Behaviors of vanadium and chromium in coal-based direct reduction of high-chromium vanadium-bearing titanomagnetite concentrates followed by magnetic separation

The reduction behaviors of FeO·V2O3 and FeO·Cr2O3 during coal-based direct reduction have a decisive impact on the efficient utilization of high-chromium vanadium-bearing titanomagnetite concentrates. The effects of molar ratio of C to Fe n(C)/n(Fe) and temperature on the behaviors of vanadium and chromium during direct reduction and magnetic separation were investigated. The reduced samples were characterized by X-ray diffraction(XRD), scanning election microscopy(SEM) and energy dispersive spectrometry(EDS) techniques. Experimental results indicate that the recoveries of vanadium and chromium rapidly increase from 10.0% and 9.6% to 45.3% and 74.3%, respectively, as the n(C)/n(Fe) increases from 0.8 to 1.4. At n(C)/n(Fe) of 0.8, the recoveries of vanadium and chromium are always lower than 10.0% in the whole temperature range of 1100-1250 °C. However, at n(C)/n(Fe) of 1.2, the recoveries of vanadium and chromium considerably increase from 17.8% and 33.8% to 42.4% and 76.0%, respectively, as the temperature increases from 1100 °C to 1250 °C. At n(C)/n(Fe) lower than 0.8, most of the FeO·V2O3 and FeO·Cr2O3 are not reduced to carbides because of the lack of carbonaceous reductants, and the temperature has little effect on the reduction behaviors of FeO·V2O3 and FeO·Cr2O3, resulting in very low recoveries of vanadium and chromium during magnetic separation. However, at higher n(C)/n(Fe), the reduction rates of FeO·V2O3 and FeO·Cr2O3 increase significatly because of the excess amount of carbonaceous reductants. Moreover, higher temperatures largely induce the reduction of FeO·V2O3 and FeO·Cr2O3 to carbides. The newly formed carbides are then dissolved in the γ(FCC) phase, and recovered accompanied with the metallic iron during magnetic separation.

Coal-based reduction mechanism of low-grade laterite ore

A low-grade nickel laterite ore was reduced at different reduction temperatures. The morphology of metallic particles was investigated by scanning electron microscopy （SEM） and energy dispersive spectroscopy （EDS）. Experimental results indicate that the metallic nickel and iron gradually assemble and grow into larger spherical particles with increasing temperature and prolonging time. After reduction, the nickel laterite ore obviously changes into two parts of Fe-Ni metallic particles and slag matrix. An obvious relationship is found between the reduction of iron magnesium olivine and its crystal chemical properties. The nickel and iron oxides are reduced to metallic by reductant, and the lattice of olivine is destroyed. The entire reduction process is comprised of oxide reduction and metallic phase growth.

A review of the synthesis and application of zeolites from coal-based solid wastes

Zeolite derived from coal-based solid wastes(coal gangue and coal fly ash)can overcome the environmental problems caused by coal-based solid wastes and achieve valuable utilization.In this paper,the physicochemical properties of coal gangue and coal fly ash are introduced.The mechanism and application characteristics of the pretreatment processes for zeolite synthesis from coal-based solid wastes are also introduced.The synthesis processes of coal-based solid waste zeolite and their advantages and disadvantages are summarized.Furthermore,the application characteristics of various coal-based solid waste zeolites and their common application fields are illustrated.Finally,we propose an alkaline fusion-assisted supercritical hydrothermal crystallization as an efficient method for synthesizing coal-based solid waste zeolites.In addition,more attention should be given to the recycling of alkaline waste liquid and the application of coal-based solid waste zeolites in the field of volatile organic compound adsorption removal.

Migration behaviors and kinetics of phosphorus during coal-based reduction of high-phosphorus oolitic iron ore

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.

In Situ Synthesis of NaY Zeolite with Coal-Based Kaolin

NaY zeolites were in-situ synthesized from coal-based kaolin via thehydrothermal method. The effects of various factors on the structure of the samples were extensivelyinvestigated. The samples were characterized by N_2 adsorption, XRD, IR and DTG-DTA methods, andthe results show that the crystallization temperature and amount of added water play an importantrole in the formation of the zeolite structure. The 4A and P zeolites are the competitive phasepresent in the resulting product. However, NaY zeolites with a higher relative crystallinity,excluding impure crystals and the well hydrothermal stability, can be synthesized from coal-basedkaolin. These zeolites possess a larger surface area and a narrow pore size distribution, and thismeans that optimization of this process might result in a commercial route to synthesize NaYzeolites from coal-based kaolin.

Study on methanol synthesis from coal-based syngas

The intrinsic kinetic models of the Langmuir-Hinshelwood type were investigated in terms of the reaction rates of CO hydrogenation and CO_2 hydrogenation in theform of reactant fugacity. The parameters were estimated by the Universal Global Optimization using the Marquardt method. Residual error distribution and statistic tests show thatthe intrinsic kinetic models are reliable and acceptable. The mathematic model of a combined converter formed by gas-cooled and water-cooled reactor was developed and thegas-cooled reactor and the water-cooled reactor were characterized with one-dimensionalmathematic model. The distributions of temperature and concentration in the catalytic bedof the gas-cooled reactor and the water-cooled reactor in a combined converter with ayield of 1.2 Mt/a were simulated. The parallel cross linking pore model was used to describe the transfer process of multi-component diffusion system in the catalyst. The calculated value computed by the internal diffusion efficiency factor calculation model established for methanol synthesis catalyst fit the experimental value very well.

Adsorption and Regeneration of Volatile Organic Compounds(VOCs)on Coal-Based Activated Carbon by Ferric Nitrate Modification

In this study,the Heishan coal was used to prepare a series of activated carbon(AC)samples via a vapor deposition method.The effects of the Fe(NO_(3))3/coal weight ratio on the physicochemical properties of the activated carbon were systematically investigated,and the AC samples were analyzed by the N2 adsorption-desorption technique,the scanning electron microscopy,the X-ray diffraction,the Raman spectroscopy,and the Fourier transform infrared spectroscopy.Furthermore,the adsorption properties of ethyl acetate were investigated.The results indicated that as the Fe(NO_(3))3/coal mass ratio increased from 1:8 to 1:2,the specific surface area,the total pore volume and the micropore volume initially increased and then decreased.The specific surface area increased from 560.86 m^(2)/g to 685.90 m^(2)/g,and then decreased to 299.56 m^(2)/g.The total pore volume and micropore volume increased from 0.29 cm^(3)/g and 0.17 cm^(3)/g to 0.30 cm^(3)/g and 0.22 cm^(3)/g,and then decreased to 0.16 cm^(3)/g and 0.10 cm^(3)/g,respectively.The optimized ratio was 1:8.During the activation process,iron ions infiltrated the activated carbon to promote the development of the pore structure,the pore size of which was between 2.5 nm and 3 nm in daimeter.This approach could enhance the capacity for adsorption of ethyl acetate.It is worth noting that the ACs displaying the largest specific surface area and total pore volume(685.90 m^(2)/g and 0.30 cm^(3)/g)were formed under the optimized activation conditions(950℃,20%(volume)of CO_(2),ratio 1:5),and the maximum AC capacity for adsorption of ethyl acetate was 962.62 mg/g.After seven repeated thermal regeneration experiments,the saturated AC adsorption capacity was still above 90%.

Purification process of coal-based coke powder as anode for Li-ion batteries

A process of purification of coal-based coke powder as anode the treatment of coke powder with dilute hydrofluoric acid solution, for Li-ion batteries was attempted. The process started with followed by united-acid-leaching using sulfuric acid and hydrochloric acid. The effects of altering the hydrofluoric acid addition, hydrofluoric acid concentration, contact time, temperature and acid type were investigated. A minimum ash content of 0.35% was obtained when proper conditions were applied. The electrochemical performance of purified coke powder shows greatly improved electrochemical performance. The as-purified coke powder presented an initial reversible capacity of 257.4 mAh/g and a retention rate of 95% after 50 cycles. The proposed purification process paves a way to prepare a promising anode material with good performance with low cost of coke powder for Li-ion batteries.

Effect of reducing agents on reducing atmosphere in coal-based direct reduction of beach titanomagnetite

Beach titanomagnetite(TTM)provides a cheap alternative source of Fe and Ti,but this ore is difficult to process to make suitable concentrates for the blast furnace.Recently studies showed that it is feasible to separate Fe and Ti by coal-based direct reduction.In this study,beach TTM was selected as the research object,the effects of reducing agents on reducing atmosphere in coal-based direct reduction of beach TTM were analyzed,and the role of volatiles was also studied.The results showed that when bitumite and coke were used as reducing agents of TTM,the CO produced from volatiles was involved in the reduction reaction,and the generated CO_(2) provided the raw material for the reaction of TTM.The reduction effect of bitumite was better than that of coke.The reason is that bitumite+TTM had a higher gas generation rate and produced a higher CO partial pressure,while coke+TTM had a lower gas generation rate and produced a lower CO partial pressure.When graphite was used as a reducing agent,there was a solid-solid reaction in the early stage in the reaction.With the continuous accumulation of CO_(2),the Boudouad reaction started and accelerated.Graphite+TTM also produced a higher CO partial pressure.

Role of Ni(NO_3)_2 in the preparation of a magnetic coal-based activated carbon

The role of Nil（NO3）2 in the preparation of a magnetic activated carbon is reported in this paper. Magnetic coal-based activated carbons （MCAC） were prepared from Taixi anthracite with low ash content in the presence of Ni（NO3）2. The MCAC materials were characterized by a vibrating sample magnetometer （VSM）, X-ray diffraction （XRD）, a scanning electric microscope （SEM）, and by N2 adsorption. The cylindri- cal precursors and derived char were also subjected to thermogravimetric analysis to compare their behavior of weight losses during carbonization. The results show that MCAC has a larger surface area （1074 m21g） and a higher pore volume （0.5792 cm3/g） with enhanced mesopore ratio （by about 10~）. It also has a high saturation magnetization （1.6749 emu/g） and low coercivity （43.26 Oe）, which allows the material to be magnetically separated. The MCAC is easily magnetized because the nickel salt is con- vetted into Ni during carbonization and activation. Metallic Ni has a strong magnetism on account of electrostatic interaction. Added Ni（NO3）2 catalyzes the carbonization and activation process by accelerat- ing burn off of the carbon, which contributes to the development of mesopores and macropores in the activated carbon.

Review on coal-based reduction and magnetic separation for refractory iron-bearing resources

The application of coal-based reduction in the efficient recovery of iron from refractory iron-bearing resources is comprehensively reviewed.Currently,the development and beneficiation of refractory iron-bearing resources have attracted increasing attention.However,the effect of iron recovery by traditional beneficiation methods is unacceptable.Coal-based reduction followed by magnetic separation is proposed,which adopts coal as the reductant to reduce iron oxides to metallic iron below the melting temperature.The metallic iron particles aggregate and grow,and the particle size continuously increases to be suitable for magnetic separation.The optimization and application of coal-based reduction have been abundantly researched.A detailed literature study on coal-based reduction is performed from the perspectives of thermodynamics,reduction kinetics,growth of metallic iron particles,additives,and application.The coal-based reduction industrial equipment can be developed based on the existing pyrometallurgical equipments,rotary hearth furnace and rotary kiln,which are introduced briefly.However,coal-based reduction currently mainly adopts coal as a reductant and fuel,which may result in high levels of carbon dioxide emissions,energy consumption,and pollution.Technological innovation aiming at decreasing carbon dioxide emissions is a new trend of green and sustainable development of the steel industry.Therefore,the substitution of coal with clean energy(hydrogen,biomass,etc.)for iron oxide reduction shows promise in the future.

Making Ferronickel from Laterite Nickel Ore by Coal-Based Self-Reduction and High Temperature Melting Process

Based on the process of coal-based self-reduction and melting separation at high temperature, it was investigated that the effect of process factors on the reduction of iron and nickel oxide, the metal yield and the nickel content in ferronickel about the laterite nickel ore, was from Philippines and contented low nickel, high iron and aluminum. The results showed that if the C/O mole ratio was not higher than 0.5 and the reduction temperature was kept as 1200°C and then increased up to 1500°C, the metal could not separate from molten slag for the A series of experiments, which were only added CaF2. However, when the C/O ratio was added up to 0.6 - 0.8, the metal could separate well from the slag, and the yields of Fe and Ni increased gradually. But the nickel content in the metal declined from 1.79% to 1.34%. When the C/O ratio increased to 1.2, and the temperature of melting products obtained at 1200°C and rose to 1550°C, the separation of metal from slag could not be realized in B group of tests, which were only added hydrated lime. However, when both of CaF2 and hydrated lime were added, the metal could separate from slag in C group. In order to increase the content of nickel in the metal, it is necessary to restrain the reduction of iron oxide. When the C/O mole ratio is 0.6, the nickel content of metal could be 1.79%, which was higher than the theoretical ratio 1.65% of Ni/(Ni + Fe) of the latcritic nickel ore, but the yield of nickle was only 71.3%.

Characterization of semi-coke generated by coal-based direct reduction process of siderite

Solid wastes derived from metallurgical industries pose a significant threat to environment. The utilization and disposal of these solid wastes are the major concern in the world. Semi-coke generated in coal-based direct reduction process of iron ore is a by-product and its suitable utilization is not available so far. In order to handle it properly, the characteristics of this by-product were comprehensively investigated. A series of analysis methods were used to demonstrate its mineral compositions, petrography and physico-chemical properties. The results reveal that the semi-coke has poor washability. The fixed carbon content of semi-coke reaches 76.11% and the gross calorific value is 28.10 MJ/kg, both of which are similar to those of traditional sinter coke breeze. Also, semi-coke ash possesses lower content of SiO2, Al2O3, S and higher content of CaO and MgO, which could improve the strength of sinter ore when partially substituting for coke breeze in sintering. Semi-coke features well-development porous structure and higher reaction activity, which predicts that the sintering speed could be elevated to some extent when employing it as a partial replacement of coke breeze, so the studies further suggest that the potential adverse effect of the high reactivity on sintering process could be weakened by adequately coarsening the semi-coke's particle size.

Modeling and simulation of tube-shell reactor for dimethyl-ether synthesis from coal-based synthesis ga

Mathematical simulation was performed on tube-shell reactor for dimethyl ether （DME） synthesis from coal-based syngas. The model was established based on kinetics of dimethyl-ether synthesis from syngas over a bifunctional catalyst, which is mixed by methanol synthesis catalyst and dehydration catalyst as 1：1 mass ratio. Methanol synthesis from CO and CO2 and methanol dehydration were selected as three-independent reactions, CO, CO2, and DME as key components to estab- lish the one-dimensional mathematical model of the reactor. The gas concentration and temperature profiles inside the reactor tubes were obtained. The operating conditions affecting DME synthesis were also discussed based on the model. The simula- tions indicate that higher pressure and lower temperature at the inlet and rich hydrogen in the reactant are favorable in direct DME synthesis in fixed-bed process, and the temperature of boiling water affect the reactor performance seriously.

不同工艺渗碳淬火和深冷处理后20CrNi2Mo轴承钢的组织与性能

对正火态20CrNi2Mo轴承钢分别进行渗碳油淬+回火、二次渗碳油淬+回火、渗碳气淬+渗碳油淬+回火等3种渗碳淬火+回火处理以及在上述工艺的回火前增加深冷处理的渗碳淬火+深冷+回火处理,研究了不同工艺处理后轴承钢的显微组织、力学性能和耐磨性能。结果表明:渗碳淬火+回火后轴承钢的组织均为针状马氏体+残余奥氏体+碳化物,渗碳气淬+渗碳油淬+回火后的马氏体更细小,残余奥氏体更少,此工艺下轴承钢的硬度、抗拉强度和断后伸长率均高于其他2种渗碳淬火+回火工艺,磨痕宽度和深度较小;与渗碳淬火+回火相比,渗碳淬火+深冷+回火处理后轴承钢中奥氏体含量减少,硬度提高,磨痕宽度和深度减小,并且在200 N载荷下的磨损质量损失明显减少;较优的工艺是渗碳气淬+渗碳油淬+深冷+回火。

20CrMnTiH钢渗碳齿轮弯曲疲劳性能研究

利用扫描电镜、金相显微镜、疲劳试验机和硬度计等测试手段研究20CrMnTiH钢渗碳齿轮弯曲疲劳性能。研究表明:20CrMnTiH钢渗碳齿轮主要沿齿根部位断裂。随着载荷的增加,弯曲疲劳寿命降低,当载荷在50~100kN时,齿轮疲劳寿命增加数倍,建议生产应用在此范围载荷内能发挥该材料最佳性能。

18CrNiMo7-6渗碳合金钢电解抛光参数研究

为提高18CrNiMo7-6渗碳合金钢表面变质层的电解抛光加工质量,开展18CrNiMo7-6渗碳合金钢表面变质层不同渗碳层深度下的电解抛光工艺分析与试验。结果表明,选择浓磷酸与浓硫酸混合溶液作为电解液,温度为40~45℃,首先研究18CrNiMo7-6渗碳合金钢表层试样在不同抛光电压、抛光电流及抛光时间工艺参数下电解抛光后的表面质量,得到18CrNiMo7-6渗碳合金钢表层的最佳电解抛光参数为10 V、1.8~1.9 A、70 s;再对得到的表层最佳参数进行微调,得到不同渗碳深度下试样的最佳电解抛光参数,次表层电解抛光参数为10 V、1.6~1.7 A、65 s,心部电解抛光参数为10 V、1.5~1.6A、60 s。

Effect of solid carburization on surface microstructure and hardness of Ti-6Al-4V alloy and(TiB+La_2O_3)/Ti-6Al-4V composite

Solid carburization was employed to improve the hardness of Ti-6Al-4V alloy and （TiB＋La2O3）/Ti composite. The samples wrapped in graphite powder were placed in sealed quartz tubes, followed by solid carburization at 1227 K for 24 h. Microstructure and phase analysis indicated that TiC reinforcements and Ti-C solid solutions were introduced after solid carburization. Moreover, the volume fraction of equiaxedα-Ti phase in diffusion layer decreased obviously with increasing sample depth. Hardness testing results indicated that both the carburized surfaces performed significant improvement of about 100% in micro-hardness compared with untreated materials. The variation of carbon contents with increasing sample depth resulted in a hardened layer of 300 μm in the carburized samples. Meanwhile, slight influence on the internal microstructure and hardness indicated that solid carburization was an effective method in strengthening the surface of titanium alloy and titanium matrix composite.

750℃高温CO_(2)掺杂SO_(2)环境中Super304H及Inconel625的腐蚀行为

研究掺杂气体对合金的腐蚀行为及作用机理对超临界二氧化碳(supercritical carbon dioxide,S-CO_(2))发电技术具有重要意义。该文开展Super304H及Inconel625合金的高温CO_(2)腐蚀试验,并结合腐蚀增重法、扫描电镜观察及XRD分析,研究两种耐热合金在750℃CO_(2)及掺杂SO_(2)环境中的腐蚀行为。结果表明,两种合金在750℃CO_(2)、750℃CO_(2)+SO_(2)环境中的腐蚀动力学均遵循抛物线规律,Inconel625抗腐蚀能力优于Super304H,具有较少的腐蚀增重;Super304H在750℃CO_(2)腐蚀初期增重高于CO_(2)+SO_(2)环境,而120 h后在CO_(2)+SO_(2)环境中腐蚀增重较高。两种环境中腐蚀500 h后,Super304H表面氧化膜为单层Cr_(2)O_(3)及外层疏松瘤状富铁氧化物与内氧化物FeCr_(2)O_(4)组成的局部双层氧化膜;Inconel625为单层均匀致密Cr_(2)O_(3)氧化膜,平均厚度不到1μm。高温CO_(2)腐蚀环境中,Cr含量对提高合金抗腐蚀性能具有至关重要的作用。高温CO_(2)掺杂SO_(2)对于Cr_(2)O_(3)形成合金具有抑制渗碳的作用,对于氧化铁形成合金具有加速腐蚀及渗碳作用。

乙炔选择加氢反应中碳化钯的动态精细调控: 气氛和氧化锌助剂的作用

碳化钯通常被认为是乙炔选择加氢反应中原位生成的活性相,其生成有助于抑制次表面非选择性的氢化钯物种,从而实现高选择性乙炔加氢制乙烯的目标.次表面上碳化钯和氢化钯物种之间的竞争很大程度上决定了乙炔加氢反应的选择性.然而,由于实际反应环境的复杂性,反应环境下的两种物种之间的动态转化过程和竞争关系尚不清晰.特别是,反应环境(比如氢气组分)对碳化钯物种的调控机制仍不明确,也使得对碳化钯活性物种的精准调控变得困难.此外,氧化锌助剂作为乙炔选择加氢反应中最常用的助剂之一,存在典型的金属-氧化物界面相互作用,也会对渗碳过程产生重要影响.因此,从动态视角理解碳化钯物种的原位形成过程,对于精准设计和合成高性能乙炔选择加氢钯基催化剂具有重要的科学意义.近年来,先进原位表征光谱技术的不断发展使得从原子、分子层面理解原位过程机制成为可能.本文旨在通过先进的原位表征技术揭示乙炔选择加氢反应中碳化钯物种的动态生成过程,并进一步探究气氛环境、温度、助催化剂等参数对碳化钯物种的动态调控机制,从而为高性能乙炔选择加氢催化剂的精准设计和合成提供有力支撑.原位研究结果表明,在氢气升温还原条件下,空气焙烧后新鲜催化剂中氧化钯相首先转变为氢化钯相;随着还原温度升高,氢化钯相的含氢量逐渐降低.当切换至乙炔选择加氢反应原料气时,氢化钯相迅速分解为金属钯,并随着恒温碳化时间的延长,烃类裂解产生的碳原子逐渐渗入钯的体相,最终形成稳定的碳化钯活性相.通过移除乙炔加氢反应原料气氛中的氢气,考察了反应气中的氢气组分对碳化钯形成的调控机制.实验发现,在仅有乙炔和乙烯存在时,碳化过程仍能发生;而引入少量氢气(体积分数2.2%)后,碳化程度显著增强,C/Pd原子比从0.136提升至0.154.相变机理研究表明,氢气的引入促进了氢化钯物种的形成,并通过晶格扩张作用促进渗碳过程.此外,还研究了氧化锌助剂对原位渗碳过程的影响,揭示了氧化锌助剂对碳化钯的抑制作用.结合原位CO吸附漫反射红外光谱、准原位X射线光电子能谱分析发现,低温氢气还原下Pd-ZnO界面作用促进了微量表面PdZn合金的生成,从而抑制了碳的渗入.这种现象在不含氢气的碳化气氛中尤为显著,碳含量降低一个数量级(C/Pd原子比仅为0.019).在此基础上,通过调节反应条件,实现了对碳化钯物种碳含量的精准调控,并与反应活性关联,揭示了碳化钯含量与乙炔选择加氢反应活性之间的线性关系.电子结构表征和同位素实验进一步表明,Pd-C的电子相互作用促进了向Pd中心原子的电子转移,从而提高了氢气的活化解离能力和乙炔加氢反应活性.综上,本工作原位解析了碳化钯的动态形成过程,阐明了氢气辅助插碳和ZnO抑制插碳的微观机制,实现了碳化钯活性物种的精准调控,揭示了碳化程度与反应活性的线性关系,为高性能乙炔选择加氢催化剂设计提供了参考.