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

The gas-based direct reduction of iron ore pellets was carried out by simulating the typical gas composition in coal gasification process, Midrex and Hyl-III processes. The influences of gas composition and temperature on reduction were studied. Results show that the increasing of H2 proportion is helpful to improve the reduction rate. However, when φ(H2):φ(CO)>1.6:1, changes of H2 content have little influence on it. Appropriate reduction temperature is about 950 °C, and higher temperature (1000 °C) may unfavorably slow the reduction rate. From the kinetics analysis at 950 °C, 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 °C, the key step in reduction course is the 3rd stage (FeO→Fe), and the utilization of reducing gas increases with the rise of H2 proportion.

Upcycling end of lithium cobalt oxide batteries to electrocatalyst for oxygen reduction reaction in direct methanol fuel cell via sustainable approach

Recycling spent lithium-ion batteries(SLIBs)has become essential to preserve the environment and reclaim vital resources for sustainable development.The typical SLIBs recycling concentrated on separating valuable components had limitations,including high energy consumption and complicated separation processes.This work suggests a safe hydrometallurgical process to recover usable metallic cobalt from depleted LiCoO_(2)batteries by utilizing citric acid as leachant and hydrogen peroxide as an oxidizing agent,with ethanol as a selective precipitating agent.The anode graphite was also recovered and converted to graphene oxide(GO).The above components were directly resynthesized to cobaltintegrated nitrogen-doped graphene(Co@NG).The Co@NG showed a decent activity towards oxygen reduction reaction(ORR)with a half-wave potential of 0.880 V vs.RHE,almost similar to Pt/C(0.888 V vs.RHE)and with an onset potential of 0.92 V vs.RHE.The metal-nitrogen-carbon(Co-N-C)having the highest nitrogen content has decreased the barrier for ORR since the reaction was enhanced for Co@NG-800,as confirmed by density functional theory(DFT)simulations.The Co@NG cathode catalyst coupled with commercial Pt-Ru/C as anode catalyst exhibits excellent performance for direct methanol fuel cell(DMFC)with a peak power density of 34.7 mW cm^(-2)at a discharge current density of120 m A cm^(-2)and decent stability,indicating the promising utilization of spent battery materials in DMFC applications.Besides,lithium was recovered from supernatant as lithium carbonate by coprecipitation process.This work avoids sophisticated elemental separation by utilizing SLIBs for other renewable energy applications,lowering the environmental concerns associated with recycling.

Thermodynamic studies on gas-based reduction of vanadium titano-magnetite pellets

Numerous studies have focused on the reduction thermodynamics of ordinary iron ore;by contrast, the literature contains few thermodynamic studies on the gas-based reduction of vanadium titano-magnetite (VTM) in mixed atmospheres of H2, CO, H2O, CO2, and N2. In this paper, thermodynamic studies on the reduction of oxidized VTM pellets were systematically conducted in an atmosphere of a C–H–O system as a reducing agent. The results indicate that VTM of an equivalent valence state is more difficult to reduce than ordinary iron ore. A reduction equilibrium diagram using the C–H–O system as a reducing agent was obtained;it clearly describes the reduction process. Experiments were performed to investigate the effects of the reduction temperature, the gas composition, and two types of iron ores on the reduction of oxidized VTM pellets. The results show that the final reduction degree increases with increasing reduction temperature, increasing molar ratio of H2/(H2 + CO), and decreasing H2O, CO2, and N2 contents. In addition, the reduction processes under various conditions are discussed. All of the results of the reduction experiments are consistent with those of theoretical thermodynamic analysis. This study is expected to provide valuable thermodynamic theory on the industrial applications of VTM.

Effect of reductant type on the embedding direct reduction of beach titanomagnetite concentrate

Iron and titanium were recovered from beach titanomagnetite(TTM) concentrate by embedding direct reduction and magnetic separation. The reduction products and the effects of the reductant type and reduction temperature on the reduction behavior were investigated. The results showed that the reduction of TTM concentrate was strongly related to the gasification reactivity of the reductant. Bitumite presented a better product index than wheat-straw biochar and coke, mainly because the gasification reactivity of bitumite was better than that of the other reductants. In addition, high temperatures were not beneficial to embedding direct reduction because of the emergence of a molten phase and iron-joined crystals, which in turn reduced the diffusion rate of the reducing gas and impeded the reduction reaction in the central area of the roasted briquette. The use of bitumite as the reductant at a C/Fe molar ratio of 1.4 and a reduction temperature of 1200°C for 120 min resulted in direct-reduction iron powder assaying 90.28 wt% TFe and 0.91 wt% TiO_2 with an iron recovery of 91.83% and titanium concentrate assaying 46.01 wt% TiO_2 with a TiO_2 recovery of 91.19%. Titanium existed mainly in the form of anosovite and ilmenite in the titanium concentrate.

An Innovative Process for Direct Reduction of Cold bound Pellets from Iron Concentrate with a Coal-based Rotary Kiln

Successfully developed an innovative process of direct reduction of cold bound pellets from iron ore concentrate with a coal based rotary kiln, in comparison with the traditional direct reduction of fired oxide pellets in coal based rotary kilns , possesses such advantages as: shorter flowsheet, lower capital investment, greater economic profit, good quality of direct reduced iron. The key technologies , such as the composite binder and corresponding feasible techniques were employed in practice. A mill utilizing this process and with an annual capacity of 50 thousand ton DRI has been put into operation.

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.

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.

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%.

A Comparative Study on the Close Reduction of Arytenoid Dislocation under Indirectand Direct Laryngoscope

To assess the curative effects of different reduction techniques on the dislocation of cricoarytenoid joint caused by intubation,indirect laryngoscope (IL ) and direct laryngoscope (DL ) were utilized for the closed reduction of the displaced arytenoid under local anesthesia.2 3patients who underwent the reduction for dislocated arytenoid under IL or DL from January1991to June 2 0 0 1were reviewed.The data were collected on the duration of the laryngeal injury,tim es of re- ceiving reduction,side- effects after the treatment and the period for voice to return to normal. The relationship between the duration of the laryngeal lesion and the period of the voice rehabilita- tion was examined.13patients received the reduction under IL and 10 patients under DL .Except the tim es of the reduction,which showed significant difference,no differences were found between IL group and DL group in the course and the period of voice rehabilitation,as well as sore throat after the manipulation.The patients'voice recovery was positively related to their course of dis- ease in both IL and DL group.Itis concluded thatthe recovery of normal voice is obviously affect- ed by the duration of arytenoid dislocation.The reduction under IL is as effective as under DL in the treatment of arytenoid dislocation.Reduction by DL is better suit the patients with long tim e course of disease.

INFLUENCE OF ADDITIVES ON SLAG－IRON SEPARATION DURING DIRECT REDUCTION OF COAL－BASE HIGH－IRON－CONTENTREDMUD

ＩＮＦＬＵＥＮＣＥＯＦＡＤＤＩＴＩＶＥＳＯＮＳＬＡＧ－ＩＲＯＮＳＥＰＡＲＡＴＩＯＮＤＵＲＩＮＧＤＩＲＥＣＴＲＥＤＵＣＴＩＯＮＯＦＣＯＡＬ－ＢＡＳＥＨＩＧＨ－ＩＲＯＮ－ＣＯＮＴＥＮＴＲＥＤＭＵＤＱｉｕＧｕａｎｚｈｏｕ；ＬｉｕＹｏｎｇｋａｎｇ；Ｊｉａｎｇ...

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.

Mathematical simulation of direct reduction process in zinc-bearing pellets

A one-dimensional unsteady mathematical model was established to describe direct reduction in a composite pellet made of metallurgical dust. The model considered heat transfer, mass transfer, and chemical reactions including iron oxide reductions, zinc oxide reduction and carbon gasification, and it was numerically solved by the tridiagonal matrix algorithm （TDMA）. In order to verify the model, an experiment was performed, in which the profiles of temperature and zinc removal rate were measured during the reduction process. Results calculated by the mathematical model were in fairly good agreement with experimental data. Finally, the effects of furnace temperature, pellet size, and carbon content were investigated by model calculations. It is found that the pellet temperature curve can be divided into four parts according to heating rate. Also, the zinc removal rate increases with the increase of furnace temperature and the decrease of pellet size, and carbon content in the pellet has little influence on the zinc removal rate.

Preparing high-purity iron by direct reduction?smelting separation of ultra-high-grade iron concentrate

A new process for preparing high-purity iron(HPI)was proposed,and it was investigated by laboratory experiments and pilot tests.The results show that under conditions of a reduced temperature of 1075°C,reduced time of 5 h,and CaO content of 2.5wt%,a DRI with a metallization rate of 96.5%was obtained through coal-based direct reduction of ultra-high-grade iron concentrate.Then,an HPI with a Fe purity of 99.95%and C,Si,Mn,and P contents as low as 0.0008wt%,0.0006wt%,0.0014wt%,and 0.0015wt%,respectively,was prepared by smelting separation of the DRI using a smelting temperature of 1625°C,smelting time of 45 min,and CaO content of 9.3wt%.The product of the pilot test with a scale of 0.01 Mt/a had a lower impurity content than the Chinese industry standard.An HPI with a Fe purity of 99.98wt%can be produced through the direct reduction?smelting separation of ultra-high-grade iron concentrate at relatively low cost.The proposed process shows a promising prospect for application in the future.

Hydrogen-based direct reduction of iron oxide at 700℃:Heterogeneity at pellet and microstructure scales

Steel production causes a third of all industrial CO_(2) emissions due to the use of carbon-based substances as reductants for iron ores,making it a key driver of global warming.Therefore,research efforts aim to replace these reductants with sustainably produced hydrogen.Hydrogen-based direct reduction(HyDR)is an attractive processing technology,given that direct reduction(DR)furnaces are routinely operated in the steel industry but with CH_(4) or CO as reductants.Hydrogen diffuses considerably faster through shaft-furnace pellet agglomerates than carbon-based reductants.However,the net reduction kinetics in HyDR remains extremely sluggish for high-quantity steel production,and the hydrogen consumption exceeds the stoichiometrically required amount substantially.Thus,the present study focused on the improved understanding of the influence of spatial gradients,morphology,and internal microstructures of ore pellets on reduction efficiency and metallization during HyDR.For this purpose,commercial DR pellets were investigated using synchrotron high-energy X-ray diffraction and electron microscopy in conjunction with electron backscatter diffraction and chemical probing.Revealing the interplay of different phases with internal interfaces,free surfaces,and associated nucleation and growth mechanisms provides a basis for developing tailored ore pellets that are highly suited for a fast and efficient HyDR.

Comprehensive recovery of lead, zinc, and iron from hazardous jarosite residues using direct reduction followed by magnetic separation

Lead, zinc, and iron were recovered from jarosite residues using direct reduction followed by magnetic separation. The influence of the coal dosage, reduction temperature, and reduction time on the volatilization rates of lead and zinc and the metallization rate of iron were investigated. The results show that the volatilization rates of lead and zinc were 96.97% and 99.89%, respectively, and the iron metallization rate was 91.97% under the optimal reduction roasting conditions of a coal dosage of 25.0 wt% and reduction roasting at 1250°C for 60 min. The magnetic concentrate with an iron content of 90.59 wt% and an iron recovery rate of 50.87% was obtained under the optimum conditions in which 96.56% of the reduction product particles were smaller than 37 μm and the magnetic field strength was 24 k A/m. Therefore, the results of this study demonstrate that recovering valuable metals such as lead, zinc, and iron from jarosite residues is feasible using the developed approach.