Reduction kinetics of iron oxide pellets with H_2 and CO mixtures

Reduction of hematite pellets using H2-CO mixtures with a wide range of H2/CO by molar （1：0, 3：1, 1：1, 1：3, and 0：1） at different reducing temperatures （1073, 1173, and 1273 K） was conducted in a program reducing furnace. Based on an unreacted core model, the effective diffusion coefficient and reaction rate constant in several cases were determined, and then the rate-control step and transition were analyzed. In the results, the effective diffusion coefficient and reaction rate constant increase with the rise in temperature or hydrogen content. Reduction of iron oxide pellets using an H2-CO mixture is a compound control system; the reaction rate is dominated by chemical reaction at the very beginning, competition during the reduction process subsequently, and internal gas diffusion at the end. At low hydrogen content, increasing temperature takes the transition point of the rate-control step to a high reduction degree, but at high hydrogen content, the effect of temperature on the transition point weakens.

Comparison of kinetic models for isothermal CO_2 gasification of coal char–biomass char blended char

This study investigated the isothermal gasification reactivity of biomass char （BC） and coal char （CC） blended at mass ratios of 1：3, 1：1, and 3：1 via isothermal thermogravimelric analysis （TGA） at 900, 950, and 1000℃ under CO2. With an increase in BC blending ra- tio, there were an increase in gasification rate and a shortening of gasification time. This could be attributed to the high specific surface area of BC and the high uniformity of carbon structures in CC when compared to those in BC. Three representative gas-solid kinetic models, namely, the volumetric model （VM）, grain model （GM）, and random pore model （RPM）, were applied to describe the reaction behavior of the char. Among them, the RPM model was considered the best model to describe the reactivity of the char gasification reaction. The activa- tion energy of BC and CC isothermal gasification as determined using the RPM model was found to be 126.7 kJ/mol and 210.2 kJ/mol, re- spectively. The activation energy was minimum （123.1 kJ/mol） for the BC blending ratio of 75%. Synergistic effect manifested at all mass ratios of the blended char, which increased with the gasification temperature.

Using HyperCoal to prepare metallurgical coal briquettes via hot-pressing

HyperCoal was prepared from low-rank coal via high-temperature solvent extraction with N-methylpyrrolidone as an extraction solvent and a liquid-to-solid ratio of 50 mL/g in a high-temperature and high-pressure reactor. When HyperCoal was used as a binder and pulverized coal was used as the raw material, the compressive strength of the hot-pressed briquettes(each with a diameter of 20 mm and mass of 5 g) under different conditions was studied using a hot-pressing mold and a high-temperature furnace. The compressive strength of the hot-pressed briquettes was substantially improved and reached 436 N when the holding time period was 15 min, the hot-pressing temperature was 673 K, and the HyperCoal content, was 15 wt%. Changes in the carbonaceous structure, as reflected by the intensity ratio between the Raman G-and D-bands(IG/ID), strongly affected the compressive strength of hot-pressed briquettes prepared at different hot-pressing temperatures. Compared with cold-pressed briquettes, hot-pressed briquettes have many advantages, including high compressive strength, low ash content, high moisture resistance, and good thermal stability; thus, we expect that hot-pressed briquettes will have broad application prospects.

The mechanism and products for co-thermal extraction of biomass and low-rank coal with NMP

The high-value utilization of low-rank coal would allow for expanding energy sources,improving energy efficiencies,and alleviating environmental issues.In order to use low-rank coal effectively,the hypercoals(HPCs)were co-extracted from two types of low-rank coal and biomass via N-methyl-2-purrolidinone(NMP)under mild conditions.The structures of the HPCs and residues were characterized by proximate and ultimate analysis,Raman spectra,and Fourier transform infrared(FT-IR)spectra.The carbon structure changes within the raw coals and HPCs were discussed.The individual thermal dissolution of Xibu(XB)coal,Guandi(GD)coal,and the biomass demonstrated that the biomass provided the lowest thermal dissolution yield Y1 and the highest thermal soluble yield Y2 at 280℃,and the ash content of three HPCs decreased as the extraction temperature rose.Co-thermal extractions in NMP at various coal/biomass mass ratios were performed,demonstrating a positive synergic effect for Y2 in the whole coal/biomass mass ratios.The maximum value of Y2 was 52.25wt% for XB coal obtained with a XB coal/biomass of 50wt% biomass.The maximum value of Y2 was 50.77wt% for GD coal obtained with a GD coal/biomass of 1:4.The difference for the optimal coal/biomass mass ratios between XB and GD coals could be attributed to the different co-extraction mechanisms for this two type coals.

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.

Load reduction sintering for increasing productivity and decreasing fuel consumption

The technical and economical indexes and the physical properties of load reduction sintering processes with the supporting stands of installation at different height levels （300, 350, and 400 mm）： in a sintering bed were studied under the same conditions of raw material, bed height, and sintering parameters. Sintering pot tests with different bed heights and fuel ratios of the mixture with or without supporting stands were performed to decrease the fuel consumption. The airflow rate through the sintering bed was measured with an anemoscope fixed on the bed surface to reveal the effects of supporting stands. The utilization of load reduction sintering can improve the permeability of the sintering bed, and the airflow rate through the sintering bed is increased. When the stand height is half of the sintering bed, the productivity increases by 27.9%, and the drum index slightly decreases. Keeping at the same productivity level with normal sintering, the utilization of load reduction sintering can decrease the solid fuel consumption by 9.2%.

Innovative method for boron extraction from iron ore containing boron

A novel process for boron enrichment and extraction from ludwigite based on iron nugget technology was proposed. The key steps of this novel process, which include boron and iron separation, crystallization of boron-rich slag, and elucidation of the boron extraction be- havior of boron-rich slag by acid leaching, were performed at the laboratory. The results indicated that 95.7% of the total boron could be en- riched into the slag phase, thereby forming a boron-rich slag during the iron and slag melting separation process. Suanite and kotoite were observed to be the boron-containing crystalline phases, and the boron extraction properties of the boron-rich slag depended on the amounts and grain sizes of these minerals. When the boron-rich slag was slowly cooled to 1100℃, the slag crystallized well and the efficiency of ex- traction of boron （EEB） of the slag was the highest observed in the present study. The boron extraction property of the slow-cooled bo- ron-rich slag obtained in this study was much better than that of szaibelyite ore under the conditions of 80% of theoretical sulfuric acid amount, leaching time of 30 min, leaching temperature of 40℃ ,and liquid-to-solid ratio of 8 mL/g.

Exploring a new path of green and efficient utilization of sinter return fine to produce composite pellets

Efficient utilization of sinter return fine is an important measure to reduce cost,increase efficiency,save energy and reduce emission.A new path of green and efficient utilization of return fine was proposed to produce composite pellets.The metallurgical properties of composite pellets under the condition of hydrogen-rich blast furnace were studied.The experimental results indicate that the coated concentrate was consolidated for the composite pellets through normal Fe_(2)O_(3) recrystallization.Near the surface of core return fine,the liquid phase formed due to its low-melting point,assimilated the adjacent concentrate,and then consolidated with the temperature decreasing.Compared with regular pellets,the com-pressive strength and reduction swelling index of composite pellets were decreased,but the reducibility index and softening-melting properties were improved.In addition,the reduction degradation index of composite pellets was sig-nificantly higher than that of sinter.Therefore,adding composite pellets was conducive to indirect reduction in blast furnace,reducing fuel ratio and improving production efficiency.According to the effect of the roasting system on the metallurgical properties,the roasting temperature and time were determined as 1250℃and 30 min,respectively.The composite pellets can be produced under the traditional pelletizing process.

Improving mathematical model of burden distribution and correcting chute angle to cope with fluctuation of stock line

Accurate evaluations of the burden distribution are of critical importance to stabilize the operation of blast furnace.The mathematical model and discrete element method(DEM)are two attractive methods for predicting burden distribution.Based on DEM,the initial velocities of the pellet,sinter,and coke were calculated,and the velocity attenuations of the above three particles between the burden and the chute were analyzed.The initial velocity and velocity attenuation were applied to a mathematical model for improving the accuracy.Additionally,based on the improved model,a scheme for rectifying the chute angles was proposed to address the fluctuation of the stock line and maintain a stable burden distribution.The validity of the scheme was confirmed via a stable burden distribution under different stock lines.The mathematical model has been successfully applied to evaluate the online burden distribution and cope with the fluctuation of the stock line.

Effect of atmosphere and basicity on softening-melting behavior of primary slag formation in cohesive zone

The softening-melting characteristics of ferrous burden play a crucial role in the thickness and position of the cohesive zone.The influence of the basicity and experimental atmosphere on the softening-melting behavior of primary slag under slag-coke interaction was investigated using in situ visualization method.The mechanism was analyzed using the FactSage software,X-ray diffraction,and electron probe microanalysis.The softening and melting temperatures of the samples increased with increasing basicity under different atmospheres.The difference between softening and melting temperatures is smaller in a H_(2) atmosphere than in a CO atmosphere;in H_(2) atmosphere,the range of softening zone in the cohesive zone was significantly thinner.The formed low-melting-point FeO-bearing phases decrease when H_(2) was used as the reducing agent.In addition,according to FactSage calculations,the high content of metallic iron reduced in the H_(2) atmosphere raised the softening temperature of the primary slag.It also narrowed and moved downward the cohesive zone due to an increase in softening and melting temperatures.Meanwhile,the increase in basicity promoted the decrease in liquid ratio and improved the permeability of cohesive zone.

Mathematical model of burden distribution in bell-less top blast furnace

The burden distribution in the shaft of blast furnace is known to affect the gas distribution,heat transfer,and chemical reactions inside the furnace.However,the internal layer structure of burden in the shaft cannot be directly measured.Hence,a mathematical model for evaluating burden profile and layer structure was established.A sensitivity analysis based on the model was implemented to elucidate the effect of some factors on the burden distribution,including the stockline height and the mass of central coke.The results show that the width of funnel zone widens with the increase in stockline height,and the mass percentage of ore to coke in this zone slightly increases.Besides,the mass of central coke shows a significant influence on the width of coke channel,and 2%of batch mass of coke is recommended to implement central coke charging operation.The model has been indirectly verified by the gas temperature in operating blast furnace and successfully applied to online evaluate burden distribution.

Softening and melting behaviors of ferrous burden in hydrogen-rich blast furnace cohesive zone

The changes in the softening and melting behaviors of ferrous burden in the cohesive zone and the characteristics of the slag–iron–coke interface in a blast furnace were investigated by simulating an actual blast furnace under hydrogen-rich conditions.According to the variation in the transient shrinkage of the burden under different atmospheres,the shrinkage start temperature of the sinter was higher than that of the pellets.The negative shrinkage rate of the pellets was greater than that of the sinter.Additionally,the softening start temperature in the blast furnace decreased under hydrogen-rich conditions,giving the blast furnace a broader range of softening zones.The softening start temperatures of the pellets and sinter decreased from 1102 to 949℃ and 1152 to 1080℃,respectively.The hydrogen-rich traditional blast furnace conditions narrowed the melting zone temperature range and shifted it toward the high-temperature zone,significantly improving the burden layer permeability.However,under the hydrogen-rich oxygen blast furnace conditions,there were a decrease in the melting start temperature,a shift of the melting zone location to the low-temperature zone,and an increase in the burden layer permeability and pressure difference.A comparison of the slag–iron–coke interface characteristics under different atmospheric conditions showed that the carbon content in metallic iron decreased under hydrogen-rich traditional blast furnace conditions compared with traditional blast furnace conditions.Contrastingly,under hydrogen-rich oxygen blast furnace conditions,the carbon content in metallic iron increased compared with oxygen blast furnace conditions.These findings provide guidance for the development of low-carbon ironmaking processes in blast furnaces.

Dissolution kinetics of solid fuels used in COREX gasifier and its influence factors

Carbon dissolution from solid fuels used in a COREX gasifier was investigated in a high-temperature furnace to investigate the influences of temperature, carbon structure and ash properties of solid fuels into molten iron on carbon dissolution behavior. The results showed that the final carbon content of molten iron and dissolution reaction rate of carbon increased as the temperature increased. However, the dissolution behavior of different solid fuels varied with their properties. At the same temperature, the dissolution reaction rate of solid fuel from high to low was coke, semi-coke and lump coal. The apparent reaction rate constants of solid fuel were calculated using the piecewise fitting method based on the experimental data. The analyzed results showed that the dissolution rates of solid fuels had a good correlation with their microcrystalline structures. Moreover, the carbon crystallite structures of solid fuels used in COREX had greater influence on dissolution behavior than their ash properties.

CO_2 Gasification Characteristics of High and Low Reactivity Cokes

In order to effectively utilize the high reactivity coke, the gasification characteristics of high and low reactivity cokes were investigated at 1100 ℃. Low reactivity coke A and high reactivity coke B were chosen and charged into the reaction tube in two methods. The results indicated that the mass loss ratio of high reactivity coke in mixed cokes was more significant than that of single high reactivity coke in the middle stage of reaction. Nevertheless, the mass loss ratio of low reactivity coke in mixed cokes was less than that of single low reactivity coke. It was mainly attributed to gas diffusion and internal reaction of coke. When high and low reactivity cokes were mixed, the practical average mass loss ratio was nearly the same as the weighted average. The microscopic structures of coke indicated that with the increase of reaction time, the external and internal layers of low reactivity coke reacted more uniformly with CO2, whereas the reaction degree of external layer of high reactivity coke was obviously higher.

Thermogravimetric Analysis of Coal Char Combustion Kinetics

Four chars prepared from pulverized coals were subjected to non-isothermal and isothermal combustion tests in a thermogravimetric analysis （TGA） device. Three different test methods, i. e. , non-isothermal single heat- ing rate （A）, non-isothermal multiple heating rate （B）, and isothermal test （C）, were conducted to calculate the ki- netic parameters of combustion of coal char. The results show that the combustion characteristics of bituminous coal char is better than that of anthracite char, and both increase of heating rate and increase of combustion temperature can obviously improve combustion characteristics of coal char. Activation energies of coal char combustion calculated by different methods are different, with activation energies calculated by methods A, B and C in the range of 103.12-- 153.77, 93.87--119.26, and 46.48--76.68 kJ/mol, respectively. By using different methods, activation energy of anthracite char is always higher than that of bituminous coal char. In non-isothermal tests, with increase of combus- tion temperature, the combustion process changed from kinetic control to diffusion control. For isothermal combus- tion, the combustion process was kinetically controlled at temperature lower than 580 ℃ for bituminous coal char and at temperature lower than 630 ℃ for anthracite char.

Mechanisms of Swelling of Iron Ore Oxidized Pellets in High Reduction Potential Atmosphere

The influences of the time, temperature and atmosphere on the reduction swelling of oxidized pellets were investigated by single factor experiments. The mechanisms of reduction swelling of oxidized pellets were analyzed and investigated by SEM （scanning electron microscopy） and XRD （X-ray diffractometer） analysis. The results show that the change rules of reduction swelling index of oxidized pellets in different reduction atmospheres are very similar. With the increase of reduction time, the reduction swelling index moves up firstly and then down. When the reduction temperature is above 900 ℃, α-quartz turns into α-tridymite, and the transition generates additional volume expansion effect. The reduction swelling index changes faster in H2 atmosphere than in CO atmosphere. Increasing Ha content in the reduction atmosphere is useful to decrease the reduction swelling index, but it is also easy to cause oxidized pellets cracking.

Microstructure evolution of coke under CO2 and H2O atmospheres

The microstructure of coke has an important influence on its thermal properties.The solution loss reactions of coke in CO2 and H2O atmospheres were investigated by in situ observation.The results showed that the isotropic components had a more vigorous reaction than the anisotropic components,and the solution loss reaction of the fine-grained mosaic structure was faster than that of the coarse-grained mosaic structure under the CO2 and H2O atmospheres.The coarse-grained mosaic structure and the flowing structure had a relatively higher anti-erosion ability in the CO2 atmosphere than in the H2O atmosphere,and there was no distinct difference in the solution loss of the isotropic structure under the CO2 and H2O atmospheres.The electron probe microanalysis showed that the Al-Si-Fe compounds in the carbon matrix had positive influence on the solution loss reaction of the anisotropic structure.The iron compounds were able to destroy the pore walls of coke and accelerate the solution loss rate of coke.

Comprehensive Mathematical Model and Optimum Process Parameters of Nitrogen Free Blast Furnace

According to different energy utilization in different regions, blast furnace is divided into raceway zone, bottom heat exchange zone （BHZ）, thermal reserve zone （TRZ）, and top heat exchange zone （THZ）, and a mathe- matical model of nitrogen free blast furnace （NF-BF） is established. The optimum process parameters of two kinds of nitrogen free blast furnaces are calculated by the new mathematical model. The results show that for the nitrogen free blast furnace with a single row of tuyeres, the optimum process parameters are coke ratio of 220 kg/t, coal ratio of 193 kg/t, and volume of recycling top gas of 577 m3/t; for two rows of tuyeres, the process parameters are coke ratio of 202 kg/t, coal ratio of 211 kg/t, volume of recycling top gas in upper area of 296 m3/t, and volume of recy- cling top gas in lower area of 295 ma/t. Energy balances are reached in different regions. Theoretical combustion temperature （TCT） in raceway zone is largely affected by different processes, and a lower TCT should be adopted for the single row of tuyeres, but for two rows of tuyeres, a higher TCT should be maintained. Compared with tradi- tional blast furnace, in NF-BF, the emission of CO2 would be reduced by 45.91% and 49.02G for a single row of tuyeres and two rows of tuyeres, respectively, and combined with CO2 sequestration technology, zero emission of CO2 could be realized.

Coking properties of thermal soluble constituents of coals by N-methyl-2-pyrrolidone solvent

Four types of coals, KL, XB, ZS and GD with different coal ranks, were dissolved with the organic solvent N-methyl-2- pyrrolidone at 350 ℃ and around 3.0 MPa pressure to obtain thermal soluble constituents （TSCs）. The yield, component and maceral group were investigated as well as their coking properties, including caking index and thermoplasticity. The results indicated that the yields of the four coals were of the following order： KL 〉 XB 〉 ZS 〉 GD. Based on the yield and the vitrinite content, coals were ranked from high to low. The ash contents of TSCs were significantly less than that of raw coals, and the TSCs contain more light components, leading to an increase in volatile matter. The patterns of Fourier transform infrared spectroscopy indicated that carbonyl was enriched in TSCs. Regarding the maceral group, TSCs were mainly composed of vitrinite which is the main reactive material and converts into binder phase in cokemaking process. Higher caking index values and fluidity were obtained in TSCs compared with the raw coals. The coking experiments with different amounts of TSCs addition were carried out. The results demonstrated that the proper TSCs addition could enhance the coke strength due to its high caking index and good fluidity.

Effect of quaternary basicity on softening-melting behavior of primary slag based on magnesium flux pellet

It is generally accepted that the softening-melting properties of ferrous burden play a vital role in optimizing the shape and position of cohesive zone.The effect of quaternary basicity and atmosphere on softening,melting and permeation temperatures of primary slag based on magnesium flux pellet was investigated by visualization method.The mechanisms were analyzed utilizing thermodynamic calculation,X-ray diffraction analysis and electron probe microanalysis.The results indicated that the softening and melting temperatures of oxide samples increased by approximately 120℃with increasing quaternary basicity from 0.3 to 1.2 owing to the formation of slag phases with high melting point and solid Fe.Meanwhile,the difference between softening and melting temperatures decreased from 21 to 11℃.The permeation temperature was not affected by the quaternary basicity and fluctuated around a level of 1250 C,given that the permeation temperature depends on the wettability between slag and coke bed.On the other hand,as the ratios of CO/CO_(2) varied from 3/7 to 7/3,there were no significant differences in either the softening or melting temperatures,whereas the permeation temperature was increased from 1239 to 1271℃ since the reduction of FeO-bearing phases to solid Fe could decrease the wettability between slag and coke bed.