铁基凹凸棒载氧体制备及煤化学链燃烧性能研究

以Fe(NO3)3·9H2O、Fe2O3和Fe3O4为前驱体,凹凸棒(ATP)为惰性载体制备了系列Fe2O3/ATP载氧体。在流化床反应器内,以水蒸气作为气化-流化介质,900℃为还原温度,研究了载氧体与神木煤的反应活性及循环反应性能,同时考察了载氧体的抗磨损性能。实验结果表明:以Fe(NO3)3·9H2O为前驱体制备的Fe4ATP6(N)载氧体具有很高的反应活性和抗磨损能力。对其进行的10次还原/氧化循环实验表明:尾气中CO2平均含量先下降后升高,但都保持在95%以上,停留时间t95从14.8 min增加到16.1 min。SEM分析表明随着循环反应的进行载氧体表面小颗粒变成大颗粒,发生轻微烧结。     

流化床中超细颗粒的聚团破碎与供料的实验研究

在内径为40 mm的流化床中,以平均粒径为10 μm的超细硅粉为物料,在引入振动力和搅拌力、添加粗颗粒的条件下,考察了振动强度、搅拌转速、粗颗粒粒径和添加比例、氮气流速等因素对超细颗粒聚团破碎和供料过程的影响.实验表明,对于10μm的超细硅粉,流化床供料的最佳操作条件为:搅拌转速90 r/min,振动频率13.9 Hz,粗颗粒粒径300 μm,添加比例20%.此时,可以有效破碎聚团,消除节涌,抑制沟流,降低临界流化速度和夹带速度,显著改善超细颗粒的供料效果.     

基于分子动力学模拟的Fe2O3纳米颗粒烧结机制研究

氧化铁是化工、冶金和能源等领域重要的原料,其在高温下的烧结性对产品性能至关重要。通过分子动力学模拟(MDS)研究了不同温度、粒径与空位缺陷浓度条件下Fe₂O₃纳米颗粒的烧结机制。结果表明,Fe₂O₃纳米颗粒粒径由3 nm增加至5 nm,烧结后收缩率由25.0%降低至10.8%,相对颈部宽度由96.6%降低至49.5%。当温度由900 K升高至1300 K,烧结过程原子扩散系数由1.758×10^-3 nm²/ps增至4.303×10^-3 nm²/ps,增大1.45倍。高温下(1300 K)原子迁移使颗粒部分结构由HCP和BCC结构转变为非晶结构,非晶原子比例为66.7%。含10.0%初始空位缺陷浓度纳米颗粒烧结过程的扩散活化能相比完美晶体(0空位浓度)降低约63.5%,原子迁移性及烧结致密化程度增强。研究结果对氧化铁颗粒高温热处理工艺优化具有指导意义。     

流化床法除碳对微硅粉性能影响

利用流化床法对微硅粉进行除碳,通过单因素实验确定最佳工艺条件为反应温度800℃,反应时间3 h。在此条件下微硅粉中SiO_2的含量由75.64%增加到83.16%,游离碳的含量由4.14%降低到0.15%,去除率达到96.38%。利用XRD、SEM、BET等手段对流化前后的微硅粉进行分析。结果表明:流化后的微硅粉仍呈非晶态结构;颗粒表面光滑且呈规则圆球形;由于流化过程中气体将细小颗粒带出,流化后的微硅粉粒径变大,比表面积稍有减小;流化后微硅粉的流动性优于流化前,更有利于工业生产。     

金属铁颗粒高温流化特性

利用高温可视流化床研究了金属铁颗粒的高温流化特性和粘结失流化行为。探讨了流化气速,颗粒尺寸对粘结温度的影响。结果表明,气速越高,粒径越大,粘结失流化越难发生。不同温度下颗粒初始流化速率的测定结果表明,初始流化速率在高温下随温度升高而增大。热机械分析表明,随着温度的升高,颗粒表面粘度降低,颗粒间粘性力增大。结合粘性流理论,探讨了金属铁颗粒流化特性转变和粘结失流化的机理。     

磁性Fe3O4@SiO2颗粒结构对其吸附DNA的影响

采用共沉淀法和水热法制备了不同结构的超顺磁性Fe3O4@SiO2纳米颗粒,对其进行表征,研究了其吸附DNA的性能及磁分离性能. 结果表明,20?750 nm范围内粒径较大的颗粒与DNA结合时可提供更多单位平面结合位点,使结合的稳定性和结合几率增加,DNA结合量提高. 不同核?壳结构的Fe3O4@SiO2纳米颗粒的磁分离响应时间不同,内核大小相近时,壳层厚度增加会导致颗粒在磁场中受到的磁力与阻力的比值减小,磁响应时间增加,DNA回收率降低. 粒径约为200 nm的Fe3O4@SiO2纳米颗粒用于纯化全血中DNA最好,提取率为95.2%,磁响应时间为10 s.     

褐铁矿颗粒低温CO磁化还原焙烧的实验研究与数值模拟

在673~893 K低温条件下,用CO将褐铁矿颗粒中的Fe2O3还原为Fe3O4,提出基于一维球坐标下的还原模型,包括颗粒内的传热、传质方程及含变化孔隙的随机孔转化方程. 通过实验与数值模拟,得到不同气体浓度、不同温度下颗粒还原度随时间的变化关系. 结果表明,磁化焙烧还原过程受化学反应、气体内扩散及孔隙变化共同的影响,CO浓度为10%(mol)、孔隙率为0.5的100 mm的褐铁矿颗粒在673 K下还原度为1时所需还原时间为15 min.     

Al2O3/Fe纳米复合粉体的制备及其陶瓷的性能研究

以纳米α-Al2O3和Fe(NO3)3·9H2O为原料,采用非均相沉淀法制备了Fe包裹Al2O3的纳米复合粉体.经XRD、SEM分析发现:复合粉体前驱体经500 ℃焙烧,在H2中700 ℃还原可以得到纳米Fe包裹Al2O3的纳米复合粉体.粉体分散良好,Al2O3表面的纳米Fe粒子呈非连续状态,颗粒为球形,尺寸为30 nm左右,分布均匀.将复合粉体在热压下(30 MPa)烧结获得Al2O3/Fe复合陶瓷,当加入5mol%Fe时,陶瓷的热压烧结温度比单相Al2O3陶瓷降低将近100 ℃.含量为10mol%Fe的陶瓷样品在1500 ℃热压烧结后,断裂韧性可达到5.62 MPa,与相同条件下烧结的单相Al2O3陶瓷(KIc=3.57 MPa)相比提高了近57%.     

γ-FeNi包裹Al2O3复合微球的制备

利用非均相沉淀包裹技术,在室温于水溶液中,以球形α-Al2O3、硫酸镍、硫酸亚铁和碳酸氢铵为原料,先制备了无定形碱式碳酸镍和水合氧化铁包裹氧化铝球形微粉前驱体.然后,前驱体在600℃经氢气还原2 h制备表面光滑、致密的γ-FeNi包裹Al2O3复合微球.利用扫描电镜、能量散射分光仪、X射线衍射和热重分析仪等表征了复合微球前驱体及还原产物的表面和断面形貌、成分以及前驱体热分解过程.对被包裹氧化铝含量、加料速度、搅拌速度、反应时间及表面活性剂等影响因素进行了分析.初步得到优化制备条件,即15 g/L α-Al2O3,加料速度为5 mL/min,搅拌速度为1 000 r/min,反应时间为1 h,表面活性剂添加量为5 mL/L.γ-FeNi的热膨胀系数接近于氧化铝,因而使两者形成了较好的界面结合.这种γ-FeNi包裹Al2O3复合微球可用作新型吸波材料.     

铁矿微粉低温快速氢还原实验研究

通过实验进行了铁矿微粉在输送过程中低温(180~570℃)、低压(<0.2 MPa)条件下用氢预还原的可行性研究. 分别考虑了反应温度、矿粉粒径、固气比、反应时间等参数对矿粉还原率的影响. 结果表明,粒径为61.7 mm的矿粉在加热温度570℃、固气比0.22 g/L、反应时间40 s时,还原率可达39.2%. 对还原样品粉末进行X射线衍射分析表明,铁矿粉中的Fe2O3已还原为Fe3O4并开始出现金属铁.     

Agglomeration of coal ash in fluidized beds

The defluidization behaviour of ash derived from Indian coal by combustion in a fluidized bed has been studied. Sintering temperatures for ash in several ranges of particle size were measured with a dilatometer. In agreement with the earlier work on other coals it was found that above the sintering temperature pairs of complementary, limiting values of fluidization velocity and bed temperatures exist which mark the onset of defluidization when the ash particles are heated in a fluidized bed. A linear relation was observed between bad temperature and limiting defluidization velocity. The constants in the corresponding equations were calculated for two size ranges of particles.     

几种典型铁矿粉的流化特性

利用内径150 mm的D型有机玻璃流化床模型,对澳矿、巴西矿、北方矿和钒钛矿典型铁矿粉的流化特性进行了实验研究,获得了其流化特性曲线、初始流化速度和最大床层压降,并将初始流化速度的实测值和理论计算值进行了比较分析. 结果表明,矿粉粒度是影响其流化特性的最主要因素,粒径越大,床层所需要的初始流化速度越大,实测值和理论估算值基本相符;粒度小于0.125 mm钒钛矿流动性较差,在流化过程中易出现沟流现象;粒度范围较宽的矿粉,完全流态化时,细矿粉随气流夹带逸出明显;在粒度相同的情况下,几种不同的铁矿粉的开始流化速度接近,而床层压降有较大差异,巴西矿的床层压降明显大于其他三种铁矿粉. 最大床层压降的最小值均出现在粒度为0.25~0.425 mm,为铁矿粉流态化还原过程中较适宜的粒度范围.     

High-temperature de fluidization

Operation of fluidized beds at high temperatures is limited by the tendency of the bed particles to agglomerate, causing defluidization. This operating limit is important in several processes, including coal conversion, iron ore reduction, and cement manufacture.At lower temperatures, the bed remains fluidized at velocities above the normal minimum fluidization velocity. Once the bed is operating above an ‘Initial Sintering Temperature’, the fluid velocity must be well above the normal minimum fluidization velocity in order to prevent defluidization. The defluidization velocity increases with increasing operating temperature. The ‘Initial Sintering Temperature’ can be estimated using a dilatometer to measure thermal expansion and contraction of a loosly packed sample of the bed particles.     

Efficient synthesis of iron nanoparticles by self‐agglomeration in a fluidized bed

A two‐stage, fluidized reduction route is proposed to synthesize iron nanoparticles (NPs), with the aim of enhancing the quality of fluidization and preventing sintering activity. At both low and high temperatures, the degree of metallization η is approximately 80% due to the defluidization. Defluidization is mainly caused by the rapid sintering of the newly formed Fe NPs. The proposed two‐stage fluidization approach successfully resolves the defluidization problem through the self‐agglomeration of nanoparticles cultivated at low temperatures. These self‐agglomerated NPs showed an improved resistance to sintering at high temperatures. The high‐purity Fe NPs prepared by this approach exhibited excellent combustion activity, indicative of the potential as oxygen carriers in chemical looping combustion systems. © 2016 American Institute of Chemical Engineers AIChE J, 63: 459–468, 2017     

钒钛磁铁矿流态化直接还原技术现状与发展趋势

钒、钛是重要的生产生活资料,90%以上赋存于钒钛磁铁矿中. 我国钒钛磁铁矿资源储量丰富,但在当前高炉?转炉工业流程中,受高炉冶炼条件限制,钒钛磁铁精矿中的钛元素未能得到回收利用. 面对钒钛磁铁精矿铁钒钛资源全面提取利用难题和资源环保集约综合利用的迫切需求,直接还原?电炉熔分两步法流程受到广泛关注,其中流化床法因直接采用粉矿入炉、工序流程短、低温综合反应效率高,在直接还原工序中优势突出. 本工作阐述并对比了钒钛磁铁精矿流化床直接还原工艺,分析了钒钛磁铁精矿难还原的原因,重点介绍了流态化预氧化强化还原方法,同时归纳流化床直接还原过程中影响粘结失流的主要因素,总结了5种抑制铁矿粉粘结失流的直接方法,并提出了添加MgO惰性添加剂、碳包覆及改进床型结构的研究发展方向.     

The effects of agglomeration/defluidization on emission of heavy metals for various fluidized parameters in fluidized-bed incineration

The agglomeration/defluidization may be produced to generate the secondary pollutant during incineration. However, the effects of agglomeration/defluidization on heavy metal distribution have rarely been examined. Therefore, the effects of the agglomeration/defluidization process on heavy metal emission in flue gas are studied. The artificial waste is employed to simulate municipal waste and to form agglomerates, which contain alkali metals, earth alkali metals, a mixture of metals (Pb, Cr and Cd) and sawdust. The fluidized parameters (including gas velocity, sand particle size and static bed height) are varied to determine their influences on heavy metal emission. The results indicate that addition of Na increases the risk of agglomeration/defluidization, but the emission concentration of heavy metals decreases during agglomeration/defluidization. The heavy metals may react with Na to form the eutectics or are covered and adhered by the liquid-phase eutectics of Na to stay in sand particle and lead to a decrease in the emission of heavy metals.The system was operated at a low gas velocity that not only easily resulted in agglomeration/defluidization but also increased the emission concentration of heavy metals. Large particles (920 μm), which have a poor fluidized quality, had the highest emission concentration. Small particles (645 μm) were uniformly fluidized to enhance the fluidization quality and to decrease the emission concentration. Additionally, adding Ca did not decrease the heavy metal emission concentration, but maintained the fluidization during eutectic accumulation. The Ca prevented the sand bed from quickly achieving defluidization and prolonged the increased emission of heavy metals after defluidization.     

AGGLOMERATION BEHAVIOR IN A BUBBLING FLUIDIZED BED AT HIGH TEMPERATURE

Minimum fluidization velocity and agglomeration behavior were investigated at high temperature in an 80?×?30?mm two-dimensional quartz fluidized bed and in an 82?mm i.d. circular fluidized bed. Bed materials tested were two sizes of glass beads as well as three sizes of fluidized bed combustor (FBC) ash. The minimum fluidization velocity decreased with increasing bed temperature, whereas the minimum sintering fluidization velocity increased with the bed temperature. The sintering of glass beads belongs to visco plastic sintering, the first type. FBC ash agglomerate has higher amounts of SiO₂, Al₂O₃, Na₂O, K₂O, and SiO₂ than in the original ash, indicating that low melting eutectics were formed and that the liquid phase in a silicate system was formed. The agglomeration of FBC ash belongs to the second type, an excessive quantity of liquid being formed by melting or chemical reaction.     

双组分颗粒声场流态化的实验研究

在内径为56 mm的玻璃声场流化床中,以5~10 nm未改性和有机改性的SiO2为实验物料主体颗粒,Fe3O4(粒径小于0.053 mm)为客体颗粒,在声压级为90~105 dB时系统考察了声场频率、声场强度和主客体颗粒不同配比关系对超细颗粒流化行为和聚团尺寸的影响。结果表明,当声场频率处于50 Hz,声压级大于100 dB时,声波可以有效地消除节涌、抑制沟流、降低临界流化速度,减小聚团尺寸,显著改善超细颗粒的流化质量。声场频率一定,声场强度越大,颗粒团聚体的直径越小。客体颗粒的添加比例存在一适宜范围。     

高温流化床结焦特性

分析了近年来高温流化床结焦研究的状况，总结了流化床结焦现象及其影响因素、流化床结焦时的最小流化速度及影响因素、流化床结焦机理，并分析了研究中存在的问题，探讨了高温流化床结焦特性研究的方向。     

在具有锥形料腿的循环流化床中流化CaCO3超细颗粒

根据粘附性颗粒在流化过程中形成的聚团具有较宽粒径分布并因此导致大聚团在流化床中沉积和死床的问题,提出了循环流化床的锥形回料系统设计. 该回料系统包括两部分：锥形料腿和带辅助进气的V型阀. 实验证明,锥形料腿通过提供变化的表观流化气速,克服了流化聚团沉积死床等现象;而V型阀的辅助进气,对于保证V型阀顺利输送粘附性颗粒具有关键性作用. 借助这种回料系统,实现了高粘附性超细CaCO3颗粒在循环流化床的稳定快速流化. 从提升管内部拍摄的照片显示,尽管提升管采用较高的流化气体速度,但超细CaCO3颗粒仍然是以聚团的形式被流化. 对在提升管不同高度采集的聚团分析表明,处于快速流化状态的CaCO3聚团的直径远小于传统流化床中聚团的直径,并且在提升管高度方向聚团直径没有较大的变化. 同时实验还显示,提升管轴向空隙率呈S型分布,而径向则体现环-核结构,具有典型的快速床特征.