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.     

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1123~1323 K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95.448 kJ·mol-1降低到68.131 kJ·mol-1.     

还原气氛对流态化还原铁矿粉黏结失流的影响

采用热态可视流化床装置研究了973～1173 K不同气氛条件对流态化还原铁矿粉黏结失流的影响.研究发现,一定表观气速条件下温度和还原气氛组成对失流时铁矿粉的金属化率影响不大,而失流时颗粒微观形态受还原气种类和温度的影响较显著,但还原气体积分数对形态的影响较小.此外,流化时间随着还原气体积分数的增大而逐渐缩矩,并通过线性拟合得到了不同温度时二者间的数学关系式.     

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。     

高磷矿氢气还原过程的原位研究

通过原位观察的方法,研究了H2气氛、不同温度下高磷矿还原过程的矿相结构演变规律和温度对金属铁析出形态的影响。高磷矿的鲕状结构在还原过程中未被破坏掉;随着温度的提高,矿相结构的演变加快,温度较高时Fe发生明显偏聚,金属铁从赤铁矿相中加快析出。还原温度对高磷矿中金属铁的析出形态影响显著：在700℃时金属铁析出在矿石颗粒表面形成致密铁层;800℃时析出的金属铁形貌复杂化,铁层致密度下降,出现孔洞,同时有少量的短小铁晶须;900℃时铁晶须数量明显增多,同时伴随着大量多孔海绵铁的析出。因此,可以通过调节还原温度和时间,使得气基还原过程避免黏结失流,同时高效还原高磷矿。     

H_2-CO-CO_2气氛中添加V_2O_3二步法制备碳化铁的动力学分析

在853～973 K以及H2-CO-CO2气氛中,研究了添加质量分数为1%的V2O3对二步法制备碳化铁的影响.结果表明,添加V2O3对还原转化速率影响不大,对碳化转化速率有明显的促进作用,并且随着温度的升高,添加V2O3对碳化反应终点转化率的影响越来越显著.应用有固体产物层的未反应核模型分析反应的动力学过程,结果表明,还原和碳化反应过程都由界面化学反应控制,添加V2O3对界面化学反应有促进作用.     

氢气还原褐铁矿实验研究与动力学分析

本文旨在研究不同温度下氢气对褐铁矿还原度和还原速率的影响,并以此为基础分析动力学相关问题.通过热重分析深入了解褐铁矿失水状况.使用粒度为8~12 mm褐铁矿焙烧后,分别在750~950℃五个不同温度下使用4 L·min-1 H2进行还原,并分析还原率和还原速率随时间的变化关系.研究发现：随着反应进行,试样还原率逐渐增大,五条还原率曲线在t>28 min后与还原温度排序一致.通过动力学研究计算得反应表观活化能E=15.323 kJ·mol-1,从而确定扩散为还原反应的限制环节.     

矿粉粒度及反应温度对高磷鲕状赤铁矿制备碳化铁的影响

为探索利用高磷鲕状赤铁矿作为炼钢原料的新途径,在CH4-H2气氛下对高磷鲕状赤铁矿制备碳化铁进行了实验研究,探讨了矿粉粒度对还原和碳化的影响。采用热重法、SEM-EDS和XRD分别对实验中试样还原失重过程、高磷鲕状赤铁矿矿相和碳化产物进行了分析。实验得到120~160目粒度矿粉的反应活化能最低,还原反应活化能为44.95kJ/mol,碳化阶段表观活化能为9.71kJ/mol。从反应速率的角度,利用高磷鲕状赤铁矿制备碳化铁的最佳温度为1 023K,矿粉的最佳粒度为120~160目,总体来讲,温度比矿粉粒度对高磷鲕状赤铁矿制备碳化铁反应速率的影响大。     

基于氧气高炉的烧结矿还原动力学分析

采用热天平减重法在氧气高炉气氛下进行烧结矿的还原实验,考察还原度RI和还原速率RI′的变化情况,并进行烧结矿还原动力学分析。结果表明：在氧气高炉气氛900 ℃下还原时,烧结矿的还原度RI高达98.2%;还原终了时间随还原温度的提高而缩短,由900 ℃时的117 min缩短到1 100 ℃时的63 min;氧气高炉气氛下,烧结矿还原的开始阶段由界面化学反应控速,还原约20 min后转变为由界面化学反应和内扩散混合控速;氧气高炉气氛900～1100 ℃时,烧结矿还原反应开始阶段的表观活化能为38.30 kJ/mol。     

信息动态

采用液相还原法合成了一系列非晶态合金Ni-Fe-B,考察了铁物质的量比、反应温度和表面活性剂对非晶态合金Ni-Fe-B的物相、形貌以及催化活性的影响.借助X射线粉末衍射、透射电镜对产物进行了表征分析.以NaBH4的催化水解制氢作为探针反应,对所得非晶态合金Ni-Fe-B的催化活性进行了评价.研究结果表明:所得产物Ni-Fe-B具有相对稳定的非晶态物相结构,铁物质的量比的升高,促使产物向晶态化转变.当铁物质的量比为0.5,反应温度为333 K时,所得Ni-Fe-B的催化活性最高,产氢速率可达1.70 mL/min.非离子型表面活性剂辅助所得非晶态产物的粒径小、分散度最高,催化活性进一步增强,产氢速率可提高到1.98mL/min.     

Phase transformation and reduction kinetics during the hydrogen reduction of ilmenite concentrate

The reduction of ilmenite concentrate by hydrogen gas was investigated in the temperature range of 500 to 1200°C. The microstructure and phase transition of the reduction products were studied by X-ray diffraction (XRD), scanning electron microscopy (SEM), and optical microscopy (OM). It was found that the weight loss and iron metallization rate increased with the increase of reduction temperature and reaction time. The iron metallization rate could reach 87.5% when the sample was reduced at 1150°C for 80 min. The final phase constituents mainly consist of Fe, M₃O₅ solid solution phase (M=Mg, Ti, and Fe), and few titanium oxide. Microstructure analysis shows that the surfaces of the reduction products have many holes and cracks and the reactions take place from the exterior of the grain to its interior. The kinetics of reduction indicates that the rate-controlling step is diffusion process control with the activation energy of 89 kJ·mol⁻¹.     

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 54.889 kJ/mol for hydrogen absorption. X-ray diffraction (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.     

射频等离子体处理对氧化石墨烯的影响

分别使用氢气和氩气射频等离子体放电处理氧化石墨烯溶液,快速的对氧化石墨烯进行还原,同时得到了三维多孔的表面形貌。结果显示,还原性气体(氢气)对氧化石墨烯的还原程度高于惰性气体(氩气)对其的还原;通过改变射频等离子体的放电功率,表明放电功率越大,氧化石墨烯的还原程度越高。用射频等离子体还原氧化石墨烯,方法更有效且环境友好,处理后得到的三维多孔形貌的还原氧化石墨烯有望进一步应用于超级电容器、锂电池、传感器等领域。     

Effect of reduction roasting by using bio-char derived from empty fruit bunch on the magnetic properties of Malaysian iron ore

Beneficiation of Malaysian iron ore is becoming necessary as iron resources are depleting. However, the upgrading process is challenging because of the weak magnetic properties of Malaysian iron ore. In this study, bio-char derived from oil palm empty fruit bunch （EFB） was utilized as an energy source for reduction roasting. Mixtures of Malaysian iron ore and the bio-char were pressed into briquettes and subjected to reduction roasting processes at 873-1173 K. The extent of reduction was estimated on the basis of mass loss, and the mag-netization of samples was measured using a vibrating sample magnetometer （VSM）. When reduced at 873 K, the original goethite-rich ore was converted into hematite. An increase in temperature to 1073 K caused a significant conversion of hematite into magnetite and enhanced the magnetic susceptibility and saturation magnetization of samples. The magnetic properties diminished at 1173 K as the iron ore was par-tially reduced to wustite. This reduction roasting by using the bio-char can assist in upgrading the iron ore by improving its magnetic proper-ties     

Thermal performance and reduction kinetic analysis of cold-bonded pellets with CO and H<Subscript>2</Subscript> mixtures

Cold-bonded pellets, to which a new type of inorganic binder was applied, were reduced by H₂–CO mixtures with different H₂/CO molar ratios (1:0, 5:2, 1:1, 2:5, and 0:1) under various temperatures (1023, 1123, 1223, 1323, and 1423 K) in a thermogravimetric analysis apparatus. The effects of gas composition, temperature, and binder ratio on the reduction process were studied, and the microstructure of reduced pellets was observed by scanning electron microscopy–energy-dispersive spectrometry (SEM-EDS). The SEM-EDS images show that binder particles exist in pellets in two forms, and the form that binder particles completely surround ore particles has a more significant hinder effect on the reduction. The reduction equilibrium constant, effective diffusion coefficient, and the reaction rate constant were calculated on the basis of the unreacted core model, and the promotion effect of temperature on reduction was further analyzed. The results show that no sintering phenomenon occurred at low temperatures and that the increasing reaction rate constant and high gas diffusion coefficient could maintain the promotion effect of temperature; however, when the sintering phenomenon occurs at high temperatures, gas diffusion is hindered and the promotion effect is diminished. The contribution of the overall equilibrium constant to the promotion effect depends on the gas composition.     

后处理温度对Ni/ZrO2催化剂上甲烷水蒸气重整反应转化率及选择性的影响

制备了Ni/ZrO2催化剂,并研究了该催化剂的还原温度、载体焙烧温度对催化剂性能的影响.研究表明,当焙烧温度在823 K~1 023 K时,随着温度的升高,CH4的转化率也随之发生变化,焙烧温度为923 K时,CH4的转化率达到74.87%;当还原温度在723 K~1 023 K范围内时,随着还原温度的升高,CH4的转化率降低.     

Kinetic studies on the reduction of iron ore nuggets by devolatilization of lean-grade coal

An isothermal kinetic study of a novel technique for reducing agglomerated iron ore by volatiles released by pyrolysis of lean-grade non-coking coal was carried out at temperature from 1050 to 1200°C for 10–120 min. The reduced samples were characterized by scanning electron microscopy, energy-dispersive X-ray spectroscopy, and chemical analysis. A good degree of metallization and reduction was achieved. Gas diffusion through the solid was identified as the reaction-rate-controlling resistance; however, during the initial period, particularly at lower temperatures, resistance to interfacial chemical reaction was also significant, though not dominant. The apparent rate constant was observed to increase marginally with decreasing size of the particles constituting the nuggets. The apparent activation energy of reduction was estimated to be in the range from 49.640 to 51.220 kJ/mol and was not observed to be affected by the particle size. The sulfur and carbon contents in the reduced samples were also determined.     

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．     

印度尼西亚海砂氧化性球团氢气还原机理

对印度尼西亚海砂矿氧化性球团氢气还原的规律做了较详细的研究。实验采用失重的方法,通过对反应过程的物相变化、热力学以及动力学方面的分析,探究了海砂球团矿氢气还原的机理。结果表明：温度在800℃和850℃,还原反应的最终产物主要是FeTiO3,整个反应限制环节是由两个不同阶段的过程组成,反应开始阶段由界面化学反应控制,之后由界面化学反应与内扩散共同控制；在900、950和1000℃三个温度下,反应产物中有钛氧化物出现,整个还原反应由三个不同的限制性环节组成,开始由界面化学反应控制,反应中间阶段是由界面化学反应和内扩散共同控制,反应后期则是由内扩散控制为主。