Effects of long-term application of different green manures on ferric iron reduction in a red paddy soil in Southern China

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.

Dissimilatory iron reduction contributes to anaerobic mineralization of sediment in a shallow transboundary lake

Dissimilatory iron reduction(DIR)coupled with carbon cycling is increasingly being recognized as an influential process in freshwater wetland soils and sediments.The role of DIR in organic matter(OM)mineralization,however,is still largely unknown in lake sediment environments.In this study,we clarified rates and pathways of OM mineralization in two shallow lakes with seasonal hydrological connectivity and different eutrophic situations.We found that in comparison with the domination of DIR(55%)for OM mineralization in Lake Xiaoxingkai,the contribution of methanogenesis was much higher(68%)in its connected lake(Lake Xingkai).The differences in rates and pathways of sediment OM mineralization between the two lakes were attributed to higher concentrations of carbonate associated iron oxides(Fecarb)in Lake Xiaoxingkai compared to Lake Xingkai(P=0.002),due to better deposition mixing,more contributions of terrigenous detrital materials,and higher OM content in Lake Xiaoxingkai.Results of structural equation modeling showed that Fecarb and total iron content(TFe)regulated 25%of DIR in Lake Xiaoxingkai and 76%in Lake Xingkai,accompanied by a negative effect of TFe on methanogenesis in Lake Xingkai.The relative abundance and diversity of Fe-reducing bacteria were significantly different between the two lakes,and showed a weak effect on sediment OM mineralization.Our findings emphasize the role of iron minerals and geochemical characterizations in regulating rates and pathways of OM mineralization,and deepen the understanding of carbon cycling in lake sediments.

Kinetics of nitrobenzene degradation coupled to indigenous microorganism dissimilatory iron reduction stimulated by emulsified vegetable oil

Widespread contamination by nitrobenzene（NB） in sediments and groundwater requires better understanding of the biogeochemical removal process of the pollutant. NB degradation, coupled with dissimilatory iron reduction, is one of the most efficient pollutant removal methods. However, research on NB degradation coupled to indigenous microorganism dissimilatory iron reduction stimulated by electron donors is still experimental. A model for remediation in an actual polluted site does not currently exist.Therefore, in this study, the dynamics was derived from the Michaelis–Menten model（when the mass ratio of emulsified vegetable oil and NB reached the critical value 91：1）. The effect of SO4^（2-）, NO3^-, Ca^（2＋）/Mg^（2＋）, and the grain size of aquifer media on the dynamics were studied, and the NB degradation dynamic model was then modified based on the most significant factors. Utilizing the model, the remediation time could be calculated in a contaminated site.

Recovery of iron from high phosphorus oolitic iron ore using coal-based reduction followed by magnetic separation

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.

Effect of carbon species on the reduction and melting behavior of boron-bearing iron concentrate/carbon composite pellets

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.

Upgrading and dephosphorization of Western Australian iron ore using reduction roasting by adding sodium carbonate

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.

Formation and characterization of metallic iron grains in coal-based reduction of oolitic iron ore

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.

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

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

Kinetic studies on the reduction of iron ore nuggets by devolatilization of lean-grade coal

An isothermal kinetic study of a novel technique for reducing agglomerated iron ore by volatiles released by pyrolysis of lean-grade non-coking coal was carried out at temperature from 1050 to 1200℃ for 10-120 min. The reduced samples were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and chemical analysis. A good degree of metallization and reduction was achieved. Gas diffusion through the solid was identified as the reaction-rate-controlling resistance; however, during the initial period, particularly at lower temperatures, resistance to interfacial chemical reaction was also significant, though not dominant. The apparent rate constant was observed to increase marginally with decreasing size of the particles constituting the nuggets. The apparent activation energy of reduction was estimated to be in the range from 49.640 to 51.220 kJ/mol and was not observed to be affected by the particle size. The sulfur and carbon contents in the reduced samples were also determined.

Corrosion of Magnesia-chrome Brick by Smelting Reduction Slag with Iron Bath

Effects of FeO content （0, 5%, 10%, and 15% in mass, respectively ） in lab-synthesized smelting redttc- tion slag with iron bath and test temperature （1 450, 1 500, 1550, anti 1 600 ℃ ） on corrosion am,amount and microstructure of fused rebonded magnesia - chrome brick with 26.02 massqc of Cr2O3 were researched by rotary cylinder method. The results show that ： （ 1 ） the corro- sion amolult of magnesia -chrome brick by slag without FeO is higher than that by the slag with 5% FeO, and the vorrosion amount increases when FeO content increa- ses from 5% to 15% ; （2） the test temperature is one of the important factors affecting the slag corrosion resist- ance of magnesia - chrome brick, and the corrosion of smelting reduction slag to brick increases with the temperature rising.

Characterization of iron diagenesis in marine sediments using refined iron speciation and quantized iron(Ⅲ)-oxide reactivity:a case study in the Jiaozhou Bay,China

As a case study, refined iron（Fe） speciation and quantitative characterization of the reductive reactivity of Fe（Ⅲ）oxides are combined to investigate Fe diagenetic processes in a core sediment from the eutrophic Jiaozhou Bay.The results show that a combination of the two methods can trace Fe transformation in more detail and offer nuanced information on Fe diagenesis from multiple perspectives. This methodology may be used to enhance our understanding of the complex biogeochemical cycling of Fe and sulfur in other studies. Microbial iron reduction（MIR） plays an important role in Fe（Ⅲ） reduction over the upper sediments, while a chemical reduction by reaction with dissolved sulfide is the main process at a deeper（〉 12 cm） layer. The most bioavailable amorphous Fe（Ⅲ） oxides [Fe（Ⅲ）am] are the main source of the MIR, followed by poorly crystalline Fe（Ⅲ） oxides [Fe（Ⅲ）pc）]and magnetite. Well crystalline Fe（Ⅲ） oxides [Fe（Ⅲ）wc] have barely participated in Fe diagenesis. The importance of the MIR over the upper layer may be a combined result of the high availability of highly reactive Fe oxides and low availability of labile organic matter, and the latter is also the ultimate factor limiting sulfate reduction and sulfide accumulation in the sediments. Microbially reducible Fe（Ⅲ） [MR-Fe（Ⅲ）], which is quantified by kinetics of Fe（II）-oxide reduction, mainly consists of the most reactive Fe（Ⅲ）am and less reactive Fe（Ⅲ）pc. The bulk reactivity of the MR-Fe（Ⅲ） pool is equivalent to aged ferrihydrite, and shows down-core decrease due to preferential reduction of highly reactive phases of Fe oxides.

STUDY ON THE VARIATION MECHANISM OF CARBON CONTENT OF LIQUID IRON IN MELTING GASIFIER

This paper studied the changing principles of carbon content in direct reduction iron (DRI) and liquid iron in the COREX melting gasifier. Under the normal working conditions of experimental equipment, liquid nitrogen was poured into the melting gasifier from its tuyere to cool down quickly. And then seven cross sections were made to study the carburization reaction and its characteristics of the solid iron and the liquid iron, and also the reaction of carbon between the slag and the metal. According to the results, the influences of the thickness of the semi-coke layer and the temperature on the carbon content of liquid iron in the COREX melting gasifier were confirmed.

Microbially-mediated formation of Ca-Fe carbonates during dissimilatory ferrihydrite reduction:Implications for the origin of sedimentary ankerite

The origin of sedimentary dolomite has become a long-standing problem in the Earth Sciences.Some carbonate minerals like ankerite have the same crystal structure as dolomite,hence their genesis may provide clues to help solving the dolomite problem.The purpose of this study was to probe whether microbial activity can be involved in the formation of ankerite.Bio-carbonation experiments associated with microbial iron reduction were performed in batch systems with various concentrations of Ca^(2+)(0–20 mmol/L),with a marine iron-reducing bacterium Shewanella piezotolerans WP3 as the reaction mediator,and with lactate and ferrihydrite as the respective electron donor and acceptor.Our biomineralization data showed that Ca-amendments expedited microbially-mediated ferrihydrite reduction by enhancing the adhesion between WP3 cells and ferrihydrite particles.After bioreduction,siderite occurred as the principal secondary mineral in the Ca-free systems.Instead,Ca-Fe carbonates were formed when Ca^(2+)ions were present.The CaCO_(3) content of microbially-induced Ca-Fe carbonates was positively correlated with the initial Ca2+concentration.The Ca-Fe carbonate phase produced in the 20 mmol/L Ca-amended biosystems had a chemical formula of Ca_(0.8)Fe_(1.2)(CO_(3))_(2),which is close to the theoretical composition of ankerite.This ankeritelike phase was nanometric in size and spherical,Ca-Fe disordered,and structurally defective.Our simulated diagenesis experiments further demonstrated that the resulting ankerite-like phase could be converted into ordered ankerite under hydrothermal conditions.We introduced the term“proto-ankerite”to define the Ca-Fe phases that possess near-ankerite stoichiometry but disordered cation arrangement.On the basis of the present study,we proposed herein that microbial activity is an important contributor to the genesis of sedimentary ankerite by providing the metastable Ca-Fe carbonate precursors.

Thermodynamic and experimental study of high-temperature roasting of blast furnace gas ash for recovery of metallic zinc and iron

A high-temperature reduction roasting method was used to achieve metallic iron and zinc recovery from blast furnace gas ash(BFA).The reduction processes for Zn-containing and Fe-containing oxides were analyzed in detail by using ther-modynamic equilibrium calculation and the principle of minimum free energy.The results showed that the main reaction in the system is the reduction of ZnFe_(2)_(4)and iron oxides.Over the full temperature range,iron oxides were more easily reduced than zinc oxides.Regardless of the amount of CO contained in the system,the reduction of ZnO to Zn was difficult to proceed below the boiling point(906℃)of Zn.When the reduction temperature is below 906℃,the reduction process of zinc ferrate was ZnFe_(2)_(4)→ZnO;when the reduction temperature is above 906℃,its reduction process becomed ZnFe_(2)_(4)→ZnO→Zn(g).The metallization and dezincification rates of the BFA gradually increased with increasing reaction temperature.As the C/O ratio increased,the metallization and dezincification rates first increased and then decreased.The effect of reduction time on BFA reduction was similar to that of reaction temperature.

Anaerobic biodegradation of benzene series compounds by mixed cultures based on optional electronic acceptors

A series of batch experiments were performed using mixed bacterial consortia to investigate biodegradation performance of benzene, toluene, ethylbenzene and three xylene isomers （BTEX） under nitrate, sulfate and ferric iron reducing conditions. The results showed that toluene, ethylbenzene, m-xylene and o-xylene could be degraded independently by the mixed cultures coupled to nitrate, sulfate and ferric iron reduction. Under ferric iron reducing conditions the biodegradation of benzene and p-xylene could be occurred only in the presence of other alkylbenzenes. Alkylbenzenes can serve as the primary subs＇rates to stimulate the transformation of benzene and p-xylene under anaerobic conditions. Benzene and p-xylene are more toxic than toluene and ethylbenzene, under the three terminal electron acceptors conditions, the degradation rates decreased with toluene 〉 ethylbenzene 〉 m-xylene 〉 o-xylene〉 benzene 〉 p- xylene. Nitrate was a more favorable electron acceptor compared to sulfate and ferric iron. The ratio between sulfate consumed and the loss of benzene, toluene, ethylbenzene, o-xylene, m-xylene, p-xylene was 4.44, 4.51, 4.42, 4.32, 4.37 and 4.23, respectively; the ratio between nitrate consumed and the loss of these substrates was 7.53, 6.24, 6.49, 7.28, 7.81, 7.61, respectively; the ratio between the consumption of ferric iron and the loss of toluene, ethylbenzene, o-xylene, m-xylene was 17.99, 18.04, 18.07, 17.97, respectively.

Validation of CFD-DEM model for iron ore reduction at particle level and parametric study

Iron ore reduction is a primary unit operation in current metallurgy processes and dominates the energy consumption and greenhouse gas(GHG)emissions of the iron-making process,Therefore,even a slight improvement of the energy efficiency or GHG emissions of iron ore reduction would yield considerable benefits to the cost of pig iron and,more importantly,to mitigation of the associated carbon footprint.The current study presents a discrete model that describes the iron ore reduction process for a single pellet.The transient reaction progress can be predicted and is validated against experimental measurements under various operating conditions,including different reducing gases and temperatures.The effects of pressure,isothermality,gas composition,and flow rate on reduction are investigated.The reduction rate increases significantly with increasing pressure until 5 atm,and the entire reduction process occurs more slowly under non-isothermal conditions than under isothermal conditions.This work provides a solid foundation for the development of a comprehensive particulate system model that considers both heat and mass transfer.

Fluidization behavior and reducibility of iron ore fines during hydrogen-induced fluidized bed reduction

A laboratory fluidized bed reactor was used to investigate the fluidization behavior and reducibility of various iron ore fines.Hydrogen was chosen as a reducing agent across a temperature range of 873-1073 K.The magnetite ore used exhibited strong sticking behavior after the initiation of metallic iron formation.All other tested ores fluidized sufficiently well when subjected to the same high reduction temperatures.Parallel kinetic analysis was conducted using a previously developed model to include three rate-limiting step types.The trend of apparent activation energy was correlated with the degree of reduction.Additionally,the influence of varying the specific gas rate was investigated.The results show the variation in reducibility as a result of different interactions,which influence the rate-limiting mechanisms of nucleation and the undertaken chemical reactions,which vary as a function of temperature and degree of conversion.The apparent activation energies,determined from the reduction of wtistite to metallic iron,were in the range of 15-60 kJ/mol,depending on the iron ore used and the degree of conversion.The change in apparent activation energy deriving from the increased specific gas rate can be explained by an increasing nucleation effect,especially at lower reduction temperatures.

Correlation between aggregation structure and tailing mineral crystallinity

Direct reduction is an emerging technology for the utilization of refractory iron ore. With this technology, iron oxides in the ore can be reduced to recoverable elemental iron. The structure of granular aggregates in direct reduction products was investigated by X-ray diffraction （XRD）. The results show that iron is mainly generated as a shell in the outer edge of the aggregates. The thermal conductivity of the iron shell is higher than that of other minerals. Thus, minerals close to the iron shell cool faster than those in the inner shells and do not crystallize well. These minerals mainly become stage 2 tailings. Hence the XRD intensity of stage 2 tailings is lower than that of stage 1 tailhags. When iron is mainly generated in the interior of the aggregates, the crystallinity of stage 2 tailings will be higher than that of stage 1 tailings. This indicates that the crystallinity of tailings can be used as a marker for the aggregate structure.

Effects of embedding direct reduction followed by magnetic separation on recovering titanium and iron of beach titanomagnetite concentrate

Embedding direct reduction followed by magnetic separation was conducted to fully recover iron and titanium separately from beach titanomagnetite （TTM）. The influences of reduction conditions, such as molar ratio of C to Fe, reduction time, and reduction temperature, were studied. The results showed that the TTM concentrate was reduced to iron and iron-titanium oxides, depending on the reduction time, and the reduction sequence at 1 200℃ was suggested as follows ： Fe2.75 Ti0.25O4→Fe2TiO4→FeTiO3→FeTi2O5. The reduction temperature played a considerable role in the reduction of TTM concentrates. Increasing temperature from 1 100 to 1 200℃ was beneficial to recovering titanium and iron, whereas the results deteriorated as temperature increased further. The results of X-ray diffraction and scanning electron microscopy analyses showed that low temperature （≤1100℃） was unfavorable for the gasification of reductant, resulting in insufficient reducing atmosphere in the reduction process. The molten phase was formed at high temperatures of 1250-1 300℃, which accelerated the migration rate of metallic particles and suppressed the diffusion of reduction gas, resulting in poor reduction. The optimum conditions for reducing TTM concentrate are as follows： molar ratio of C to Fe of 1.68, reduction time of 150 min, and reduction temperature of 1 200℃. Under these conditions, direct reduction iron powder, assaying 90.28 mass% TFe and 1.73 mass% TiO2 with iron recovery of 90.85%, and titanium concentrate, assaying 46.24 mass% TiO2 with TiO2 recovery of 91.15%, were obtained.

Effect of Ca-Fe oxides additives on NOx reduction in iron ore sintering

As the emission control regulations get stricter,the NO;reduction in the sintering process becomes an important environmental concern owing to its role in the formation of photochemical smog and acid rain.The NOxemissions from the sintering machine account for 48% of total amount from the iron and steel industry.Thus,it is essential to reduce NO;emissions from the sintering machine,for the achievement of clean production of sinter.Ca-Fe oxides,serving as the main binding phase in the sinter,are therefore used as additives into the sintering mixture to reduce NOxemissions.The results show that the NO;reduction ratio achieves 27.76% with 8% Ca-Fe oxides additives since the Ca-Fe oxides can advance the ignition and inhibit the nitrogen oxidation compared with the conventional condition.Meanwhile,the existence of Ca-Fe oxides was beneficial to the sinter quality since they were typical low melting point compounds.The optimal mass fraction of Ca-Fe oxides additives should be less than 8%since the permeability of sintering bed was significantly decreased with a further increase of the Ca-Fe oxides fines,inhibiting the mineralization reaction of sintering mixture.Additionally,the appropriate particle size can be obtained when mixing an equal amount of Ca-Fe oxides additives of-0.5 mm and 0.5-3.0 mm in size.