Pressure increase and “dynamic effective diffusivity” within a powder bed during reaction-reduction of iron oxide powders by hydrogen at 900°C

α-Hematite powder having an average diam of 8.1 μm was packed in a vertical quartz reactor (I.D. 14.6 mm) and was reduced by feeding hydrogen toward the top of the packed bed at 900°C under atmospheric pressure. A large increase in pressure as high as 118 mmHg was observed within the powder bed during the course of reaction. The stoichiometric condition that the diffusion rate of the reactant gas, H₂, should be equal to that of the product gas, H₂O, gave rise to this pressure increase within the bed. When the pressure within the bed were uniform, the ratio of the diffusional fluxes of the reactant gas, H₂, and of the product gas, H₂O, would be equal to the square root of the ratio of the molecular weight of H₂O and of H₂. An effective diffusivity which includes not only the diffusional term but also the hydrodynamic term was introduced into the equations for the flow of gases with chemical reactions. The pressure variations within the powder bed calculated from the proposed flow equations agreed quite well with those observed during the course of the three-step reduction of hemattte (Fe₂O₃) to magnetite (Fe₃O₄), then to wustite (Fe_1?y O), and finally to iron. It was also found that, during the reduction, the presence of pressure gradient within the bed reduced the effective diffusivity of hydrogen to about one third of that without the pressure gradient.     

Kinetics of manganese ore reduction by carbon monoxide

A step has been made in the direction of understanding the fundamental chemical processes taking place inside electric are furnaces producing manganese alloys. The reduction of higher manganese oxides to MnO by carbon monoxide has been studied in the temperature range 700 °C to 1100 °C. A topochemical pattern with a single shrinking core inside the ore particles has been observed in most cases. It has been found that the reduction of some manganese silicates (braunite minerals) is influenced by reaction interface kinetics, whereas the reduction rate of manganese oxides (bixbyite and hausmannite) is mostly determined by product shell pore diffusion. Sintering kinetics and the extent of natural porosity determine the product shell pore diffusivity. As the melting point of the reaction product is approached, rapid sintering leads to a decrease in diffusivity.     

Development of a mathematical model for multihearth roasters

A simultaneous heat and mass transfer model has been developed for the multiheart roasters, considering dead roasting of chalcopyrite as a typical roasting reaction. Various mass and energy balances have been worked out during the development of this model yielding coupled nonlinear partial differential equations with highly complex boundary conditions. These equations have been solved numerically using a line-by-line finite difference approach to obtain profiles of gas temperature, solid temperature, oxygen concentration, and solid fraction reacted in the roaster. The trend of the computed results appears to be realistic and can be easily explained from simple physical considerations. The effects of gas preheating and the heat transfer coefficient between the solid and the gas upon the roasting process are examined. The results show that gas preheating is beneficial for the roasting process, and the process parameters, such as particle size, gas flow rate,etc., must be adjusted so as to give the desirable value of the heat transfer coefficient needed for proper roasting.     

对流扩散对多孔介质气固反应的影响

针对填充床中的气固反应aA(g) bB(s)=cC(g) dD(s),在微元体动力学研究的基础上,考虑到气体的压缩性和惰性组分的存在,从渗流力学观点出发,导出了反应气体与产物气体的非线性对流反应扩散方程和混合流体渗流方程,用有效容积法求方程的数值解,通过实例计算,分析了不同条件下的反应转化情况.结果表明,颗粒尺度和反应器长度对反应进程有明显影响,这些影响可以用Thiele数、Peclet数及它们的比值来衡量,适当选取颗粒尺度和反应器长度可以改善反应器性能.     

In Situ measurement of effective gas diffusivity through hematite pellets during stepwise reductions

The Wicke-Kallenbach (W-K) method for effective gas diffusivity measurements could only be used in the vicinity of ambient temperatures. However, in the present study, this technique has been extended to temperatures of about 1273 K through use of a high-temperature cement. This newly developed high-temperature W-K method was applied toin situ measurements of the diffusive and viscous fluxes through hematite pellets during stepwise reductions. When the sam-ple (acid and basic pellets) is reduced, it swells significantly. However, a gas-tight seal between the holder and specimen was successfully maintained by use of a high-temperature cement. This cement, composed mainly of Na₂O (20 mass pct) and SiO₂, separates into a solid and liquid phase at elevated temperatures. Thus, it can move in the same direction as the expansion of sample and thereby maintain the gas-tight seal. With this new technique, the structural param-eters of gases based on the “dusty gas model” for D’Arcy’s flow, Knudsen diffusion, and mo-lecular diffusion were obtained. These parameters were compared with those estimated through pore structure models.     

Simulation of tuyere–raceway system in blast furnace

Abstract

A uniform distribution of the blast is an important prerequisite of a balanced blast furnace operation, because the blast is the main source of the hot gases that are needed to preheat, reduce and melt iron ores. The supply of hot gas from the raceways is not necessarily uniform along the furnace periphery, but depends on flow resistances encountered on the individual bustle main tuyere–raceway–raceway boundary routes. A model for this system has been developed in order to study and analyse the effects of changes in tuyere parameters and boundary conditions. Variables such as the total blast volume, blast pressure, tuyere diameter and the combustion degree of injected reductants in the tuyeres can be studied. An online version of the model has also been developed to track how the conditions on the tuyere level change with time in operating blast furnaces.     

Modeling of fluidized bed chlorination of rutile

A model has been developed for fluidized bed chlorination of rutile in the presence of coke to produce titanium tetrachloride. At various reaction conditions, the model can predict the conversion of chlorine, particle size distribution in the bed, composition of the product gas, and reaction temperature. The bubble assemblage model is used to calculate the reactant gas mass transfer rate from the bubble phase to the emulsion phase. The population balance is employed to determine the size distribution of particles in the bed. The reaction in the freeboard zone is neglected. The model predictions have been compared with the results from a pilot-scale experiment, and the model gives good agreement between computed and experimental results. The effects of various reaction parameters on the reaction rate are discussed using the model.     

钢铁厂高能效利用副产煤气的可行途径

钢铁厂在生产过程中,副产了大量可燃煤气。副产煤气热值范围在3～20MJ/Nm3,所含的热量可被利用,如:电厂、焦炉、热风炉、热轧厂等所需燃料,可用副产煤气部分替代天然气,减少煤气放散,降低公司的能耗成本和环境污染。使用副产煤气虽能得益却也面临难题。副产煤气的产量和成分取决于生产和工艺状况,煤气用户必须随之调整其操作。用气设备的启停操作改变了煤气用量,造成煤气管网压力波动,副产煤气成分变化则会引起热值波动,一旦管网压力波动或成分改变,将对管网上用气单元的燃烧过程产生不利影响。针对副产煤气利用的复杂情况,AMB、AMEH和BFI公司开发了高能效利用副产煤气的途径,应用于部分钢铁厂,如:改善煤气管网压力和流量分布的技术,具备供需分布显示和预报功能的煤气管理系统。介绍了煤气管网压力波动控制以及副产煤气利用的结果和经验。     

Influence of pressure on the kinetics of synthetic llmenite reduction in hydrogen

In-situ thermogravimetric measurements were used in the hydrogen reduction of poly-granular synthetic ilmenite discs at temperatures in the range 823 to 1173 K and at pressures in the range 1.2 to 13 atm. A symmetrical beam microbalance was used, coupled with twin reactors and twin furnaces, to minimize buoyancy and drag effects. Stable operation was achieved at high gas flow rates where gas film transport effects were negligible. Polishing the ilmenite discs prior to reduction eliminated the formation of dense surface metallic iron films that can impede gas diffusion into the discs. Macroscopically, the reduction reaction proceeded topochemically and a shrinking core reaction model was found to be appropriate to predict conversion-time relationships. It was necessary to allow for water vapor adsorption onto the reacting interface in order to model the effect of pressure on the reduction kinetics. The observed reduction rate increased sharply with pressure up to approximately 3 atm and then approached a plateau with further pressure increase. The porosity in the reduced ilmenite samples was very fine, with pore diameters of typically 0.05 to 0.3 μm. Intragrain gas pressure buildup in the fine pores due to the influence of Knudsen diffusion was incorporated into the modeling of the kinetic data.     

Calculation results and analysis of gas flow properties in tuyère under the influence of heat source

The flow properties of the gases in an annular‐tube type tuyère used for an 18 t AOD vessel were analyzed using the equations and calculation formulas presented in Part I of this work. The influence of the heating and friction effects, the gas supply pressure, and the gas type and composition, on the properties were examined. The results showed that the properties in a tuyère are significantly changed due to the presence of a heat source. This has a similar effectiveness as increasing the friction action and obviously reduces the gas flowrate at the tuyère outlet. When designing a tuyère used in a practical process of metallurgy and calculating the flow properties of gas in the tuyère, the heating effect from the high temperature melt and refractory lining should be taken into account. The gas supply pressure has a decisive effect on the properties. The type and composition of the blowing gas will also influence the properties. For a given tuyère and blowing system, appropriate blowing pressures for different gases, particularly for subtuyère gases, should be used according to the technological requirements of the different refining periods.     

纳微米级孔隙气体流动数学模型及应用

对纳微米级孔隙多孔介质内的气体流动进行了研究.利用克努森数划分流态,绘制了流态图版,阐明了不同区域的流动特征.基于Beskok-Karniadakis模型,对渗透率校正系数进行了改进,引入多项式修正系数,将Beskok-Karniadakis模型简化为二项式方程,并利用最小二乘法分段拟合得出多项式修正系数的取值.模型对比显示,简化后的模型具有较高的精确度.应用此模型推导出了纳微米级孔隙气体流量的计算公式.进行了室内微观渗流模拟实验,得到气体平面单向渗流规律,与由纳微米级孔隙气体流量公式计算所得渗流特征进行对比,结果显示本模型与实验数据拟合较好.采用本模型进行编程计算,对其影响因素进行分析,发现气体流量随压力平方差增加而增大,且增加趋势越来越快,并随多孔介质渗透率和克努森扩散系数的增加而增大.      

Prediction of temperature in secondary steelmaking: mathematical modelling of fluid flow and heat transfer in gas purged ladle

As a first step towards prediction of temperatures in secondary steelmaking, mathematical modelling of fluid flow and heat transfer in ladle furnace was undertaken. A two‐dimensional quasi‐single phase model has been developed for turbulent recirculating flow by solving Reynolds averaged Navier‐Stokes equations along with a two‐equation k‐? model. The model was then extended to include thermal transport in a conjugate domain (i.e., molten steel + refractory shell + steel shell). The flow model was validated with water model data reported in literature by different researchers. Good agreement for velocity field and satisfactory agreement for turbulent kinetic energy field were obtained. The thermal model showed good agreement with results predicted in literature. The paper also presents findings of tests for sensitivity of flow on modelling and process parameters. By comparison with water model experiments, it has been demonstrated that the flow field in a ladle with a porous plug can be represented using a gas voidage fraction in the plume obtained from experiments with nozzles for axial gas injection from the bottom. Flow and thermal fields were insensitive to initial turbulence level at nozzle. Maximum temperature inhomogeneity in the melt was 2 °C after 1.5 min and negligible after 3 min of onset of gas purging.     

Kinetics of sulfation of chalcopyrite with steam and oxygen in the presence of ferric oxide

The kinetics of suifation of chalcopyrite with/without ferric oxide addition has been studied in the fixed bed for the temperature range 673 to 773 K in the absence of external mass transfer effects such as particle size of ore and flow rate of oxidizing gases such as steam and oxygen. The suifation reaction was observed to be topochemical. The activation energy value of 30.5 kJ/mol was found when no catalytic addition was made. The rate of suifation increases with the addition of ferric oxide. The rate constant values obtained without and with 10 pct Fe₂O₃ were 5.5 × 10³ min^?1 and 7.00 × 10³ min^?1, respectively. The activation energy value for the roasting in the presence of the catalyst was 29.2 kJ/mol under these conditions. Examination of the kinetic data indicates that the reaction occurred on the surface of the mineral particles and proceeded through the reactant and product phase boundary. The sulfated products were also characterized by metallography, scanning electron microscopy-energy dispersive spectroscopy (SEM-EDS), and X-ray diffractometry (XRD) studies.     

A Mathematical Model of a Blast Furnace Injection Tuyere

One way to further utilise produced gases in an integrated metallurgical plant is to replace oil with gas as a reducing agent in a modern blast furnace. Accordingly, it is of great interest to study the injection of reducing gas into the blast furnace. Therefore, a three‐dimensional mathematical model has been developed which simulates the injection of the gas by lances into the tuyere. The model includes the coupled solution of the flow field and the chemical reaction of the gases in the tuyere. Two different types of fuel gas, coke oven gas (COG) and basic oxygen furnace gas (BOF) have been modelled using one injection lance. The modelling technique is presented and discussed as well as the implied results. Furthermore, process parameters such as different gas compositions etc. are investigated using the developed model. Not surprisingly, the main results show that the COG is combusted more completely than BOF gas, which leads to higher flame temperature of the blast putting demand forward to lower the heat load of the tuyere. However, the modelling of the raceway is as far not included in the model, hence the influence of the outlet boundary condition at the tuyere is not reflected in the presented results.     

复杂压裂缝网页岩气储层压力传播动边界研究

页岩气储层中存在大量的纳微米孔隙,且孔隙裂缝结构复杂,气体渗流阻力大,存在多尺度渗流的问题;页岩气储层压力扰动随时间向外传播并非瞬时到达无穷远,其渗流规律就是一个压力扰动边缘动边界的问题。基于对以上问题的研究,本文建立了渗透率分形分布和高斯分布的渗透率表征模型,对不同形态缝网压裂特征就渗流规律进行了描述,并利用稳态依次替换法,考虑页岩储层中扩散、滑移及解吸作用,进一步研究了多级压裂水平井不稳定渗流压力扰动的传播模型,得到不同压裂条件下压力扰动边界随时间变化的关系,并结合我国南方海相龙马溪组页岩气藏储层参数,应用MATLAB编程。研究表明:压力传播动边界随时间增加逐渐向外扩展,渗透率越小,压力传播越慢;未压裂储层压力传播速度<渗透率分形分布压裂储层传播速度<渗透率高斯分布压裂储层传播速度。对于渗透率极低的页岩气储层,压力传播慢,气井自然产能低,必须对页岩气储层进行大规模的储层压裂改造,并控制压裂程度,以提高页岩气开发效果;基于压力传播动边界的扩展优化页岩储层压裂井段间距90 m,优化渗透率分形分布压裂井井间距318 m,渗透率高斯分布压裂井井间距252 m。因此应合理控制页岩储层压裂改造规模,实现优产高产。模型模拟结果与实际生产数据拟合较好,验证了本研究理论模型的适用性。      

钢铁工业副产煤气资源化利用分析及案例

 在钢铁产品的生产过程中,同时产生大量的副产煤气,即高炉煤气（BFG）、焦炉煤气（COG）和转炉煤气（LDG）,在钢铁企业的能源平衡中占有十分重要的地位（约占全部二次能源产生总量的70%）。目前钢铁企业副产煤气大多数是燃料化利用,而副产煤气高附加值利用的另一个方向是开发副产煤气中碳元素和氢元素（H2、CmHn和CO等）价值,实现资源化利用。钢厂推进副产煤气资源化利用的核心是进行能量流（煤气流）的解析及其网络的优化,副产煤气资源化利用的主要途径有制取氢气、甲醇、液化天然气（LNG）、合成天然气（SNG）、压缩天然气（CNG）、合成氨、二甲醚、乙二醇、烯烃等化工产品。四川达钢焦炉煤气和转炉煤气制甲醇的案例研究表明,副产煤气资源化利用不仅能使钢铁企业的副产煤气资源得到高效利用,而且有显著的经济和环境效益。     

Mathematical modelling of wustite pellet reduction: grain model in comparison with USCM

A mathematical time-dependent and non-isothermal model has been carried out on the basis of the grain model to study the behaviour of a wustite pellet undergoing chemical reactions with reducing gases. The behaviour of wustite pellet reduction analysed by the grain model has been compared with unreacted shrinking core model (USCM). The results show, unlike the grain model, USCM cannot properly predict the impact of gas mixture parameters and pellet characteristics on the local reduction degree. The results also display that when the grain diameter, temperature and tortuosity increase, the diffusivity resistance in the pellet increases which causes more heterogeneous reduction. However, an increment in porosity causes gases to easily diffuse in the pellet and as a result a less heterogeneous reduction will occur.     

Morphology and reduction kinetics of fluxed iron ore pellets

Abstract

The present paper describes studies of the reduction and sintering behaviour, followed by examination of the structural changes taking place, during direct reduction of fluxed composite (ore plus coal) pellets. The kinetics and morphological aspects of the direct reduction of fluxed composite pellets are compared with those for the gaseous reduction of fluxed ore pellets without carbon addition. It is shown that the chemical reaction is the rate limiting factor for fluxed composite pellets, and the mass transport of reactant gas through the reaction product iron layer governs the overall reduction process in the case of fluxed ore pellets. Microscopic analysis of the fluxed composite pellets has indicated no tendency to form a reduction inhibition iron shell towards the end of the reduction, as found in the case of gaseous reduction of fluxed ore pellets under identical reduction process conditions. The effects of basicity, Fe/C, temperature, and other variables on morphological and microstructural changes in the directly reduced fluxed composite pellets have been experimentally investigated in the present work.     

Regenerative heat transfer in rotary kilns

A mathematical model has been developed to determine the temperature distribution in the wall of a rotary kiln. The model, which incorporates a detailed formulation of the radiative and convective heat-transfer coefficients in a kiln, has been employed to examine the effect of different kiln variables on both the regenerative and the overall heat transfer to the solids. The variables include rotational speed, pct loading, temperature of gas and solids, emissivity of wall and solids, convective heattransfer coefficients at the exposed and covered wall, and thermal diffusivity of the wall. The model shows that the regenerative heat flow is most important in the cold end of a rotary kiln, but that generally the temperature distribution and heat flows are largely independent of these variables. Owing to this insensitivity it has been possible to simplify the model with the aid of a resistive analog. Calculations are presented indicating that both the shell loss and total heat flow to the bed may be estimated to within 5 pct using this simplified model.     

Nozzle design in impinging jet steelmaking processes

A criterion to determine throat diameter of a supersonic nozzle is determined from conservation equations of flow of gases and applied successfully to nozzles used in impinging jet steelmaking processes. Influence of surroundings on the nozzle design is evaluated in terms of the force coefficient. It is suggested that a supersonic nozzle design delivering gas at exit pressures slightly greater than the surrounding pressure or overdriving a correctly designed nozzle is beneficial under the conditions of impinging jet steelmaking practice.