Cross-upgrading of biomass hydrothermal carbonization and pyrolysis for high quality blast furnace injection fuel production:Physicochemical characteristics and gasification kinetics analysis

The paper proposes a biomass cross-upgrading process that combines hydrothermal carbonization and pyrolysis to produce high-quality blast furnace injection fuel.The results showed that after upgrading,the volatile content of biochar ranged from 16.19%to 45.35%,and the alkali metal content,ash content,and specific surface area were significantly reduced.The optimal route for biochar pro-duction is hydrothermal carbonization-pyrolysis(P-HC),resulting in biochar with a higher calorific value,C=C structure,and increased graphitization degree.The apparent activation energy(E)of the sample ranges from 199.1 to 324.8 kJ/mol,with P-HC having an E of 277.8 kJ/mol,lower than that of raw biomass,primary biochar,and anthracite.This makes P-HC more suitable for blast furnace injection fuel.Additionally,the paper proposes a path for P-HC injection in blast furnaces and calculates potential environmental benefits.P-HC of-fers the highest potential for carbon emission reduction,capable of reducing emissions by 96.04 kg/t when replacing 40wt%coal injec-tion.

Coke behavior with H_(2)O in a hydrogen-enriched blast furnace:A review

Hydrogen-enriched blast furnace ironmaking has become an essential route to reduce CO_(2)emissions in the ironmaking process.However,hydrogen-enriched reduction produces large amounts of H_(2)O,which places new demands on coke quality in a blast furnace.In a hydrogen-rich blast furnace,the presence of H_(2)O promotes the solution loss reaction.This result improves the reactivity of coke,which is 20%-30%higher in a pure H_(2)O atmosphere than in a pure CO_(2)atmosphere.The activation energy range is 110-300 kJ/mol between coke and CO_(2)and 80-170 kJ/mol between coke and H_(2)O.CO_(2)and H_(2)O are shown to have different effects on coke degradation mechanisms.This review provides a comprehensive overview of the effect of H_(2)O on the structure and properties of coke.By exploring the interactions between H_(2)O and coke,several unresolved issues in the field requiring further research were identified.This review aims to provide valuable insights into coke behavior in hydrogen-rich environments and promote the further development of hydrogen-rich blast furnace ironmaking processes.

Research progress and future prospects in the service security of key blast furnace equipment

The safety and longevity of key blast furnace(BF)equipment determine the stable and low-carbon production of iron.This pa-per presents an analysis of the heat transfer characteristics of these components and the uneven distribution of cooling water in parallel pipes based on hydrodynamic principles,discusses the feasible methods for the improvement of BF cooling intensity,and reviews the pre-paration process,performance,and damage characteristics of three key equipment pieces:coolers,tuyeres,and hearth refractories.Fur-thermoere,to attain better control of these critical components under high-temperature working conditions,we propose the application of optimized technologies,such as BF operation and maintenance technology,self-repair technology,and full-lifecycle management techno-logy.Finally,we propose further researches on safety assessments and predictions for key BF equipment under new operating conditions.

A Novel Sensing Imaging Equipment Under Extremely Dim Light for Blast Furnace Burden Surface:Starlight High-Temperature Industrial Endoscope

Blast furnace(BF)burden surface contains the most abundant,intuitive and credible smelting information and acquiring high-definition and high-brightness optical images of which is essential to realize precise material charging control,optimize gas flow distribution and improve ironmaking efficiency.It has been challengeable to obtain high-quality optical burden surface images under high-temperature,high-dust,and extremelydim(less than 0.001 Lux)environment.Based on a novel endoscopic sensing detection idea,a reverse telephoto structure starlight imaging system with large field of view and large aperture is designed.Combined with a water-air dual cooling intelligent self-maintenance protection device and the imaging system,a starlight high-temperature industrial endoscope is developed to obtain clear optical burden surface images stably under the harsh environment.Based on an endoscope imaging area model,a material flow trajectory model and a gas-dust coupling distribution model,an optimal installation position and posture configuration method for the endoscope is proposed,which maximizes the effective imaging area and ensures large-area,safe and stable imaging of the device in a confined space.Industrial experiments and applications indicate that the proposed method obtains clear and reliable large-area optical burden surface images and reveals new BF conditions,providing key data support for green iron smelting.

Process metallurgy and data-driven prediction and feedback of blast furnace heat indicators

The prediction and control of furnace heat indicators are of great importance for improving the heat levels and conditions of the complex and difficult-to-operate hour-class delay blast furnace(BF)system.In this work,a prediction and feedback model of furnace heat indicators based on the fusion of data-driven and BF ironmaking processes was proposed.The data on raw and fuel materials,process op-eration,smelting state,and slag and iron discharge during the whole BF process comprised 171 variables with 9223 groups of data and were comprehensively analyzed.A novel method for the delay analysis of furnace heat indicators was established.The extracted delay variables were found to play an important role in modeling.The method that combined the genetic algorithm and stacking efficiently im-proved performance compared with the traditional machine learning algorithm in improving the hit ratio of the furnace heat prediction model.The hit ratio for predicting the temperature of hot metal in the error range of±10℃ was 92.4%,and that for the chemical heat of hot metal in the error range of±0.1wt%was 93.3%.On the basis of the furnace heat prediction model and expert experience,a feedback model of furnace heat operation was established to obtain quantitative operation suggestions for stabilizing BF heat levels.These sugges-tions were highly accepted by BF operators.Finally,the comprehensive and dynamic model proposed in this work was successfully ap-plied in a practical BF system.It improved the BF temperature level remarkably,increasing the furnace temperature stability rate from 54.9%to 84.9%.This improvement achieved considerable economic benefits.

Extraction of Valuable Metals from Titanium-bearing Blast Furnace Slag by Acid Leaching

To realize the resource utilization of the valuable metals in the titanium-containing blast furnace slag,the process route of “hydrochloric acid leaching-electrolysis-carbonization and carbon dioxide capture-preparation of calcium carbonate” was proposed.In this study,the influences of process conditions on the leaching rates of calcium,magnesium,aluminum,and iron and the phases of the leaching residue were investigated for the leaching process.The experimental results show that the HCl solution could selectively leach the elements from the titanium-containing blast furnace slag.The better leaching conditions are the HCl solution concentration of 4 mol/L,the leaching time of 30 min,the ratio of liquid volume to solid gas of 10 mL/g,and the stirring paddle speed of 300 r/min.Under the conditions,the leaching rates of calcium,magnesium,aluminum,and iron can reach 85.87%,73.41%,81.35%,and 59.08%,and the leaching rate of titanium is 10.71%.The iron and the aluminum are removed from the leachate to obtain iron-aluminum water purification agents,and the magnesium is removed from the leachate to obtain magnesium hydroxide.The leaching residue phase is dominated by perovskite,followed by magnesium silicate and tricalcium aluminate,and the titaniumrich material could be obtained from the leaching residue by desiliconization.

Analysis and Prospect of Waste Heat Utilization from Blast Furnace Slag Flushing

Estimating the residual heat of blast furnace slag flushing in China,classifying and introducing the current proposed methods of slag flushing waste heat utilization,and listing existing cases.In order to better save energy and water in the slag flushing process of blast furnaces,an ideal comprehensive cascade utilization system scheme for annual recovery of waste heat is proposed.Based on the measured waste heat data of a steel plant,design calculations are carried out to further analyze the economic feasibility of the new scheme and provide reference for its promotion and application.

Preparation of UV-visible light responsive photocatalyst from titania-bearing blast furnace slag modified with(NH_4)_2SO_4

Sulfate-modified titanium dioxide-bearing blast furnace slag（STBBFS） photocatalysts were prepared by the high energy ball milling method with（NH4）2SO4 and titanium dioxide-bearing blast furnace slag（TBBFS） as raw materials.X-ray photoelectron spectroscopy（XPS）,X-ray diffraction（XRD）,scanning electron microscopy（SEM）,thermogravimetric analysis（TGA）,UV-visible diffuse reflectance absorption spectra（UV-Vis）,adsorption experiment and photocatalytic degradation measurement were conducted to characterize the structure,surface status,light absorption capacity,adsorption capacity and photocatalytic activity of the obtained photocatalysts.The adsorption equilibrium was described by the Langmuir isotherm model with a maximum adsorption capacity of 8.25 mg/g of Cr（VI） ions onto the STBBFS photocatalysts.As a result,sulfation of TBBFS improved the photocatalytic activities of STBBFSx photocatalysts.At a low calcination temperature,the photocatalytic activity of STBBFS300 photocatalyst was markedly higher compared with TBBFSx prepared at high calcination temperature,indicating that the photocatalytic activity of STBBFSx photocatalyst was determined by the balanced result between adsorption capacity and perovskite content.

Synthesis of (Ca, Mg)-α′-Sialon-AlN-BN powders from boron-rich blast furnace slag by microwave carbothermal reduction-nitridation

(Ca, Mg)-α′-Sialon-AlN-BN powders were synthesized by the carbothermal reduction and nitridation (CRN) method using boron-rich slag, one of the intermediate products from pyrometallurgy separation of pageit, as the staring material. The influences of synthesis temperature and holding time on the phase composition and microstructure during the microwave CRN were studied by XRD, SEM and EDS. The comparison between two heating techniques, conventional and microwave heating, on the synthesized powder was presented as well. The experimental results revealed that the phase compositions and microstructures of the synthesized products were greatly affected by the synthesis temperature and holding time. With an increase in the synthesis temperature or holding time, the relative amount of α′-Sialon increased and α′-Sialon became the main crystalline phase at 1400 °C for 6 h. The synthesized products also contained AlN, BN and a small amount of β-SiC. Elongated α′-Sialon grains, short rod AlN grains, aggregate nanoscale BN grains were observed in the synthesized powders. The reaction temperature of microwave heating method was reduced by 80 °C, the reaction time was shortened by 2 h, and more elongated α′-Sialon grains with large aspect ratio were observed.

Mechanism of zinc damaging to blast furnace tuyere refractory

The phenomena of tuyere upward-warp have been found at No.6 blast furnace in Kunming Steel Company China after its blow-in, which has made a great impact on the practical production of the furnace. Thus, a number of efforts have been made to elucidate the mechanism of this phenomenon. The results of investigation and tests revealed that the enrichment and expansion of zinc in the tuyere bricks is the main factor leading to the tuyere upward-warp. The eroding behavior of zinc is that the inner structure of the tuyere bricks turns from dense to loose with entering, enriching and expanding of zinc, which forms spot-like→stripe-like→ditch-like→vein-like→tumorlike eroding passage. Additionally, it is found that the sequence of deleterious ele- ments entering the tuyere refractory is K, Na, Zn and Pb, respectively. Finally, the phenomena and process of zinc crystallization and growth in the refractory have been clearly observed and recorded during this investigation.

Preparation,characterization and photocatalytic activity of sulfuric acid-modified titanium-bearing blast furnace slag

The feasibility of reducing Cr(VI)from the aqueous solution by sulfuric acid-modified titanium-bearing blast furnace slag(SATBBFS)as a photocatalyst was investigated.The photocatalysts were examined by X-ray diffraction(XRD),UV-vis diffuse reflectance spectra,thermogravimetric analysis(TG)and Fourier transform infrared spectroscopy(FTIR).The photocatalytic activities of the different catalysts were evaluated by the photocatalytic reduction of Cr(VI)under UV-vis light irradiation.The results show that the photocatalytic activities of SATBBFS catalysts are strongly dependent on CaTiO3-to-TiO2 mass ratio,adsorption capacity and surface acidity,and SATBBFS calcined at 400°C shows a higher photocatalytic activity compared with other catalysts.

Influence of aluminium nitride as a foaming agent on the preparation of foam glass-ceramics from high-titanium blast furnace slag

To effectively reuse high-titanium blast furnace slag （TS）, foam glass-ceramics were successfully prepared by powder sintering at 1000℃. TS and waste glass were used as the main raw materials, aluminium nitride （AIN） as the foaming agent, and borax as the fluxing agent. The influence of the amount of A1N added （lwt%-5wt%） on the crystalline phases, microstructure, and properties of the produced foam glass-ceramics was studied. The results showed that the main crystal phases were perovskite, diopside, and augite. With increasing A1N content, a transformation from diopside to augite occurred and the crystallinity of the pyroxene phases slightly decreased. Initially, the aver- age pore size and porosity of the foam glass-ceramics increased and subsequently decreased; similarly, their bulk density and compressive strength decreased and subsequently increased. The optimal properties were obtained when the foam glass-ceramics were prepared by adding 4wt% AIN.

Mechanisms of phosphate removal from aqueous solution by blast furnace slag and steel furnace slag

We report the adsorption of phosphate and discuss the mechanisms of phosphate removal from aqueous solution by burst furnace slag (BFS) and steel furnace slag (SFS). The results show that the adsorption of phosphate on the slag was rapid and the majority of adsorption was completed in 5~10 min. The adsorption capacity of phosphate by the slag was reduced dramatically by acid treatment. The relative contribution of adsorption to the total removal of phosphate was 26%~28%. Phosphate adsorption on BFS and SFS follows the Freundlich isotherm, with the related constants of k 6.372 and 1/n 1.739 for BFS, and of k 1.705 and 1/n 1.718 for SFS. The pH and Ca2+ concentration were decreased with the addition of phosphate, suggesting the formation of calcium phosphate precipitation. At pH 2.93 and 6.93, phosphate was desorbed by about 36%~43% and 9%~11%, respectively. These results indicate that the P adsorption on the slag is not completely reversible and that the bond between the slag particles and adsorbed phosphate is strong. The X-ray diffraction (XRD) patterns of BFS and SFS before and after phosphate adsorption verify the formation of phosphate salts (CaHPO4·2H2O) after adsorption process. We conclude that the removal of phosphate by BFS and SFS is related to the formation of phosphate calcium precipitation and the adsorption on hydroxylated oxides. The results show that BFS and SFS removed phosphate nearly 100%, indicating they are promising adsorbents for the phosphate removal in wastewater treatment and pollution control.

Simultaneous preparation of TiO2 and ammonium alum,and microporous SiO2 during the mineral carbonation of titanium-bearing blast furnace slag

In this study,a route for simultaneous mineralization of CO2 and production of titanium dioxide and ammonium alum,and microporous silicon dioxide from titanium-bearing blast furnace slag(TBBF slag)was proposed,which is comprised of(NH4)2 S04 roasting,acid leaching,ammonium alum crystallization,silicic acid flocculation and Ti hydrolysis.The effects of relevant process parameters were systematically investigated.The re sults showed that under the optimal roasting and leaching conditions about 85%of titanium and 84.6%of aluminum could be extracted while only 30%of silicon entered the leachate.84%of Al^3+was crystallized from the leachate in the form of ammonium aluminum sulfate dodecahydrate with a purity up to 99.5 wt%.About 85%of the soluble silicic acid was flocculated with the aid of secondary alcohol polyoxyethylene ether 9(AEO-9)to yield a microporous SiO2 material(97.4 wt%)from the crystallized mother liquor.The Al-and Si-depleted solution was then hydrolyzed to generate a titanium dioxide(99.1 wt%)with uniform particle size distribution.It was figured out that approximately 146 kg TiO2 could be produced from 1000 kg of TBBF slag.Therefore,the improved process is a promising method for industrial application.

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.

Indirect mineral carbonation of blast furnace slag with(NH4)2SO4 as a recyclable extractant

Large quantities of COand blast furnace slag are discharged in the iron and steel industry. Mineral carbonation of blast furnace slag can offer substantial COemission reduction and comprehensive utilisation of the solid waste. In this study, a recyclable extractant,（NH）SO, was used to extract calcium and magnesium from blast furnace slag（main phases of gehlenite and akermanite） by using low-temperature roasting to fix COthrough aqueous carbonation. The process parameters and efficiency of the roasting extraction, mineralisation, and Al recovery were investigated in detail. The results showed that the extractions of Ca, Mg, and Al can reach almost 100% at an（NH4）SO-to-slag mass ratio of 3:1 and at 370°C in 1 h. Adjusting the p H value of the leaching solution of the roasted slag to 5.5 with the NHreleased during the roasting resulted in 99% Al precipitation, while co-precipitation of Mg was lower than 2%. The Mg-rich leachate after the depletion of Al and the leaching residue（main phases of CaSOand SiO） were carbonated using（NH）COand NHHCOsolutions, respectively, under mild conditions. Approximately 99% of Ca and 89% of Mg in the blast furnace slag were converted into CaCOand（NH）Mg（CO）·4 HO,respectively. The latter can be selectively decomposed to magnesium carbonate at 100-200 °C to recover the NHfor reuse. In the present route, the total COsequestration capacity per tonne of blast furnace slag reached up to 316 kg, and 313 kg of Al-rich precipitate, 1000 kg of carbonated product containing CaCOand SiO, and 304 kg of carbonated product containing calcium carbonate and magnesium carbonate were recovered simultaneously. These products can be used, respectively, as raw materials for the production of electrolytic aluminium, cement, and light magnesium carbonate to replace natural resources.

Kinetics of the leaching of TiO_2 from Ti-bearing blast furnace slag

Ti-bearing blast furnace slag is a valuable secondary resource containing about 24 percent of TiO2.In this paper a process of leaching Ti-bearing blast furnace slag with sulfuric acid to recover TiO2,and the kinetics of that reaction,are described.Under laboratory conditions the rate is controlled by a chemical reaction.The leaching reaction is in accord with a shrinking unre- acted-core model.The apparent reaction order of the leaching reaction was 1.222 and the apparent activation energy was 87.01 kJ/mol.The model fits the observed data well until 90%of the TiO2 has be leached from the particles.The model disagrees with observations during later periods of the reaction because the solution becomes supersaturated with Ti ions,which precipitate as H2TiO4.The assumptions of constant reactant concentration and that there is no effect from the product layer on diffusion,also cause the model to deviate from the actual values.

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.

Study on the early warning mechanism for the security of blast furnace hearths

The campaign life of blast furnace （BF） hearths has become the limiting factor for safety and high efficiency production of modern BFs. However, the early warning mechanism of hearth security has not been clear. In this article, based on heat transfer calculations, heat flux and erosion monitoring, the features of heat flux and erosion were analyzed and compared among different types of hearths. The primary detecting elements, mathematical models, evaluating standards, and warning methods were discussed. A novel early warning mechanism with the three-level quantificational standards was proposed for BF hearth security.

Numerical Simulation of Innovative Operation of Blast Furnace Based on Multi-Fluid Model

A multi-fluid blast furnace model was simply introduced and was used to simulate several innovative ironmaking operations. The simulation results show that injecting hydrogen bearing materials, especially injecting natural gas and plastics, the hydrogen reduction is enhanced, and the furnace performance is improved simultaneously. Total heat input shows obvious decrease due to the decrease of heat consumption in direct reduction, solution loss and silicon transfer reactions. If carbon composite agglomerates are charged into the furnace, the temperature of thermal reserve zone will obviously decrease, and the reduction of iron-bearing burden materials will be retarded. However, the efficiency of blast furnace is improved just due to the decrease in heat requirements for solution loss, sinter reduction, and silicon transfer reactions, and less heat loss through top gas and furnace wall. Finally, the model is used to investigate the performance of blast furnace under the condition of top gas recycling together with plastics injection, cold oxygen blasting and carbon composite agglomerate charging. The lower furnace temperature, extremely accelerated reduction rate, drastically decreased CO2 emission and remarkably enhanced heat efficiency were obtained by using the innovative operations, and the blast furnace operation with superhigh efficiency can be realized.