Development and prospects of molten steel deoxidation in steelmaking process

In the long traditional process of steelmaking,excess oxygen is blown into the converter,and alloying elements are used for deoxidation.This inevitably results in excessive deoxidation of products remaining within the steel liquid,affecting the cleanliness of the steel.With the increasing requirements for steel performance,reducing the oxygen content in the steel liquid and ensuring its high cleanliness is necessary.After more than a hundred years of development,the total oxygen content in steel has been reduced from approximately 100×10^(-6)to approximately 10×10^(-6),and it can be controlled below 5×10^(-6)in some steel grades.A relatively stable and mature deoxidation technology has been formed,but further reducing the oxygen content in steel is no longer significant for improving steel quality.Our research team developed a deoxidation technology for bearing steel by optimizing the entire conventional process.The technology combines silicon–manganese predeoxidation,ladle furnace diffusion deoxidation,and vacuum final deoxidation.We successfully conducted industrial experiments and produced interstitial-free steel with natural decarbonization predeoxidation.Non-aluminum deoxidation was found to control the oxygen content in bearing steel to between 4×10^(-6) and 8×10^(-6),altering the type of inclusions,eliminating large particle Ds-type inclusions,improving the flowability of the steel liquid,and deriving a higher fatigue life.The natural decarbonization predeoxidation of interstitial-free steel reduced aluminum consumption and production costs and significantly improved the quality of cast billets.

New steelmaking process based on clean deoxidation technology

After the converter steelmaking process,a considerable number of ferroalloys are needed to remove dissolved oxygen from the molten steel,but it also forms a lot of oxide inclusions that cannot be completely removed.At the same time,it increases the carbon emis-sions in the steel production process.After years of research,our team have developed a series of clean deoxidation technologies,includ-ing carbon deoxidation,hydrogen deoxidation,and waste plastic deoxidation of molten steel to address the aforementioned issues.In this study,thermodynamic calculations and laboratory experiments were employed to verify that carbon and hydrogen can reduce the total oxygen content in the molten steel melt to below 5×10^(-6) and 10×10^(-6),respectively.An analysis of the deoxidation mechanisms and ef-fects of polyethylene and polypropylene was also conducted.In addition,the applications of carbon deoxidation technology in different steels with the hot-state experiment and industrial production were discussed carefully.The carbon deoxidation experimental results of different steels were as follows:(1)the oxygen content of bearing steel was effectively controlled at 6.3×10^(-6) and the inclusion number density was lowered by 74.73%compared to aluminum deoxidized bearing steel;(2)the oxygen content in gear steel was reduced to 7.7×10^(-6) and a 54.49%reduction of inclusion number density was achieved with almost no inclusions larger than 5μm from the average level of industry gear steels;(3)a total oxygen content of M2 high-speed steel was as low as 3.7×10^(-6).In industrial production practice,car-bon deoxidation technique was applied in the final deoxidation stage for non-aluminum deoxidized bearing steel,and it yielded excellent results that the oxygen content was reduced to below 8×10^(-6) and the oxide inclusions in the steel mainly consist of silicates,along with small amounts of spinel and calcium aluminate.

Deoxidation of H13 tool steel with CaF_(2)-MgO-CaO-Al_(2)O_(3)-SiO_(2) slags at 1873 K

Laboratory-scale experiments were performed to investigate the deoxidation of H13 tool steel with CaF_(2)-MgO-Al_(2)O_(3)-CaO-SiO_(2) slags at 1873 K.The calculation of thermodynamics and kinetics was also verified through the experimental results.The results show that[Si]-[O]reaction is the control reaction,and with the increase of basicity of slag,the limitation of deoxidation was decreased.The limitation of deoxidation is the lowest for the slag with basicity of 2.0.Under the conditions of the basicity of 2.0 and the content of CaF_(2) more than 50%,the limitation of deoxidation is less than 10×10^(−6),and it does not depend on the contents of Al_(2)O_(3) and CaF_(2) in slags.The mass transport of oxygen in the metal phase is the rate-controlling step,and the slag composition has no effect on the equilibrium time of deoxidation.Based on this finding,the optimized slag composition is designed and it contains the following components:51.5%CaF_(2),20.3%MgO,16.2%Al_(2)O_(3),8.2%CaO and 3.8%SiO_(2).In the case of the optimized deoxidizing slag,the total oxygen content in H13 steel can be reduced from 25×10^(−6) to 6×10^(−6).

Thermodynamic model for deoxidation of liquid steel considering strong metal-oxygen interaction in the quasichemical model framework

Herein,a thermodynamic model aimed at describing deoxidation equilibria in liquid steel was developed.The model provides explicit forms of the activity coefficient of solutes in liquid steel,eliminating the need for the minimization of internal Gibbs energy preliminarily when solving deoxidation equilibria.The elimination of internal Gibbs energy minimization is particularly advantageous during the coupling of deoxidation equilibrium calculations with computationally intensive approaches,such as computational fluid dynamics.The model enables efficient calculations through direct embedment of the explicit forms of activity coefficient in the computing code.The proposed thermodynamic model was developed using a quasichemical approach with two key approximations:random mixing of metallic elements(Fe and oxidizing metal) and strong nonrandom pairing of metal and oxygen as nearest neighbors.Through these approximations,the quasichemical approach yielded the activity coefficients of solutes as explicit functions of composition and temperature without requiring the minimization of internal Gibbs energy or the coupling of separate programs.The model was successfully applied in the calculation of deoxidation equilibria of various elements(Al,B,C,Ca,Ce,Cr,La,Mg,Mn,Nb,Si,Ti,V,and Zr).The limitations of the model arising from these assumptions were also discussed.

Optimum Slag Basicity for Deoxidation DuringSecondary Refining Process

According to the coexistence theory of slag structures, the calculating model of the oxidizing capabilityfor CaO-MgO-FeO-Al2O3-SiO2 refining slag system has been deduced. Based on this model, the concept and thecalculating method of the optimum slag basicity are put forward. The results have proved that at this basicity,steel with lower oxygen content can be obtained and non-metallic indigenous globular inclusions can be avoidedmore effectively than at other basicity.

Calculation of phase diagram of Ti-Ni-O system and application to deoxidation of TiNi alloy

The Ti-Ni-O ternary system was assessed by means of Calphad method using ternary experimental data in previous study.Isothermal sections at 1 173 and 1 273 K were calculated.The result shows that the present calculated results are in good agreement with most of the experimental results.The consistent model parameter set determined in this work may provide theoretical guidance for the deoxidation of TiNi alloy.

EAF steelmaking process with increasing hot metal charging ratio and improving slagging regime

A new electric arc furnace （EAF） steelmaking process with increasing hot metal charging ratio and improving slagging regime simultaneously was developed and applied in a 50 t electric arc furnace for more than a year at No. 1 Steelmaking Plant of Shanxi Taigang Stainless Corporation Limited. The essential fact of the new EAF steelmaking process was to charge hot metal in two portions or steps： firstly, 35wt%-40wt% hot metal was pretreated by blowing oxygen in a specially designed reactor for decar burization and improving hot metal temperature and melting premelted slag; secondly, 30wt% hot metal was charged into EAF with high basicity refining slags from ladle furnace （LF）-vacuum degassing furnace （VD） refining process. The results show that the hot metal charging ratio can reach to about 65wt%-70wt% for the new EAF steelrnaking process; meanwhile, the tap-to-tap time of a 50 t EAF can shorten by 5-10 min, the electricity consumption can decrease by 35-50 kW·h/t, the lime consumption can reduce by 10.5 kg/t of molten steel, and the content of harmful heavy metals in molten steel can be easily controlled to less than the upper limits of aimed steel specification or grade compared with the traditional EAF steelmaking process. In addition, the dephosphorization ability shows a slight strengthening, however, a small degree of lessening for desulphurization ability is observed for the new EAF steelmaking process, but the weakness of desulphurization ability cannot become an obstacle to its further application since a stronger desulphurization ability can be achieved during secondary refining of LF coupled with VD after EAF steelmaking process.

Deoxidation Behavior of Alloys Bearing Barium in Molten Steel

The deoxidation behaviors of alloys bearing barium in pipe steel were researched with MgO crucible under argon atmosphere in MoSi2 furnace at 1 873 K.The total oxygen contents of molten steel,the distribution,size and morphology of deoxidation products in the steel were surveyed.The metamorphic mechanism for deoxidation products of alloy bearing barium was also discussed.The results show that applying alloy bearing barium to the pipe steel,very low total oxygen contents can be obtained,and deoxidation products,which easily float up from molten steel,can be changed into globular shape and uniformly distributed in steel.The equilibrium time of total oxygen is about 25 min,and the terminal total oxygen contents range from 0.002 0%to 0.002 2% after treating with SiCa wire.The best deoxidizers are SiAlBaCa and SiAlBaCaSr.

Al Preparation from Solid Al_2O_3 by Direct Electrochemical Deoxidation in Molten CaCl_2-NaCl at 550℃

Al was prepared by a new method in molten salt at low temperature. Sintered alumina pellets were used as cathode; graphite rod was employed as anode; and the molten CaCl2-NaCl was the electrolyte. A constant 3.2 V voltage was applied in this experiment, and oxygen in solid alumina cathode was reduced by direct electrochemical deoxidation at 550℃. In this process, the current gradually decreased with increasing time and the alumina pellets became grey and porous. The metallic particles were obtained and characterized by XRD （X-ray diffraction） and SEM （scanning electron microscopy）.

Lowering ash slagging and fouling tendency of high-alkali coal by hydrothermal pretreatment

High-alkali species in coal are notorious for causing ash slagging and fouling incidents.In this paper,four high-alkali coals were individually subject to hydrothermal pretreatment(HTP),within a batch-type autoclave at 300 -C for 1 h,and the treated coals were analyzed,along with the oxygen-containing functional groups determined by Fourier transform infrared spectrometer(FT-IR).Then the alkali species and other components in the coal ash were quantified by X-ray fluorescence(XRF)for evaluating the ash slagging and fouling tendency.Apart from this,FactSage was adopted to simulate the occurrence and transformation of alkali species during coal thermal conversion ending at various temperatures.The findings indicate that the treated coals are superior to the parent ones in terms of certain remarkable changes via HTP.The moisture,oxygen and sulfur of the hydrothermally treated coals decline obviously,while the calorific value rises sharply.HTP could reduce the alkali species to less than 2%(%,by weight,equivalent to Na2O in dry ash),with a maximum removal ratio of 88.9%,lowering the ash slagging and fouling tendency.The proposed mechanism of HTP was that the alkali species in coal matrix became released due to the breakage of the coal functional groups and micropores during HTP.

Ultrahigh cycle fatigue fracture mechanism of high-quality bearing steel obtained through different deoxidation methods

The mechanism of oxide inclusions in fatigue crack initiation in the very-high cycle fatigue(VHCF)regime was clarified by subjecting bearing steels deoxidized by Al(Al-deoxidized steel)and Si(Si-deoxidized steel)to ultrasonic tension-compression fatigue tests(stress ratio,R=−1)and analyzing the characteristics of the detected inclusions.Results show that the main types of inclusions in Si-and Al-deoxidized steels are silicate and calcium aluminate,respectively.The content of calcium aluminate inclusions larger than 15μm in Si-deoxidized steel is lower than that in Al-deoxidized steel,and the difference observed may be attributed to different inclusion generation processes during melting.Despite differences in their cleanliness and total oxygen contents,the Si-and Al-deoxidized steels show similar VHCF lives.The factors causing fatigue failure in these steels reveal distinct differences.Calcium aluminate inclusions are responsible for the cracks in Al-deoxidized steel.By comparison,most fatigue cracks in Si-deoxidized steel are triggered by the inhomogeneity of a steel matrix,which indicates that the damage mechanisms of the steel matrix can be a critical issue for this type of steel.A minor portion of the cracks in Si-deoxidized steel could be attributed to different types of inclusions.The mechanisms of fatigue fracture caused by calcium aluminate and silicate inclusions were further analyzed.Calcium aluminate inclusions first separate from the steel matrix and then trigger crack generation.Silicate inclusions and the steel matrix are closely combined in a fatigue process;thus,these inclusions have mild effects on the fatigue life of bearing steels.Si/Mn deoxidation is an effective method to produce high-quality bearing steel with a long fatigue life and good liquid steel fluidity.

Preparation of low-oxygen Ti powder from TiO_(2) through combining self-propagating high temperature synthesis and electrodeoxidation

An effective method was reported to prepare low-oxygen Ti powder,which included two experimental steps:the fast conversion of TiO_(2) to TiO_(x<1) powder by self-propagating high-temperature synthesis(SHS)process and the generation of low-oxygen Ti powder by electrodeoxidizing TiO_(x<1) powder at the cathode in molten CaCl_(2).The key intermediate steps were analyzed by XRD,SEM and electrochemical testing techniques.The results demonstrated that TiO_(x<1) powder(TiO_(0.325) and TiO_(0.97))was generated after acid leaching MgO in SHS products with TiO_(2)/Mg molar ratio of 1:2,and the TiO_(x<1) powder with 16.3 wt.%oxygen could be transformed into pure titanium powder with 0.121 wt.%oxygen by electrodeoxidation at a constant potential of−3.3 V for 10 h.The electrodeoxidation of TiO_(x<1) powder in CaCl_(2) molten salt follows the step-by-step deoxidation mode,and the lattice of TiO_(x<1) powder after electrodeoxidation shrinks.

Electro-deoxidation of V_2O_3 in molten CaCl_2-NaCl-CaO

The electro-deoxidation of V2O3 precursors was studied. Experiments were carried out with a two-terminal electrochemical cell, which was comprised of a molten electrolyte of CaCl2 and NaC1 with additions of CaO, a cathode of compact V2O3, and a graphite anode under the potential of 3.0 V at 1173 K. The phase constitution and composition as well as the morphology of the samples were studied by X-ray diffraction （XRD） and scanning electron microscopy （SEM）. 3 g of V2O3 could be converted to vanadium metal powder within the processing time of 8 h. The kinetic pathway was investigated by analyzing the product phase in samples prepared at different reduction stages. CaO added in the reduction path of V2O3 formed the intermediate product CaV2O4.

Visual investigation of slagging characteristics in a pilot-scale facility:Influence of deposition surface

Slagging is a major problem in boilers,especially the low-rank coal applied in boilers.In this study,the influence of heat transfer surface on the slagging characteristics of a pilot-scale furnace was investigated.Ni coatings were applied in modifying the deposition surface to control slagging.The growth characteristics of the slag were studied using an online digital image technique.Scanning electron microscopy linked with energy-dispersive X-ray analysis and X-ray diffraction(XRD)were applied to investigate the microstructure,semi-quantitative chemical composition,and mineralogy of slag samples.Ni coating demonstrated a positive effect on the mitigation of slagging.Results revealed that the thicknesses of the slag initially increased with experimental time and then inclined toward stable values for both cases(Case 1:substrate material;Case 2:modified surface).The stable thicknesses for Cases 1 and 2 were 4.91 mm and 3.95 mm,respectively.The heat transfer efficiency was improved by approximately 18.2%with the application of Ni coating for probe surface modification.The mechanism of the mitigation of slagging was investigated in this study.XRD results revealed that the content of alkali reduced when the surface was coated with Ni.The alkali significantly affected the adhesion behavior of the deposition.Hence,Ni coating showed potential in reducing slagging and increasing the efficiency of boilers.The overall study makes a contribution to a deep understanding of the effect of Ni coating on the growth characteristics of the slag.

Effect of Zr-Ti combined deoxidation on impact toughness of coarse-grained heat-affected zone with high heat input welding

In this study, the effects of Zr-Ti combined deoxidation and AI deoxidation on the impact toughness of coarse- grained heat-affected zone in high-strength low-alloy steels were investigated. More fine oxides were formed in the Zr-Ti-killed steel than in Al-killed steel. It was also found that more acicular ferrite grains were formed in the coarse-grained heat-affected zone in the Zr-Ti-killed steel than in Al-killed steel. The impact toughness of coarse-grained heat-affected zone of Zr-Ti-kiUed steel was higher than that of Al-killed steel. The good impact toughness was attributable to the pinning effect of fine oxides and the formation of acicular ferrite grains on fine oxides.

Fault Diagnostics on Steam Boilers and Forecasting System Based on Hybrid Fuzzy Clustering and Artificial Neural Networks in Early Detection of Chamber Slagging/Fouling

The slagging/fouling due to the accession of fireside deposits on the steam boilers decreases boiler efficiency and availability which leads to unexpected shut-downs. Since it is inevitably associated with the three major factors namely the fuel characteristics, boiler operating conditions and ash behavior, this serious slagging/fouling may be reduced by varying the above three factors. The research develops a generic slagging/fouling prediction tool based on hybrid fuzzy clustering and Artificial Neural Networks (FCANN). The FCANN model presents a good accuracy of 99.85% which makes this model fast in response and easy to be updated with lesser time when compared to single ANN. The comparison between predictions and observations is found to be satisfactory with less input parameters. This should be capable of giving relatively quick responses while being easily implemented for various furnace types.

Refractories Utilizability for Slagging Gasifiers

Slagging coal gasification process became a highlight of coal chemical industry in China during the last decade. Refractory lining＇ s life of slagging gasifiers is one of the most critical factors for a cost - effective operation. The paper introduces current status of coal gasification in China, lining structure of slagging gasifiers and performance of refractory lining. It also summarizes the major factors impacting on refractory wear in slagging coal gasifiers in four Chinese chemical plants, based on ten years of industrial experience. The utilizability is discussed in terms of cost -effectiveness of high chromia refractories and possibility of the alternatives.

Effects of iron oxide on crystallization behavior and spatial distribution of spinel in stainless steel slag

Chromium plays a vital role in stainless steel due to its ability to improve the corrosion resistance of the latter.However,the re-lease of chromium from stainless steel slag(SSS)during SSS stockpiling causes detrimental environmental issues.To prevent chromium pollution,the effects of iron oxide on crystallization behavior and spatial distribution of spinel were investigated in this work.The results revealed that FeO was more conducive to the growth of spinels compared with Fe2O3 and Fe3O4.Spinels were found to be mainly distrib-uted at the top and bottom of slag.The amount of spinel phase at the bottom decreased with the increasing FeO content,while that at the top increased.The average particle size of spinel in the slag with 18wt%FeO content was 12.8μm.Meanwhile,no notable structural changes were observed with a further increase in FeO content.In other words,the spatial distribution of spinel changed when the content of iron oxide varied in the range of 8wt%to 18wt%.Finally,less spinel was found at the bottom of slag with a FeO content of 23wt%.

Analysis of Spent High Chrome Brick in Slagging Gasifier

Wear of the spent high chrome brick in slagging gasifier was studied. The result shows that erosion and spalling are the m, ain wear mechanism of high chrome brick and the CaO content of coal slag is crucial to wear of high chrome brick.

Structural properties of residual carbon in coal gasification fine slag and their influence on flotation separation and resource utilization:A review

Coal gasification fine slag(FS)is a typical solid waste generated in coal gasification.Its current disposal methods of stockpil-ing and landfilling have caused serious soil and ecological hazards.Separation recovery and the high-value utilization of residual carbon(RC)in FS are the keys to realizing the win-win situation of the coal chemical industry in terms of economic and environmental benefits.The structural properties,such as pore,surface functional group,and microcrystalline structures,of RC in FS(FS-RC)not only affect the flotation recovery efficiency of FS-RC but also form the basis for the high-value utilization of FS-RC.In this paper,the characteristics of FS-RC in terms of pore structure,surface functional groups,and microcrystalline structure are sorted out in accordance with gasification type and FS particle size.The reasons for the formation of the special structural properties of FS-RC are analyzed,and their influence on the flotation separation and high-value utilization of FS-RC is summarized.Separation methods based on the pore structural characterist-ics of FS-RC,such as ultrasonic pretreatment-pore-blocking flotation and pore breaking-flocculation flotation,are proposed to be the key development technologies for improving FS-RC recovery in the future.The design of low-cost,low-dose collectors containing polar bonds based on the surface and microcrystalline structures of FS-RC is proposed to be an important breakthrough point for strengthening the flotation efficiency of FS-RC in the future.The high-value utilization of FS should be based on the physicochemical structural proper-ties of FS-RC and should focus on the environmental impact of hazardous elements and the recyclability of chemical waste liquid to es-tablish an environmentally friendly utilization method.This review is of great theoretical importance for the comprehensive understand-ing of the unique structural properties of FS-RC,the breakthrough of the technological bottleneck in the efficient flotation separation of FS,and the expansion of the field of the high value-added utilization of FS-RC.