Pre-reduction of WO_(3)-Co_(3)O_(4)by H_(2)-C_(2)H_4 in a fluidized bed

In order to avoid the formation ofηphase(W_(6)Co_(6)C or W_(3)Co_(3)C)that adversely affects the sintering process and its products in the preparation process of ultra-fine WC-Co powder,a technical route of prereduction of WO_(3)-Co_(3)O_(4)to WO_(2)-Co and then deep reduction carbonization to WC-Co powder has been proposed.This study mainly investigates the influence of gas partial pressure on the pre-reduction process of WO_(3)-Co_(3)O_(4)under a mixed atmosphere of H_(2)-C_(2)H_(4)-Ar at 600℃and establishes the kinetic equations of pre-reduction and carbon evolution.The results indicate that increasing the partial pressure of hydrogen is conducive to the rapid and complete conversion of WO_(3) to WO_(2).High carbon content can be generated by the deposition of C_(2)H_(4),and it hinders the diffusion of the reducing gas;WO_(3)still cannot be completely reduced to WO_(2)as the partial pressure of C_(2)H_(4) increases to 60%.For the carbon evolution of C_(2)H_(4),the carbon amount is positively related to the H_(2)partial pressure,but it shows the highest amount and evolution rate when the ethylene partial pressure is 20%.Based on the reduction rate curves of WO_(3) and carbon evolution rate curves of C_(2)H_(4),the rate equations of pre-reduction and carbon evolution of WO_(3)-Co_(3)O_(4)system at 600℃are established.The pre-reduction reaction belongs to the first-order reaction,and its equation is expressed as follows:r=-(dw_(WO_(3)))/dt=(9±0.15)×10^(-2)×P_(H_(2))^(0.44)P_(C_(2)H_(4))&(0.57)The carbon deposition rate equation of C_(2)H_(4) can be expressed as follows:r=-(dc_C)/dt=r_f-r_b≌7.35×10^(-2)×P_(C_(2)H_(4))^(0.31)

Preparation of ultrafine WC-Co powder via fluidized bed

In this study,the effects of reaction parameters on the deep-reduction and carbonization process of WO_(2)-Co to WC-Co were studied.The results indicate that the oxygen loss rate of WO_(2) is positively correlated with temperature and methane partial pressure.The partial pressure of methane has no significant effect on the formation rate of WC.The carbon content and particle size of the product increase with the increase of CH_(4) partial pressure.By synergistically regulating the reaction temperature to 950℃,the CH_(4) partial pressure to 1.25%,and the reaction time to 60 min,ultrafine WC-Co powder without η phase can be obtained.The particle size of the composite powder is 128 nm,with total carbon content of 6.16%,free carbon content of 0.4%,and residual oxygen content of 0.05%,respectively.The growth rate relationship of tungsten carbide is as follows:δ(t)=1.21×10^(-13)exp(-12809.72/T)√t.

Preparation of nano-sized tungsten carbide via fluidized bed

Ultrafine or nano-sized of tungsten carbide(WC)is the key material to prepare ultrafine grained cemented carbides.In this paper,nano-sized WC powders were directly prepared by using industrial nano-needle violet tungsten oxide(WO2.72)as the raw material,a fluidized bed as the reactor,and CO as the carbonization gas.The relationship between particle sizes and reaction temperatures,residence times,atmospheres has been investigated systematically.In addition,the physical–chemical indexes(such as residual oxygen,total carbon and free carbon)of the products were measured.The results indicated that the particle size of WC increased with the increase of temperature from 800 to 950°C.As the residence time increased,the particle size decreased gradually,and then increased due to slight sintering.The introduction of hydrogen reduced the carbonization rate,and is not beneficial to obtaining nano-sized WC.Products that satisfy the standard were obtained when WO2.72 reacted with CO at 850°C,900°C and 950°C for 3.0 h,2.5 h and 2.0 h,respectively.The particle sizes of the three samples calculated from the specific surface area were 46.4 nm,53.2 nm and 52.1 nm,respectively.

Oxidation Kinetics,Structural Changes and Element Migration during Oxidation Process of Vanadium-titanium Magnetite Ore

The oxidation kinetics, structural changes, and elements migration during the oxidation process of the va- nadium-titanium magnetite （VTM） ore were analyzed. Kinetics analysis indicated that the oxidation process was con- trolled by diffusion control and could be divided into interface diffusion and lattice diffusion with apparent activation energy of 99.69 kJ/mol and 144.08 kJ/mol in the range of 800--1000℃, respectively. The surface structure changed with the oxidization temperature as follows： dense surface→nano sized sheets→submicron particles→molten particles. The compact structure changed into porous one because of the elements migration and enrichment. Both Fe and Ti elements migrated in the opposite direction during the oxidation process. The V etement in the raw ore stably existed in the form of V^5＋ state, some vanadium migrated and occupied the tetrahedral sites of the hematite during the oxidation process.

Evolution of deposited carbon during multi-stage fluidized-bed reduction of iron ore fines

The influence of reduction conditions on carbon deposition during fiuidized-bed pre-reduction of iron ore fines was investigated experimentally.The results showed that reduction temperature and the composition of reducing gases had a significant effect on the rate of carbon deposition and the type of carbon deposits (graphite and Fe3C).Low reduction temperature,high CO content,and addition of H2favored the deposition of carbon,especially graphite.The reduction conditions also significantly affected the surface morphology of the as-reduced iron ore fines.As the amount of deposited graphite increased,the formation of fibrous iron disappeared and graphite filaments were observed.The pre-reduced iron ore fines were further fiuidized in pure CO at 850℃ for final reduction.The results showed that graphite could suppress the formation of fibrous iron and decrease the surface viscosity,thereby inhibiting agglomeration during the final high-temperature reduction stage.Reactions that consume the deposited carbon during the final high-temperature reduction were identified and graphite was shown to be more reactive than Fe3C.To enhance the application of fluidization technology in producing sponge iron,a novel solid-state high-temperature reduction method via deposited carbon was proposed and demonstrated to be feasible.

过程工程所流化床直接还原技术研究进展

“双碳”背景下,钢铁工业亟待低碳重塑,氢气直接还原(常称为“氢冶金”)是国内外竞相研发的重要方向。流态化直接还原是过程工程所六十多年来一直坚持的研究方向。值此叶渚沛先生诞辰120周年之际,本综述回顾并概述了过程工程所在流态化直接还原基础理论和工业应用两方面所取得的一系列重要成果。基础理论方面包括颗粒间黏着力与分离力相互竞争黏结机制、聚团流化和慢速失流的发现、不同铁形貌析出机理和黏结特性,以及降低颗粒间黏结力(颗粒包覆改性、调控铁析出形貌)和增大颗粒间分离力(增强颗粒运动、增大颗粒尺寸、施加外场力)等一系列抑制黏结失流方法;工业应用方面包括100公斤/天流化床氢气直接还原、1吨/天钒钛磁铁矿流化床直接还原和千吨级钒钛磁铁矿直接还原-电炉熔分等中间试验,目前正在与鞍钢集团等单位合作开展全球首套1万吨直接还原铁/年流化床绿氢直接还原工程示范。谨以此文缅怀叶渚沛先生、郭慕孙先生等老一辈科学家,以期推动流化床直接还原基础理论和技术研发的进步,为钢铁工业低碳重塑贡献智慧和力量。

Effect of high stirring speed on the agglomerate behaviors for cohesive SiO_(2) powders in gas fluidization

The effects of superficial gas velocity and mechanical stirring speed on the precise regulation of flow regimes for cohesive SiO2 powders(mean diameter is 16μm)were experimentally investigated in a stirring-assisted fluidized bed.The results showed that compared with the agglomerates formed in the non-assisted fluidization of cohesive SiO2 powders,the introduction of mechanical stirring could effectively reduce the size of agglomerates and well disperse the agglomerates during fluidization.The best regulation range of agglomerate particulate fluidization can be achieved at 600 rpm when agglomerate sizes were reduced to below 200μm.Further investigation based on the operational phase diagram revealed that transformations of flow regimes were dominated by both stirring speed and gas velocity.The stirring applied enlarges the operational range of agglomerate particulate fluidization(APF)with a delayed onset of bubbling for cohesive particles.However,the exorbitant speed increases the collision velocity and contact area between small agglomerates,which results in the formation of unstable agglomerates and the whirlpool of powder.