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

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

Development of Direct Reduced Iron in China:Challenges and Pathways

The steel industry is considered an important basic sector of the national economy,and its high energy consumption and carbon emissions make it a major contributor to climate change,especially in China.The majority of crude steel in China is produced via the energy-and carbon-intensive blast furnace–basic oxygen furnace(BF–BOF)route,which greatly relies on coking coal.In recent years,China’s steel sector has made significant progress in energy conservation and emission reduction,driven by decarbonization policies and regulations.However,due to the huge output of crude steel,the steel sector still produces 15%of the total national CO_(2) emissions.The direct reduced iron(DRI)plus scrap–electric arc furnace(EAF)process is currently considered a good alternative to the conventional route as a means of reducing CO_(2) emissions and the steel industry’s reliance on iron ore and coking coal,since the gas-based DRI plus scrap–EAF route is expected to be more promising than the coal-based one.Unfortunately,almost no DRI is produced in China,seriously restricting the development of the EAF route.Here,we highlight the challenges and pathways of the future development of DRI,with a focus on China.In the short term,replacing natural gas with coke oven gas(COG)and byproduct gas from the integrated refining and chemical sector is a more economically feasible and cleaner way to develop a gas-based route in China.As the energy revolution proceeds,using fossil fuels in combination with carbon capture,utilization,and storage(CCUS)and hydrogen will be a good alternative due to the relatively low cost.In the long term,DRI is expected to be produced using 100%hydrogen from renewable energy.Both the development of deep processing technologies and the invention of a novel binder are required to prepare high-quality pellets for direct reduction(DR),and further research on the one-step gas-based process is necessary.

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.

A Fe-N-C catalyst with highly dispersed iron in carbon for oxygen reduction reaction and its application in direct methanol fuel cells

Exploring non‐precious metal catalysts for the oxygen reduction reaction （ORR） is essential for fuel cells and metal–air batteries. Herein, we report a Fe‐N‐C catalyst possessing a high specific surface area （1501 m2/g） and uniformly dispersed iron within a carbon matrix prepared via a two‐step pyrolysis process. The Fe‐N‐C catalyst exhibits excellent ORR activity in 0.1 mol/L NaOH electrolyte （onset potential, Eo=1.08 V and half wave potential, E1/2=0.88 V vs. reversible hydrogen electrode） and 0.1 mol/L HClO4 electrolyte （Eo=0.85 V and E1/2=0.75 V vs. reversible hydrogen electrode）. The direct methanol fuel cells employing Fe‐N‐C as the cathodic catalyst displayed promising per‐formance with a maximum power density of 33 mW/cm2 in alkaline media and 47 mW/cm2 in acidic media. The detailed investigation on the composition–structure–performance relationship by X‐ray diffraction, X‐ray photoelectron spectroscopy and Mo-ssbauer spectroscopy suggests that Fe‐N4, together with graphitic‐N and pyridinic‐N are the active ORR components. The promising direct methanol fuel cell performance displayed by the Fe‐N‐C catalyst is related to the intrinsic high catalytic activity, and critically for this application, to the high methanol tolerance.

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.

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.

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

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

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%.

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

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

Study on Direct Reduction Characteristics of Iron Ore Coal Mixed Pellets

In order to get DRI iron ore coal mixed pellets are reduced isothermally. The mechanisms of reduction desulphurization, iron oxide reduction and the structure regenesis of the coal mixed pellets during reduction have been studied. The effect of various processing factors on the quality of DRI and economy technological indices including compression strength, desulphurization rate, recovery rate, reaction fraction, carbon content and metallization are also researched.

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

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

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.

COMBINED TECHNOLOGY OF SMELTING REDUCTION IRON-MAKING AND CLEAN FUEL MANUFACTURE

Smelting reduction is a front iron making technology for the 21st century. It can produce liquid iron by direct using common coal but not charred coal. The process has many attractive advantages such as concise flow, low investment and production cost, low environmental pollution and high quality molten iron. Combined with a reciprocal chemical technology, energy efficiency can be further improved by transforming mass coal gas, by-produced in smelting reduction,into dimethyl ether, a clean fuel. Method and characteristics of the combined technology are discussed in this paper.

Swelling behavior of hot preheated pellets in reduction roasting process

One kind of facile coal-based direct reduction process is using hot preheated pellets for reduction in grate kiln. In this work, effects of reduction parameters on swelling index of hot preheated pellets were investigated by photographic technique under isothermal conditions. Experimental results show that swelling index of pellets is firstly increased then gradually decreased with increasing reduction time, while that is found to be an obvious decrease from 175 % to 30% with the variation of temperature from 900℃ to 1100℃. Results of XRD combined with SEM reveal that swelling behavior of pellets is decided by structure of newly formed metal iron grains. The formation and growth of fibers iron grains promote the increase in volume. Low temperature and low CO content are favored to the formation and orientated growth of metal iron grains in the one step process.

不同铁矿物对酱香型白酒封窖泥厌氧消化的影响

通过向废弃窖泥厌氧消化系统中分别添加强氧化性的水铁矿和弱氧化性但有导电性的磁铁矿,考察Fe(Ⅱ)、有机物、微生物群落结构等的变化,探究不同类型Fe(Ⅲ)矿物对窖泥厌氧消化的影响。结果表明,水铁矿组富集铁还原菌,Fe(Ⅱ)含量第12天迅速增加至900 mg/L,表明水铁矿发生了异化铁还原。磁铁矿组与对照组中Fe(Ⅱ)含量几乎一致,说明磁铁矿没有发生异化铁还原。水铁矿组和磁铁矿组中COD去除量分别比空白组增加了16.1%和4.9%,表明水铁矿和磁铁矿均促进了有机物的去除。磁铁矿组富集了Geobacter和Methanosarcina,促进了直接种间电子传递(DIET),增加了23.4%的甲烷产量,而水铁矿抑制甲烷化,降低了32.2%的甲烷产量。

处理含铁尘泥的DRI工艺优选及废气污染防治

将高炉炼铁及炼钢时产生的含铁尘泥作为配料回用于烧结生产是目前较常使用的方法,但是这些尘泥之中的重金属Zn和Pb可能会对烧结和后续的高炉炼铁产生不良影响,通过对直接还原铁的工艺和设备进行综合对比,确定以转底炉为主要设备的煤基直接还原工艺较为适合处理炼铁及炼钢的含铁尘泥,并对转底炉工艺的原理及污染防治措施进行了讨论,最后提出了该工艺和钢铁联合企业之间的循环经济产业链。

铁精矿氧化球团回转窑直接还原试验研究

采用新疆某地生产的铁精矿氧化球团,在Φ2.8 m×48 m回转窑中试装置开展煤基直接还原试验,研究外配碳量、投料量、还原时间、供风结构等因素对铁精矿氧化球团还原效果的影响。试验结果表明,在投料量4 t/h、外配碳比40%、还原时间266 min、采用窑背风机多点供风模式下,金属化球团的金属化率可以达到87.55%。

碳包覆棒状纳米氧化铁非等温还原动力学

纳米氧化铁作为一种兼具优良光学属性、磁响应特性等多种功能优势的纳米材料,结合碳包覆工艺,极大地促进了新功能材料的开发与应用。为确定碳包覆棒状纳米氧化铁还原过程中的动力学参数,试验通过水热炭化法制备碳包覆棒状纳米氧化铁,在氮气气氛条件下,对样品的失重曲线分析,结合FWO法与CR法进行交叉验证。结果显示:碳包覆棒状纳米氧化铁反应活化能约为102.06 kJ/mol,反应机理为三级化学反应模型。