Behavior and mechanism of pre-oxidation improvement on fluidization in the fluidized reduction of titanomagnetite

The direct reduction process is an important development direction of low-carbon ironmaking and efficient comprehensive utilization of poly-metallic iron ore,such as titanomagnetite.However,the defluidization of reduced iron particles with a high metallization degree at a high temperature will seriously affect the operation of fluidized bed reduction.Coupling the pre-oxidation enhancing reduction and the particle surface modification of titanomagnetite,the behavior and mechanism of pre-oxidation improvement on fluidization in the fluidized bed reduction of titanomagnetite are systematically studied in this paper.Pre-oxidation treatment of titanomagnetite can significantly lower the critical stable reduction fluidization gas velocity to 0.17 m/s,which is reduced by 56%compared to that of titanomagnetite reduction without pre-oxidation,while achieving a metallization degree of>90%,Corresponding to the different reduction fluidization behaviors,three pre-oxidation operation regions have been divided,taking oxidation degrees of 26%and 86%as the boundaries.Focusing on the particle surface morphology evolution in the pre-oxidation-reduction process,the relationship between the surface morphology of pre-oxidized ore and the reduced iron with fluidization properties is built.The improving method of pre-oxidation on the reduction fluidization provides a novel approach to prevent defluidization by particle surface modification,especially for the fluidized bed reduction of poly-metallic iron ore.

Mechanism of phosphorus removal in beneficiation of high phosphorous oolitic hematite by direct reduction roasting with dephosphorization agent

High phosphorous oolitic hematite ore is one of typical intractable iron ores in China, and the conventional beneficiation methods are found to be impracticable to , remove phosphorus from the ore effectively. Better beneficiation index were gotten by direct reduction roasting with dephosphorization agent followed by two stages of grinding and magnetic separation. P content decreases from 0.82% in the raw ore to 0.06% in the magnetic concentrate, and the total iron grade increases from 43.65% to 90.23%, the recovery of iron can reach 87%. Mechanisms of phosphorus removal in the beneficiation of high phosphorous oolitic hematite ore by direct reduction roasting with dephosphorization agent were studied using XRD, SEM and EPMA. The results showed that about 20% of the apatite in the raw ore transferred into phosphorus and volatilized with the gas in the process of reduction roasting, while the rest 80% apatite was not involved in the reaction of generation of phosphorus, and remained as apatite in the roasted products, which was removed to tailings by grinding and magnetic separation. A small amount of phosphorus existed in the magnetic concentrate as apatite. The oolitic texture of raw ore was partly changed during roasting, resulting in the formation of nepheline in the reaction between the dephosphorization agent, SiO2 and Al2O3 in the raw ore, which greatly improved the liberation degree of minerals in the roasted products, and it was beneficial to the subsequent grinding and magnetic separation.

Behaviors of vanadium and chromium in coal-based direct reduction of high-chromium vanadium-bearing titanomagnetite concentrates followed by magnetic separation

The reduction behaviors of FeO·V2O3 and FeO·Cr2O3 during coal-based direct reduction have a decisive impact on the efficient utilization of high-chromium vanadium-bearing titanomagnetite concentrates. The effects of molar ratio of C to Fe n(C)/n(Fe) and temperature on the behaviors of vanadium and chromium during direct reduction and magnetic separation were investigated. The reduced samples were characterized by X-ray diffraction(XRD), scanning election microscopy(SEM) and energy dispersive spectrometry(EDS) techniques. Experimental results indicate that the recoveries of vanadium and chromium rapidly increase from 10.0% and 9.6% to 45.3% and 74.3%, respectively, as the n(C)/n(Fe) increases from 0.8 to 1.4. At n(C)/n(Fe) of 0.8, the recoveries of vanadium and chromium are always lower than 10.0% in the whole temperature range of 1100-1250 °C. However, at n(C)/n(Fe) of 1.2, the recoveries of vanadium and chromium considerably increase from 17.8% and 33.8% to 42.4% and 76.0%, respectively, as the temperature increases from 1100 °C to 1250 °C. At n(C)/n(Fe) lower than 0.8, most of the FeO·V2O3 and FeO·Cr2O3 are not reduced to carbides because of the lack of carbonaceous reductants, and the temperature has little effect on the reduction behaviors of FeO·V2O3 and FeO·Cr2O3, resulting in very low recoveries of vanadium and chromium during magnetic separation. However, at higher n(C)/n(Fe), the reduction rates of FeO·V2O3 and FeO·Cr2O3 increase significatly because of the excess amount of carbonaceous reductants. Moreover, higher temperatures largely induce the reduction of FeO·V2O3 and FeO·Cr2O3 to carbides. The newly formed carbides are then dissolved in the γ(FCC) phase, and recovered accompanied with the metallic iron during magnetic separation.

Effect of titanium on the sticking of pellets based on hydrogen metallurgy shaft furnace:Behavior analysis and mechanism evolution

Direct reduction based on hydrogen metallurgical gas-based shaft furnace is a promising technology for the efficient and low-carbon smelting of vanadium-titanium magnetite.However,in this process,the sticking of pellets occurs due to the aggregation of metal-lic iron between the contact surfaces of adjacent pellets and has a serious negative effect on the continuous operation.This paper presents a detailed experimental study of the effect of TiO2 on the sticking behavior of pellets during direct reduction under different conditions.Results showed that the sticking index(SI)decreased linearly with the increasing TiO2 addition.This phenomenon can be attributed to the increase in unreduced FeTiO3 during reduction,leading to a decrease in the number and strength of metallic iron interconnections at the sticking interface.When the TiO2 addition amount was raised from 0 to 15wt%at 1100°C,the SI also increased from 0.71%to 59.91%.The connection of the slag phase could be attributed to the sticking at a low reduction temperature,corresponding to the low sticking strength.Moreover,the interconnection of metallic iron became the dominant factor,and the SI increased sharply with the increase in re-duction temperature.TiO2 had a greater effect on SI at a high reduction temperature than at a low reduction temperature.

Direct electrochemical reduction of solid vanadium oxide to metal vanadium at low temperature in molten CaCl_2-NaCl

V205 sintered pellets and graphite rods were employed as the cathode and the anode, respectively; a molten CaC12-NaCI salt was used as the electrolyte. Then, V205 was directly reduced to metal vanadium by the Fray-Farthing-Chen （FFC） method at 873 K to realize low-temperature electrolysis. Two typical experimental conditions, electrolysis time and voltage, were taken into account to investigate the current efficiency and remaining oxygen content in electrolyzed products. The composition and microstmcture of the products were charac- terized by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. SEM observations show that a higher voltage （1.8-3.4 V） and a longer electrolysis time （2-5 h） can improve the product quality separately, that is, a lower remaining oxygen content and a more uniform microstructure. The products with an oxygen content of 0.205wt% are successfully obtained below 3.4 V for 10 h. However, the current effi- ciency is low, and further work is required.

Numerical simulation of the direct reduction of pellets in a rotary hearth furnace for zinc-containing metallurgical dust treatment

A mathematical model was established to describe the direct reduction of pellets in a rotary hearth furnace （RHF）. In the model, heat transfer, mass transfer, and gas-solid chemical reactions were taken into account. The behaviors of iron metallization and dezincification were analyzed by the numerical method, which was validated by experimental data of the direct reduction of pellets in a Si-Mo furnace. The simulation results show that if the production targets of iron metallization and dezincification are up to 80% and 90%, respectively, the furnace temperature for high-temperature sections must be set higher than 1300~ C. Moreover, an undersupply of secondary air by 20% will lead to a decline in iron metallization rate of discharged pellets by 10% and a decrease in dezincing rate by 13%. In addition, if the residence time of pellets in the furnace is over 20 min, its further extension will hardly lead to an obvious increase in production indexes under the same furnace temperature curve.

Basic properties of steel plant dust and technological properties of direct reduction

Basic physicochemical properties of the dust from Laiwu Iron and Steel Co. Ltd. were studied. It is found that C, Zn, K, Na, etc. exist in the fabric filter dust, off gas （OG） sludge, fine ash in converter, and electrical field dust in sinter. Among these, OG sludge gives the finest particle, more than 90% of which is less than 2.51 mm. The dust can lead to a serious negative influence on the production of sintering and blast furnaces （BF） if it is recycled in sintering. The briquette and reduction experimental results showed that the qualified strength could be obtained in the case of 8wt% molasses or 4wt% QT-10 added as binders. Also, more than 75% of metallization ratio, more than 95% of dezincing ratio, as well as more than 80% of K and Na removal rates were achieved for the briquettes kept at 1250℃ for 15 min during the direct reduction process. SEM observation indicated that the rates of indirect reduction and carbonization became dominating when the bri-quettes were kept at 1250℃ for 6 min.

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.

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 NaeS formed by the reaction of Na2SO4 with CO reacts with SiO2 at the FeO surface to generate FeS and Na2Si2Os. 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.

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%.

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→Fe O, and Fe O→Fe, which start at 912 K, 1255 K, and 1397 K, respectively. The CO content in the evolved gas is lower than the CO2content in the Fe2O3→Fe3O4stage but is substantially greater than the CO2 contents in the Fe3O4→Fe O and Fe O→Fe stages, where gasification starts at approximately 1205 K. The activation energy（E） of the three stages are 126–309 k J/mol, 628 k J/mol, and 648 k J/mol, respectively. The restrictive step of the total reduction is Fe O→Fe. If the rate of the total reduction is to be improved, the rate of the Fe O→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 FexOy reduction by CO, which are the restrictive step in the last two stages, require further study.

Action rules of H_2 and CO in gas-based direct reduction of iron ore pellets

Alastraet： The gas-based direct reduction of iron ore pellets was carried out by simulating the typical gas composition in coal gasification process, Midrex and HyMII processes. The influences of gas composition and temperature on reduction were studied. Results show that the increasing of HE proportion is helpful to improve the reduction rate. However, when ~o（H2）：~o（CO）〉1.6：1, changes of HE content have little influence on it. Appropriate reduction temperature is about 950 ℃, and higher temperature （1 000 ℃） may unfavorably slow the reduction rate. From the kinetics analysis at 950 ℃, the most part of reduction course is likely controlled by interfacial chemical reaction mechanism and in the final stage controlled by a combined effect of gaseous diffusion and interfacial chemical reaction mechanisms. From the utilizations study of different reducing gases at 950 ℃, the key step in reduction course is the 3rd stage （FeO→Fe）, and the utilization of reducing gas increases with the rise of HE proportion.

Pilot scale test of producing nickel concentrate from low-grade saprolitic laterite by direct reduction-magnetic separation

The enrichment of Ni from a low-grade saprolitic laterite ore,which has been pre-treated by high pressure grinding roller（HPGR） to be 74% passing 0.074 mm and contains 0.92% Ni,18.47% Fe,10.61% MgO and 42.27% SiO2,was conducted by using pelletizing,rotary kiln reduction and magnetic separation process on a semi industrial scale,and the effects of reduction duration,mass ratio of coal to pellets（C/P）,the types of magnetic separator,the sections of grinding-separation and the grinding fineness on the recovery of Ni and Fe were examined.It is shown that nickel concentrate containing 3.13 % Ni and 59.20 % Fe was achieved at recoveries of 84.36 % and 71.51% for Ni and Fe,respectively under the following conditions：reducing at （1120±40） ℃ for 120 min,C/P being 1.0,wet grinding of reduced pellets up to 70%-87% passing 0.074 mm and a magnetic field intensity of 238.8 kA/m during the first section of grinding-magnetic separation,and a grinding fineness of 84%-91% passing 0.045 mm and a magnetic intensity of 39.8 kA/m during the second section of grinding-magnetic separation.The enriched Ni containing concentrate has a low content of S and P,and can be used for further processing to produce high-grade ferronickel alloy.

Preparing low-oxygen Ti-6Al-4V alloy powder through direct reduction of oxides and its synergistic reaction mechanism

Ti-6Al-4V alloy powder was prepared through a two-step reduction of a mixture of TiO_(2),V_(2)O_(5) and Al_(2)O_(3) in this study.The oxide mixture was first reduced by Mg in MgCl_(2) at 750℃ in argon,where oxygen was reduced to 2.47 wt%from 40.02 wt%.The oxygen content in the final powder was eventually reduced to an extremely low level(0.055 wt%)using calcium at 900℃ in argon,and the final powder had the composition of 90.12 wt%Ti,5.57 wt%Al,and 3.87 wt%V,which meets the standard specification of Ti-6Al-4V(ASTM F1108-09).Between the two reductions,a heat treatment step was designed to help controlling the specific surface area and particle size.The effect of the heat treatment temperature on the morphology,and composition uniformity of the powder was investigated in detail.Heat treatment above 1300℃ attributed to a dense powder with a controlled specific surface area.Thermodynamic modeling and experimental results indicated that onlyα-Ti enriched with Al andβ-Ti enriched with V exist in the final powder,and other possible phases including Al-Mg and Al-V were excluded.This study also offers a triple-step thermochemical process for producing high-purity Ti-based alloy powder.

Sticking of iron ore pellets in direct reduction with hydrogen and carbon monoxide:Behavior and prevention

A series of reduction experiments of iron ore pellets with hydrogen,carbon monoxide and their mixture were carried out in a laboratory scale shaft furnace.The sticking behavior accompanying reduction of iron ore pellets was investigated.And morphology of the sticking interface forming during reduction was analyzed by SEM equipped with EDS.In order to evaluate the effects of the temperature and gas composition on sticking properties,reduction of iron ore pellets were conducted at 800-1000 ℃.The results show that the sticking strength of the pellets increases with temperature,however,decreases with hydrogen content in reducing gas.For an efficient shaft furnace operation in direct reduction(DR),relative prevention of sticking such as coating of pellets was also developed to solve sticking problem.The results show that CaO is a suitable material for the coating method.

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.

Preparation of novel Ni-Ir/γ-Al_2O_3 catalyst via high-frequency cold plasma direct reduction process

The novel Ni-Ir/γ-Al2O3 catalyst, denoted as NIA-P, was prepared by high-frequency cold plasma direct reduction method under ambient conditions without thermal treatment, and the conventional sample, denoted as NIA-CR, was prepared by impregnation, thermal calcination, and then by H2 reduction method. The effects of reduction methods on the catalysts for ammonia decomposition were studied, and they were characterized by XRD, N2 adsorption, XPS, and H2-TPD. It was found that the plasma-reduced NIA-P sample showed a better catalytic performance, over which ammonia conversion was 68.9%, at T = 450℃, P = 1 atm, and GHSV = 30, 000 h^-1. It was 31.7% higher than that of the conventional NIA-CR sample. XRD results showed that the crystallite size decreased for the sample with plasma reduction, and the dispersion of active components was improved. There were more active components on the surface of the NIA-P sample from the XPS results. This effect resulted in the higher activity for decomposition of ammonia. Meanwhile, the plasma process significantly decreased the time of preparing catalyst.

Recovery of iron from copper tailings via low-temperature direct reduction and magnetic separation: process optimization and mineralogical study

Currently, the majority of copper tailings are not effectively developed. Worldwide, large amounts of copper tailings generated from copper production are continuously dumped, posing a potential environmental threat. Herein, the recovery of iron from copper tailings via low-temperature direct reduction and magnetic separation was conducted; process optimization was carried out, and the corresponding mineralogy was investigated. The reduction time, reduction temperature, reducing agent (coal), calcium chloride additive, grinding time, and magnetic field intensity were examined for process optimization. Mineralogical analyses of the sample, reduced pellets, and magnetic concentrate under various conditions were performed by X-ray diffraction, optical microscopy, and scanning electron microscopy-energy-dispersive X-ray spectrometry to elucidate the iron reduction and growth mechanisms. The results indicated that the optimum parameters of iron recovery include a reduction temperature of 1150A degrees C, a reduction time of 120 min, a coal dosage of 25%, a calcium chloride dosage of 2.5%, a magnetic field intensity of 100 mT, and a grinding time of 1 min. Under these conditions, the iron grade in the magnetic concentrate was greater than 90%, with an iron recovery ratio greater than 95%.

Direct reduction of carburized pre-reduced pellets by microwave heating

A new iron-making process using carburized pre-reduced iron ore pellets and microwave heating is investigated. The pre-reduced pellets, with a porous structure, and fine particles are carburized homogeneously at 400-650 ℃ in a CO atmosphere. The carburized carbon not only acts reaction as a reduction agent, but also absorbs microwave in the reduction process. Hence, the carburized pre-reduced pellets can be rapidly reduced by microwave heating. There are three procedures involved in the process, namely, gas-based pre-reduction, low-temperatttre carburization and deep reduction by microwave heating. Carburized pre-reduced iron ore pellets show a rapid temperature rise that is twice as fast as the results for pre-reduced pellets in the laboratory. This not only improves the efficiency of the microwave heating, but also accelerates the reduction of iron oxides. The temperature of the pre-reduced pellets rises to 1050 ℃ in 45 min when the carburization rate is 2.02%, and the metallization rate and compressive strength reach 94.24% and 1725 N/pellet, respectively.

Mathematical model of the direct reduction of dust composite pellets containing zinc and iron

Direct reduction of dust composite pellets containing zinc and iron was examined by simulating the conditions of actual production process of a rotary hearth furnace （RHF） in laboratory. A mathematical model was constructed to study the reduction kinetics of iron oxides and ZnO in the dust composite pellets. It was validated by comparing the calculated values with experimental results. The effects of furnace temperature, pellet radius, and pellet porosity on the reduction were investigated by the model. It is shown that furnace temperature has obvious influence on both of the reduction of iron oxides and ZnO, but the influence of pellet radius and porosity is much smaller. Model calculations suggest that both of the reduction of iron oxides and ZnO are under mixed control with interface reactions and Boudouard reaction in the early stage, but only with interface reactions in the later stage.