Thermal performance and reduction kinetic analysis of cold-bonded pellets with CO and H2 mixtures

Cold-bonded pellets, to which a new type of inorganic binder was applied, were reduced by H2~CO mixtures with different HJCO 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 daermogravimetric analysis appaxatus. The effects of gas composition, temperature, and binder ratio on the reduction process were studied, and the microstxucture of re- duced 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 hin- der 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 main- tain 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 overaJl equilibrium constant to the promotion effect depends on the gas composition.

Effect of CO_2 and H_2O on gasification dissolution and deep reaction of coke

To more comprehensively analyze the effect of CO_2 and H_2O on the gasification dissolution reaction and deep reaction of coke, the reactions of coke with CO_2 and H_2O using high temperature gas–solid reaction apparatus over the range of 950–1250°C were studied, and the thermodynamic and kinetic analyses were also performed. The results show that the average reaction rate of coke with H_2O is about 1.3–6.5 times that with CO_2 in the experimental temperature range. At the same temperature, the endothermic effect of coke with H_2O is less than that with CO_2. As the pressure increases, the gasification dissolution reaction of coke shifts to the high-temperature zone. The use of hydrogen-rich fuels is conducive to decreasing the energy consumed inside the blast furnace, and a corresponding high-pressure operation will help to suppress the gasification dissolution reaction of coke and reduce its deterioration. The interfacial chemical reaction is the main rate-limiting step over the experimental temperature range. The activation energies of the reaction of coke with CO_2 and H_2O are 169.23 kJ ·mol-1 and 87.13 kJ·mol^(-1), respectively. Additionally, water vapor is more likely to diffuse into the coke interior at a lower temperature and thus aggravates the deterioration of coke in the middle upper part of blast furnace.

Formation mechanism of the protective layer in a blast furnace hearth

A variety of techniques, such as chemical analysis, scanning electron microscopy-energy dispersive spectroscopy, and X-ray diffraction, were applied to characterize the adhesion protective layer formed below the blast furnace taphole level when a certain amount of titanium-bearing burden was used. Samples of the protective layer were extracted to identify the chemical composition, phase assemblage, andistribution. Furthermore, the formation mechanism of the protective layer was determined after clarifying the source of each componenFinally, a technical strategy was proposed for achieving a stable protective layer in the hearth. The results show that the protective layemainly exists in a bilayer form in the sidewall, namely, a titanium-bearing layer and a graphite layer. Both the layers contain the slag phaswhose major crystalline phase is magnesium melilite（Ca2Mg Si2O7） and the main source of the slag phase is coke ash. It is clearly determinethat solid particles such as graphite, Ti（C,N） and Mg Al2O4play an important role in the formation of the protective layer, and the key factofor promoting the formation of a stable protective layer is reasonable control of the evolution behavior of coke.

Basic characteristics of Australian iron ore concentrate and its effects on sinter properties during the high-limonite sintering process

The basic characteristics of Australian iron ore concentrate (Ore-A) and its effects on sinter properties during a high-limonite sintering process were studied using micro-sinter and sinter pot methods. The results show that the Ore-A exhibits good granulation properties, strong liquid flow capability, high bonding phase strength and crystal strength, but poor assimilability. With increasing Ore-A ratio, the tumbler index and the reduction index (RI) of the sinter first increase and then decrease, whereas the softening interval (Delta T) and the softening start temperature (T (10%)) of the sinter exhibit the opposite behavior; the reduction degradation index (RDI+3.15) of the sinter increases linearly, but the sinter yield exhibits no obvious effects. With increasing Ore-A ratio, the distribution and crystallization of the minerals are improved, the main bonding phase first changes from silico-ferrite of calcium and aluminum (SFCA) to kirschsteinite, silicate, and SFCA and then transforms to 2CaO center dot SiO2 and SFCA. Given the utilization of Ore-A and the improvement of the sinter properties, the Ore-A ratio in the high-limonite sintering process is suggested to be controlled at approximately 6wt%.

Direct reduction of iron ore by biomass char

By using thermogravimetric analysis the process and mechanism of iron ore reduced by biomass char were investigated and compared with those reduced by coal and coke. It is found that biomass char has a higher reactivity. The increase of carbon-to-oxygen mole ratio （C/O） can lead to the enhancement of reaction rate and reduction fraction, but cannot change the temperature and trend of each reaction. The reaction temperature of hematite reduced by biomass char is at least 100 K lower than that reduced by coal and coke, the maximum reaction rate is 1.57 times as high as that of coal, and the final reaction fraction is much higher. Model calculation indicates that the use of burden composed of biomass char and iron ore for blast furnaces can probably decrease the temperature of the thermal reserve zone and reduce the CO equilibrium concentration.

Optimization model coupling both chemical compositions and high-temperature characteristics of sintering materials for sintering burden

We developed a mathematical optimization model coupling chemical compositions and high-temperature characteristics of sintering materials, targeting the best quality and lowest cost. The simplex algorithm was adopted to solve this model. Four kinds of imported iron ores, two kinds of Chinese iron ore concentrates, and two kinds of fluxes were selected to verify both the model and the algorithm. The results confirmed the possibility of considering both chemical compositions and high-temperature characteristics of iron ores in the optimization model. This model provides a technical roadmap to obtain a precise mathematical correlation between the lowest cost and the grade of iron in sinters based on the condition of given raw materials, which can provide a reference to adjust the grade of iron in the sintering process for enterprise.

Effect of aluminum oxide on the compressive strength of pellets

Analytical-reagent-grade Al2O3 was added to magnetite ore during the process of pelletizing, and the methods of mercury intru-sion, scanning electron microscopy, and image processing were used to investigate the effect of Al2O3 on the compressive strength of the pellets. The results showed that, as the Al2O3 content increased, the compressive strength of the pellets increased slightly and then decreased gradually. When a small amount of Al2O3 was added to the pellets, the Al2O3 combined with fayalite （2FeO＆#183;SiO2） and the aluminosilicate （2FeO＆#183;2Al2O3＆#183;5SiO2） was generated, which releases some iron oxide and reduces the inhibition of fayalite to the solid phase of consolidation. When Al2O3 increased sequentially, high melting point of Al2O3 particles hinder the oxidation of Fe3O4 and the recrystallization of Fe2O3, making the internal porosity of the pellets increase, which leads to the decrease in compressive strength of the pellets.

Effect of organic binders on the activation and properties of indurated magnetite pellets

In the ironmaking process,the addition of an organic binder to replace a portion of bentonite has the potential to improve the per-formance of pellets.The interaction between original bentonite(OB)and organic binder was investigated.Results indicated that the micromor-phology of organic composite bentonite(OCB)became porous and the infrared difference spectrum exhibited a curved shape.In addition,the residual burning rates of OB and organic binder were determined to be 82.72%and 2.30%,respectively.Finally,the influence of OCB on the properties of pellets was investigated.The compressive strength of OCB-added green pellets(14.7 N per pellet)was better than that of OB-ad-ded pellets(10.3 N per pellet).Moreover,the range of melting temperature of OCB-added green pellets(173℃)was narrower than that of OB-added pellets(198℃).The compressive strength of OCB-added green pellets increased from 2156 to 3156 N per pellet with the increase in roasting temperature from 1200 to 1250℃.

Formation mechanism of the graphite-rich protective layer in blast furnace hearths

A long campaign life of blast furnaces is heavily linked to the existence of a protective layer in their hearths. In this work, we conducted dissection studies and investigated damage in blast furnace hearths to estimate the formation mechanism of the protective layer. The results illustrate that a significant amount of graphite phase was trapped within the hearth protective layer. Furthermore, on the basis of the thermodynamic and kinetic calculations of the graphite precipitation process, a precipitation potential index related to the formation of the graphite-rich protective layer was proposed to characterize the formation ability of this layer. We determined that, under normal operating conditions, the precipitation of graphite phase ~om hot metal was thermodynamically possible. Among elements that exist in hot metal, C, Si, and P favor graphite precipitation, whereas Mn and Cr inhibit this process. Moreover, at the same hot-face temperature, an increase of carbon concentration in hot metal can shorten the precipitation time. Finally, the results suggest that measures such as reducing the hot-face tem- perature and increasing the degree of carbon saturation in hot metal are critically important to improve the precipitation potential index.

Softening–melting behavior of mixed burden based on low-magnesium sinter and fluxed pellets

A low MgO content in sinter is conducive to reduce the MgO content in blast furnace slag.This study investigated the effect of MgO content in sinter on the softening–melting behavior of the mixed burden based on fluxed pellets.When the MgO content increased from 1.31 wt% to 1.55 wt%, the melting temperature of sinter increased to 1521℃.Such an increase was due to the formation of the high-meltingpoint slag phase.The reduction degradation index of sinter with 1.31 wt% MgO content was better than that of others.The initial softening temperature of the mixed burden increased from 1104 to 1126℃ as MgO content in sinter increased from 1.31 wt% to 1.55 wt%, and the melting temperature decreased from 1494 to 1460℃.The permeability index(S-value) of mixed burden decreased to 594.46 kPa·℃ under a high MgO content with 1.55 wt%, indicating that the permeability was improved.The slag phase composition of burden was mainly akermarite(Ca_(2)MgSiO_(7)) when the MgO content in sinter was 1.55 wt%.The melting point of akermarite is 1450℃, which is lower than other phases.

Reduction mechanisms of pyrite cinder-carbon composite pellets

The non-isothermal reduction mechanisms of pyrite cinder-carbon composite pellets were studied at laboratory scale under argon （Ar） atmosphere. The composite pellets as well as the specimens of separate layers containing pyrite cinder and coal were tested. The degree of reduction was measured by mass loss. The microstmctures of the reduced composite pellets were characterized by scanning electron mi- croscopy （SEM）. It is found that the reduction processes of the composite pellets may be divided into four stages： reduction via CO and H2 from volatiles in coal at 673-973 K, reduction via H2 and C produced by cracking of hydrocarbon at 973-1123 K, direct reduction by carbon via gaseous intermediates at 1123-1323 K, and direct reduction by carbon at above 1323 K. Corresponding to the four stages, the apparent activation energies （E） for the reduction of the composite pellets are 86.26, 78.54, 72.01, and 203.65 kJ.mol-1, respectively.

Characteristics of combustion zone and evolution of mineral phases along bed height in ore sintering

Quantitative parameters of bed combustion, including the thickness of the combustion zone(TCZ), the maximum temperature of the combustion zone(MTCZ), and the bed shrinkage, were characterized through a series of sinter pot tests in transparent quartz pots. The results showed that TCZ first ascended and then descended as the sintering process proceeded. The sintering process was divided into four stages according to the variation rate of the TCZ. A "relative-coordinate" method was developed to obtain the actual reaction temperature of sinter along the height direction. With increasing the sintering temperature, the reactants transformed and entered into liquid phases. The mineral composition and microstructure of the sinter were characterized through X-ray diffraction and scanning electron microscopy–energy-dispersive X-ray spectroscopy. Liquid phases with greater Fe and Al contents were more likely to form acicular-like silico-ferrite of calcium and aluminum after crystallization because of the outward spread of Al, which led to a better fluidity of the liquid. An evolution mechanism of "solid-state reaction—liquid phases formation—crystallization" of the mineral phases is proposed.

Reduction behavior and kinetics of vanadium–titanium sinters under high potential oxygen enriched pulverized coal injection

In this work, the reduction behavior of vanadium–titanium sinters was studied under five different sets of conditions of pulverized coal injection with oxygen enrichment. The modified random pore model was established to analyze the reduction kinetics. The results show that the reduction rate of sinters was accelerated by an increase of CO and H2contents. Meanwhile, with the increase in CO and H2contents, the increasing range of the medium reduction index (MRE) of sinters decreased. The increasing oxygen enrichment ratio played a diminishing role in improving the reduction behavior of the sinters. The reducing process kinetic parameters were solved using the modified random role model. The results indicated that, with increasing oxygen enrichment, the contents of CO and H2in the reducing gas increased. The reduction activation energy of the sinters decreased to between 20.4 and 23.2 kJ/mol. © 2017, The Author(s).

Phase transformation behavior of titanium during carbothermic reduction of titanomagnetite ironsand

The reduction of titanomagnetite（TTM） ironsand, which contains 11.41wt% TiO_2 and 55.63wt% total Fe, by graphite was performed using a thermogravimetric analysis system under an argon gas atmosphere at 1423–1623 K. The behavior and effects of titanium in TTM ironsand during the reduction process were investigated by means of thermogravimetric analysis, X-ray diffraction, scanning electron microscopy, and energy-dispersive X-ray spectroscopy. During the reduction procedure, the titanium concentrated in the slag phase, where the phase transformation followed this sequence： Fe O ＋ FeTiO_3 → Fe_2 TiO_4 → FeTiO_3 → FeTi_2O_5 → TiO_2. The calculated results for the reduction kinetics showed that the carbothermic reduction was controlled by the diffusion of ions through the product layer. Furthermore, the apparent activation energy was 170.35 k J·mol^（-1）.

Infiltration behavior of sintering liquid on nuclei ores during low-titanium ore sintering process

Sinter strength is dependent not only on the self-intensity of the residual rude and bonding phase but also on the bonding degree between them. The infiltration behavior of sintering liquid on nuclei ores influences the bonding degree, which ultimately determines the sinter strength. Infiltration tests were conducted using micro-sinter equipment. The infiltration area index of original liquid（IAO）, infiltration volume index of secondary liquid（IVS）, and sinter body bonding strength（SBS） were proposed to study the melt infiltration behavior. The results show that the IVS first increases and then decreases with increasing TiO2 content in adhering fines, whereas the IAO exhibits the opposite behavior. Compared with the original liquid, the secondary liquid shows lower porosity, smaller pores, and more uniform distribution. The SBS increases first and then decreases with increasing IAO and TiO2 content, and reaches a maximum when the IAO and TiO2 contents are approximately 0.5 and 2.0wt%, respectively. The SBS first increases and then tends to be stable with increasing IVS. The TiO2 content is suggested to be controlled to approximately 2.0wt% in low-titanium ore sintering.

Combustion characteristics and kinetics of anthracite with added chlorine

The combustion process of Yangquan anthracite（YQ） with the addition of 0.045wt%, 0.211wt%, 1.026wt%, and 2.982wt% chlorine was investigated using a thermogravimetric method from an ambient temperature to 1173 K in an air atmosphere. Results show that the YQ combustion characteristics are not significantly affected by an increase in chlorine content. Data acquired for combustion conversion are then further processed for kinetic analysis. Average apparent activation energies determined using the model-free method（specifically the KAS method） are 103.025, 110.250, 99.906, and 110.641 k J/mol, respectively, and the optimal kinetic model for describing the combustion process of chlorine-containing YQ is the nucleation kinetic model, as determined by the z（α） master plot method. The mechanism function of the nucleation kinetic model is then employed to estimate the pre-exponential factor, by making use of the compensation effect. The kinetic models to describe chlorine-containing YQ combustion are thus obtained through advanced determination of the optimal mechanism function, average apparent activation energy, and the pre-exponential factor.

Magnesium-containing pellet regulating blast furnace ferrous burden interaction:softening-melting behavior and mechanism

MgO participates in all stages of sintering,pelletizing,and blast furnace ironmaking,and synergistically optimizing the distribution of MgO in ferrous burden can effectively enhance the interaction within the ferrous burdens and optimize the softening-melting properties of the mixed burden.Magnesium-containing pellets mixed with low-MgO sinter or mixed with high-MgO sinter in the blast furnace ferrous burden structure have opposite softening-melting performance laws.When the structure of the ferrous burden is magnesium-containing pellets mixed with low-MgO sinter,the magnesium-containing pellets can enhance the interaction of the ferrous burden in the process of softening-melting,which can optimize the composition of the slag phase and improve the slag liquidity.When the structure of the ferrous burden is magnesium-containing pellets mixed with high-MgO sinter,the magnesium-containing pellets weaken the interaction of the ferrous burden in the process of softening-melting,increase the content of the high melting point solid-phase particles in the slag,lead to an increase in the viscosity of the slag and difficult separation of the slag and iron,and decrease the permeability of the charge layer.Therefore,to ensure good permeability of the mixed burden,the following measures are suggested:optimizing the MgO distribution of the ferrous burden,reducing the MgO content of the sinter to 1.96 wt.%,increasing the MgO content of the pellets to 1.03-1.30 wt.%,controlling the MgO/Al_(2)O_(3) ratio of the mixed burden within 1.15-1.32,narrowing the position of the cohesive zone,and maintaining an S value(permeability index)of approximately 150 kPa℃.

Mineralogical properties and co-sintering characteristics of fluxed iron ore with magnetite concentrates

To investigate the feasibility of co-sintering of fluxed iron ore with magnetite concentrates, the mineralogical properties of a novel fluxed iron ore were studied using particle size analysis, microscopic morphology characterization, and X-ray diffraction Rietveld analysis. Following that, the experiments for granulation performance and basic sintering characteristics were designed under seven different fluxed iron ore ratios, and the integrated ranking of different fluxed iron ore ratios was determined using gray relation analysis. Finally, the results of the industrial trails were combined with the feasibility analysis. Test and experimental results show that the fraction of the fluxed iron ore particles larger than 0.5 mm can account for more than 48%, and the particles have two morphologies: spherical-rough and flaky-smooth. Ca elements are found in the form of calcite (CaCO3) and dolomite (CaMg(CO3)2). The average particle size of granules and powder removal rate can be improved from 2.50 to 3.16 mm and 39.60% to 24.20%, respectively, with the increase in the fluxed iron ore ratio. Furthermore, the fluxed iron ore can improve assimilability and liquid fluidity of magnetite concentrates. In terms of overall granulation performance and sintering characteristics, the fluxed iron ore ratios are graded from best to worst as follows: 12%, 15%, 9%, 18%, 21%, 6% and 3%. The industrial trails show that when the fluxed iron ore ratio is increased, the beneficial effect of the superior sintering characteristics of the fluxed iron ore itself is ideally balanced with the negative effect of the lower amount of additional CaO at 12% ratio, and thus, it is feasible to bring the fluxed iron ore into production at a level of roughly 12%.

Proposing a machine learning approach to analyze and predict basic high-temperature properties of iron ore fines and its factors

The basic high-temperature properties of iron ore play a crucial role in optimizing sintering and ore blending,but the testing process for these properties is complex and has significant lag time,which cannot meet the actual needs of ore blending.A prediction model for the basic high-temperature properties of iron ore fines was thus proposed based on a combination of machine learning algorithms and genetic algorithms.First,the prediction accuracy of different machine learning models for the basic high-temperature properties of iron ore fines was compared.Then,a random forest model optimized by genetic algorithms was built,further improving the prediction accuracy of the model.The test results show that the random forest model optimized by genetic algorithms has the highest prediction accuracy for the lowest assimilation temperature and liquid phase fluidity of iron ore,with a determination coefficient of 0.903 for the lowest assimilation temperature and 0.927 for the liquid phase fluidity after optimization.The trained model meets the fluctuation requirements of on-site testing and has been successfully applied to actual production on site.

O_(2) adsorption on Fe_(3)O_(4) (110) surface and effect of gangue element Al doping: combined study of binding experiment and ab initio molecular dynamics

At high temperature,the chemical reaction mechanism at the interface of magnetite and the influence mechanism of gangue element Al on the oxidation performance of magnetite are not clear.In addition,due to the limitation of existing experimental equipment,it is difficult to clarify the interface reaction mechanism in the oxidation process and the influence mechanism of Al on the surface oxidation reaction of Fe_(3)O_(4) at an atomic scale at high temperature.The surface oxidation reaction mechanism of magnetite and the influence mechanism of Al on the oxidation of magnetite were studied by experiments and AIMD(ab initio molecular dynamics).The experimental results show that the existence of Al_(2)O_(3) will reduce the initial oxidation temperature and comprehensive oxidation performance of magnetite.The AIMD results show that aluminum can accelerate the interface reaction rate of Fe_(3)O_(4) in the high-temperature oxidation atmosphere,but the strong Al-O binding ability is not conducive to the transfer of O atoms in the oxidation process.