Effect of calcium compounds on direct reduction and phosphorus removal of high-phosphorus iron ore

The increasing demand for iron ore in the world causes the continuous exhaustion of magnetite resources.The utilization of high-phosphorus iron ore becomes the focus.With calcium carbonate(CaCO_(3)),calcium chloride(CaCl_(2)),or calcium sulfate(CaSO_(4))as additive,the process of direct reduction and phosphorus removal of high-phosphorus iron ore(phosphorus mainly occurred in the form of Fe_(3)PO_(7) and apatite)was studied by using the technique of direct reductiongrinding-magnetic separation.The mechanism of calcium compounds to reduce phosphorus was investigated from thermodynamics,iron metallization degree,mineral composition and microstructure.Results showed that Fe_(3)PO_(7) was reduced to elemental phosphorus without calcium compounds.The iron-phosphorus alloy was generated by react of metallic iron and phosphorus,resulting in high phosphorus in reduced iron products.CaCO_(3) promoted the reduction of hematite and magnetite,and improved iron metallization degree,but inhibited the growth of metallic iron particles.CaCl_(2) strengthened the growth of iron particles.However,the recovery of iron was reduced due to the formation of volatile FeCl_(2).CaSO_(4) promoted the growth of iron particles,but the recovery of iron was drastically reduced due to the formation of non-magnetic FeS.CaCO_(3),CaCl_(2) or CaSO_(4) could react with Fe_(3)PO_(7) to form calcium phosphate(Ca_(3)(PO_(4))_(2)).With the addition of CaCO_(3),Ca_(3)(PO_(4))_(2) was closely combined with fine iron particles.It is difficult to separate iron and phosphorus by grinding and magnetic separation,resulting in the reduced iron product phosphorus content of 0.18%.In the presence of CaCl_(2) or CaSO_(4),the boundary between the generated Ca_(3)(PO_(4))_(2) and the metallic iron particles was obvious.Phosphorus was removed by grinding and magnetic separation,and the phosphorus content in the reduced iron product was less than 0.10%.

Migration behaviors and kinetics of phosphorus during coal-based reduction of high-phosphorus oolitic iron ore

To understand the migration mechanisms of phosphorus(P)during coal-based reduction,a high-phosphorus oolitic iron ore was reduced by coal under various experimental conditions.The migration characteristics and kinetics of P were investigated by a field-emission electron probe microanalyzer(FE-EPMA)and using the basic principle of solid phase mass transfer,respectively.Experimental results showed that the P transferred from the slag to the metallic phase during reduction,and the migration process could be divided into three stages:phosphorus diffusing from the slag to the metallic interface,the formation of Fe P compounds at the slag metal interface and P diffusing from the slag metal interface to the metallic interior.The reduction time and temperature significantly influenced the phosphorus content of the metallic and slag phases.The P content of the metallic phase increased with increasing reduction time and temperature,while that of the slag phase gradually decreased.The P diffusion constant and activation energy were determined and a migration kinetics model of P in coal-based reduction was proposed.P diffusion in the metallic phase was the controlling step of the P migration.

Distribution behavior of phosphorus in the coal-based reduction of high-phosphorus-content oolitic iron ore

This study focuses on the reduction of phosphorus from high-phosphorus-content oolitic iron ore via coal-based reduction. The distribution behavior of phosphorus （i.e., the phosphorus content and the phosphorus distribution ratio in the metal, slag, and gas phases） during reduction was investigated in detail. Experimental results showed that the distribution behavior of phosphorus was strongly influenced by the reduction temperature, the reduction time, and the C/O molar ratio. A higher temperature and a longer reaction time were more favor-able for phosphorus reduction and enrichment in the metal phase. An increase in the C/O ratio improved phosphorus reduction but also hin-dered the mass transfer of the reduced phosphorus when the C/O ratio exceeded 2.0. According to scanning electron microscopy analysis, the iron ore was transformed from an integral structure to metal and slag fractions during the reduction process. Apatite in the ore was reduced to P, and the reduced P was mainly enriched in the metal phase. These results suggest that the proposed method may enable utilization of high-phosphorus-content oolitic iron ore resources.

Synchronous enrichment of phosphorus and iron from a high-phosphorus oolitic hematite ore to prepare Fe-P alloy by direct reduction-magnetic separation process

In this study,direct reduction-magnetic separation process was applied to enrich phosphorus and iron to prepare Fe-P crude alloy from a high phosphorus oolitic hematite ore(HPOH).The results show that at lower temperatures and with absence of any of additives,Fe cannot be effectively recovered because of the oolitic structure is not destroyed.In contrast,under the conditions of 15%Na_(2)SO_(4)and reducing at 1050℃ for 120 min with a total C/Fe ratio(molar ratio)of 8.5,a final Fe-P alloy containing 92.40%Fe and 1.09%P can be obtained at an overall iron recovery of 95.43%and phosphorus recovery of 68.98%,respectively.This metallized Fe-P powder can be applied as the burden for production of weathering resistant steels.The developed process can provide an alternative for effective and green utilization of high phosphorus iron ore.

Thermodynamic analysis of the carbothermic reduction of a high-phosphorus oolitic iron ore by FactSage

A thermodynamic analysis of the carbothermic reduction of high-phosphorus oolitic iron ore（HPOIO） was conducted by the Fact Sage thermochemical software. The effects of temperature, C/O ratio, additive types, and dosages both on the reduction of fluorapatite and the formation of liquid slag were studied. The results show that the minimum thermodynamic reduction temperature of fluorapatite by carbon decreases to about 850°C, which is mainly ascribed to the presence of SiO_2, Al_2O_3, and Fe. The reduction rate of fluorapatite increases and the amount of liquid slag decreases with the rise of C/O ratio. The reduction of fluorapatite is hindered by the addition of CaO and Na_2CO_3, thereby allowing the selective reduction of iron oxides upon controlled C/O ratio. The thermodynamic results obtain in the present work are in good agreement with the experimental results available in the literatures.

Clean production of Fe-based amorphous soft magnetic alloys via smelting reduction of high-phosphorus iron ore and apatite

Separated preparation of prealloys and amorphous alloys results in severe solidification-remelting and beneficial element removal-readdition contradictions,which markedly increase energy consumption and emissions.This study offered a novel strategy for the direct production of FePC amorphous soft magnetic alloys via smelting reduction of high-phosphorus iron ore(HPIO)and apatite.First,the thermodynamic conditions and equilibrium states of the carbothermal reduction reactions in HPIO were calculated,and the element content in reduced alloys was theoretically determined.The phase and structural evolutions,as well as element migration and enrichment behaviors during the smelting reduction of HPIO and Ca_(3)(PO_(4))_(2),were then experimentally verified.The addition of Ca_(3)(PO_(4))_(2)in HPIO contributes to the enrichment of the P element in reduced alloys and the subsequent development of Fe_(3)P and Fe_(2)P phases.The content of P and C elements in the range of 1.52 wt% -14.63 wt% and 0.62 wt% -2.47 wt%,respectively,can be well tailored by adding 0-50 g Ca_(3)(PO_(4))_(2)and controlling the C/O mole ratio of 0.8-1.1,which is highly consistent with the calculated results.These FePC alloys were then successfully formed into amorphous ribbons and rods.The energy consumption of the proposed strategy was estimated to be 2.00×10^(8) kJ/t,which is reduced by 30% when compared with the conventional production process.These results are critical for the comprehensive utilization of mineral resources and pave the way for the clean production of Fe-based amorphous soft magnetic alloys.

Diffusion and reaction mechanism of limestone and quartz in fluxed iron ore pellet roasting process

The increase to the proportion of fluxed pellets in the blast furnace burden is a useful way to reduce the carbon emissions in the ironmaking process.In this study,the interaction between calcium carbonate and iron ore powder and the mineralization mechanism of fluxed iron ore pellet in the roasting process were investigated through diffusion couple experiments.Scanning electron microscopy with energy dispersive spectroscopy was used to study the elements’diffusion and phase transformation during the roasting process.The results indicated that limestone decomposed into calcium oxide,and magnetite was oxidized to hematite at the early stage of preheating.With the increase in roasting temperature,the diffusion rate of Fe and Ca was obviously accelerated,while the diffusion rate of Si was relatively slow.The order of magnitude of interdiffusion coefficient of Fe_(2)O_(3)-CaO diffusion couple was 10^(−10) m^(2)·s^(−1) at a roasting temperature of 1200℃for 9 h.Ca_(2)Fe_(2)O_(5) was the initial product in the Fe_(2)O_(3)-CaO-SiO_(2) diffusion interface,and then Ca_(2)Fe_(2)O_(5) continued to react with Fe_(2)O_(3) to form CaFe_(2)O_(4).With the expansion of the diffusion region,the sillico-ferrite of calcium liquid phase was produced due to the melting of SiO_(2) into CaFe_(2)O_(4),which can strengthen the consolidation of fluxed pellets.Furthermore,andradite would be formed around a small part of quartz particles,which is also conducive to the consolidation of fluxed pellets.In addition,the principle diagram of limestone and quartz diffusion reaction in the process of fluxed pellet roasting was discussed.

Ore-blending optimization model for sintering process based on characteristics of iron ores

An ore-blending optimization model for the sintering process is an intelligent system that includes iron ore characteristics, expert knowledge and material balance. In the present work, 14 indices are proposed to represent chemical composition, granulating properties and high temperature properties of iron ores. After the relationships between iron ore characteristics and sintering performance are established, the ＂two-step＂ method and the simplex method are introduced to build the model by distinguishing the calculation of optimized blending proportion of iron ores from that of other sintering materials in order to improve calculation efficiency. The ore-blending optimization model, programmed by Access and Visual Basic, is applied to practical production in steel mills and the results prove that the present model can take advantage of the available iron ore resource with stable sinter yield and quality performance but at a lower cost.

Strengthening iron enrichment and dephosphorization of high-phosphorus oolitic hematite using high-temperature pretreatment

The efficient development and utilization of high-phosphorus oolitic hematite is of great strategic significance for the sustainable supply of iron-ore resources in China.In this paper,the mechanism of high-temperature pretreatment for enhancing the effect of iron enrichment and dephosphorization in the magnetization roasting–leaching process was studied by X-ray diffraction(XRD),vibration sample magnetometer(VSM),scanning electron microscopy and energy dispersive spectrometry(SEM–EDS).Compared with the process without high-temperature pretreatment,the iron grade of the magnetic separation concentrate after high-temperature pretreatment had increased by 0.98%,iron recovery rate had increased by 1.33%,and the phosphorus content in the leached residue had decreased by 0.12%.High-temperature pretreatment resulted in the dehydration and decomposition of hydroxyapatite,the dehydration of limonite and the thermal decomposition of siderite,which can produce pores and cracks and weaken the compactness of the ore,improve the magnetization characteristics of roasted ore,and strengthen the iron enrichment and dephosphorization during the magnetization roasting and leaching process.

Removal of phosphorus from iron ores by chemical leaching

Alkali-leaching and acid-leaching were proposed for the dephosphorization of Changde iron ore, which contains an average of 1.12% for phosphorus content. Sodium hydroxide, sulfuriced, hydrochloric and nitric acids were used for the preparation of leach solutions. The results show that phosphorus occurring as apatite phase could be removed by alkali-leaching, but those occurring in the iron phase could not. Sulfuric acid is the most effective among the three kinds of acid. 91.61% phosphorus removal was attained with 1% sulfuric acid after leaching for 20 rain at room temperature. Iron loss during acid-leaching can be negligible, which was less than 0.25%.The pH value of solution after leaching with1% sulfuric acid was about 0.86, which means acid would not be exhausted during the process and it could be recycled, and the recycle of sulfuric acid solution would make the dephosphorization process more economical.

Influence of gangue existing states in iron ores on the formation and flow of liquid phase during sintering

Gangue existing states largely affect the high-temperature characteristics of iron ores. Using a micro-sintering method and scan- ning electron microscopy, the effects of gangue content, gangue type, and gangue size on the assimilation characteristics and fluidity of liquid phase of five different iron ores were analyzed in this study. Next, the mechanism based on the reaction between gangues and sintering mate- dais was unraveled. The results show that, as the SiO2 levels increase in the iron ores, the lowest assimilation temperature （LAT） decreases, whereas the index of fluidity of liquid phase （IFL） increases. Below 1.5wt%, Al2O3 benefits the assimilation reaction, but higher concentra- tions proved detrimental. Larger quartz particles increase the SiO2 levels at the local reaction interface between the iron ore and CaO, thereby reducing the LAT. Quartz-gibbsite is more conductive to assimilation than kaolin. Quartz-gibbsite and kaolin gangues encourage the forma- tion of liquid-phase low-Al2O3-SFCA with high IFL and high-Al2O3-SFCA with low IFL, respectively.

Effects of particle characteristics on the granulation ability of iron ores during the sintering process

The granulation behavior of iron ores is essential for subsequent parameter optimization and efficient granulation, especially under changing material conditions. In this study, the effects of surface properties and particle size were analyzed using a laboratory granulation method; an estimation of the granulation of sintering blends was subsequently conducted for the base ores. Circularity and porosity were observed to negatively affect the granulation of iron ores, whereas wettability positively affected the granulation and was the most influential factor, indicating that wetting of iron ores is desirable during granulation. When iron ores with complex size distributions were granulated, the equivalent surface area was the main influencing factor for coarse particles larger than 1 mm and the ratio of adhering fines to intermediates was the main factor for fine particles smaller than 1 mm. By combining the granulation of coarse and fine particles with their proportioning, we proposed a calculation method for estimating the granulation ability of sintering blends. Good verification was demonstrated with the designed schemes. The results suggest that the developed method is effective for predicting the granulation of iron ore mixtures.

Bulk geochemistry,Rb-Sr,Sm-Nd,and stable O-H isotope systematics of the Metzimevin high-grade iron ore deposit,Mbalam iron ore district,southern Cameroon

Bulk geochemistry,Sr,Nd,and O-H isotope systematics are reported for the first time on banded iron formation(BIF)-hosted high-grade iron ore at the northwestern segment of Congo Craton(CC).Located in Mbalam iron ore district,Southern Cameroon,Metzimevin iron ore deposit is a hematite-magnetite BIF system,dominated by SiO_(2)+Fe_(2)O_(3)(97.1 to 99.84 wt%),with low concentrations of clastic elements e.g.,Al_(2)O_(3),TiO_(2),and HFSE,depicting a nearly pure chemical precipitate.The REE+Y signature of the iron deposit displays strong positive Eu anomaly,strong negative Ce anomaly,and chondritic to superchondritic Y/Ho ratios,suggestive of formation by mixed seawater-high temperature hydrothermal fluids in oxidising environment.The^(87)Sr/^(86)Sr ratios of the BIF are higher than the maximum^(87)Sr/^(86)Sr evolution curves for all Archean reservoirs(bulk silicate earth,Archean crust and Archean seawater),indicating involvement of continentally-derived components during BIF formation and alteration.TheƐ_(Nd)(t)(+2.26 to+3.77)and Nd model age indicate that chemical constituents for the BIF were derived from undifferentiated crustal source,between 3.002 and 2.88 Ga.The variable and diverse O and H isotope data(−1.9‰to 17.3‰and−57‰to 136‰respectively)indicate that the Metzimevin iron ore formed initially from magmatic plumes and later enriched by magmatic-metamorphic-modified meteoric fluids.Mass balance calculations indicate mineralisation by combined leaching and precipitation,with an average iron enrichment factor of>2.67 and SiO_(2)depletion factor of>0.99.This is associated with an overall volume reduction of 28.27%,reflecting net leaching and volume collapse of the BIF protholith.

Recovering limonite from Australia iron ores by flocculation-high intensity magnetic separation

Successful recovery of limonite from iron fines was achieved by using flocculation-high intensity magnetic separation （FIMS） and adding hydrolyzed and causticized flocculants according to the characteristic of iron fines. The separation results of the three iron samples are as follows： iron grade 66.77%- 67.98% and the recovery of iron 69.26%-70.70% by the FIMS process with flocculants. The comparative results show that under the same separation conditions the F1MS process can effectively increase the recovery of iron by 10. 97%- 15.73%. The flowsheet results confirm the reliability of the process in a SHP high intensity magnetic separator. The concentrate product can he used as raw materials for direct reduction iron-smelting. The hydrolyzed and causticized flocculants can selectively flocculate fine feebly-magnetic iron mineral particles to increase their apparent separation sizes. The larger the separation size, the stronger the magnetic force. By comparing the separation results of the three samples it is found that among the three samples the higher the limonite content, the better the separation result. This means that the separation result relates closely to the flocculation process and the adding pattern of the flocculant.

Detection of the assimilation characteristics of iron ores: Dynamic resistance measurements

Resistance in iron ore undergoes a sharp change of up to several orders of magnitude when the sintered solid phase changes to liquid phase.In view of the insufficiency of existing assimilation detection methods,a timing-of-assimilation reaction is proposed,which was judged by continuously detecting the changes in resistance at the reaction interface.Effects of pole position and additional amounts of iron ore on assimilation reaction timing were investigated.The results showed that the suitable depth of pole groove was about 2 mm,and there was no obvious impact when the distance of the poles changed from 4 to 6 mm,or the amount of iron ore changed from 0.4 to 0.6 g.The temperature of sudden change of resistance in the temperature-resistant image was considered to be the lowest assimilation temperature of iron ore.The accuracy of this resistance method was clarified by X-ray diffraction,optical microscope,and scanning electron microscope/energy dispersive spectrometer(SEM/EDS)analyses.

Influencing factors and mechanism of water absorption process of iron ores during sintering

The appropriate content and distribution of sinter moisture play an important role in the granulation of iron ores. In this study, the effects of porosity, size distribution, and particle shape on the water absorption rate （WAR） of four types of iron ores were analyzed by using the immersion method and capillary water absorption method. In addition, the mechanism underlying the water absorption process in iron ores was unraveled. It is found that the WARs of iron ores decrease quickly with the increase in water absorption time at the initial stages of water absorption. With further increase in absorption time, the WARs decrease gradually, until near 0. Iron ores with higher porosity, smaller particle size, and plate-like structure have the higher WARs. Compared with pores in the single-particle iron ore, voids among particles in the multi-particle iron oxide play an important role at the initial stages of water absorption. The water absorption mechanism of all single-particle and multi-particle iron ores analyzed in this study includes four steps, wherein the first three steps play a significant role in the sintering pro-cess.

Determination of critical state line(CSL)for silty-sandy iron ore tailings subjected to low-high confining pressures

The disposal of filtered tailings in high dry stacks can induce particle breakage,changing the material's behaviour during the structure's lifetime.The grading changes influence material properties at the critical state,and this is not mature for intermediate artificial soils(tailings)in a broad range of confining pressures.In this paper,it aims to describe the behaviour of iron ore tailings in a spectrum of confining pressures broader than the reported in previous studies.A series of consolidated drained(CD)triaxial tests was carried out with confining pressures ranging from 0.075 MPa to 120 MPa.These results show that the amount of breakage plays an essential role in the response of iron ore tailings.The existence of curved critical state line(CSL)in both specific volume(ν)-logarithm of mean effective stress(p′)and deviatoric stress(q)-mean effective stress(p′)planes,and different responses in the deviatoric stress-axial strain-volumetric strain curves were verified.An inverse S-shaped equation was proposed to represent the silty-sandy tailings'behaviour up to high pressures onν-lnp′plane.The proposed equation provides a basis for enhancing constitutive models and considers the evolution of the grading up to severe loading conditions.The adjustment considered three regions with different responses associated with particle breakage at different pressure levels.

Magnetite Quartzite-Type Iron Ores – China's Most Important Current Iron Ore Source

China is abundant in iron-ore resources, with proven ore reserves of 576.62×10^8 t and proven reserves of 210×10^8 t, containing an average iron content of 33%. However, the rich iron-ore reserves of 10.85×10^8 t only account for 1.9% of all proven reserves. China＇s iron-ore resources are characterized by many lean ores and a few rich ones.

Effects of CaO and Na2CO3 on the Reduction of High Silicon Iron Ores

The effects of CaO and Na2CO3 on the reduction of high silicon iron ores at 1 250 ℃ were studied. The experimental results showed that the metallization rate was significantly hindered by the addition of CaO and Na2CO3, particularly at the early stage of roasting, compared to the rate without additives. In the absence of additives, iron oxides were quickly reduced to metallic iron, and fayalite was difficult to form. When CaO and Na2CO3 were added, the low reducible iron-containing silicate compounds formed and melted, subsequently retarding the metallization process. The inhibition of Na2CO3 was more noticeable than that of CaO, and higher Na2CO3 doses resulted in stronger inhibition of the increased metallization rate. However, when Na2CO3 was added prior to CaO, the liquid phase formed, which facilitated the growth of the metallic phase. To reinforce the separation of the metallic phase and slag, an appropriate amount of liquid phase generated during the reduction is necessary. It was shown that when 10% CaO and 10% Na2CO3 were added, a high metallization rate and larger metallic iron particles were obtained, thus further decreasing the required Na2CO3 dosage.

Application of Different Models for the Prediction of the Kinetics of Direct Reduction of Natural Iron Ores

Simulation of the direct reduction conditions was performed in a laboratory furnace. Lump samples from natural hematite iron ore were reduced by a gas mixture of H2 and CO (H2/CO =1.5) at temperatures of 700°C, 800°C and 900°C. The effect of reduction temperature on the reduction degree, reduction rate of samples and carbon deposition were investigated and discussed in this study. The thermo-gravimetric data obtained from the reduction experiments was run in a programme that calculates the solid conversion rate. Also, three models: 1) Grain Model (GM), 2) Volumetric Model (VM), and 3) the Random Pore Model (RPM), were used to estimate the reduction kinetics of natural iron ores. It was found that the RPM model result agreed best with the obtained experimental results. Furthermore, it gave better predictions of the natural iron oxide conversion and thereby the reduction kinetics.