Ammonia-induced CuO/13X for H_(2)S removal from simulated blast furnace gas at low temperature

Blast furnace gas(BFG)is an important by-product energy for the iron and steel industry and has been widely used for heating or electricity generation.However,the undesirable contaminants in BFG(especially H_(2)S)generate harmful environmental emissions.The desulfurization of BFG is urgent for integrated steel plants due to the stringent ultra-low emission standards.Compared with other desulfurization materials,zeolite-based adsorbents represent a viable option with low costs and long service life.In this study,an ammonia-induced CuO modified 13X adsorbent(NH_(3)–CuO/13X)was prepared for H_(2)S removal from simulated BFG at low temperature.The XRD,H_(2)-TPR and TEM analysis proved that smaller CuO particles were formed and the dispersion of Cu on the surface of 13X zeolite was improved via the induction of ammonia.Evaluation on H_(2)S adsorption performance of the adsorbent was carried out using simulated BFG,and the results showed that NH_(3)–CuO/13X-3 has better breakthrough sulfur capacity,which was more than twice the sulfur capacity of CuO/13X.It is proposed that the enhanced desulfurization performance of NH_(3)–CuO/13X is attributed to an abundant pore of 13X,and combined action of 13X and CuO.This work provided an effective way to improve the sulfur capacity of zeolite-based adsorbents via impregnation method by ammonia induction.

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.

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.

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.

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.

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.

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.

Numerical Simulation of the Flow of a Molten Blast Furnace Slag in an Open Channel

Despite its industrial importance, the flow of molten blast furnace slag in open channels has not been sufficiently studied. In this work, the unsteady non-uniform flow of a molten blast furnace slag in a rectangular open channel is numerically studied by solving the Saint-Venant equations by means of an explicit backwards finite difference scheme. An Arrhenius-type dependence of the viscosity of the slag on temperature is assumed. To calculate that viscosity, four temperatures are considered, namely 1450˚C, 1500˚C, 1550˚C and 1600˚C. To study the dynamic response of the system, a half-sinusoidal pulse with duration of 5 s is imposed at the channel entrance. According to the numerical simulations, for all the temperatures considered, the slag flow in the channel for an angle of 5 degrees is supercritical in nature. However, for an angle of 1 degree, the flow is transcritical, that is, it presents a transition from subcritical to supercritical.

Modelling of blast furnace ironmaking process based on digital twin

The blast furnace ironmaking process is a crucial step in the steel industry.Effectively modelling the blast furnaces is significant in ensuring smooth operation and accelerating the digitalisation transformation of blast furnaces.The authors focus on the mechanism modelling of the blast furnace operation process,using a digital twin model development platform to simulate the main reaction processes inside the blast furnaces.Under on-site production conditions,Si,Mn and Ti contents of molten iron and the corresponding indicators for model accuracy are calculated.For Si,Mn,and Ti content,the Root Mean Square Error values are 0.0678,0.0108 and 0.0093 for dataset 1,while 0.0933,0.0120 and 0.0111 for dataset 2,respectively,indicating that the model has a small simulation error and high accuracy.By comparing the simulation results with accurate laboratory results,the model is validated to have satisfactory simulation reliability and compensates for the existing shortcomings in the blast furnace mechanism modelling field.

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.

Study on the stability control technology of large-scaled blast furnaces

Nowadays,there are two major trends,which are the increasing blast furnace （BF） working volume and the decreasing fuel resource as well as the decline in its quality,in the ironmaking filed. The two trends lead to the difficulty in the BF operation. The decline of the BF stability requires higher and more elaborate operational techniques. A reasonable and compatible BF comprehensive operating system,as the base of the BF stabilization,is desired to satisfy the demand of large-scaled BF developments. Based on the practical operation of Baosteel No. 3 BF in 2010, the present work analyzes and discusses the basic rules of large-scaled BF stable control techniques,and further optimizes and improves its gas flow control techniques, develops strategies against the decline in fuel quality, which will contribute to the promotion of largescaled BF operational techniques progress.

Environmental-friendly Ramming Materials for Mud Package and Taphole of Large-scaled Blast Furnaces

The compositions, structures and properties of envi- ronmental-friendly ramming materials for mud package and taphole of large-scaled blast furnaces were studied. The results show that the formation of silica fibers makes structure of ramming materials dense. During the process of extruding mud and ramming materials, SiC is partly oxidized ; CaO , F% 03 and carbon penetrate towards the outer wall. The improvement of ramming materials can inhibit the penetration of molten slag, iron and carbon. The bulk density of environmental-friendly ramming ma- terials dried at 200 ℃ is 2.90 g · cm-3, the cold com- pressive strength of this kind of ramming materials dried at 200 ℃ is about 17. 0 MPa and fired at I 450 ℃ is about 39. 2 MPa.

Technical Questions in Castables Innovation for Main Iron Trough in Large-scaled Blast Furnaces of WISCO

The technical .wtors of castables innovation of matin iron trough in blust furnaces of WISCO in recent ten years were analyed, and corrosion process of dense corundum, sub-white corundum and brown corundum aggregates in the castables for the main iron trough was researched. It is regarded tha.t there is no inevitable relation between castables properties and service life, and it must be considered that whether the normal technical in- dex in. the stan＆trd can be used as judgment basis. Based on the improvement of matrix, the service hfe （once throughput of hot metal ） of castables used in main iron trough increases from 90 000 tons to 140 000 - 180 000 tons ; the properties of different raw materials are Jidly applied, and structure improvement of iron trough and progress of material technique are very important reasons.

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.

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.

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.

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.

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.