Pore structure evolution during the coke graphitization process in a blast furnace

Pore structure is an important factor influencing coke strength, while the property of coke is essential to maintaining gas and liquid permeability in a blast furnace. Therefore, an in-depth understanding of the pore structure evolution during the graphitization process can reveal the coke size degradation behavior during its descent in a blast furnace. Coke graphitization was simulated at different heating temperatures from 1100 to 1600℃ at intervals of 100℃. The quantitative evaluation of the coke pore structure with different graphitization degree was determined by vacuum drainage method and nitrogen adsorption method. Results show that the adsorption and desorption curves of graphitized coke have intersection points, and the two curves did not coincide, instead forming a "hysteresis loop." Based on the hysteresis loop analysis, the porous structure of the graphitized coke mostly appeared in the shape of a "hair follicle." Furthermore, with an increase in heating temperature, the apparent porosity, specific surface area, total pore volume, and amount of micropores showed good correlation and can divided into three stages: 1100–1200, 1200–1400, and 1400–1600℃. When the temperature was less than 1400℃, ash migration from the inner part mainly led to changes in the coke pore structure. When the temperature was greater than 1400℃, the pore structure evolution was mainly affected by the coke graphitization degree. The results of scanning electron microscopy, energy dispersive spectrometry, and ash content analyses also confirmed that the migration of the internal ash to the surface of the matrix during the graphitization process up to 1400℃ contributed to these changes.     

Gasification kinetics of bulk coke in the CO2/CO/H2/H2O/N2 system simulating the atmosphere in the industrial blast furnace

The gasification characteristics and gasification kinetics of coke in complex CO₂/CO/H₂/H₂O/N₂ systems similar to the gas system of industrial blast furnace (BF) were studied by the method of isothermal thermogravimetric analysis. The experimental gas compositions and the corresponding temperature were chosen according to data reported for industrial BFs. The gasification behavior of coke was described by the Random Pore Model (RPM), Volumetric Model (VM), and Grain Model (GM). Results showed that the gas composition of the coke gasification zone in BF changes slightly and that the temperature is the most important factor affecting coke gasification. The lower activation energy of coke samples (Coke Reaction Index (CRI) > 50) is due to the high Fe₂O₃ in the ash, lower degree of graphitization, and larger pore structure. In addition, the choice of kinetic model does not differ substantially in describing the gasification mechanism of coke in a BF.     

Synthesis of aluminum nitride in a coke – calcium reduction bed using nitrogen in air

An experimental study on the heating of a mixture of aluminum and lithium hydroxide(LiOH) powders in a reductive bed under air atmosphere is reported. The formation of aluminum nitride(AlN) during this process was the focus of this study. The formation of Al N was achieved using LiOH as an additive and heating the sample in a resistance furnace in a specially designed double crucible within a bed of a mixture of coke and filamentous calcium. The temperature range of the reaction was between 700°C and 1100°C. The optimum temperature of 1100°C and the optimum Li OH amount(5wt%) required to achieve maximum yield were determined by powder X-ray diffraction(XRD) analysis. Scanning electron microscopy(SEM) micrographs clearly indicated the transformation of grain structures from rods(700°C) to cauliflower shapes(1100°C).     

Synthesis of aluminum nitride in a coke-calcium reduction bed using nitrogen in air

An experimental study on the heating of a mixture of aluminum and lithium hydroxide (LiOH) powders in a reductive bed under air atmosphere is reported. The formation of aluminum nitride (AlN) during this process was the focus of this study. The formation of AlN was achieved using LiOH as an additive and heating the sample in a resistance furnace in a specially designed double crucible within a bed of a mixture of coke and filamentous calcium. The temperature range of the reaction was between 700°C and 1100°C. The optimum tem-perature of 1100°C and the optimum LiOH amount (5wt%) required to achieve maximum yield were determined by powder X-ray diffrac-tion (XRD) analysis. Scanning electron microscopy (SEM) micrographs clearly indicated the transformation of grain structures from rods (700°C) to cauliflower shapes (1100°C).     

The fate of injectant coal in blast furnaces: The origin of extractable materials of high molecular mass in blast furnace carryover dusts

The aim of the work was to investigate the fate of injectant coal in blast furnaces and the origin of extractable materials in blast furnace carryover dusts. Two sets of samples including injectant coal and the corresponding carryover dusts from a full sized blast furnace and a pilot scale rig have been examined. The samples were extracted using 1-methyl-2-pyrrolidinone (NMP) solvent and the extracts studied by size exclusion chromatography (SEC). The blast furnace carryover dust extracts contained high molecular weight carbonaceous material, of apparent mass corresponding to 10⁷?10⁸ u, by polystyrene calibration. In contrast, the feed coke and char prepared in a wire mesh reactor under high temperature conditions did not give any extractable material. Meanwhile, controlled combustion experiments in a high-pressure wire mesh reactor suggest that the extent of combustion of injectant coal in the blast furnace tuyeres and raceways is limited by time of exposure and very low oxygen concentration. It is thus likely that the extractable, soot-like material in the blast furnace dust originated in tars is released by the injectant coal. Our results suggest that the unburned tars were thermally altered during the upward path within the furnace, giving rise to the formation of heavy molecular weight (soot-like) materials.     

用焦煤和氧化钙制备含CaO碳球团: 热解炉中温度、孔分布和碳结构对球团抗压强度的影响

CaO-containing carbon pellets (CCCP) were successfully prepared from well-mixed coking coal (CC) and calcium oxide (CaO) and roasted at different pyrolysis temperatures. The effects of temperature, pore distribution, and carbon structure on the compressive strength of CCCP was investigated in a pyrolysis furnace (350–750°C). The results showed that as the roasting temperature increased, the compressive strength also increased and furthermore, structural defects and imperfections in the carbon crystallites were gradually eliminated to form more organized char structures, thus forming high-ordered CC. Notably, the CCCP preheated at 750°C exhibited the highest compressive strength. A positive relationship between the compressive strength and pore-size homogeneity was established. A linear relationship between the compressive strength of the CCCP and the average stack height of CC was observed. Additionally, a four-stage caking mechanism was developed.     

Preparation of CaO-containing carbon pellets from coking coal and calcium oxide: Effects of temperature,pore distribution and carbon structure on compressive strength in pyrolysis furnace

CaO-containing carbon pellets(CCCP) were successfully prepared from well-mixed coking coal(CC) and calcium oxide(CaO) and roasted at different pyrolysis temperatures. The effects of temperature, pore distribution, and carbon structure on the compressive strength of CCCP was investigated in a pyrolysis furnace(350–750°C). The results showed that as the roasting temperature increased, the compressive strength also increased and furthermore, structural defects and imperfections in the carbon crystallites were gradually eliminated to form more organized char structures, thus forming high-ordered CC. Notably, the CCCP preheated at 750°C exhibited the highest compressive strength. A positive relationship between the compressive strength and pore-size homogeneity was established. A linear relationship between the compressive strength of the CCCP and the average stack height of CC was observed. Additionally, a four-stage caking mechanism was developed.     

基于低镁烧结矿和熔剂性球团的综合炉料熔滴性能研究

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 1.31wt% to 1.55wt%, the melting temperature of sinter increased to 1521°C. Such an increase was due to the formation of the high-melting-point slag phase. The reduction degradation index of sinter with 1.31wt% MgO content was better than that of others. The initial softening temperature of the mixed burden increased from 1104 to 1126°C as MgO content in sinter increased from 1.31wt% to 1.55wt%, and the melting temperature decreased from 1494 to 1460°C. The permeability index (S-value) of mixed burden decreased to 594.46 kPa·°C under a high MgO content with 1.55wt%, indicating that the permeability was improved. The slag phase composition of burden was mainly akermarite (Ca₂MgSiO₇) when the MgO content in sinter was 1.55wt%. The melting point of akermarite is 1450°C, which is lower than other phases.     

Feedback control strategy of longitudinal temperature and finished carbonization time for coke oven and its application

Based on the detailed analysis of the third coke oven in BaoSteel, a feedback control strategy of longitudinal temperature and finished carbonization time of coke ovens was proposed and it was applied to the third coke oven in BaoSteel. As a result, the ratio of the instance that the absolute deviation of the longitudinal temperature is within ±7°C and the finished carbonization time within ± 10 min is more than 80%, having acquired the patent saving effect of an energy consumption lowered by 2.92%. At the same time, it can provide an example for the same coke ovens inside and outside the nation.     

Micromorphology and safety properties of meager and meager-lean coal for blast furnace injection

Four types of meager and meager-lean coal and one type of high-quality anthracite were selected based on the safety requirements for blast furnace coal injection and domestic coal quality to conduct microstructure and component analyses.The analyses of the organic and inorganic macerals and the chemical compositions of the selected coal samples indicate that the four types of meager and meager-lean coal have low volatilization,low ash content,and low sulfur content;these qualities are suitable for blast furnace injection.Grindability test was conducted on the four types of meager and meager-lean coal and the anthracite mixed coal samples.Results indicate that the mixture of meager and meager-lean coal and anthracite is beneficial to improve the grindability of pulverized coal.The explosive tests reveal that the selected coal samples are non-explosive or weakly explosive.When the proportion of meager and meager-lean coal is less than 40wt%,the mixed coal powder would not explode during the blowing process.The minimum ignition temperature test determines that the minimum ignition temperatures of the four types of meager and meager-lean coal and anthracite are 326,313,310,315,and 393°C,respectively.This study provides a guiding research idea for the safety of meager and meager-lean coal used in blast furnace injection.     

高炉炼铁数据的异常值处理

Blast furnace data processing is prone to problems such as outliers. To overcome these problems and identify an improved method for processing blast furnace data, we conducted an in-depth study of blast furnace data. Based on data samples from selected iron and steel companies, data types were classified according to different characteristics; then, appropriate methods were selected to process them in order to solve the deficiencies and outliers of the original blast furnace data. Linear interpolation was used to fill in the divided continuation data, the K-nearest neighbor (KNN) algorithm was used to fill in correlation data with the internal law, and periodic statistical data were filled by the average. The error rate in the filling was low, and the fitting degree was over 85%. For the screening of outliers, corresponding indicator parameters were added according to the continuity, relevance, and periodicity of different data. Also, a variety of algorithms were used for processing. Through the analysis of screening results, a large amount of efficient information in the data was retained, and ineffective outliers were eliminated. Standardized processing of blast furnace big data as the basis of applied research on blast furnace big data can serve as an important means to improve data quality and retain data value.     

Effect of CO<Subscript>2</Subscript> and H<Subscript>2</Subscript>O on gasification dissolution and deep reaction of coke

To more comprehensively analyze the effect of CO₂ and H₂O on the gasification dissolution reaction and deep reaction of coke, the reactions of coke with CO₂ and H₂O using high temperature gas-solid reaction apparatus over the range of 950-1250℃ were studied, and the thermodynamic and kinetic analyses were also performed. The results show that the average reaction rate of coke with H₂O is about 1.3-6.5 times that with CO₂ in the experimental temperature range. At the same temperature, the endothermic effect of coke with H₂O is less than that with CO₂. 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 CO₂ and H₂O 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.     

Microstructure and properties of high emissivity coatings

A new coating on lining in industrial furnace for energy saving has been developed. Properties and microstructure of the coatings were revealed by emissivity instrument,X-ray diffraction (XRD),transmission electron microscope (TEM) and scanning electron microscope (SEM),respectively. The result indicates that the emissivity of coatings is higher than 0.90 and the thickness of coatings is about 200 μm. ZrO₂,Cr₂O₃ and SiC in the coating benefit practical applications of coatings at high temperature with durable high emissivity and the continuous structure between the coatings and the substrate makes the coatings high cohesion and excellent adhesion for both specimens with and without sintering at high temperature. Result from laboratory experiment shows that the heating speed of specimen with coating is higher than that of controlled specimen and the temperature increases 30℃ during the heating. The average temperature drop of specimen with coatings has a 13.5% improvement in the cooling speed. The application of coatings on the checker brick in a blast furnace of 1750m3 indicates that the coating causes the blast temperature to an average increase of 28℃,reduces the fluctuation of blast temperature before the blowing-in and leads to a fuel saving of 10% approximately.     

An Improved Artificial Neural Network Model for Predicting Silicon Content of Blast Furnace Hot Metal

Based on the skills of initializing weight distribution, adding an impulse in a neural network and expanding the ideal of plural weights, an artificial neural network model with three connection weights between one and another neural unit was established to predict silicon content of blast furnace hot metal. After the neural network was trained in the off-line state on the basis of a large number of practical data of a commercial blast furnace and making many learning patterns, satisfactory testing and simulating results of the model were obtained.     

利用赤泥与烟气脱硫粉煤灰制备道路基材及其耐久性和微观结构的分析

The present study aimed to investigate the durability and microstructure evolution of road base materials (RBM) prepared from red mud and flue gas desulfurization fly ash. The durability testing showed that the strength of RBM with the blast furnace slag addition of 1wt%, 3wt% and 5wt% reached 3.81, 4.87, and 5.84 MPa after 5 freezing–thawing (F–T) cycles and reached 5.21, 5.75, and 6.98 MPa after 20 weting–drying (W–D) cycles, respectively. The results also indicated that hydration products were continuously formed even during W–D and F–T exposures, resulting in an increase of the strength and durability of RBM. The observed increase of macropores (>1 μm) after F–T and W–D exposures suggested that the mechanism of RBM deterioration is pore enlargement due to cracks that develop inside their matrix. Moreover, the F–T exposure showed a greater negative effect on the durability of RBM compared to the W–D exposure. The leaching tests showed that sodium and heavy metals were solidified below the minimum requirement, which indicates that these wastes are suitable for use as a natural material replacement in road base construction.     

烧结铁矿中FeO含量对其在富氢高炉中还原行为的影响

Japan started the national project “COURSE 50” for CO₂ reduction in the 2000s. This project aimed to establish novel technologies to reduce CO₂ emissions with partially utilization of hydrogen in blast furnace-based ironmaking by 30% by around 2030 and use it for practical applications by 2050. The idea is that instead of coke, hydrogen is used as the reducing agent, leading to lower fossil fuel consumption in the process. It has been reported that the reduction behavior of hematite, magnetite, calcium ferrite, and slag in the sinter is different, and it is also considerably influenced by the sinter morphology. This study aimed to investigate the reduction behavior of sinters in hydrogen enriched blast furnace with different mineral morphologies in CO–CO₂–H₂ mixed gas. As an experimental sample, two sinter samples with significantly different hematite and magnetite ratios were prepared to compare their reduction behaviors. The reduction of wustite to iron was carried out at 1000, 900, and 800°C in a CO–CO₂–H₂ atmosphere for the mineral morphology-controlled sinter, and the following findings were obtained. The reduction rate of smaller amount of FeO led to faster increase of the reduction rate curve at the initial stage of reduction. Macro-observations of reduced samples showed that the reaction proceeded from the outer periphery of the sample toward the inside, and a reaction interface was observed where reduced iron and wustite coexisted. Micro-observations revealed three layers, namely, wustite single phase in the center zone of the sample, iron single phase in the outer periphery zone of the sample, and iron oxide-derived wustite FeO and iron, or calcium ferrite-derived wustite 'FeO' and iron in the reaction interface zone. A two-interface unreacted core model was successfully applied for the kinetic analysis of the reduction reaction, and obtained temperature dependent expressions of the chemical reaction coefficients from each mineral phases.     

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, and distribution. Furthermore, the formation mechanism of the protective layer was determined after clarifying the source of each component. Finally, a technical strategy was proposed for achieving a stable protective layer in the hearth. The results show that the protective layer mainly exists in a bilayer form in the sidewall, namely, a titanium-bearing layer and a graphite layer. Both the layers contain the slag phase whose major crystalline phase is magnesium melilite (Ca₂MgSi₂O₇) and the main source of the slag phase is coke ash. It is clearly determined that solid particles such as graphite, Ti(C,N) and MgAl₂O₄ play an important role in the formation of the protective layer, and the key factor for promoting the formation of a stable protective layer is reasonable control of the evolution behavior of coke.     

Fe–0.3C–9Mn–2Al中锰钢的热塑性行为

The hot ductility of a Fe–0.3C–9Mn–2Al medium Mn steel was investigated using a Gleeble3800 thermo-mechanical simulator. Hot tensile tests were conducted at different temperatures (600–1300°C) under a constant strain rate of 4 × 10?3 s?1. The fracture behavior and mechanism of hot ductility evolution were discussed. Results showed that the hot ductility decreased as the temperature was decreased from 1000°C. The reduction of area (RA) decreased rapidly in the specimens tested below 700°C, whereas that in the specimen tested at 650°C was lower than 65%. Mixed brittle–ductile fracture feature is reflected by the coexistence of cleavage step, intergranular facet, and dimple at the surface. The fracture belonged to ductile failure in the specimens tested between 720–1000°C. Large and deep dimples could delay crack propagation. The change in average width of the dimples was in positive proportion with the change in RA. The wide austenite–ferrite intercritical temperature range was crucial for the hot ductility of medium Mn steel. The formation of ferrite film on austenite grain boundaries led to strain concentration. Yield point elongation occurred at the austenite–ferrite intercritical temperature range during the hot tensile test.     

Topography,structure,and formation kinetic mechanism of carbon deposited onto nickel in the temperature range from 400 to 850°C

The carbon deposition behavior on nickel particles was observed within the temperature range from 400 to 800°C in a pure methane atmosphere.The topography,properties,and molecular structure of the deposited carbon were investigated using field-emission scanning electron microscopy(FESEM),temperature-programmed oxidation(TPO) technology,X-ray diffraction(XRD),and Raman spectroscopy.The deposited carbon is present in the form of a film at 400–450°C,as fibers at 500–600°C,and as particles at 650–800°C.In addition,the structure of the deposited carbon becomes more ordered at higher temperatures because both the TPO peak temperature of deposited carbon and the Raman shift of the G band increase with the increase in experimental temperature,whereas the intensity ratio between the D bands and the G band decreases.An interesting observation is that the carbon deposition rate is suppressed in the medium-temperature range(M-T range) and the corresponding kinetic mechanism changes.Correspondingly,the FWHM of the G and D1 bands in the Raman spectrum reaches a maximum and the intensities of the D2,D3,and D4 bands decrease to low limits in the M-T range.These results indicate that carbon structure parameters exhibit two different tendencies with respect to varying temperature.Both of the two group parameters change dramatically as a peak function with increasing reaction temperature within the M-T range.     

Study of a ceramic burner for shaftless stoves

A multi-burner-port annular flameless ceramic burner (MAFCB) of the shaftless stove for blast furnaces was designed. The characteristics of pressure drop, homogeneousness of the flows at burner ports, and distribution of the flows in the chambers and joint were studied by cold model experiments. This type of ceramic burner was successfully applied in 6# blast furnace at Liuzhou Iron & Steel Co. Ltd. (LISC) and this practice proved that it could be used in the hot blast stove and other stoves with a higher efficiency and a higher steadiness of hot blast temperature at 1200℃. With the combustion of blast furnace gas alone, the thermal efficiency was up to 78.95%, saving energy remarkably.