas diffusion and interface reaction.     

Re-oxidation Kinetics of Flash-Reduced Iron Particles in H2-H2O(g) Atmosphere Relevant to a Novel Flash Ironmaking Process

A novel flash ironmaking process based on hydrogen-containing reduction gases is under development at the University of Utah. The goal of this work was to study the possibility of the re-oxidation of iron particles in a H₂-H₂O gas mixture in the lower part of the flash reactor from the kinetic point of view. The last stage of hydrogen reduction of iron oxide, i.e., the reduction of wustite, is limited by equilibrium. As the reaction mixture cools down, the re-oxidation of iron could take place because of the decreasing equilibrium constant and the high reactivity of the freshly reduced fine iron particles. The effects of temperature and H₂O partial pressure on the re-oxidation rate were examined in the temperature range of 823 K to 973 K (550 °C to 700 °C) and H₂O contents of 40 to 100 pct. The nucleation and growth kinetics model was shown to best describe the re-oxidation kinetics. The partial pressure dependence with respect to water vapor was determined to be of first order, and the activation energy of re-oxidation reaction was 146 kJ/mol. A complete rate equation that adequately represents the experimental data was developed.     

Effects of Binder on the Properties of Iron Ore-Coal Composite Pellets

Large amounts of fines and superfines are generated in Indian iron ore and coal mines due to mechanized mining and mineral dressing operations. Utilization of these fines for extracting metal is of vital concern for resource utilization and pollution control. For agglomeration of these fines, a suitable binder is required. Iron ore-coal composite pellets were prepared by cold bonding. Various binders such as lime, Ca(OH)₂, slaked lime, dextrose, molasses, and sodium polyacrylate (SPA), alone or in combination, were employed for making composite briquettes. The slaked lime–dextrose combination produced the highest strength among the various binders employed for producing composite briquettes and was therefore selected for producing composite pellets for the smelting reduction. In cold bonding, the composite pellets attain the requisite properties due to physico-chemical changes of the binder in ambient conditions. It was possible to obtain a dry strength of more than 300 N per pellet in some cases and more than 200 N per pellet in many trials. Drop strength and shatter index values of composite pellets were also measured. In the present paper an attempt has been made to evaluate the mechanical properties of cold-bonded composite pellets so as to throw some light on the capacity of these pellets to withstand stresses during handling and transportation.     

LEACHING RATES OF ICEL-YAVCA DOLOMITE IN HYDROCHLORIC ACID SOLUTION

Additives can give rise to obvious, step-wise changes both in the oxidation process and in the sintering process. Therefore, the oxidation and sintering characteristics measured in dried pellets prepared from pure magnetite concentrates can not be representative for those characteristics in dried pellets containing additives. The oxidation and sintering characteristics of magnetite iron ore pellets balled with a novel complex binder (namely MHA) were mainly investigated by batch isothermal oxidation measurements in this research. Combined results reveal that the thermal decomposition of MHA binder influences the oxidation and sintering processes of dried pellets. Oxidation rate of pellets increases obviously with increasing the oxidation temperature in the range from 800°C to 1000°C. And the remaining FeO content declines gradually when separately heated for 10 min at low temperature (<1000°C). However, the oxidation rate of pellets decreases distinctly when oxidation temperature is higher than 1000°C. In addition, when oxidation temperature increases from 1000°C to 1250°C, the FeO content of pellets goes up obviously, particularly at 1250°C. The FeO content in the core of sintered pellets heated at 1250°C can even reach 29.68%. SEM spectrum analysis demonstrate that some iron appears in forms of wustite in sintered pellets, which indicates that the reduction reaction of iron oxide occurs during the high temperature sintering process. This is explained by the occurrence of reducing atmospheres because of the pyrogenic decomposition of MHA binder.     

Effect of CaO on the reduction behaviour of iron ore–coal composite pellets in multi-layer bed rotary hearth furnace

The effect of CaO on the reduction behaviour of iron ore–coal composite pellets has been studied in a laboratory scale multi-layer bed rotary hearth furnace at 1250°C for 20?min. Reduced pellets have been characterised through weight loss, porosity measurement, phase analysis by XRD, and morphology study by SEM. The addition of CaO to the composite pellets showed different effects at different carbon levels. For higher carbon-containing pellets (C/Fe₂O₃ molar ratio at the upper stoichiometric level of 3), the addition of CaO increased the extent of reduction for all three layers significantly up to a certain limit (4?wt-%); and thereafter the degree of reduction is decreased with a further increase in CaO percentage in the pellets. For low carbon-containing pellets (C/Fe₂O₃ molar ratio of 1.66), the addition of CaO to the pellets did not show any beneficial effect.     

Preparation of Aluminum Metal Matrix Composite with Novel In situ Ceramic Composite Particulates, Developed from Waste Colliery Shale Material

A novel method is adapted to prepare an in situ ceramic composite from waste colliery shale (CS) material. Heat treatment of the shale material, in a plasma reactor and/or in a high temperature furnace at 1673 K (1400 °C) under high vacuum (10^?6 Torr), has enabled in situ conversion of SiO₂ to SiC in the vicinity of carbon and Al₂O₃ present in the shale material. The composite has the chemical constituents, SiC-Al₂O₃-C, as established by XRD/EDX analysis. Particle sizes of the composite range between 50 nm and 200 μm. The shape of the particles vary, presumably rod to spherical shape, distributed preferably in the region of grain boundaries. The CS composite so produced is added to aluminum melt to produce Al-CS composite (12 vol. pct). For comparison of properties, the aluminum metal matrix composite (AMCs) is made with Al₂O₃ particulates (15 vol. pct) with size <200 μm. The heat-treated Al-CS composite has shown better mechanical properties compared to the Al-Al₂O₃ composite. The ductility and toughness of the Al-CS composite are greater than that of the Al-Al₂O₃ composite. Fractographs revealed fine sheared dimples in the Al-CS composite, whereas the same of the Al-Al₂O₃ composite showed an appearance of cleavage-type facets. Abrasion and frictional behavior of both the composites have been compared. The findings lead to the conclusion that the in situ composite developed from the colliery shale waste material has a good future for its use in AMCs.     

The Effect of Reduction Parameters on Iron Nugget Production From Composite Pellets

Composite pellets which contain a reducing agent and are produced only by cold bonding process are improved instead of traditionally hardened pellets by sintering. The new ironmaking technologies that are able to utilize these pellets have been developed from pilot plant to commercial scale. Iron nuggets which have a similar composition to pig iron can be produced by using composite pellets at high temperatures (1350–1400°C) and in a short reduction time (15–20 min) by smelting reduction process. In this study, the effect of reduction parameters and basicity of composite pellets on the reduction properties and product quality are investigated. Composite pellets containing magnetite concentrate with a reducing agent (coke) and a flux are processed at different temperature and at times by smelting reduction process. The increasing temperature and time has a positive effect on reduction and melting of the pellets. Excessive carbon prevents the metal droplets from coalescing. The iron nugget that is produced from the sample with the basicity (CaO/SiO₂) of 0.68 has the optimal physical and chemical properties. It is also determined that a decrease or increase of basicity has a negative effect on the properties of the iron nuggets.     

Strength and high temperature behaviour of carbon composite pellets containing BOF fine dust

Abstract

Steel plants produce significant amounts of dust and sludge during iron and steel production. These wastes contain valuable elements, such as Fe, Cr, Ni, C, K and Na and should be handled properly to prevent them from polluting the environment. In order to utilise the BOF fine dust, the effects of the dust on cold bonded pelletising, solid state reduction and reduction melting behaviours of composite pellets made from iron ore and anthracite with added BOF fine dust were investigated at laboratory scale. The BOF dust was found to improve the cold compressive strength of the wet green carbon composite pellet, and increased with increasing dust content. Almost four times the amount of dust was needed to get the same effect on the strength of the pellet when it was used to replace bentonite. The carbothermic reduction of the composite pellet proceeded effectively at temperatures above 1200°C. The BOF dust had a positive effect on the reduction rate of the pellet, and the rate increased with increased dust content. The reduction of iron oxide was topochemical and conformed to a shrinking core kinetic model. The dust was found to improve the iron and slag melting separation rate of reduced pellets at 1400°C when its content was less than 23·11 wt-%. The liquidus temperature of the slag would decrease with the content of BOF dust increasing from zero to ～30 wt-% and then increase if the content continued to become more in the experiment. Utilising the BOF dust as the binder and flux to adjust the composition of the slag system can potentially reduce the slag ratio and production cost compared with using bentonite and limestone. This work can help to find a new process for the effective utilisation of BOF dust in a more appropriate and environmentally friendly way.     

Trace Elements in the Si Furnace-Part II: Analysis of Condensate in Carbothermal Reduction of Quartz

Silicon feedstock for production of solar-grade silicon should be as pure as possible to decrease the cost of manufacturing of solar cells. Impurities in quartz, carbonaceous materials, electrodes, and refractories are mostly present in the form of oxides. These oxides can be reduced to volatile gaseous compounds in presence of SiO(g) and CO(g) atmosphere and potentially leave the furnace or stay in the condensed reaction products, metal, and slag. This work investigates the conditions under which volatile impurities report to the gas phase in laboratory experiments with lumpy and pelletized mixtures of SiO₂, SiC, and Si at 1923 K and 2123 K (1650 °C and 1850 °C), respectively, were carried out. The volatile compounds were generated by the reduction of quartz and collected in the form of condensate. The effects of the reaction temperature, quartz type, charge composition, pellets, and lumps on the composition of the condensate were studied. The trace elements in the charge input, reacting charge, and condensate were analyzed using inductively coupled plasma (ICP)-mass spectroscopy (MS) and X-ray diffraction (XRD). CO(g) and SiO(g), which are the major components in reduction reactions, formed four types of condensate: white, brown, green, and orange. The condensate constituents were amorphous SiO₂, 3C:SiC, Si, and α-quartz. Each impurity present in the quartz charge entered the gas phase during quartz reduction and was detected in the condensate. Al and Fe show limited volatility. The volatility of Mn, P, and B depends on the charge mix: a higher P_CO enhances the concentration of these elements in the gas phase. Fluid inclusions, common in hydrothermal quartz, enhance the distribution of the contaminants to the gas phase. Industrial campaigns on Si and Fe-Si production confirm the experimental results.     

ASSESSMENT OF REDUCTION BEHAVIOR OF HEMATITE IRON ORE PELLETS IN COAL FINES FOR APPLICATION IN SPONGE IRONMAKING

Studies on isothermal reduction kinetics (with F grade coal) in fired pellets of hematite iron ores, procured from four different mines of Orissa, were carried out in the temperature range of 850–1000°C to provide information for the Indian sponge iron plants. The rate of reduction in all the fired iron ore pellets increased markedly with a rise of temperature up to 950°C, and thereafter it decreased at 1000°C. The rate was more intense in the first 30 minutes. All iron ores exhibited almost complete reduction in their pellets at temperatures of 900 and 950°C in < 2 hours' heating time duration, and the final product morphologies consisted of prominent cracks. The kinetic model equation 1 ? (1 ? α)^1/3 = kt was found to fit best to the experimental data, and the values of apparent activation energy were evaluated. Reductions of D. R. Pattnaik and M. G. Mohanty iron ore pellets were characterized by higher activation energies (183 and 150 kJ mol^?1), indicating carbon gasification reaction to be the rate-controlling step. The results established lower values of activation energy (83 and 84 kJ mol^?1) for the reduction of G. M. OMC Ltd. and Sakaruddin iron ore pellets, proposing their overall rates to be controlled by indirect reduction reactions.     

Behaviour of iron ore–fuel oil composite pellets in isothermal and non-isothermal reduction conditions

Abstract

Self-fluxing iron ore pellets as an alternative to the agglomeration process led to the use of low price fuel oil as a binder and reducing material. Composite pellets containing 5–15% fuel oil were isothermally and non-isothermally reduced at 750–1000°C in a flow of H₂ or N₂ gases. The total weight loss resulting from O₂ removal from the reduction of Fe₂ O₃ and from the thermal decomposition of fuel oil was continuously recorded as a function of time at different reduction conditions. The actual reduction extent at a given time was calculated from the chemical analysis of partially reduced samples at a given time and temperature. Microscopic examination and X-ray phase analysis were applied to characterise the reduction products. The isothermal reduction of composite pellets indicated that the reduction rate increased with the increase in fuel oil content at the early stages. At the later stages, the reduction rate increased in the order 12>10>5> 15% fuel oil containing pellets. The non-isothermal reduction of composite pellets in N₂ atmosphere showed the presence of an incubation period at initial reduction stages. The low intensity magnetic separation technique was applied with the aim of increasing the iron content at the expense of associated impurities. The magnetic and non-magnetic fractions were analysed and the overall recovery was determined.     

Reduction of Sn-Bearing Iron Concentrate with Mixed H<Subscript>2</Subscript>/CO Gas for Preparation of Sn-Enriched Direct Reduced Iron

The development of manufacturing technology of Sn-bearing stainless steel inspires a novel concept for using Sn-bearing complex iron ore via reduction with mixed H₂/CO gas to prepare Sn-enriched direct reduced iron (DRI). The thermodynamic analysis of the reduction process confirms the easy reduction of stannic oxide to metallic tin and the rigorous conditions for volatilizing SnO. Although the removal of tin is feasible by reduction of the pellet at 1223 K (950 °C) with mixed gas of 5 vol pct H₂, 28.5 vol pct CO, and 66.5 vol pct CO₂ (CO/(CO + CO₂) = 30 pct), it is necessary that the pellet be further reduced for preparing DRI. In contrast, maintaining Sn in the metallic pellet is demonstrated to be a promising way to effectively use the ore. It is indicated that only 5.5 pct of Sn is volatilized when the pellet is reduced at 1223 K (950 °C) for 30 minutes with the mixed gas of 50 vol pct H₂, 50 vol pct CO (CO/(CO + CO₂) = 100 pct). A metallic pellet (Sn-bearing DRI) with Sn content of 0.293 pct, Fe metallization of 93.5 pct, and total iron content of 88.2 pct is prepared as a raw material for producing Sn-bearing stainless steel. The reduced tin in the Sn-bearing DRI either combines with metallic iron to form Sn-Fe alloy or it remains intact.     

Oxide Transformation in Cr-Mn-Prealloyed Sintered Steels: Thermodynamic and Kinetic Aspects

The main obstacle for utilization of Cr and Mn as alloying elements in powder metallurgy is their high oxygen affinity leading to oxidation risk during powder manufacturing, handling, and especially during further consolidation. Despite the high purity of the commercially available Cr- and Mn-prealloyed iron powder grades, the risk of stable oxide formation during the sintering process remains. Thermodynamic and kinetic simulation of the oxide formation/transformation on the former powder surface during heating and sintering stages using thermodynamic modeling tools (Thermo-Calc and HSC Chemistry) was performed. Simulation is based on the results from the analysis of amount, morphology, and composition of the oxide phases inside the inter-particle necks in the specimens from interrupted sintering trials utilizing advanced analysis tools (HRSEM + EDX and XPS). The effect of the processing parameters, such as sintering atmosphere composition, temperature profile as well as graphite addition on the possible scenarios of oxide reduction/formation/transformation for Fe-Cr-Mn-C powder systems, was evaluated. Results indicate that oxide transformation occurs in accordance with the thermodynamic stability of oxides as follows: Fe₂O₃ → FeO → Fe₂MnO₄ → Cr₂FeO₄ → Cr₂O₃ → MnCr₂O₄ → MnO/MnSiO _x  → SiO₂. Spinel MnCr₂O₄ was identified as the most stable oxide phase at applied sintering conditions up to 1393 K (1120 °C). Controlled conditions during the heating stage minimize the formation of stable oxide products and produce oxide-free sintered parts.     

Texture Evolution as Determined by In situ Neutron Diffraction During Annealing of Iron Deformed by Equal Channel Angular Pressing

In situ neutron diffraction experiments were performed to follow the annealing behavior of iron deformed by equal-channel angular pressing at room temperature using route B _c to a total von Mises strain of ε _vM = 9.2. The temperature was varied from room temperature to 1223 K (950 °C), while neutron diffraction data for quantitative texture analysis were collected at a given temperature when holding for 5 minutes. Pole figures and orientation distribution function maps from neutron diffraction and electron backscatter diffraction measurements were used to follow the changes in crystallographic texture and grain size during annealing. In situ neutron diffraction experiments allowed understanding and identifying texture-related changes that occur during recrystallization, grain growth, and phase transformation in iron.     

Reduction Behaviour of Iron Ore–Coal Composite Pellets in Rotary Hearth Furnace (RHF): Effect of Pellet Shape,Size, and Bed Packing Material

Reduction of iron ore–coal composite pellets in multi-layers at rotary hearth furnace (RHF) is limited by heat and mass transfer. Effect of various parameters like pellet shape, size, and bed packing material that are supposed to influence the heat and mass transfer in the pellet bed, have been investigated, on the reduction behaviour of iron ore–coal composite pellets at 1250 °C for 20 min in a laboratory scale RHF. Reduced pellets have been characterised through weight loss measurement, estimation of shrinkage, porosity, and qualitative, quantitative phase analysis by XRD. A significant difference in the degree of reduction is observed layer-wise in the pellet bed with the variation in pellet shape and size. Pellet bed without any packing material or packed with coal have demonstrated higher degrees of reduction compared to the pellet bed packed with graphite and sand.     

Oxidation of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> Scale-Forming MAX Phases in Turbine Environments

High temperature oxidation of alumina-forming MAX phases, Ti₂AlC and Cr₂AlC, were examined under turbine engine environments and coating configurations. Thermogravimetric furnace tests of Ti₂AlC showed a rapid initial transient due to non-protective TiO₂ growth. Subsequent well-behaved cubic kinetics for alumina scale growth were shown from 1273 K to 1673 K (1000 °C to 1400 °C). These possessed an activation energy of 335 kJ/mol, consistent with estimates of grain boundary diffusivity of oxygen (~375 kJ/mol). The durability of Ti₂AlC under combustion conditions was demonstrated by high pressure burner rig testing at 1373 K to 1573 K (1100 °C to 1300 °C). Here good stability and cubic kinetics also applied, but produced lower weight gains due to volatile TiO(OH)₂ formation in water vapor combustion gas. Excellent thermal stability was also shown for yttria-stabilized zirconia thermal barrier coatings deposited on Ti₂AlC substrates in 2500-hour furnace tests at 1373 K to 1573 K (1100 °C to 1300 °C). These sustained a record 35 µm of scale as compared to 7 μm observed at failure for typical superalloy systems. In contrast, scale and TBC spallation became prevalent on Cr₂AlC substrates above 1423 K (1150 °C). Cr₂AlC diffusion couples with superalloys exhibited good long-term mechanical/oxidative stability at 1073 K (800 °C), as would be needed for corrosion-resistant coatings. However, diffusion zones containing a NiAl-Cr₇C₃ matrix with MC and M₃B₂ particulates were commonly formed and became extensive at 1423 K (1150 °C).     

Use of Iron Ore Fines in Cold-Bonded Self-Reducing Composite Pellets

The feasibility of producing direct reduced iron from cold-bonded, self-reducing composite pellets, constituted from beneficiated iron ore slime, coke, and different binders (dextrin, bentonite, calcium lignosulfonate, and carboxymethyl-cellulose [CMC]) was studied. This was done using a design of experiments approach. It was found that as-received beneficiated iron ore slime is suitable as a raw material for the production of self-reducing composite pellets with carboxymethylcellulose as the most suitable binder. Dry strengths in excess of 300 N/pellet were attained by curing the pellets under ambient conditions. The composite pellets reduced within 20 min to degrees of metallization in excess of 90% at 1100°C, with decrepitation indices significantly below 5%. The degree of metallization of composite pellets increased with an increase in reduction temperature (from 1000 to 1100°C), reduction time (20 min. vs. 40 min), and coke quantity (15% vs. 20%). CMC was identified as the most economical and suitable binder for the Sishen concentrate.