Effect of reduction roasting by using bio-char derived from empty fruit bunch on the magnetic properties of Malaysian iron ore

Beneficiation of Malaysian iron ore is becoming necessary as iron resources are depleting. However, the upgrading process is challenging because of the weak magnetic properties of Malaysian iron ore. In this study, bio-char derived from oil palm empty fruit bunch (EFB) was utilized as an energy source for reduction roasting. Mixtures of Malaysian iron ore and the bio-char were pressed into briquettes and subjected to reduction roasting processes at 873–1173 K. The extent of reduction was estimated on the basis of mass loss, and the magnetization of samples was measured using a vibrating sample magnetometer (VSM). When reduced at 873 K, the original goethite-rich ore was converted into hematite. An increase in temperature to 1073 K caused a significant conversion of hematite into magnetite and enhanced the magnetic susceptibility and saturation magnetization of samples. The magnetic properties diminished at 1173 K as the iron ore was partially reduced to wustite. This reduction roasting by using the bio-char can assist in upgrading the iron ore by improving its magnetic properties.     

Isothermal reduction of titanomagnetite concentrates containing coal

The isothermal reduction of the Panzhihua titanomagnetite concentrates (PTC) briquette containing coal under argon atmosphere was investigated by thermogravimetry in an electric resistance furnace within the temperature range of 1250–1350℃. The samples reduced in argon at 1350℃ for different time were examined by X-ray diffraction (XRD) analysis. Model-fitting and model-free methods were used to evaluate the apparent activation energy of the reduction reaction. It is found that the reduction rate is very fast at the early stage, and then, at a later stage, the reduction rate becomes slow and decreases gradually to the end of the reduction. It is also observed that the reduction of PTC by coal depends greatly on the temperature. At high temperatures, the reduction degree reaches high values faster and the final value achieved is higher than at low temperatures. The final phase composition of the reduced PTC-coal briquette consists in iron and ferrous-pseudobrookite (FeTi₂O₅), while Fe_2.75Ti_0.25O₄, Fe_2.5Ti_0.5O₄, Fe_2.25Ti_0.75O₄, ilmenite (FeTiO₃) and wustite (FeO) are intermediate products. The reaction rate is controlled by the phase boundary reaction for reduction degree less than 0.2 with an apparent activation energy of about 68 kJ·mol?1 and by three-dimensional diffusion for reduction degree greater than 0.75 with an apparent activation energy of about 134 kJ·mol?1. For the reduction degree in the range of 0.2–0.75, the reaction rate is under mixed control, and the activation energy increases with the increase of the reduction degree.     

Phase transformation and reduction kinetics during the hydrogen reduction of ilmenite concentrate

The reduction of ilmenite concentrate by hydrogen gas was investigated in the temperature range of 500 to 1200℃. The microstructure and phase transition of the reduction products were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), and optical microscopy (OM). It was found that the weight loss and iron metallization rate increased with the increase of reduction temperature and reaction time. The iron metallization rate could reach 87.5% when the sample was reduced at 1150℃ for 80 min. The final phase constituents mainly consist of Fe, M₃O₅ solid solution phase (M=Mg, Ti, and Fe), and few titanium oxide. Microstructure analysis shows that the surfaces of the reduction products have many holes and cracks and the reactions take place from the exterior of the grain to its interior. The kinetics of reduction indicates that the rate-controlling step is diffusion process control with the activation energy of 89 kJ·mol-1.     

Effects of Na<Subscript>2</Subscript>SO<Subscript>4</Subscript> on iron and nickel reduction in a high-iron and low-nickel laterite ore

This study investigates the reactions of Na₂SO₄ and its effects on iron and nickel reduction in the roasting of a high-iron and low-nickel laterite ore through gas composition, X-ray diffraction, and scanning electron microscope analyses. Results showed that a reduction reaction of Na₂SO₄ to SO₂ was performed with roasting up to 600℃. However, no clear influence on iron and nickel reductions appeared, because only a small amount of Na₂SO₄ reacted to produce SO₂. Na₂SO₄ reacted completely at 1000℃, mainly producing troilite and nepheline, which remarkably improves selective reduction of nickel. Furthermore, the production of low-melting-point minerals, including troilite and nepheline, accelerated nickel reduction and delayed iron reduction, which is attributed to the concurrent production of magnesium magnetite, whose structure is more stable than the structure of magnetite. Reduction reactions of Na₂SO₄ resulted in weakening of the reduction atmosphere, and the main product of Na₂SO₄ changed and delayed the reduction of iron. Eventually, iron metallization was effectively controlled during laterite ore reduction roasting, leading to iron mainly being found in wustite and high iron-containing olivine.     

添加CaCO3后碳热还原钒钛磁铁矿精矿过程中钛酸钙的形成

The formation of calcium titanate in the carbothermic reduction of vanadium titanomagnetite concentrate (VTC) by adding CaCO₃ was investigated. Thermodynamic analysis was employed to show the feasibility of calcium titanate formation by the reaction of ilmenite and CaCO₃ in a reductive atmosphere, where ilmenite is more easily reduced by CO or carbon in the presence of CaCO₃. The effects of CaCO₃ dosage and reduction temperature on the phase transformation and metallization degree were also investigated in an actual roasting test. Appropriate increase of CaCO₃ dosages and reduction temperatures were found to be conducive to the formation of calcium titanate, and the optimum conditions were a CaCO₃ dosage of 18wt% and a reduction temperature of 1400°C. Additionally, scanning electron microscopy–energy dispersive spectrometry (SEM–EDS) analysis shows that calcium titanate produced via the carbothermic reduction of VTC by CaCO₃ addition was of higher purity with particle size approximately 50 μm. Hence, the separation of calcium titanate and metallic iron will be the focus in the future study.     

Carbothermal reduction process of the Fe-Cr-O system

Understanding the reduction behaviors and characteristics of the end products of Fe-Cr-O systems is very important not only for maximizing the recovery of metals from stainless steel dust but also for the subsequent reuse in metallurgical process. The present work first predicted the possible products thermodynamically when FeCr₂O₄ was reduced by C. The reduction behaviors by graphite of three kinds of Fe-Cr-O systems, i.e., FeCr₂O₄, Fe₂O₃+Cr₂O₃, and Fe+Cr₂O₃, were then investigated in 1350–1550℃. Further, the microstructures of final products and element distribution conditions were examined. The results suggest that, thermodynamically, the mass of products for the carbothermal reduction of FeCr₂O₄ is a strong function of temperature, and the initial carbon content is used. More Fe-Cr-C solution and less residual carbon content are obtained at higher temperatures and lower n_C:n_O ratios (the initial molar ratio of C to O in the sample). Experimental data show that the sample amount tends to affect the reduction rate, and the residual carbon content strongly depends on n_C:n_O. With regard to the phases present in products during the reaction process, metal carbides tend to form in the initial stage, whereas Fe-Cr-C solution forms when the degree of reduction is sufficiently high.     

Reduction kinetics of iron oxide pellets with H_2 and CO mixtures

Reduction of hematite pellets using H2–CO mixtures with a wide range of H2/CO by molar(1:0, 3:1, 1:1, 1:3, and 0:1) at different reducing temperatures(1073, 1173, and 1273 K) was conducted in a program reducing furnace. Based on an unreacted core model, the effective diffusion coefficient and reaction rate constant in several cases were determined, and then the rate-control step and transition were analyzed. In the results, the effective diffusion coefficient and reaction rate constant increase with the rise in temperature or hydrogen content. Reduction of iron oxide pellets using an H2–CO mixture is a compound control system; the reaction rate is dominated by chemical reaction at the very beginning, competition during the reduction process subsequently, and internal gas diffusion at the end. At low hydrogen content, increasing temperature takes the transition point of the rate-control step to a high reduction degree, but at high hydrogen content, the effect of temperature on the transition point weakens.     

钙化合物对钒钛磁铁矿精矿碳热还原的影响

Effects of calcium compounds on the carbothermic reduction of vanadium titanomagnetite concentrate (VTC) were investigated. It was found that calcium compounds had great effects on the metallization rate of the reduction product, the order of the metallization rate of reduction product being CaCO₃ > no additive > CaSO₄ > CaCl₂, which indicated that the addition of CaCO₃ was more conducive to promoting the reduction of iron than other calcium compounds. Gas analysis showed that there were mainly two processes in the carbothermic reduction of VTC, a solid–solid and a solid–gas reaction. The concentrations of CO and CO₂ were highest when CaCO₃ was added, while that in a roasting system decreased the most when CaCl₂ was added. X-ray diffraction (XRD) analysis showed that calcium compounds could change the reduction process of ilmenite in VTC. The phase compositions of the reduction products were changed from metallic iron (Fe) and anosovite (FeTi₂O₅) to metallic iron (Fe) and perovekite (CaTiO₃) when calcium compounds were added. Additionally, CaSO₄ and CaCl₂ could significantly promote the growth of metallic iron particles, though the existence of Fe-bearing Mg₂TiO₄ in reduction products was not conducive to the reduction of iron. The formation of FeS would further hinder the reduction of iron after adding CaSO₄.     

Direct reduction of iron ore by biomass char

By using thermogravimetric analysis the process and mechanism of iron ore reduced by biomass char were investigated and compared with those reduced by coal and coke. It is found that biomass char has a higher reactivity. The increase of carbon-to-oxygen mole ratio (C/O) can lead to the enhancement of reaction rate and reduction fraction, but cannot change the temperature and trend of each reaction. The reaction temperature of hematite reduced by biomass char is at least 100 K lower than that reduced by coal and coke, the maximum reaction rate is 1.57 times as high as that of coal, and the final reaction fraction is much higher. Model calculation indicates that the use of burden composed of biomass char and iron ore for blast furnaces can probably decrease the temperature of the thermal reserve zone and reduce the CO equilibrium concentration.     

Ultra-fine grinding and mechanical activation of mine waste rock using a high-speed stirred mill for mineral carbonation

CO₂ sequestration by mineral carbonation can permanently store CO₂ and mitigate climate change. However, the cost and reaction rate of mineral carbonation must be balanced to be viable for industrial applications. In this study, it was attempted to reduce the carbonation costs by using mine waste rock as a feed stock and to enhance the reaction rate using wet mechanical activation as a pre-treatment method. Slurry rheological properties, particle size distribution, specific surface area, crystallinity, and CO₂ sequestration reaction efficiency of the initial and mechanically activated mine waste rock and olivine were characterized. The results show that serpentine acts as a catalyst, increasing the slurry yield stress, assisting new surface formation, and hindering the size reduction and structure amorphization. Mechanically activated mine waste rock exhibits a higher carbonation conversion than olivine with equal specific milling energy input. The use of a high-speed stirred mill may render the mineral carbonation suitable for mining industrial practice.     

Agglomeration Mechanism of Rich Hematite Sinter with Lowering SiO2 Content

The mini-sintering test was introduced. The experiments of specimens of rich hematite with lowering SiO₂ content were carried out by the mini-sintering test. The strength and mechanism of agglomeration were studied mainly when silica content in sintered specimens was decreased gradually. The relationships between SiO₂ volume and morphology of sinter were also investigated. It is considered that high grade sinter can be developed by raising sinter basicity so as to enhance complex calcium ferrite content or lowering sinter basicity so as to make Fe₂O₃ bonding for strength.     

Staged reaction kinetics and characteristics of iron oxide direct reduction by carbon

Staged reduction kinetics and characteristics of iron oxide direct reduction by carbon were studied in this work. The characteristics were investigated by simultaneous thermogravimetric analysis, X-ray diffraction (XRD), and quadrupole mass spectrometry. The kinetics parameters of the reduction stages were obtained by isoconversional (model-free) methods. Three stages in the reduction are Fe₂O₃→Fe₃O₄, Fe₃O₄→FeO, and FeO→Fe, which start at 912 K, 1255 K, and 1397 K, respectively. The CO content in the evolved gas is lower than the CO₂ content in the Fe₂O₃→Fe₃O₄ stage but is substantially greater than the CO₂ contents in the Fe₃O₄→FeO and FeO→Fe stages, where gasification starts at approximately 1205 K. The activation energy (E) of the three stages are 126–309 kJ/mol, 628 kJ/mol, and 648 kJ/mol, respectively. The restrictive step of the total reduction is FeO→Fe. If the rate of the total reduction is to be improved, the rate of the FeO→Fe reduction should be improved first. The activation energy of the first stage is much lower than those of the latter two stages because of carbon gasification. Carbon gasification and Fe_xO_y reduction by CO, which are the restrictive step in the last two stages, require further study.     

Morphological and mineralogical characterizations of oolitic iron ore in the Exi region, China

The morphological and mineralogical characterizations of a Chinese oolitic iron ore (Exi deposit) were studied by scanning electron microscopy and energy-dispersive X-ray spectroscopy in this work. It is shown that the Exi ore is mainly composed of hematite, quartz, apatite, and chlorite. The hematite is present as the oolitic layers and in the spaces between the aggregated ooids; quartz exists as granular particles in the spaces and as nucleuses in ooids; the harmful mineral, apatite, is associated with hematite as the oolitic layers, fine dissemination, granular particles in the spaces, and nucleuses in ooids. From the viewpoint of mineral beneficiation, it is hard to separate apatite and chlorite but easy to separate quartz from hematite in the Exi iron ore in recovering the iron values.     

Generation process of FeS and its inhibition mechanism on iron mineral reduction in selective direct reduction of laterite nickel ore

Numerous studies have demonstrated that Na₂SO₄ can significantly inhibit the reduction of iron oxide in the selective reduction process of laterite nickel ore. FeS generated in the process plays an important role in selective reduction, but the generation process of FeS and its inhibition mechanism on iron reduction are not clear. To figure this out, X-ray diffraction and scanning electron microscopy analyses were conducted to study the roasted ore. The results show that when Na₂SO₄ is added in the roasting, the FeO content in the roasted ore increases accompanied by the emergence of FeS phase. Further analysis indicates that Na₂S formed by the reaction of Na₂SO₄ with CO reacts with SiO₂ at the FeO surface to generate FeS and Na₂Si₂O₅. As a result, a thin film forms on the surface of FeO, hindering the contact between reducing gas and FeO. Therefore, the reduction of iron is depressed, and the FeO content in the roasted ore increases.     

基于优化氧化铁皮和焦粉配比的铁矿烧结过程NOx减排研究

Reducing NO_x emission of iron ore sintering process in a cost effective manner is a challenge for the iron and steel industry at present. Effects of the proportion of mill scale and coke breeze on the NO_x emission, strength of sinter, and sinter indexes were studied by combustion and sinter pot tests. Results showed that the peak value of NO concentration, total of NO emission, and fuel-N conversion rate gradually decreased as the proportions of the mill scale increased because NO was reduced to N₂ by Fe₃O₄, FeO, and Fe in the mill scale. The strength of sinter reached the highest value at 8.0wt% mill scale due to the formation of minerals with low melting point. The fuel-N conversion rate slightly fluctuated and total NO_x emission significantly decreased with the decreased proportions of coke breeze because CO formation and content of N element in the sintered mixture decreased. However, the sinter strength also decreased due to the decrease in the amount of the melting minerals. Furthermore, results of the sinter pot tests indicated that NO_x emission decreased. The sinter indexes performed well when the proportions of mill scale and coke breeze were 8.0wt% and 3.70wt% respectively in the sintered mixture.     

Kinetics of Hydrogen Absorption in Hydrogen Storage Alloy

Hydrogenation kinetics of MLNi_3.8(Co,Mn,Al)_1.2 and MLNi_3.7(Co,Mn,Al)_1.2Cu_0.1 alloy in α + β phase at the temperature range of 30~70 ℃ has been studied. The kinetic mechanism of hydrogen absorption is not affected by initial hydrogen pressure. Temperature does not influence the rate of hydrogen absorption obviously. In the prior and later period of hydrogen absorption the rate-controlling step is chemical reaction and hydrogen diffusion in the hydride phase respectively for MLNi_3.8(Co,Mn,Al)_1.2 alloy. Adding Cu, the rate-controlling step changes from chemical reaction to the nucleation and growth of β phase in the prior period and the process of hydrogen absorption still controlled by diffusion in the later period.     

Comparison of reduction disintegration characteristics of TiO2-rich burdens prepared with sintering process and composite agglomeration process

To reveal the impact of the composite agglomeration process (CAP) on the reduction disintegration properties of TiO₂-rich ironmaking burden for a blast furnace, the reduction disintegration indices (RDIs), mineral constituents, and microstructure of the products prepared by the CAP and the traditional sintering process (TSP) were investigated. The results showed that, compared to the sinter with a basicity of 2.0 prepared by the TSP, the RDI_+6.3 and the RDI_+3.15 of the CAP product with the same basicity increased by 28.2wt% and 13.7wt%, respectively, whereas the RDI_-0.5 decreased by 2.7wt%. The analysis of the mineral constituents and microstructure of the products indicated that the decreasing titanohematite content decreased the volume expansion during reduction. Meanwhile, the decreasing perovskite content decreased its detrimental effect on the reduction disintegration properties. In addition, the higher silicoferrite of calcium and aluminum (SFCA) content improved the strength of the CAP product. Together, these factors result in an improvement of the RDI of the CAP products. In addition, compared to the sinter, the reduced CAP products clearly contained fewer cracks, which also led to mitigation of reduction disintegration.     

Magnetic and flotation studies of banded hematite quartzite (BHQ) ore for the production of pellet grade concentrate

To identify and establish beneficiation techniques for banded hematite quartzite (BHQ) iron ore, a comprehensive research on BHQ ore treatment was carried out. The BHQ ore was assayed as 38.9wt% Fe, 42.5wt% SiO₂, and 1.0wt% Al₂O₃. In this ore, hematite and quartz are present as the major mineral phases where goethite, martite, and magnetite are present in small amounts. The liberation of hematite particles can be enhanced to about 82% by reducing the particle size to below 63 μm. The rejection of silica particles can be obtained by magnetic and flotation separation techniques. Overall, the BHQ ore can be enriched to 65.3wt% Fe at 61.9% iron recovery. A flowsheet has been suggested for the commercial exploitation of the BHQ ore.     

Mechanism research on arsenic removal from arsenopyrite ore during a sintering process

The mechanism of arsenic removal during a sintering process was investigated through experiments with a sintering pot and arsenic-bearing iron ore containing arsenopyrite; the corresponding chemical properties of the sinter were determined by inductively coupled plasma atomic emission spectrometry (ICP-AES), X-ray diffraction (XRD), and scanning electron microscopy (SEM) coupled with energy-dispersive X-ray spectroscopy (EDS). The experimental results revealed that the reaction of arsenic removal is mainly related to the oxygen atmosphere and temperature. During the sintering process, arsenic could be removed in the ignition layer, the sinter layer, and the combustion zone. A portion of FeAsS reacted with excess oxygen to generate FeAsO₄, and the rest of the FeAsS reacted with oxygen to generate As₂O₃(g) and SO₂(g). A portion of As₂O₃(g) mixed with Al₂O₃ or CaO, which resulted in the formation of arsenates such as AlAsO₄ and Ca₃(AsO₄)₂, leading to arsenic residues in sintering products. The FeAsS component in the blending ore was difficult to decompose in the preliminary heating zone, the dry zone, or the bottom layer because of the relatively low temperatures; however, As₂O₃(g) that originated from the high-temperature zone could react with metal oxides, resulting in the formation of arsenate residues.     

Carbothermic reduction of vanadium titanomagnetite with the assistance of sodium carbonate

The carbothermic reduction of vanadium titanomagnetite concentrate(VTC)with the assistance of Na₂CO₃was conducted in an argon atmosphere between 1073 and 1473 K.X-ray diffraction and scanning electron microscopy were used to investigate the phase transformations during the reaction.By investigating the reaction between VTC and Na₂CO₃,it was concluded that molten Na₂CO₃broke the structure of titanomagnetite by combining with the acidic oxides(Fe₂O₃,TiO₂,Al₂O₃,and SiO₂)to form a Na-rich melt and release FeO and MgO.Therefore,Na₂CO₃accelerated the reduction rate.In addition,adding Na₂CO₃also benefited the agglomeration of iron particles and the slag–metal separation by decreasing the viscosity of the slag.Thus,Na₂CO₃assisted carbothermic reduction is a promising method for treating VTC at low temperatures.