电热法生产铝硅合金的理论研究

本文从理论上系统研究了Al2O3-C系、SiO2-C系、Al2O3-SiO2-C系热力学。结果表明,在Al2O3-SiO2-C系中,硅在很大程度上改善了铝还原的热力学条件,中间产物Al4C3、SiC等碳化物分别与SiO2、Al2O3反应进而生成铝硅合金,使电热法铝硅合金对生产成为现实。动力学研究结果表明,在电热法铝硅合金生产中,Fe的存在使得铝硅合金生成反应的起始温度大大降低,Fe还有助于破坏碳热还原过程中容易生成的碳化物。     

真空热还原生产金属钙的现状与问题

热力学计算结果表明,硅热还原炼钙的温度比铝热还原炼钙的温度高150℃以上,在目前真空热还原技术条件下,硅热真空还原炼钙很难进行,而铝热还原生产金属钙时,最容易发生的反应方程式为6CaO(s)+2Al(l)=3Ca(v)+3CaO·Al2O3(s)和33CaO(s)+14Al(l)=21Ca(v)+12CaO·7Al2O3(s)。目前,工业铝热还原生产金属钙过程中,存在的主要问题是还原温度高,还原罐使用时间短,铝粉利用率低,还原渣的利用方式不合理,这导致生产金属钙的成本较高。     

真空热还原制取金属锂的热力学分析与试验研究

对真空条件下硅热还原氧化锂反应进行热力学分析,计算出不同条件下硅热还原氧化锂所需要的最低反应温度以及相应的露点温度.结果表明,系统压强为5 Pa时,硅热还原氧化锂得到液态冷凝锂的反应温度不应低于900 ℃,对应的露点温度为606 ℃以上.设计真空硅热还原炉进行了验证试验,得到冷凝金属锂.     

熔融还原炼镁热力学分析和模拟

为了提高现有硅热还原炼镁工艺中原料之间的反应速度,提出熔融还原炼镁新技术.在煅烧白云石中添加适量的Al2O3和SiO2,使整个体系在反应时呈完全熔融状态,从而加快反应速度.通过软件模拟、热力学分析和实验验证,在适当配比下于1 600℃可以获得完全熔化的CaO-MgO-Al2O3-SiO2四元系.通过对熔融还原反应的热力学计算得出,平衡状态下还原温度为1 600℃时,对应镁蒸汽的露点为870℃.结果表明熔融还原炼镁新技术是可行的.     

碳热还原铝土矿尾矿制取一次铝硅合金的热力学分析和实验验证

对碳热还原铝土矿尾矿可能发生的反应进行了热力学分析。利用TG、XRD、XRF、SEM-EDS等技术研究了产物的生成过程、Fe2O3对反应的影响以及产物的物相组成。结果表明,Fe2O3可以降低反应温度和S iC的生成率,提高A l2O3的还原率。碳热还原铝土矿尾矿合适的反应温度为1 900℃。整个还原过程可分为4个阶段,其中以碳化物的生成与分解阶段为主。产物中除含有铝硅铁相生成外,还有残留的A l2O3、单质铝和碳化物相存在。     

碳热还原铝土矿尾矿制取一次铝眭合撇力学分析和实验验证

对碳热还原铝土矿尾矿可能发生的反应进行了热力学分析。利用TG、XRD、XRF、SEM—EDS等技术研究了产物的生成过程、Fe2O3对反应的影响以及产物的物相组成。结果表明,Fe2O3可以降低反应温度和SiC的生成率,提高Al2O3的还原率。碳热还原铝土矿尾矿合适的反应温度为1900℃。整个还原过程可分为4个阶段,其中以碳化物的生成与分解阶段为主。产物中除含有铝硅铁相生成外,还有残留的Al2O3、单质铝和碳化物相存在。     

热还原法炼镁理论分析

通过理论计算,导出了不同还原剂硅铁、铝、硅铝热法还原金属镁热力学参数。结果表明,在相同压力下,铝比硅还原镁温度降低906.38 K;氧化钙的添加对硅还原金属镁温度影响大;提高反应区温度或降低反应区压力可加快还原反应速度。     

钛渣电铝热还原一步合成Ti-Al-xFe-ySi多元合金热力学分析

从理论上分析了钛渣铝热还原制备Ti-Al-xFe-ySi多元合金的可行性,计算并分析了钛渣中金属氧化物与铝还原过程中可能的化学反应,讨论了钛渣中氧化物还原反应顺序的优先程度。结果表明,钛渣铝热还原制备钛铝基多元合金是可行的。从热力学分析了制备的合金中可能出现的二元合金相,主要为Ti5Si3、TiAl3和TiFe,其中Ti5Si3最易生成,研究结果较好地满足了热力学分析结果,制备的合金主要物相为Al2.68Mn0.32Ti和Al3Ti0.75Fe0.25,还有少量的TiFe和Ti3SiC2相。     

基于铝热还原制备FeV50渣中钒的赋存状态

通过渣金V-O平衡及VO-Al平衡理论研究,分析了铝热还原FeV50合金制备过程不同冶炼阶段对渣中钒赋存状态的影响,计算得到钒在渣中的热力学还原极限。通过不同物相分析手段,得到铝热还原FeV50合金制备过程实际渣中钒的稳定结构。研究结果表明:渣金共存时渣中钒的稳态为VO;出渣后VO与V_2O_3的稳定性与冶炼氧分压有关,其平衡氧分压为0.41 Pa,常压条件下,VO会进一步氧化。渣中钒含量随合金铝含量的增加而降低,当合金铝质量分数分别为8.0%和20.0%时,对应渣中理论钒质量分数分别为0.16%和0.10%。实际冶炼过程中,冷态刚玉渣中的钒除了已还原FeV_x初级合金之外,主要以类质同象的形式与镁、铝、铁等元素固溶形成Mg(Al,V)_2O_4和(Mn,Fe)V_2O_4复合尖晶石结构。     

钾冰晶石—氧化钪体系中铝热还原反应过程的研究

在钾冰晶石—氧化钪熔盐中,采用铝热还原和直接电解制备铝钪合金。在引入Al3Sc相生成自由能并考虑活度后,热力学计算表明,铝热还原氧化钪反应在本试验条件下可以发生。750℃在K3AlF6-2%Sc2O3(CR=1.22)熔盐中,电解制备的合金中钪含量可达0.97%,而铝热还原反应所获合金中钪含量小于0.18%,且随反应时间的延长和熔盐中氧化钪浓度的增加,合金钪含量的增幅趋缓。电解合金中钪分布均匀,而铝热还原合金中钪主要存在于边缘区域。     

冶炼钒钛磁铁矿时铁液中钒的扩散及V2O5还原动力学

铁水中钒的扩散及其动力学特征是影响钒钛磁铁矿冶炼时钒还原及回收的关键因素。本文研究了：碳饱和铁水中钒的扩散及动力学特征；温度、铁水中钛的浓度对钒扩散的影响；铁水中钒与钛对相互间扩散的影响；分析了钒钛磁铁矿冶炼时钒还原的动力学条件及限制性环节。研究结果表明：随温度提高，钒的扩散系数提高，铁水中钛浓度提高，有利于提高钒的扩散能力，而铁水中钒会降低钛的扩散能力。钒钛磁铁矿冶炼时，钒的还原属于扩散为主要限制环节的动力学特征。     

高炉钛矿渣直流电硅热法制取硅钛铁合金时TiO2的还原

研究了直流电炉作用下渣中ＴｉＯ２还原的物理化学理现象。认为直流电硅热法冶炼硅钛铁合金时渣中ＴｉＯ２的还原是通过硅热还原，电解还原，碳热还原，重力沉降，金属液滴电泳沉降及熔池的对流动运达到的。在实验条件下进行了高炉钛矿渣电解，硅热法，直流电硅热法治中炼硅钛铁合金的试验。得到了三种条件下渣中ＴｉＯ２的还原规律。实验结果表明，直流电硅热法冶炼硅钛铁合金时渣中ＴｉＯ２的还原速度，还原反应速度常数，合金收得     

新型真空热还原法制镁工艺分析

通过对真空条件下A l-S i-Fe合金还原白云石煅白的热力学分析及实验研究,得到真空条件下还原反应的吉布斯自由能及反应临界温度,确定工艺可行性;所进行还原实验的结果表明:在还原温度1 443 K、还原时间2 h、真空度4 Pa、制团压力50 MPa条件下,可获得86.4%的镁收率,相比同等条件下硅热法镁还原率仅为73.9%。     

Effect of Ce doping into V_2O_5-WO_3/TiO_2 catalysts on the selective catalytic reduction of NO_x by NH_3

In this work, the effectiveness of V_2O_5-WO_3/TiO_2 catalysts modified with different CeO_2 contents by impregnation and co-precipitation methods on the selective catalytic reduction of NOxby NH3 have been studied comparatively by various experimental techniques. The results showed that the NO conversion of V_2O_5-WO_3/CeO_2-TiO_2 catalysts modified by co-precipitation method obviously increased with the Ce doping contents in the studied range below 20%(All Ce contents are in mass fractions), but the NO conversion of V_2O_5-WO_3/CeO_2/TiO_2 catalysts modified by impregnation methods was lower than V_2O_5-WO_3/CeO_2-TiO_2 catalysts especially beyond 2.5% Ce doping contents. The V_2O_5-WO_3/CeO_2-TiO_2 catalysts showed better SCR activity, wider reaction window, and higher sulfur and water resistance. The characterization results elucidated that the modified catalysts by co-precipitation method exhibited higher specific surface area, much better dispersity of Ce component, more Ce~(3+)species and more Br?nsted acid sites than that by impregnation. The vacancies caused by more Ce~(3+)species were favorable for more NO oxidation to NO_2, and the interaction between Ce species and WOxspecies generated more Br?nsted acid sites. It could be supposed that dispersed Ce Oxspecies and WOxspecies offered more second active centers respectively to adsorb oxygen and activate ammonia as co-catalysis to the primary active center of V ions, thus facilitated the better SCR activity of modified V_2O_5-WO_3/CeO_2-TiO_2 catalysts by coprecipitation methods. The co-precipitation methods with Ce component were more suitable for production of modified commercial V_2O_5-WO_3/TiO_2 catalysts.     

Synthesis of an Aluminum–Erbium Master Alloy from Chloride–Fluoride Melts

Available foreign power-intensive technologies and the absence of domestic production technologies for aluminum–erbium master alloys intended for improving the physicomechanical properties of aluminum alloys make the development of aluminothermic reduction technology of chloride–fluoride melts actual for manufacturing erbium compounds. Thermodynamic analysis of reduction processes is performed for various erbium compounds. Taking into account the physical and chemical properties of erbium compounds, a starting compound, namely, erbium fluoride is found to be preferable. The aluminothermic reduction of the compound from its mixture with sodium fluoride and potassium chloride to form the Al₃Er intermetallic compound is characterized by a high thermodynamic probability. Since data on thermodynamic parameters for erbium complex compound are scanty, they are determined by an indirect method. Experimental data on the aluminothermic preparation of an Al–Er master alloy at temperatures of 750–900°C using melts differing in the ErF₃/NaF ratio and the KCl content are reported; the structure and the phase composition of the prepared master alloy are studied. The phase composition of the flux used for the preparation of the Al–Er master alloy is determined.     

Thermodynamic investigations and substantiation of the aluminothermic fabrication method of calcium

To search for ways to solve the problem of decreasing the production prime cost of metallic calcium, it is proposed to consider its aluminothermic production by the example of the CaO–Al system. The thermodynamic analysis implemented for this system showed that the aluminothermic reduction of calcium from its oxide is technically performable under a pressure of 5–10 Pa and temperature of 1200–1500°C. It is revealed that the implementation of reduction under the residual pressure lower than 1 atm (101.3 Pa) considerably lowers the thermodynamic temperatures of the onset of the reaction. It is established that only three reactions, in the course of which calcium aluminates 3CaO ? Al₂O₃, 5CaO ? 3Al₂O₃ (12CaO ? 7Al₂O₃), and CaO ? Al₂O₃ are formed, can be used for the practical purposes. It is proposed, depending on the final state, to separate the process into a “low-temperature” one (up to 1200°C, the calcium yield is no higher than 64.3%) and a “high-temperature” one (up to 1500°C, up to 75% Ca). It is planned tofurther confirm these data experimentally.     

A Study of the Effect of Aluminium on the Mechanochemical Reduction of Hematite by Graphite

The effect of addition of small amounts of aluminium on mechano‐chemical reduction of hematite by graphite was studied. Various amounts of aluminium (0 to 10%) were added to a hematite‐graphite mixture, in which C/O ratio was 1:1. The hematite‐graphite‐aluminium mixtures were then subjected to ball milling followed by heating up reduction. The heating up reduction was carried out in Ar atmosphere, using TG‐DTA device. In TG‐DTA experiments, samples were heated by a constant heating rate of 10 °C/min from room temperature up to 1100 °C and maintained for 30 minutes at this temperature. To clarify the reactions which took place during milling and heating up reduction, the samples were subjected to XRD examinations. It was found that the heat generated during exothermic reaction of aluminothermic reduction of hematite promoted the endothermic reaction of carbothermic reduction. In the course of heating up reduction, the carbothermic reaction occurred just after aluminothermic reaction. Increasing of aluminum content from 0 to 10% in 2 hours ball milled samples decreased the temperature of carbothermic reaction from 1020 °C to about 860 °C. The further ball milling of the samples up to 5 and 10 hours, for the samples containing 10 and 5% aluminium respectively, caused the decrease of the temperature of aluminothermic and carbothermic reactions to around the melting point of aluminium.     

真空硅热还原法制备金属锶

采用真空硅热还原法制备了纯度达98%～99%的金属锶。研究了还原温度、保温时间、制团压力、硅铁过量系数、反应物粒度等对锶还原率的影响。结果表明,在下述最佳工艺条件下,即真空度在0～100Pa,硅铁过量30%,制团压力30MPa,还原温度1 250℃,保温2.5h,锶还原率可达57%,XRD和XRF分析表明,渣相主要物相为2SrO.SiO2和SrO.SiO2的混合物,且2SrO.SiO2占绝大部分。     

钒在高炉炉渣中还原过程的研究

钒钛磁铁矿中的钒主要是以V尖晶石的形态存在。热力学计算表明：钒氧化物的还原在铁氧化物还原完成后才能开始进行,高炉渣内的V只能用C直接还原。对V在高炉炉渣中的还原过程进行了研究,找出了炉渣温度、炉渣CaO／SiO2、MgO、Al2O3和TiO2含量对V还原过程的影响。