H_2-CO混合气体还原氧化亚铁粉体的动力学

通过热重实验获得了873、973和1173 K三个温度条件下不同组成的H_2-CO混合气体还原氧化亚铁的动力学曲线,发现在873和973 K时由于析碳反应的发生,动力学曲线较为混乱,没有规律,而在1 173 K时,还原曲线则随还原气体中H_2含量(体积分数)的增加表现出明显的规律性.通过H_2-CO与H_2-Ar气体还原氧化亚铁动力学的比较,混合气体中CO参与反应的速率与其含量(体积分数)基本符合线性关系.还原产物形貌观察的结果表明,随着反应温度的升高,还原产物孔隙增大,铁相充分发育长大并逐渐有明显的烧结现象.     

氢含量对氧化亚铁粉体还原动力学的影响

采用热重法获得了873~1 173 K氧化亚铁在不同氢含量H2-Ar还原气中的等温还原动力学曲线,发现在973~1 023 K温度范围,随着氢气含量(体积分数)的增加,反应达到的还原程度降低.结合产物的显微结构分析,在该温度范围,随着氢气含量(体积分数)增加,氧化亚铁还原的化学反应速率加快,新生成的铁相黏结加剧,阻碍反应气体的扩散,最终影响整个反应进程.同时发现,反应速率与氢含量不符合线性规律.     

微尺度氧化铁粉的低温还原机理

用热重分析法研究低温条件下(450、500、550和600℃),氢气还原微尺度氧化铁的还原动力学行为。结果表明:随氧化铁粉粒径减小和反应温度升高,初始反应速率加快,后期反应速率减慢。这是因为反应后期生成大量铁须,铁须之间形成搭桥,导致还原后的粉末严重烧结并致密化,阻碍气体的扩散,致使反应速率减慢。且随着粉体粒径减小,粉体表面吸附能增大,粉体致密程度提高,反应后期的粘结现象更加严重,反应速率相应减慢。采用Hancock-Sharp方法分析微尺度氧化铁粉恒温还原的动力学过程,发现前期阶段Fe2O3→Fe3O4,在500℃以下,相界面化学反应的阻力所占的比例较大,表明此阶段的反应控速环节为界面化学反应,温度超过500℃时,则由界面化学反应机理和相转变机理共同控制,点阵结构由Fe2O3的斜方六面体结构转变为Fe3O4的立方结构;后期阶段Fe3O4→Fe,由于粉体发生粘结,还原反应的控速环节转变为扩散控速。     

内配塑料铁鳞还原的动力学

采用等温热重法,对内配3％塑料的类Hoganas铁鳞还原体系进行动力学分析,结果表明：与基准实验相比,内配塑料后铁鳞的还原反应表观活化能降低,还原速率提高,在转化率X〈0．9时,控速环节主要为界面化学反应;当X〉0．9时,反应为界面化学反应和气体在小粒子产物层扩散混合控速．     

碳热FeO反应过程的控速环节分析

为了探讨煤基还原FeO在试验过程可能出现的控速环节,分多种条件进行了理论计算及分析。在不考虑传热条件下(加热方向物料很薄时),同一种还原剂在不同的温度段表现出不同的控速环节。气煤作为还原剂时,1 273 K以下碳的气化反应为控速环节,1 273~1 523 K为混合控速;温度超过1 523 K,则CO还原FeO转为反应的控速环节。不同煤种在同一温度下,可能表现出不同的控速环节。如1 373 K,气煤作为还原剂时,碳气化与FeO间接还原混合控速,而兰炭作为还原剂时,碳气化为控速环节。煤粉粒度与FeO粒度之比不同会使控速环节发生变化。如果物料厚度小于1 mm,则可忽略传热影响;如果物料厚度不小于4 mm,则传热将成为限制性环节;如果试验时的物料厚度介于两者之间,就有可能出现传热与反应混合控速情况。     

铁矿-生物质复合球团还原行为及还原动力学

通过分析生物质合成气气氛下,不同组分复合球团（添加和未添加生物质）的还原速率、还原度、表面微观结构和失重变化规律．对球团中添加生物质的作用机理以及含生物质球团还原过程的限制性环节展开研究．添加生物质的复合球团表面结构比无生物质球团疏松,孔隙率高,有利于后续还原的热质传递,增加产物还原度,降低反应活化能;复合球团的还原以收缩核方式进行,在1123~1323K温度范围内,界面化学反应是两种球团还原反应的主要控速环节;添加生物质后,有利于界面化学反应的进行．使得球团的还原表观活化能由95．448kJ·mol-1降低到68．131kJ·mol-1．      

1173～1473K下鲕状赤铁矿石墨还原动力学研究

采用热重法研究了1 173～1 373 K下鲕状赤铁矿的石墨还原动力学。研究了温度对还原度和还原速率的影响,采用不同固相反应机理函数对反应过程进行拟合,分析了不同还原阶段反应限制性环节,并对还原样品进行了XRD、SEM和EDX表征分析。结果表明,随着温度增加,还原度和还原反应速率增加,随着还原度增加,还原反应速率先增加后降低;在1 173～1 273 K和1 273～1 373 K两个阶段,反应过程分别符合界面化学反应1-(1-α)~(1/3)和杨德模型[1-(1-α)~(1/3)]~2,对应的表观活化能分别为60.657 kJ/mol和301.662 kJ/mol,反应的限制环节分别为界面化学反应和固态扩散;还原样品的物相组成和微观形貌分析结果与前述反应动力学机理分析结果相符合。     

GaN MOCVD生长速率及表面形貌随生长参数的变化

根据现有氮化镓(GaN)金属有机物化学气相淀积(Metalorganic Chemical Vapor Deposotion)生长动力学理论,结合具体的MOCVD反应腔体的构造,用计算流体力学和动力学蒙特卡罗方法对GaN MOcvD生长过程中的生长速率和表面形貌演变进行了计算机模拟.结果表明,在950～1350 K的温度范围内反应气体充分热分解,是适合GaN外延生长的温度区间;温度低于950 K,反应气体未能充分地分解,导致较低的生长速率;而温度高于1350 K则Ga组分的脱附现象开始变得严重,从而抑制GaN的生长速率.另一方面,较高的v/Ⅲ也会抑制GaN的生长速率.生长过程中表面形貌随时间的演变结果显示,GsN薄膜在高温下(1073～1473 K)为2D层状生长,在1373 K的温度下生长的GaN薄膜表面最为平整.     

首钢烧结矿还原动力学

采用热重法在1173~1373 K、全CO气氛条件下,对首钢烧结矿进行还原动力学实验,确定了还原反应的表观活化能,进而推断在还原反应的前期烧结矿还原速率均由界面反应控制,还原反应后期的控制环节为固相扩散.分别由未反应核模型和固相反应动力学模型,分段给出不同温度下控制环节突变的时间点;通过动力学公式计算,得出不同温度下的反应速率常数和固相扩散系数.利用光学显微镜观察了烧结矿在各还原阶段的微观形貌,验证了烧结矿还原动力学的机理,同时也证明了扩散控制阶段使用体积缩小的未反应核模型与实际情况是吻合的.      

温度对氢气还原氧化铁影响及电化学性能研究

采用纯的氧化铁进行直接还原的实验研究,利用H2作为还原气体在高温管式炉中进行焙烧还原.结果表明,随着反应时间的增加,氧化铁块还原率相应的增大.反应温度的不同,氧化铁块还原速率及电导率也相应的不同.600~900℃下经过一定时间的氢还原,还原产物的还原速率随温度的增加而增加,均可达到95%以上.通过交流阻抗法对还原产物的电导率的测试,得到了还原产物的电导率随时间和还原度的变化曲线.随着温度及时间的不同,电导率也相应变化,电导率的不同,可间接反映还原过程中产生了导电性不同的物质.     

Intrinsic kinetics of the hydrogen reduction of Cu2S

Intrinsic kinetics of the hydrogen reduction of cuprous sulfide (Cu₂S) have been measured. Experiments were carried out in the temperature range 823 to 1023 K using a thermogravimetric analysis method. The reaction was studied in detail using both thin pellets and powder samples. The reaction followed first-order kinetics with respect to the solid reactant concentration as well as the hydrogen concentration. An activation energy of 92.0 kJ/mol (22.0 kcal/g-mole) was obtained for the reaction. Copper produced from the reaction formed filaments which sintered above about 1000 K. Is now Senior Metallurgist with Cyprus Metallurgical Process Corporation     

CuO氯化过程动力学研究

铜渣中含有30 %~40 %的Fe, 对铜渣中的Fe进行回收, 有利于缓解中国依赖进口铁矿石的压力.基于热力学分析氯化除铜的可行性, 在823 K、873 K、923 K、973 K温度下, 通过热重分析研究CuO-FeCl₂体系的氯化过程动力学, 并考察反应温度和Ar气流量对反应的影响: CuO-FeCl₂体系的氯化率随温度的升高而增大, 当Ar流量为50 mL/min时, 氯化率达到最大值为62.46 %.通过推导氯化反应动力学公式, 确定CuO-FeCl₂体系的氯化反应为0级反应, 并且在873 K时由氯化过程动力学区过渡到扩散区, 动力学区的反应速率取决于CuCl₂的挥发速率, 扩散区的反应速率取决于FeCl₂向CuO表面扩散的速率.      

微纳米氧化铁粉低温还原特性的研究

研究了低温还原微纳米氧化铁粉的还原特性与机理。用高能球磨法获得的微纳米氧化铁粉在280～400 ℃内用氢气还原,并测定还原后粉末中氧、计算氧化铁粉末的还原率,通过扫描电子显微镜来观察还原铁粉的形貌;找出了氧化铁粒度、还原温度和还原时间等参数对氧化铁还原率、铁粉粒度和粒度分布、铁粉形貌等的影响。从动力学的角度,探讨了粉末细化对低温氢气还原氧化铁活化能的影响。研究结果指出,微纳米氧化铁粉的还原反应遵循吸附自动催化理论,反应动力学遵循界面化学反应理论,研究获得了反应所对应的反应机制函数和相应的动力学方程。     

微纳米氧化铁粉低温还原特性的研究

研究了低温还原微纳米氧化铁粉的还原特性与机理。用高能球磨法获得的微纳米氧化铁粉在280～400 ℃内用氢气还原,并测定还原后粉末中氧、计算氧化铁粉末的还原率,通过扫描电子显微镜来观察还原铁粉的形貌;找出了氧化铁粒度、还原温度和还原时间等参数对氧化铁还原率、铁粉粒度和粒度分布、铁粉形貌等的影响。从动力学的角度,探讨了粉末细化对低温氢气还原氧化铁活化能的影响。研究结果指出,微纳米氧化铁粉的还原反应遵循吸附自动催化理论,反应动力学遵循界面化学反应理论,研究获得了反应所对应的反应机制函数和相应的动力学方程。     

Re-oxidation Kinetics of Flash-Reduced Iron Particles in H2-H2O(g) Atmosphere Relevant to a Novel Flash Ironmaking Process

A novel flash ironmaking process based on hydrogen-containing reduction gases is under development at the University of Utah. The goal of this work was to study the possibility of the re-oxidation of iron particles in a H₂-H₂O gas mixture in the lower part of the flash reactor from the kinetic point of view. The last stage of hydrogen reduction of iron oxide, i.e., the reduction of wustite, is limited by equilibrium. As the reaction mixture cools down, the re-oxidation of iron could take place because of the decreasing equilibrium constant and the high reactivity of the freshly reduced fine iron particles. The effects of temperature and H₂O partial pressure on the re-oxidation rate were examined in the temperature range of 823 K to 973 K (550 °C to 700 °C) and H₂O contents of 40 to 100 pct. The nucleation and growth kinetics model was shown to best describe the re-oxidation kinetics. The partial pressure dependence with respect to water vapor was determined to be of first order, and the activation energy of re-oxidation reaction was 146 kJ/mol. A complete rate equation that adequately represents the experimental data was developed.     

Multistep Reduction Kinetics of Fine Iron Ore with Carbon Monoxide in a Micro Fluidized Bed Reaction Analyzer

The reduction kinetics of Brazilian hematite by CO is investigated in a Micro Fluidized Bed Reaction Analyzer (MFBRA) using an analyzing method based on Johnson-Mehl-Avrami (JMA) model at temperatures of 973 K (700 °C), 1023 K (750 °C), 1073 K (800 °C), and 1123 K (850 °C). The solid products at different reduction stages are evaluated by SEM/EDS and XRD technologies. Results indicate that the reduction process is better to be discussed in terms of a parallel reaction model that consists of the reactions of hematite to wüstite and wüstite to iron, rather than a stepwise route. Meanwhile, the controlling mechanism of the reduction process is found to vary with temperature and the degree of conversion. The overall process is controlled by the gas–solid reaction occurring at the iron/wüstite interface in the initial stages, and then is limited by the nucleation of wüstite, and finally shifts to diffusion control. Moreover, the reactions of hematite to wüstite and wüstite to iron take place simultaneously but with different time dependences, and the apparent activation energies of hematite to wüstite and wüstite to iron are determined as 83.61 and 80.40 KJ/mol, respectively.     

Effect of Metal Additions to the Reduction of Iron Oxide Composite Pellets with Hydrogen at Moderate Temperatures

The hydrogen reduction behavior of iron oxide composite pellets containing Ni, Fe, and Mn from 973 K to 1173 K was compared with iron oxide and Al₂O₃ containing reference composite pellets to determine the effect of metallic species on the kinetics of iron oxide reduction. The Mn and Ni containing pellets showed slightly faster initial reduction rates compared to the Fe and Al₂O₃ containing pellets. The effect of the metal phases was found to be more significant at lower temperatures when chemical reaction at the interface is a slower and more controlling factor. From the SEM of partially reduced pellets, a wide intermediate region between an O rich unreacted core and an Fe rich outer shell was observed. Although an initially short topochemical receding interface controlled region exists, the mixed control between the topochemical receding interface and pore diffusion was prevalent. For Fe₂O₃/Mn composite pellets, the thermodynamic stability of the MnO is higher and Mn can act as a reductant for iron oxide. Thus, the overall metallization of the Fe₂O₃/Mn composite pellets decreased compared to the other Fe₂O₃/metal composite pellets. From the temperature dependence of the iron‐oxide/metal composite pellets, the apparent activation energy was calculated to be approximately between 15 to 20 kJ/mol, which is typical of a mixed control reduction mechanism of gas diffusion and interface reaction.     

Hydrogen reduction of a Cu2O-WO3 mixture

In the present work, the reduction kinetics of Cu₂O-WO₃ mixtures by hydrogen gas was studied by thermogravimetric analyses (TGA). The reduction experiments were carried out both isothermally and nonisothermally on shallow powder beds in the temperature interval 673 to 1073 K. During the experiments, the reductant gas flow rate was kept just above the starvation rate for the reaction to ensure that chemical reaction was the rate-controlling step. The composition and microstructures of the reaction products were analyzed after each experiment by X-ray diffraction (XRD) as well as by microprobe analyses. In the temperature interval 673 to 923 K, copper oxide was found to be preferentially reduced in the early stages of the experiment followed by the reduction of tungsten oxide. The reaction mechanism was found to be affected by a reaction/transformation in the starting copper-tungsten oxide mixtures in the temperature interval 923 to 973 K. At temperatures higher than 973 K, the reduction of the complex oxide formed was found to have a strong impact on the reaction kinetics. The activation energy was evaluated, from the isothermal as well as nonisothermal reduction experiments, for the two stages of reduction identified. The XRD and scanning electron microscopy (SEM) studies indicated the formation of a metastable solution of copper in tungsten at about 923 K. The advantage of the hydrogen reduction route toward the bulk production of alloy powders in the nanosize is demonstrated.     

Interrelation between kinetics of reduction and volume change during formation of directly reduced iron rod

A kinetic study on reduction has been carried out by heating a central column of blue dust (a fine variety of iron ore) surrounded by a concentric layer of non-coking coal fines in the temperature range of 1173- 1323 K. The temperature of the periphery of blue dust column is kept constant at the temperature of experimentation, however, the temperature of the interior of the cylindrical column increases with time of residence and the change in volume of the reaction mass occurs. The loose column of blue dust gets reduced, consolidated and sintered to produce directly reduced iron rod (DRIR). The work also comprises studies concerning the effect of volume change on the reduction kinetics. The reduction phenomena are very much influenced by the change in volume of reaction mass. The kinetics of reduction shows an agreement with Ginstling-Brounshtein model whereas the kinetics of change in volume is interpreted using Johnson-Mehl equation. The rate constants k₁ and k₂ derived from kinetic analysis of reduction and volume change respectively are shown to be linearly interrelated till the change in volume with respect to the original volume becomes more or less constant.     

Hydrogen absorption behavior of TA15 alloy

The hydrogen absorption kinetics of TA15 titanium alloy at 973-1123 K was studied using a tube-type hydrogen treatment furnace.The hydrogen absorption kinetic curves obtained were analyzed according to a series of mechanism equations to reveal the kinetic parameters and mechanism of the hydrogen absorption process. The results show that both the hydrogen absorption rate and the equilibrium hydrogen pressure increase and the time to reach equilibrium is shortened with increasing temperature. It is found that only the second hydrogen absorption period exists in the hydrogen absorption process of TA15 alloy between 973 and 1123 K, and the activation energy is 54.889kJ/mol for hydrogen absorption. X-ray diffiaction (XRD) and scanning electron microscopy (SEM) results demonstrate that δ hydride forms between 973 and 1123 K, and β phase decreases with the increase of temperature. Orthorhombic α" martensite is generated at 1073-1123 K,and their amount increases with increasing temperature.