Boron is an important industrial raw material often sourced from minerals containing different compounds that cocrystallize,which makes it difficult to separate the mineral phases through conventional beneficiation.Th...Boron is an important industrial raw material often sourced from minerals containing different compounds that cocrystallize,which makes it difficult to separate the mineral phases through conventional beneficiation.This study proposed a new treatment called flash reduction-melting separation(FRMS)for boron-bearing iron concentrates.In this method,the concentrates were first flash-reduced at the temperature under which the particles melt,and the slag and the reduced iron phases disengaged at the particle scale.Good reduc-tion and melting effects were achieved above 1550℃.The B_(2)O_(3) content in the separated slag was over 18wt%,and the B content in the iron was less than 0.03wt%.The proposed FRMS method was tested to investigate the effects of factors such as ore particle size and tem-perature on the reduction and melting steps with and without pre-reducing the raw concentrate.The mineral phase transformation and morphology evolution in the ore particles during FRMS were also comprehensively analyzed.展开更多
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...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.展开更多
Although considerable research has been conducted on nitrate reduction by zero-valent iron powder (Fe^0), these studies were mostly operated under anaerobic conditions with invariable pH that was unsuitable for prac...Although considerable research has been conducted on nitrate reduction by zero-valent iron powder (Fe^0), these studies were mostly operated under anaerobic conditions with invariable pH that was unsuitable for practical application. Without reaction conditions (dissolved oxygen or reaction pH) control, this work aimed at subjecting the kinetics of denitrification by microscale Fe^0 (160-200 mesh) to analysis the factors affecting the denitrification of nitrate and the composition of iron reductive products coating upon the iron surface. Results of the kinetics study have indicated that a higher initial concentration of nitrate would yield a greater reaction rate constant. The reduction rate of nitrate increased with increasing Fe^0 dosage. The reaction can be described as a pseudo-first order reaction with respect to nitrate concentration or Fe^0 dosage. Experimental results also suggested that nitrate reduction by microscale Fe^0 without reaction condition control primarily was an acid-driven surface-mediated process, and the reaction order was 0.65 with respect to hydrogen ion concentration. The analyses of X-ray diffractometry and X-ray photoelectron spectroscopy indicated that a black coating, consisted of Fe2O3, Fe3O4 and FeO(OH), was formed on the surface of iron grains as an iron corrosion product when the system initial pH was lower than 5. The proportion of FeO(OH) increased as reaction time went on, whereas the proportion of Fe3O4 decreased.展开更多
Oolitic iron ore is one of the most important iron resources. This paper reports the recovery of iron from high phosphorus oolitic iron ore using coal-based reduction and magnetic separation. The influences of reducti...Oolitic iron ore is one of the most important iron resources. This paper reports the recovery of iron from high phosphorus oolitic iron ore using coal-based reduction and magnetic separation. The influences of reduction temperature, reduction time, C/O mole ratio, and CaO content on the metallization degree and iron recovery were investigated in detail. Experimental results show that reduced products with the metallization degree of 95.82% could be produced under the optimal conditions (i.e., reduction temperature, 1250℃; reduction time, 50 min; C/O mole ratio, 2.0; and CaO content, 10wt%). The magnetic concentrate containing 89.63wt% Fe with the iron recovery of 96.21% was obtained. According to the mineralogical and morphologic analysis, the iron minerals had been reduced and iron was mainly enriched into the metallic iron phase embedded in the slag matrix in the form of spherical particles. Apatite was also reduced to phosphorus, which partially migrated into the metallic iron phase.展开更多
Iron nugget and boron-rich slag can be obtained in a short time through high-temperature reduction of boron- bearing iron concentrate by carbonaceous material, both of which are agglomerated together as a carbon compo...Iron nugget and boron-rich slag can be obtained in a short time through high-temperature reduction of boron- bearing iron concentrate by carbonaceous material, both of which are agglomerated together as a carbon composite pellet. This is a novel flow sheet for the comprehensive utilization of boron-bearing iron concentrate to produce a new kind of man-made boron ore. The effect of reducing agent species (i.e., carbon species) on the reduction and melting process of the composite pellet was investigated at a laboratory scale in the present work. The results show that, the reduction rate of the composite pellet increases from bituminite, anthracite, to coke at temperatures ranging from 950 to 1300~C. Reduction temperature has an important effect on the microstructure of reduced pellets. Carbon species also affects the behavior of reduced metallic iron particles. The anthracite-bearing composite pellet melts faster than the bituminite- bearing composite pellet, and the coke-bearing composite pellet cannot melt due to the high fusion point of coke ash. With anthracite as the reducing agent, the recovery rates of iron and boron are 96.5% and 95.7%, respectively. This work can help us get a further understanding of the new process mechanism.展开更多
To reveal the formation and characteristics of metallic iron grains in coal-based reduction, oolitic iron ore was isothermally re- duced in various reduction times at various reduction temperatures. The microstructure...To reveal the formation and characteristics of metallic iron grains in coal-based reduction, oolitic iron ore was isothermally re- duced in various reduction times at various reduction temperatures. The microstructure and size of the metallic iron phase were investigated by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and a Bgrimm process mineralogy analyzer. In the results, the re- duced Fe separates from the ore and forms metallic iron protuberances, and then the subsequent reduced Fe diffuses to the protuberances and grows into metallic iron grains. Most of the metallic iron grains exist in the quasi-spherical shape and inlaid in the slag matrix. The cumula- tive frequency of metallic iron grain size is markedly influenced by both reduction time and temperature. With increasing reduction temperature and time, the grain size of metallic iron obviously increases. According to the classical grain growth equation, the growth kinetic parameters, i.e., time exponent, growth activation energy, and pre-exponential constant, are estimated to be 1.3759 ± 0.0374, 103.18 kJ·mol^-1, and 922.05, respec- tively. Using these calculated parameters, a growth model is established to describe the growth behavior of metallic iron grains.展开更多
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 pellet...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.展开更多
The technology of direct reduction by adding sodium carbonate (Na2CO3) and magnetic separation was developed to treat Western Australian high phosphorus iron ore. The iron ore and reduced product were investigated b...The technology of direct reduction by adding sodium carbonate (Na2CO3) and magnetic separation was developed to treat Western Australian high phosphorus iron ore. The iron ore and reduced product were investigated by optical microscopy and scanning electron microscopy. It is found that phosphorus exists within limonite in the form of solid solution, which cannot be removed through traditional ways. During reduction roasting, Na2CO3 reacts with gangue minerals (SiO2 and A1203), forming aluminum silicate-containing phosphorus and damaging the ore structure, which promotes the separation between iron and phosphorus during magnetic separation. Meanwhile, Na2CO3 also improves the growth of iron grains, increasing the iron grade and iron recovery. The iron concentrate, assaying 94.12wt% Fe and 0.07wt% P at the iron recovery of 96.83% and the dephosphorization rate of 74.08%, is obtained under the optimum conditions. The final product (metal iron powder) after briquetting can be used as the burden for steelmaking by an alactrie a.re furnace to rer)la,ce scrar) steel.展开更多
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 kinetic...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.展开更多
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 distr...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.展开更多
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 redu...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.展开更多
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 s...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.展开更多
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(XR...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.展开更多
Dissimilatory Fe(Ⅲ) reduction is an important process in the geochemical cycle of iron in anoxic environment. As the main products of dissimilatory iron reduction, the Fe(Ⅱ) species accumulation could indicate t...Dissimilatory Fe(Ⅲ) reduction is an important process in the geochemical cycle of iron in anoxic environment. As the main products of dissimilatory iron reduction, the Fe(Ⅱ) species accumulation could indicate the reduction ability. The effects of different green manures on Fe(Ⅲ) reduction in paddy soil were explored based on a 31-year rice-rice-winter green manure cropping experiment. Four treatments were involved, i.e., rice-rice-milk vetch (RRV), rice-rice-rape (RRP), rice-rice-ryegrass (RRG) and rice-rice-winter fallow (RRF). Soils were sampled at flowering stage of milk vetch and rape (S1), before transplantation (S2), at tillering (S3), jointing (S4), and mature (S5) stages of the early rice, and after the harvest of the late rice (S6). The contents of TFeHa (HCI-extractable total Fe), Fe(Ⅱ)HCI (HCI-extractable Fe(Ⅱ) species) and Fe(Ⅲ)HCI (HCI- extractable Fe(Ⅲ) species) were measured. The correlations among those Fe species with selected soil environmental factors and the dynamic characteristics of Fe(Ⅱ)HCI accumulation were investigated. The results showed that TFeHc~ in RRF was significantly higher than those in the green manure treatments at most of the sampling stages. Fe(II)Ha increased rapidly after the incorporation of green manures in all treatments and kept rising with the growth of early rice. Fe(Ⅱ)Ha in RRG was quite different from those in other treatments, i.e., it reached the highest at the S2 stage, then increased slowly and became the lowest one at the S4 and S5 stages. Fe(Ⅲ)Ha showed oppositely, and Fe(Ⅱ)HCI/Fe(Ⅲ)HCI performed similarly to Fe(Ⅱ)HCI The maximum accumulation potential of Fe(Ⅱ)HCI was significantly higher in RRF, while the highest maximum reaction rate of Fe(Ⅱ)Ha accumulation appeared in RRG. Significant correlations were found between the indexes of Fe(Ⅱ)HCI accumulation and soil pH, oxidation-reduction potential (Eh) and total organic acids, respectively. In together, we found that long-term application of green manures decreased the TFeHa in red paddy soils, but promoted the ability of Fe(lll) reduction, especially the ryegrass; Fe(Ⅱ)Ha increased along with the growth of rice and was affected by soil conditions and environmental factors, especially the water and redox ability.展开更多
The catalyst containing 0.69% (mass fraction) of Li+, Na+, or Ca2+ were synthesized, and the catalytic effect on the reduction of iron oxide/carbon composite pellets were investigated by comparing with that of additiv...The catalyst containing 0.69% (mass fraction) of Li+, Na+, or Ca2+ were synthesized, and the catalytic effect on the reduction of iron oxide/carbon composite pellets were investigated by comparing with that of additive at 850 degreesC. The effect of the catalyst was greater than that of the additive, it can be considered that catalyst promoted the formation of iron nucleus early on reduction processes of iron oxide/carbon composite pellets. In addition, both effects of catalyst and additive increased after added carbon powder into the pellets, but the extent of increase decreased when the carbon powder exceeded a suitable content (about 4%), this amount is less than that of carbon needed theoretically on the reduction from hematite to iron.展开更多
The effect of metallurgical fluxes CaO and CaCO3 on the reduction rate of iron ore pellets containing carbon in nitrogen atmosphere has been studied by a weight-loss thermal balance. The experimental results showed th...The effect of metallurgical fluxes CaO and CaCO3 on the reduction rate of iron ore pellets containing carbon in nitrogen atmosphere has been studied by a weight-loss thermal balance. The experimental results showed that adding CaO or CaCO3 can promote reduction reaction as the added CaO or CaCO3 probably decrease the apparent activation energy of iron ore concentrate-carbon-CaO or CaCO3 reaction, and the reduction rate constant changes with mass percent of CaO and CaCO3. The kinetic analysis also showed that the rate-controlling step of the reaction is inner gas diffusion.展开更多
Ludwigite is a kind of complex iron ore containing boron, iron, and magnesium, and it is the most promising boron resource in China. Selective reduction of iron oxide is the key step for the comprehensive utilization ...Ludwigite is a kind of complex iron ore containing boron, iron, and magnesium, and it is the most promising boron resource in China. Selective reduction of iron oxide is the key step for the comprehensive utilization of ludwigite. In the present work, the reduction mechanism of ludwigite was investigated. The thermogravimetry and differential scanning calorimetry analysis and isothermal reduction of ludwigite/coal composite pellet were performed. Ludwigite yielded a lower reduction starting temperature and a higher final reduction degree compared with the traditional iron concentrates. Higher specific surface area and more fine cracks might be the main reasons for the better reducibility of ludwigite. Reducing temperature highly affected the reaction fraction and microstructure of the reduced pellets, which are closely related to the separation degree of boron and iron. Increasing reducing temperature benefited the boron and iron magnetic separation. Optimum magnetic separation results could be obtained when the pellet was reduced at 1300°C. The separated boron-rich non-magnetic concentrate presented poor crystalline structure, and its extraction efficiency for boron reached 64.3%. The obtained experimental results can provide reference for the determination of the comprehensive utilization flow sheet of ludwigite.展开更多
A comparative study of treatment of simulated wastewater containing Reactive Red 195 using zero-valent iron/activated carbon (ZVI/AC), microwave discharge electrodeless lamp/sodium hypochlorite (MDEL/NaCIO) and th...A comparative study of treatment of simulated wastewater containing Reactive Red 195 using zero-valent iron/activated carbon (ZVI/AC), microwave discharge electrodeless lamp/sodium hypochlorite (MDEL/NaCIO) and the combination of ZVI/AC- MDEL/NaCIO was conducted. The preliminary results showed the two steps method of ZVI/AC-MDEL/NaCIO had much higher degradation efficiency than both single steps. The final color removal percentage was nearly up to 100% and the chemical oxygen demand reduction percentage was up to approximately 82%. The effects of operational parameters, including initial pH value of simulated wastewater, ZVI/AC ratio and particle size of ZVI were also investigated. In addition, from the discussion of synergistic effect between ZVI/AC and MEDL/NaCIO, we found that in the ZVI/AC-MEDL/NaCIO process, ZVI/AC could break the azo bond firstly and then MEDLfNaCIO degraded the aromatic amine products effectively. Reversing the order would reduce the degradation efficiency.展开更多
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 ti...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.展开更多
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. ...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%.展开更多
基金supported by the Science and Technology Special Plan Project from China Minmetals Group (No.2020ZXA01)the International Exchange and Growth Program for Young Teachers (No.QNXM20220061)the National Key Research and Development Program of China (No.2022YFC2906100).
文摘Boron is an important industrial raw material often sourced from minerals containing different compounds that cocrystallize,which makes it difficult to separate the mineral phases through conventional beneficiation.This study proposed a new treatment called flash reduction-melting separation(FRMS)for boron-bearing iron concentrates.In this method,the concentrates were first flash-reduced at the temperature under which the particles melt,and the slag and the reduced iron phases disengaged at the particle scale.Good reduc-tion and melting effects were achieved above 1550℃.The B_(2)O_(3) content in the separated slag was over 18wt%,and the B content in the iron was less than 0.03wt%.The proposed FRMS method was tested to investigate the effects of factors such as ore particle size and tem-perature on the reduction and melting steps with and without pre-reducing the raw concentrate.The mineral phase transformation and morphology evolution in the ore particles during FRMS were also comprehensively analyzed.
基金financially supported by the National Natural Science Foundation of China(Nos.52174217 and 52304354)the China Postdoctoral Science Foundation(No.2020M682495)。
文摘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.
基金supported by the Development Program for Outstanding Young Teachers in Harbin Institute of Technology (No. HITQNJS. 2007. 038)
文摘Although considerable research has been conducted on nitrate reduction by zero-valent iron powder (Fe^0), these studies were mostly operated under anaerobic conditions with invariable pH that was unsuitable for practical application. Without reaction conditions (dissolved oxygen or reaction pH) control, this work aimed at subjecting the kinetics of denitrification by microscale Fe^0 (160-200 mesh) to analysis the factors affecting the denitrification of nitrate and the composition of iron reductive products coating upon the iron surface. Results of the kinetics study have indicated that a higher initial concentration of nitrate would yield a greater reaction rate constant. The reduction rate of nitrate increased with increasing Fe^0 dosage. The reaction can be described as a pseudo-first order reaction with respect to nitrate concentration or Fe^0 dosage. Experimental results also suggested that nitrate reduction by microscale Fe^0 without reaction condition control primarily was an acid-driven surface-mediated process, and the reaction order was 0.65 with respect to hydrogen ion concentration. The analyses of X-ray diffractometry and X-ray photoelectron spectroscopy indicated that a black coating, consisted of Fe2O3, Fe3O4 and FeO(OH), was formed on the surface of iron grains as an iron corrosion product when the system initial pH was lower than 5. The proportion of FeO(OH) increased as reaction time went on, whereas the proportion of Fe3O4 decreased.
基金supported by the National Natural Science Foundation of China(Nos.51134002 and 51074036)
文摘Oolitic iron ore is one of the most important iron resources. This paper reports the recovery of iron from high phosphorus oolitic iron ore using coal-based reduction and magnetic separation. The influences of reduction temperature, reduction time, C/O mole ratio, and CaO content on the metallization degree and iron recovery were investigated in detail. Experimental results show that reduced products with the metallization degree of 95.82% could be produced under the optimal conditions (i.e., reduction temperature, 1250℃; reduction time, 50 min; C/O mole ratio, 2.0; and CaO content, 10wt%). The magnetic concentrate containing 89.63wt% Fe with the iron recovery of 96.21% was obtained. According to the mineralogical and morphologic analysis, the iron minerals had been reduced and iron was mainly enriched into the metallic iron phase embedded in the slag matrix in the form of spherical particles. Apatite was also reduced to phosphorus, which partially migrated into the metallic iron phase.
基金support by the National Natural Science Foundation of China(No.51274033)
文摘Iron nugget and boron-rich slag can be obtained in a short time through high-temperature reduction of boron- bearing iron concentrate by carbonaceous material, both of which are agglomerated together as a carbon composite pellet. This is a novel flow sheet for the comprehensive utilization of boron-bearing iron concentrate to produce a new kind of man-made boron ore. The effect of reducing agent species (i.e., carbon species) on the reduction and melting process of the composite pellet was investigated at a laboratory scale in the present work. The results show that, the reduction rate of the composite pellet increases from bituminite, anthracite, to coke at temperatures ranging from 950 to 1300~C. Reduction temperature has an important effect on the microstructure of reduced pellets. Carbon species also affects the behavior of reduced metallic iron particles. The anthracite-bearing composite pellet melts faster than the bituminite- bearing composite pellet, and the coke-bearing composite pellet cannot melt due to the high fusion point of coke ash. With anthracite as the reducing agent, the recovery rates of iron and boron are 96.5% and 95.7%, respectively. This work can help us get a further understanding of the new process mechanism.
基金financially supported by the National Natural Science Foundation of China(Nos.51134002 and 51604063)the Fundamental Research Funds for the Central Universities(No.N140108001)
文摘To reveal the formation and characteristics of metallic iron grains in coal-based reduction, oolitic iron ore was isothermally re- duced in various reduction times at various reduction temperatures. The microstructure and size of the metallic iron phase were investigated by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and a Bgrimm process mineralogy analyzer. In the results, the re- duced Fe separates from the ore and forms metallic iron protuberances, and then the subsequent reduced Fe diffuses to the protuberances and grows into metallic iron grains. Most of the metallic iron grains exist in the quasi-spherical shape and inlaid in the slag matrix. The cumula- tive frequency of metallic iron grain size is markedly influenced by both reduction time and temperature. With increasing reduction temperature and time, the grain size of metallic iron obviously increases. According to the classical grain growth equation, the growth kinetic parameters, i.e., time exponent, growth activation energy, and pre-exponential constant, are estimated to be 1.3759 ± 0.0374, 103.18 kJ·mol^-1, and 922.05, respec- tively. Using these calculated parameters, a growth model is established to describe the growth behavior of metallic iron grains.
基金The Key Project of the 9th Five year Plan of Ministry of Science andTechnology!(No .960 40 2 0 2A)the Foundation for Unive
文摘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.
基金support by China Scholarship Council(No.201206370127)support from CSIRO,Australia
文摘The technology of direct reduction by adding sodium carbonate (Na2CO3) and magnetic separation was developed to treat Western Australian high phosphorus iron ore. The iron ore and reduced product were investigated by optical microscopy and scanning electron microscopy. It is found that phosphorus exists within limonite in the form of solid solution, which cannot be removed through traditional ways. During reduction roasting, Na2CO3 reacts with gangue minerals (SiO2 and A1203), forming aluminum silicate-containing phosphorus and damaging the ore structure, which promotes the separation between iron and phosphorus during magnetic separation. Meanwhile, Na2CO3 also improves the growth of iron grains, increasing the iron grade and iron recovery. The iron concentrate, assaying 94.12wt% Fe and 0.07wt% P at the iron recovery of 96.83% and the dephosphorization rate of 74.08%, is obtained under the optimum conditions. The final product (metal iron powder) after briquetting can be used as the burden for steelmaking by an alactrie a.re furnace to rer)la,ce scrar) steel.
基金financially supported by the National Natural Science Foundation of China (No.51604063)
文摘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.
基金financially supported by the National Natural Science Foundation of China(No.51134002)the Fundamental Research Funds for the Central Universi-ties of China(No.N120601004)
文摘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.
基金financially supported by the National Natural Science Foundation of China (Nos. 51104014 and 51134008)
文摘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.
基金the Specialized Research Fund for the Doctoral Program of Higher Education of China (No.20130006110017) for the financial support for this research
文摘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.
基金financially supported by the State Key Program of National Natural Science of China(No.51234008)
文摘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.
基金supported by the Special Fund for Agroscientific Research in the Public Interest,China(201103005)the Science and Technology Innovation Project of Chinese Academy of Agricultural Sciences(2013–2017)
文摘Dissimilatory Fe(Ⅲ) reduction is an important process in the geochemical cycle of iron in anoxic environment. As the main products of dissimilatory iron reduction, the Fe(Ⅱ) species accumulation could indicate the reduction ability. The effects of different green manures on Fe(Ⅲ) reduction in paddy soil were explored based on a 31-year rice-rice-winter green manure cropping experiment. Four treatments were involved, i.e., rice-rice-milk vetch (RRV), rice-rice-rape (RRP), rice-rice-ryegrass (RRG) and rice-rice-winter fallow (RRF). Soils were sampled at flowering stage of milk vetch and rape (S1), before transplantation (S2), at tillering (S3), jointing (S4), and mature (S5) stages of the early rice, and after the harvest of the late rice (S6). The contents of TFeHa (HCI-extractable total Fe), Fe(Ⅱ)HCI (HCI-extractable Fe(Ⅱ) species) and Fe(Ⅲ)HCI (HCI- extractable Fe(Ⅲ) species) were measured. The correlations among those Fe species with selected soil environmental factors and the dynamic characteristics of Fe(Ⅱ)HCI accumulation were investigated. The results showed that TFeHc~ in RRF was significantly higher than those in the green manure treatments at most of the sampling stages. Fe(II)Ha increased rapidly after the incorporation of green manures in all treatments and kept rising with the growth of early rice. Fe(Ⅱ)Ha in RRG was quite different from those in other treatments, i.e., it reached the highest at the S2 stage, then increased slowly and became the lowest one at the S4 and S5 stages. Fe(Ⅲ)Ha showed oppositely, and Fe(Ⅱ)HCI/Fe(Ⅲ)HCI performed similarly to Fe(Ⅱ)HCI The maximum accumulation potential of Fe(Ⅱ)HCI was significantly higher in RRF, while the highest maximum reaction rate of Fe(Ⅱ)Ha accumulation appeared in RRG. Significant correlations were found between the indexes of Fe(Ⅱ)HCI accumulation and soil pH, oxidation-reduction potential (Eh) and total organic acids, respectively. In together, we found that long-term application of green manures decreased the TFeHa in red paddy soils, but promoted the ability of Fe(lll) reduction, especially the ryegrass; Fe(Ⅱ)Ha increased along with the growth of rice and was affected by soil conditions and environmental factors, especially the water and redox ability.
基金the National Natural Science Foundation of China, Contract No. 59774022.]
文摘The catalyst containing 0.69% (mass fraction) of Li+, Na+, or Ca2+ were synthesized, and the catalytic effect on the reduction of iron oxide/carbon composite pellets were investigated by comparing with that of additive at 850 degreesC. The effect of the catalyst was greater than that of the additive, it can be considered that catalyst promoted the formation of iron nucleus early on reduction processes of iron oxide/carbon composite pellets. In addition, both effects of catalyst and additive increased after added carbon powder into the pellets, but the extent of increase decreased when the carbon powder exceeded a suitable content (about 4%), this amount is less than that of carbon needed theoretically on the reduction from hematite to iron.
文摘The effect of metallurgical fluxes CaO and CaCO3 on the reduction rate of iron ore pellets containing carbon in nitrogen atmosphere has been studied by a weight-loss thermal balance. The experimental results showed that adding CaO or CaCO3 can promote reduction reaction as the added CaO or CaCO3 probably decrease the apparent activation energy of iron ore concentrate-carbon-CaO or CaCO3 reaction, and the reduction rate constant changes with mass percent of CaO and CaCO3. The kinetic analysis also showed that the rate-controlling step of the reaction is inner gas diffusion.
基金financially supported by the China Postdoctoral Science Foundation(No.2018T110046)the National Natural Science Foundation of China(No.51274033)
文摘Ludwigite is a kind of complex iron ore containing boron, iron, and magnesium, and it is the most promising boron resource in China. Selective reduction of iron oxide is the key step for the comprehensive utilization of ludwigite. In the present work, the reduction mechanism of ludwigite was investigated. The thermogravimetry and differential scanning calorimetry analysis and isothermal reduction of ludwigite/coal composite pellet were performed. Ludwigite yielded a lower reduction starting temperature and a higher final reduction degree compared with the traditional iron concentrates. Higher specific surface area and more fine cracks might be the main reasons for the better reducibility of ludwigite. Reducing temperature highly affected the reaction fraction and microstructure of the reduced pellets, which are closely related to the separation degree of boron and iron. Increasing reducing temperature benefited the boron and iron magnetic separation. Optimum magnetic separation results could be obtained when the pellet was reduced at 1300°C. The separated boron-rich non-magnetic concentrate presented poor crystalline structure, and its extraction efficiency for boron reached 64.3%. The obtained experimental results can provide reference for the determination of the comprehensive utilization flow sheet of ludwigite.
基金supported by the Major Projects on Control and Rectification of Water Body Pollution (Water Special Project) (No.2009ZX07010-001,2008ZX07526-001)the National Basic Research Program (973) of China (No.2008CB418201)
文摘A comparative study of treatment of simulated wastewater containing Reactive Red 195 using zero-valent iron/activated carbon (ZVI/AC), microwave discharge electrodeless lamp/sodium hypochlorite (MDEL/NaCIO) and the combination of ZVI/AC- MDEL/NaCIO was conducted. The preliminary results showed the two steps method of ZVI/AC-MDEL/NaCIO had much higher degradation efficiency than both single steps. The final color removal percentage was nearly up to 100% and the chemical oxygen demand reduction percentage was up to approximately 82%. The effects of operational parameters, including initial pH value of simulated wastewater, ZVI/AC ratio and particle size of ZVI were also investigated. In addition, from the discussion of synergistic effect between ZVI/AC and MEDL/NaCIO, we found that in the ZVI/AC-MEDL/NaCIO process, ZVI/AC could break the azo bond firstly and then MEDLfNaCIO degraded the aromatic amine products effectively. Reversing the order would reduce the degradation efficiency.
基金the National Natural Science Foundation of China(No.51904063)the Fundamental Research Funds for the Central Universities,China(Nos.N172503016,N172502005,and N172506011)the China Postdoctoral Science Foundation(No.2018M640259).
文摘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.
基金financially supported by the National Natural Science Foundation of China (No. 51674026)
文摘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%.