Gas-based reduction of vanadium titano-magnetite concentrate: behavior and mechanisms

The reduction of vanadium titano-magnetite pellets by H₂-CO at temperatures from 850 to 1050℃ was investigated in this paper. The influences of pre-oxidation treatment, reduction temperature, and V_H2/(V_H2 + V_CO) on the metallization degree were studied. The results showed that pre-oxidation played a substantial role in the reduction of vanadium titano-magnetite pellets. During the reduction process, the metallization degree increased with increasing temperature and increasing V_H2/(V_H2 + V_CO). The phase transformation of pre-oxidized vanadium titano-magnetite pellets during the reduction process under an H₂ atmosphere and a CO atmosphere was discussed, and the reduced samples were analyzed by scanning electron microscopy (SEM) in conjunction with back scatter electron (BSE) imaging. The results show that the difference in thermodynamic reducing ability between H₂ and CO is not the only factor that leads to differences in the reduction results obtained using different atmospheres. Some of Fe_3-xTi_xO₄ cannot be reduced under a CO atmosphere because of the densification of particles' structure and because of the enrichment of Mg in unreacted cores. By contrast, a loose structure of particles was obtained when the pellets were reduced under an H₂ atmosphere and this structure decreased the resistance to gas diffusion. Moreover, the phenomenon of Mg enrichment in unreacted cores disappeared during H₂ reduction. Both the lower resistance to gas diffusion and the lack of Mg enrichment facilitated the reduction of vanadium titano-magnetite.     

球团矿还原的动力学模型分析

基于还原炉控温还原实验,通过分析CO和H2还原球团矿过程中的反应速率模型,提出两种气体混合后还原球团矿的反应动力学模型,得到还原过程中阻力和反应速率随温度及还原度的变化规律,得出结论:CO还原球团矿时,内扩散阻力所占比例随着温度及还原度增加而变大;H2还原球团矿时,内扩散属于速率控制环节;混合气还原球团矿时,反应速率随温度升高而增大,温度低于500℃时,CO浓度增加,反应速率降低,而温度超过500℃后,反应速率则随着CO浓度的增加而增大;混合气反应速率模型的计算值与实验结果一致。     

Cathodic behavior of molten CaCl<Subscript>2</Subscript>-CaO and CaCl<Subscript>2</Subscript>-NaCl-CaO

The cathodic behavior of molten CaCl₂, CaCl₂-CaO and equimolar CaCl₂-NaCl-CaO was studied by cyclic voltammograms and constant potential polarization at temperatures of 1123 to 1173 K on molybdenum and titanium electrodes. The diffusion coefficient of Ca²⁺ (CaO) in molten CaCl₂-CaO was calculated from the linear relationship between the square root of scan rate and the peak current density. The deposition potentials and the potential temperature coefficient of CaO in molten CaCl₂-0.5mol%CaO and CaCl₂-NaCl-0.5mol%CaO were also obtained from their cyclic voltammograms. The result shows that CaO is more easily reduced than CaCl₂. The addition of NaCl in molten CaCl₂-CaO induces the underpotential electrodeposition of CaO.     

还原气氛和脉石成分对氧化球团还原膨胀的影响

以Fe2O3粉为原料,分别配加SiO2,CaO及MgO制备氧化球团,系统研究了H2和CO两种还原气氛及不同脉石成分对氧化球团还原膨胀的影响,并进行了理论分析.研究表明,还原气氛中H2含量的增加,有利于降低球团的还原膨胀率,还原后球团晶体结构完整,品质较好;Fe2O3球团中配加少量CaO,有利于焙烧时产生少量液相而改善球团的冶金性能,但CaO含量不宜过大;在保证产品质量前提下,适当控制球团矿品位,含有少量SiO2等脉石杂质,有利于焙烧时产生渣相连接,提高球团的强度,降低还原膨胀率;球团中添加MgO有利于形成稳定的晶体结构,从而改善球团的性能.     

Microwave sintering of Ca<Subscript>0.6</Subscript>La<Subscript>0.2667</Subscript>TiO<Subscript>3</Subscript> microwave dielectric ceramics

Ca_0.6La_0.2667TiO₃ ceramics were prepared by conventional and microwave sintering techniques and their sinterability, microstructure, and microwave dielectric properties were investigated in detail for comparison. Densified Ca_0.6La_0.2667TiO₃ ceramics were obtained by microwave sintering at 1350°C for 30 min and by conventional sintering at 1450°C for 4 h. An unusual phenomenon was found that some larger grains (grain size range: 8–10 μm) inclined to assemble in one area but some smaller ones (grain size range: 2–4 μm) inclined to gather in another area in the microwave sintered ceramics. The microwave dielectric properties of Ca_0.6La_0.2667TiO₃ ceramics prepared by microwave sintering at 1350°C were as follows: dielectric constant (ɛ _r) = 119.6, quality factor (Qf) = 17858.5 GHz, and temperature coefficient of resonant frequency (τ _f) = 155.5 ppm/°C. In contrast, the microwave dielectric properties of the ceramics prepared by conventional sintering at 1450°C were ɛ _r = 117.4, Qf = 13375 GHz, and τ _f = 217.2 ppm/°C.     

Isothermal reduction kinetics of Panzhihua ilmenite concentrate under 30vol% CO-70vol% N2 atmosphere

The reduction of ilmenite concentrate in 30vol% CO-70vol% N₂ atmosphere was characterized by thermogravimetric and differential thermogravimetric (TG-DTG) analysis methods at temperatures from 1073 to 1223 K. The isothermal reduction results show that the reduction process comprised two stages; the corresponding apparent activation energy was obtained by the iso-conversional and model-fitting methods. For the first stage, the effect of temperature on the conversion degree was not obvious, the phase boundary chemical reaction was the controlling step, with an apparent activation energy of 15.55-40.71 kJ·mol-1. For the second stage, when the temperatures was greater than 1123 K, the reaction rate and the conversion degree increased sharply with increasing temperature, and random nucleation and subsequent growth were the controlling steps, with an apparent activation energy ranging from 182.33 to 195.95 kJ·mol-1. For the whole reduction process, the average activation energy and pre-exponential factor were 98.94-118.33 kJ·mol-1 and 1.820-1.816 min-1, respectively.     

钢渣滤料的制备及其吸附除磷性能

将转炉渣破碎、筛分后与粘结剂和造孔剂混合,制备钢渣滤料,并考察其除磷性能。结果表明,制备钢渣滤料的最佳原料配比为钢渣：粘土：淀粉=5：2：1,最佳烧结条件为1100℃,30min;对含磷2～25mg／L的水样,达到吸附平衡的时间随着浓度的升高而延长,反应2h可保证达到吸附平衡;对pH为3—7的废水均具有理想的吸附效果,对碱性废水的吸附效果下降;不同温度条件下钢渣滤料对磷的吸附过程属于单分子层吸附,以化学吸附为主,符合Langmuir模型（线性相关系数R2〉0．98）;且最大吸附量随着温度的上升而增加,升温有利于吸附进行;通过破碎和重新造粒,可有效提高钢渣的除磷效果。     

Experimental and theoretical investigation of zinc diffusion in N-GaSb

Zinc diffusion process in N-GaSb was studied with excessive, appropriate and insufficient quantity of diffusion source (zinc pellets). Kink-and-tail type zinc concentration profiles obtained with appropriate zinc pellets quantity were successfully simulated using the assumption that the vacancy mechanism mediated by V⁰_Ga and kick-out mechanism mediated by I⁺_Ga take effect at the same time. It is found out that for diffusion temperature from 460°C to 500°C, the zinc surface concentration of the diffused samples has nearly no change and the logarithmic value of the zinc surface diffusion coefficient is linear with the reciprocal value of diffusion temperature; when the diffusion temperature is constant, both the zinc surface concentration and diffusion coefficient do not change with diffusion time.     

氢系气体喷吹对烧结污染物释放的影响规律

采用焦炉煤气和水蒸气作为氢系喷吹介质,研究了喷吹介质、喷吹方式、气体喷吹量等因素对烧结过程典型污染物释放规律的影响.结果表明,氢系气体喷吹使烧结料层温度分布明显改善,1200~1300℃的高温区间明显拓宽;喷吹0.6%(体积分数)的焦炉煤气后,烟气中的NO_○x峰值质量浓度最高降低了约100mg/m³,平均质量浓度降低21.1%,这主要是由于燃气喷吹拓宽了有利于复合铁酸钙生成的温度区间,而蒸汽喷吹对CO的减排有明显效果.蒸汽喷吹后水蒸气与烧结原料中的碳发生水煤气反应,烧结烟气中的CO从11690mg/m³最低降至9918mg/m³,降幅达29.4%;烧结料表面同时喷吹焦炉煤气和水蒸气可以实现NO_○x和CO的综合减排.     

Study on reduction of MoS<Subscript>2</Subscript> powders with activated carbon to produce Mo<Subscript>2</Subscript>C under vacuum conditions

A method of preparing Mo₂C via vacuum carbothermic reduction of MoS₂ in the temperature range of 1350-1550℃ was proposed. The effects of MoS₂-to-C molar ratio (α, α=1:1, 1:1.5, and 1:2.5) and reaction temperature (1350 to 1550℃) on the reaction were studied in detail. The phase transition, morphological evolution, and residual sulfur content of the products were analyzed by X-ray diffraction, field-emission scanning electron microscopy, and carbon-sulfur analysis, respectively. The results showed that the complete decomposition of MoS₂ under vacuum is difficult, whereas activated carbon can react with MoS₂ under vacuum to generate Mo₂C. Meanwhile, higher temperatures and the addition of more carbon accelerated the rate of carbothermic reduction reaction and further decreased the residual sulfur content. From the experimental results, the optimum molar ratio α was concluded to be 1:1.5.     

NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> reduction by coupling combustion with recycling flue gas in iron ore sintering process

A new process called ‘NO _x reduction by coupling combustion with recycling flue gas (RCCRF)’ was proposed to decrease NO _x emission during the iron ore sintering process. The simulation test of NO _x reduction was performed over sintered ore and in the process of coke combustion. Experimentally, NO _x reduction was also carried out by sintering pot test. For sintered ore, the amount of NO _x emission is reduced by 15wt%–25wt% at 400–550°C using 2.0vol% H₂ or 2.0vol% CO, or reduced by 10wt%–30wt% at 560–720°C using 0.15vol% NH₃. NO _x reduction is around 10wt% by coupling combustion of pyrolysis gas and coke, or around 16wt% by recycling flue gas into coke combustion. By RCCRF, the maximum NO _x reduction ratio is about 23wt% in coke combustion experiment and over 40wt% in sintering pot test.     

氧化亚铁颗粒氢还原过程的结构演变

采用热重法实验研究了773~1273 K氧化亚铁的等温氢还原动力学,发现873 K温度以上,反应动力学曲线有明显转折,说明反应机理发生了变化.在973~1073 K的温度范围,出现了反常的温度效应,即反应速率随温度升高而减小.为讨论产物结构对反应动力学的影响,分别对不同温度的反应产物,以及一定温度不同还原状态(不同反应时间)的产物进行形貌观察.结果显示,随着反应温度升高,还原产物表面的孔洞增多,枝状特征显著增加,而973 K和1023 K时表面的烧结现象明显.一定温度下,随着反应进行,表面的孔洞增多,并逐渐出现烧结.973 K和1023 K温度条件下反应产物大体保留原来的大颗粒外形,而1173 K时还原2 min开始,就大量出现枝状产物,并逐渐烧结.结合产物形貌变化和反应动力学曲线,反应前期为界面化学反应控速,随着反应进行,还原的金属铁发生烧结现象,致密的结构阻碍了产物气体向外扩散,反应控速环节转变为产物气体的外扩散,还原速率也随之降低.     

低渗气藏CO2驱与埋存的数值模拟

为揭示低渗气藏中注CO_2提高气藏采收率和CO_2埋存(carbon sequestration with enhanced gas recovery,CSEGR)技术的效果,以苏里格气田召10区块为例,开展了注CO_2驱气的长岩心实验,并使用数值模拟的研究手段,分析了该区块采用CSEGR技术的可行性,并重点研究了扩散、吸附、天然裂缝、井型对于CO_2突破时间、气藏采收率及CO_2埋存的影响。模拟结果表明:采用面积为3. 2 km2的平行四边形"二注七采"井网,在气藏衰竭开采至12 MPa后注CO_2,在CO_2突破时能够提高采收率14. 26%,共能实现3. 8×106t的CO_2埋存;在废弃压力3 MPa时注入CO_2采收率仅能增加2. 2%,但CO_2埋存量可提高至1. 44倍;在低渗气藏中扩散和吸附对于CO_2驱的影响不大;随着扩散系数增大,CO_2突破越快,提高采收率效果越差;吸附滞后现象会略微降低提高采收率的效果;天然裂缝的存在会使气窜现象严重,突破时间大大提前,且裂缝渗透率越高,提高采收率效果越差,但依然可以实现CO_2安全稳定埋存;与直井相比,采用水平井注气将使提高采收率效果降低6%～8%,但对埋存有利。     

转炉污泥对氧化球团还原性的影响

运用XRD,SEM和EDX从矿物组成和矿相结构研究配加转炉污泥和未配加转炉污泥球团的还原特性.研究结果表明:在相同热制度下,配加7%转炉污泥的氧化球团还原度均高于无污泥球团的还原度,其原因是污泥球团赤铁矿含量多,污泥球团的主要黏结相为钙铁橄榄石,基准球团主要为Fe2SiO4与其共熔混合物形成的玻璃质黏结相;基准球团表层致密,且基准球团内部孔隙壁被极难还原的Fe2SiO4与其共熔混合物形成的玻璃质黏结相包裹,不利于还原反应的进行,而污泥球团表层相对疏松且未形成包裹.     

Oxide coating mechanism during fluidized bed reduction: solid-state reaction characteristics between iron ore particles and MgO

Experiments on the solid-state reaction between iron ore particles and MgO were performed to investigate the coating mechanism of MgO on the iron ore particles’ surface during fluidized bed reduction. MgO powders and iron ore particles were mixed and compressed into briquettes and, subsequently, roasted at different temperatures and for different time periods. A Mg-containing layer was observed on the outer edge of the iron ore particles when the roasting temperature was greater than 1173 K. The concentration of Fe in the Mg-containing layer was evenly distributed and was approximately 10wt%, regardless of the temperature change. Boundary layers of Mg and Fe were observed outside of the iron ore particles. The change in concentration of Fe in the boundary layers was simulated using a gas–solid diffusion model, and the diffusion coefficients of Fe and Mg in these layers at different temperatures were calculated. The diffusion activation energies of Fe and Mg in the boundary layers in these experiments were evaluated to be approximately 176 and 172 kJ/mol, respectively.     

Simultaneously catalytic removal of NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> and particulate matter on diesel particulate filter

Diesel engines combine a high fuel economy with high durability and low maintenance costs and are, there-fore, used on a large scale for transportation purposes.However, the environmental pollution by diesel-engine exhausts has become more and more serious in the lastdecade, and currently the regulation of diesel emissions becomes tightened especially with respect to nitrogen ox-ides (NOx) and particulate matters (PM). Since the reduc-tion of both NOx and PM to the admitted level cannot be …     

Synthesis of crystalline perovskite-structured SrTiO<Subscript>3</Subscript> nanoparticles using an alkali hydrothermal process

We report an experimental route for synthesizing perovskite-structured strontium titanate (SrTiO₃) nanocubes using an alkali hydrothermal process at low temperatures without further heating. Furthermore, we studied the influence of heating time (at 180℃) on the crystallinity, morphology, and perovskite phase formation of SrTiO₃. The SrTiO₃ powder, which is formed via nanocube agglomeration, transforms into cubic particles with a particle size of 120–150 nm after 6 h of hydrothermal sintering. The crystallinity and percentage of the perovskite phase in the product increased with heating time. The cubic particles contained 31.24at% anatase TiO₂ that originated from the precursor. By varying the weight ratio of anatase TiO₂ used to react with the strontium salt precursor, we reduced the anatase-TiO₂ content to 18.8at%. However, the average particle size increased when the anatase-TiO₂ content decreased.     

铜基载氧体制备参数对释氧和吸氧性能的影响

在STA409PC热重分析仪上,以机械混合法和溶胶凝胶法制备的铜基载氧体为研究对象,研究了惰性载体种类、惰性载体添加比例、不同煅烧温度及煅烧时间等制备参数对铜基载氧体释氧和吸氧性能的影响.实验结果表明:三种类型载氧体释氧性能强弱顺序为Cu/Zr>Cu/Ti>Cu/Si,吸氧性能相差不大;随惰性载体添加比例的增加,载氧体的释氧和吸氧性能增强;随煅烧温度的升高,载氧体的释氧性能降低,而吸氧性能变化不大;煅烧时间的改变对载氧体的释氧-吸氧性能没有明显的影响;不同制备方法制备的载氧体,Cu/Zr和Cu/Si溶胶凝胶法好于机械混合法,Cu/Ti机械混合法好于溶胶凝胶法.     

Reaction of CH radical with O<Subscript>2</Subscript> by time-resolved FTIR spectroscopy

The Methylidyne radical, CH, plays a crucial role in several complex environments such as planetary atmos- pheres and interstellar clouds, and is one of the most im- portant and active intermediate in hydrocarbon flames[1]. The CH involving reactions, including chemiionization, oxidation of hydrocarbons, the soot formation[2—5], and especially the formation of prompt NO[6], are of funda- mental interest in combustion chemistry, owing to the high reactivity and the large enthalpy of formatio…     

含碳球团的还原性和还原冷却后的强度

在 １２７３～１５７３ Ｋ条件下研究了不同煤种、木炭和石墨与不同种类矿石制成含碳球团 的还原速度;进而讨论了温度、配碳比（Ｃ／Ｏ）、挥发分含量等因素对含碳球团还原所需时间和 金属化率的影响．通过测定含碳球团还原冷却后的强度,对影响强度因素进行了分析．还原冷 却后的强度在温度 １２７３ Ｋ时较低,配入含挥发分较高的气煤,可以使还原冷却后的强度提高, 加快反应速度．