Extraction of valuable metals from Ti-bearing blast furnace slag using ammonium sulfate pressurized pyrolysis−acid leaching processes

A novel method of extracting valuable metals from Ti-bearing blast furnace slag(TBBF slag)via pressure pyrolysis of recyclable ammonium sulfate(AS)−acid leaching process was proposed.The results show that when pressurized roasting at an AS-to-slag mass ratio 3:1 and 370℃for 90 min,the extraction rates of titanium,aluminum and magnesium reached 94.5%,91.9%and 97.4%,respectively.The acid leaching solution was subjected to re-crystallization in a boiling state to obtain a titanium product having a TiO2 content of 94.1%.The above crystallization mother liquor was adjusted to pH=6 and pH≥12.2,respectively,and then qualified Al2O3 and MgO products were obtained.The analysis through XRD and SEM−EDS proves that the main phases in roasted samples were NH4AlSO4,CaSO4 and TiOSO4.The thermodynamic analysis presents that the main minerals of perovskite,spinel and diopside in raw ore could spontaneously react with the intermediate produced by AS under optimal conditions.

Recovery of Fe,V,and Ti in modified Ti-bearing blast furnace slag

A two-stage oxidation—alkali leaching—acid leaching method was proposed to recovery Fe,V,and Ti in modified Ti-bearing blast furnace slag.The optimal experiment conditions of iron extraction were one-stage oxidation time 40 s and holding time 8 min.The recovery rate of iron was 89.93%.The optimum experiment conditions of vanadium extraction were total oxidation time of 126 s,NaOH concentration of 4.0 mol/L,leaching temperature of 95℃,leaching time of 90 min,and the number of cycle was 4.The leaching rate of vanadium was 92.13%.The optimal experiment conditions of titanium extraction were HCl concentration of 4.5 mol/L,leaching temperature of 75℃,and leaching time of 90 min.The TiO_(2)content of synthetic rutile was 98.61%.

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.

Determination of dielectric properties of titanium carbide fabricated by microwave synthesis with Ti-bearing blast furnace slag

The preparation of functional material titanium carbide by the carbothermal reduction of Ti-bearing blast furnace slag with microwave heating is an effective method for valuable metals recovery;it can alleviate the environmental pressure caused by slag stocking.The dynamic dielectric parameters of Ti-bearing blast furnace slag/pulverized coal mixture under high-temperature heating are measured by the cylindrical resonant cavity perturbation method.Combining the transient dipole and large π bond delocalization polarization phenomena, the interaction mechanism of the microwave macroscopic non-thermal effect on the titanium carbide synthesis reaction was revealed.The material thickness range during microwave heating was optimized by the joint analysis of penetration depth and reflection loss, which is of great significance to the design of the microwave reactor for the carbothermal reduction of Ti-bearing blast furnace slag.

Effects of additives on the phase transformation, occurrence state, and the interface of the Ti component in Ti-bearing blast furnace slag

The influences of additives on the phase transformation, occurrence state, and the interface of the Ti component in Ti-bearing blast furnace slag were investigated. After oxidation, most of the Ti component in the slag was enriched into the perovskite phase, which served as the Ti-rich phase during the crystallization process. The phase transformation, occurrence state, and the interface of the Ti component were observed to be affected by the addition of different types of agents. During the oxidation process, titanaugite and Ti-rich diopside phases gradually transformed into non-Ti phases（anorthite： CaMgSi2O6 and CaAl2Si2O8） in the form of dendrites or columns, which were observed to be distributed at the surface of the perovskite phase. Several more cracks appeared along the grain boundaries of the perovskite phase after the addition of P2O5, facilitating the liberation of the perovskite phase. Composite additives combining both an acid and a base, such as CaO ＋ CaF2 or P2O5 ＋ CaF2, were used. We observed that the disadvantages of using single additives were successfully overcome.

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.

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.

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.

PRECIPITATION AND GROWTH OF PEROVSKITE PHASE IN TITANIUM BEARING BLAST FURNACE SLAG

The effects of transformation of slag composition and additive agents on the morphology, the precipitation behavior, the crystal growth, and the volume fraction (VF) of perovskite (CaO·¤TiO_2) crystal in the Ti-bearing blast furnace slags were investigated. As the morphology of perovskite is dispersed in molten slags, the crystal growth mechanism of the melting of fine dendrites and the coarsening of large grains exist throughout the solidification of molten slags. With the increase of CaO and Fe_2O_3 content, VF of perovskite obviously increases. However, high basicity leads to the viscosity of slag, which results in the reduction of the average equivalent diameter (AED). The experimental results showed that the presence of the additives CaF_2 and MnO efficiently decreased the viscosity of the slags, and obviously improved the morphology of perovskite and promoted its growth.

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.

Indirect mineral carbonation of titanium-bearing blast furnace slag coupled with recovery of TiO_2 and Al_2O_3

Large quantities of CO2 and blast furnace slag are discharged in the iron and steel industry. Mineral carbonation of blast furnace slag can offer substantial CO2 emission reduction and comprehensive utilization of the solid waste. This paper describes a novel route for indirect mineral carbonation of titanium-bearing blast furnace （TBBF） slag, in which the TBBF slag is roasted with recyclable （NH4）2SO4 （AS） at low temperatures and converted into the sulphates of various valuable metals, including calcium, magnesium, aluminium and titanium. High value added Ti-and Al-rich products can be obtained through stepwise precipitation of the leaching solution from the roasted slag. The NH3 produced during the roasting is used to capture CO2 from flue gases. The NH4HCO3 and （NH4）2CO3 thus obtained are used to carbonate the CaSO4-containing leaching residue and MgSO4-rich leaching solution, respectively. In this study, the process parameters and efficiency for the roasting, carbonation and Ti and Al recovery were investigated in detail. The results showed that the sulfation ratios of calcium, magnesium, titanium and aluminium reached 92.6%, 87% and 84.4%, respectively, after roasting at an AS-to-TBBF slag mass ratio of 2：1 and 350℃ for 2 h. The leaching solution was subjected to hydrolysis at 102℃ for 4 h with a Ti hydrolysis ratio of 95.7%and the purity of TiO2 in the calcined hydrolysate reached 98 wt%. 99.7% of aluminium in the Ti-depleted leaching solution was precipitated by using NH3. The carbonation products of Ca and Mg were CaCO3 and （NH4）2Mg（CO3）2·4H2O, respectively. The latter can be decomposed into MgCO3 at 100-200℃ with simultaneous recovery of the NH3 for reuse. In this process, approximately 82.1% of Ca and 84.2% of Mg in the TBBF slag were transformed into stable carbonates and the total CO2 sequestration capacity per ton of TBBF slag reached up to 239.7 kg. The TiO2 obtained can be used directly as an end product, while the Al-rich precipitate and the two carbonation products can act, respectively, as raw materials for electrolytic aluminium, cement and light magnesium carbonate production for the replacement of natural resources.

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.

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.

Characteristics of gaseous product from municipal solid waste gasification with hot blast furnace slag

Possibility of combustible gas production from municipal solid waste （MSW） using hot blast furnace （BF） slag has been studied.The objective of this work is to generate combustible gas from MSW using heated BF slag.In this experiment,the thermal stability of the MSW was analyzed by thermogravimetric analysis,and effects of temperature,gasifying agent （air,N2,steam） and BF slag on the gas products were investigated at 600？900 ？C.The thermogravimetric analysis indicates that the weight loss of MSW includes four stages：evaporation of the moisture,combustion of volatile materials,burning of carbon residue and burnout of ash.The contents of the combustible gas increase with increasing temperature,and the lower calorific value （LCV） increases rapidly at 600？900 ？C.It is found that volume fraction of CO,H2 and CH4 at different atmospheres increases in the order N2〈air〈steam.It is believed that BF slag acts as the catalyst and the heat carrier,which promotes the gasification reactivity of MSW.

Effect of sintering temperature on the microstructure and properties of foamed glass-ceramics prepared from high-titanium blast furnace slag and waste glass

Foamed glass-ceramics were prepared via a single-step sintering method using high-titanium blast furnace slag and waste glass as the main raw materials The influence of sintering temperature(900–1060℃) on the microstructure and properties of foamed glass-ceramics was studied. The results show that the crystal shape changed from grainy to rod-shaped and finally turned to multiple shapes as the sintering temperature was increased from 900 to 1060℃. With increasing sintering temperature, the average pore size of the foamed glass-ceramics increased and subsequently decreased. By contrast, the compressive strength and the bulk density decreased and subsequently increased. An excessively high temperature, however, induced the coalescence of pores and decreased the compressive strength. The optimal properties, including the highest compressive strength(16.64 MPa) among the investigated samples and a relatively low bulk density(0.83 g/cm^3), were attained in the case of the foamed glass-ceramics sintered at 1000℃.

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.

Status and development of mineral wool made from molten blast furnace slag

This study describes the characteristics of mineral wool and its applications,and also introduces the traditional process of mineral wool made from molten blast furnace （BF） slag. Compared with high energy consumption of the traditional process,the production of mineral wool by using molten BF slag will be able to take full advantage of the sensible heat of molten slag, and also reduce production costs. However, there are also further issues to resolve such as how to obtain the required amount of molten BF slag and how to make it homogeneous. Based on the physical and chemical properties of the molten BF slag,the investigation into the relationship between temperature and viscosity under different acidity coefficients of the slag and silicon mixture was conducted. Combined with the crystallization and phase diagram of slag wool, its heat resistance, water resistance, durability and corrosion resistance were analyzed. Finally, trends of the technology development are proposed.

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.

Influence of CeO_2 addition on the preparation of foamed glass-ceramics from high-titanium blast furnace slag

Foamed glass-ceramics doped with cerium oxide（CeO_2）were successfully prepared from high-titanium blast furnace slag by one-step sintering.The influence of CeO_2 addition（1.5wt%–3.5wt%）on the crystalline phases,microstructure,and properties of foamed glass-ceramics was studied.Results show that CeO_2 improves the stability of the glass phase and changes the two-dimensional crystallization mechanism into three-dimensional one.XRD analysis indicates the presence of Ca（Mg,Fe）Si_2O_6 and Ca（Ti,Mg,Al）（Si,Al）_2O_（6 ）in all sintered samples.Added with CeO_2,Ti CeO_4 precipitates,and crystallinity increases,leading to increased thickness of pore walls and uniform pores.The comprehensive properties of foamed glass-ceramics are better than that of samples without CeO_2.In particular,the sample added with a suitable amount of CeO_2（2.5wt%）exhibits bulk density that is similar to and compressive strength（14.9 MPa）that is more than twice of foamed glass-ceramics without CeO_2.