Interphase migration and enrichment of lead and zinc during copper slag depletion

An interphase migration and enrichment model of lead and zinc during molten copper slag depletion was established.The occurrence of various components in copper slag was predicted using sulfur-oxygen potential calculations and confirmed through high-temperature experiments.The recovery rate of copper can reach 90.13%under the optimal conditions of 1200°C,an iron to silicon mass ratio of 1.0,3 wt.%ferrous sulfide,and a duration of 45 min.Lead(54.07 wt.%)and zinc(17.42 wt.%)are found in the flue dust as lead sulfate,lead sulfide,and zinc oxide,while copper matte contains lead(14.44 wt.%)and zinc sulfide(1.29 wt.%).The remaining lead and zinc are encapsulated as oxides within the fayalite phase.

Dry Mix Slag—High-Calcium Fly Ash Binder. Part Two: Durability

This work investigates durability of cement-free mortars with a binder comprised of ground granulated blast furnace slag (GGBFS) activated by high-calcium fly ash (HCFA) and sodium carbonate (Na2CO3): the soundness, sulfate resistance, alkali-silica reactivity and efflorescence factors are considered. Results of tests show that such mortars are resistant to alkali-silica expansion. Mortars are also sulfate-resistant when the amount of HCFA in the complex binder is within a limit of 10 wt%. The fineness of fly ash determines its’ ability to activate GGBFS hydration, and influence soundness of the binder, early strength development, sulfate resistance and efflorescence behavior. The present article is a continuation of authors’ work, previously published in MSA, Vol. 14, 240-254.

Properties of Sustainable High Strength Concrete with Waste Copper Slag

The present work investigates copper slag as a substitute for river sand in high-strength concrete.The concrete mixtures were manufactured with 10%,30%,50%,70%,and 100%of copper slag to evaluate the mechanical and durability properties.The experimental results indicate that replacing copper slag above 50%affects the performance characteristics of the concrete due to its high angularity and lower water absorption characteristics.The strength of concrete with 50%copper slag is improved by 5.6%,whereas the strength of concrete with 100%copper slag is reduced by 2.75%at 28 days.However,increased curing to 90days improves the strength of the former by 7.16%and reduces the latter by only 0.23%.The water absorption,porosity,and rapid chloride penetration of the concrete mixtures with 100%copper slag are increased by 10.44%,13.20%,and 19.56%compared to control concrete.Micro-structural investigations through SEM infer higher replacement of copper results in higher void formation due to its reduced water absorption.

Effect of slag composition on corrosion resistance of high chromia refractory bricks for industrial entrained-flow gasifier

The slag composition corresponding to different coals varies significantly,which directly affects the operation of industrial entrained-flow gasifier and the service life of refractory bricks.In this study,the corrosion resistance of several typical coal slags for gasification on high chromia refractory bricks was comparatively investigated by static laboratory crucible tests and thermodynamic simulations.The results demonstrated that the corrosion degree of high chromia refractory bricks by different coal slags was high-Ca/Na slag>high-Fe slag>high-Si/Al slag.The surface structure of the refractory was relatively flat after corrosion by high-Si/Al slag,and the primary corrosion reaction was the partial dissolution of the matrix by the slag.High-Fe slag was prone to the precipitation of iron phases as well as the formation of(Mg,Fe)(Al,Cr)_(2)O_(4)composite spinel layer at the slag/refractory interface.The high-Ca/Na slag was susceptible to react with the refractory to yield a low melting point phase,which led to the destruction of the matrix structure of the refractory and an isolated distribution of particles.In addition,the monoclinic ZrO_(2) in the refractory reacted with CaO in the slag to formed calcium zirconate,which loosened its phase toughening effect,was the primary factor that aggravated the refractory corrosion.

Preparation of High Activity Admixture from Steel Slag,Phosphate Slag and Limestone Powder

The problem of low disposal and utilization rate of bulk industrial solid waste needs to be solved.In this paper,a high-activity admixture composed of steel slag-phosphate slag-limestone powder was proposed for most of the solid waste with low activity and a negative impact on concrete workability,combining the characteristics of each solid waste.The paper demonstrates the feasibility and explains the principle of the composite system in terms of water requirement of standard consistency,setting time,workability,and mechanical properties,combined with the composition of the phases,hydration temperature,and microscopic morphology.The results showed that the steel slag:phosphate slag:limestone=5:2:3 gave the highest activity of the composite system,over 92%.Besides,the composite system had no significant effect on water demand and setting time compared to cement,and it could significantly increase the 7 and 28 d activity of the system.The composite system delayed the exothermic hydration of the cement and reduced the exothermic heat but had no effect on the hydration products.Therefore,the research in this paper dramatically improved the solid waste dissipation in concrete,reduced the amount of cement in concrete and positively responded to the national slogan of carbon neutral and peaking.

Dry Mix Slag—High-Calcium Fly Ash Binder. Part One: Hydration and Mechanical Properties

High-calcium fly ash (HCFA)—a residue of high-temperature coal combustion at thermal power plants, in combination with sodium carbonate presents an effective hardening activator of ground granulated blast-furnace slag (GGBFS). Substitution of 10% - 30% of GGBFS by HCFA and premixing of 1% - 3% Na2CO3 to this dry binary binder was discovered to give mortar compression strength of 10 - 30 to 30 - 45 MPa at 7 and 28 days when moist cured at ambient temperature. High-calcium fly ash produced from low-temperature combustion of fuel, like in circulating fluidized bed technology, reacts with water readily and is itself a good hardening activator for GGBFS, so introduction of Na2CO3 into such mix has no noticeable effect on the mortar strength. However, low-temperature HCFA has higher water demand, and the strength of mortar is compromised by this factor. As of today, our research is still ongoing, and we expect to publish more data on different aspects of durability of proposed GGBFS-HCFA binder later.

Synthesis of rutile from high titania slag by pyrometallurgical route

A new technique was developed for the conversion of high titania slag,containing 70%-75% TiO2 and with MgO,FeO,CaO,Al2O3 and SiO2 as main impurities,into a synthetic rutile,90%-95% TiO2,which satisfies the requirements for fluidizing chlorination process with respect to impurity contents.After a pre-oxidation at around 1 042 ℃ and a heat-treatment above 1 510 ℃,the Ti components in high titania slag can be enriched into the rutile phase which can precipitate and grow,and can be separated with dilute hydrochloric and sulfuric acid,respectively.The results show that the average crystal size of rutile phase is over 25 μm,and the synthetic rutile containing more than 95% TiO2 can be produced by selective leaching.

High temperature oxidation behavior of electroconductive TiN/O′-Sialon ceramics prepared from high titania slag-based mixture

The oxidation behavior of electroconductive TiN/O′-Sialon ceramics prepared using high titania slag as main starting material was studied at 1 200-1 300 °C in air. The isothermal and non-isothermal oxidation processes were investigated by DTA-TG. Phase compositions and morphologies of the oxidized products were analyzed by XRD, SEM and EDS. The results indicate that the oxidation of TiN and O′-Sialon occurs at about 500 °C and 1 050 °C, respectively. After oxidation at 1 200-1 300 °C, a protective scale that consists of Fe2MgTi3O10, SiO2 and TiO2 is formed on the surface of the materials, which effectively prevents the oxidation process. The formation of a protective scale is relative to TiN content and apparent porosity of the samples, the amount of SiO2 and amorphous phase in the oxidation product. At the initial oxidation stage, the oxidation kinetics of the materials follows perfectly the linear law with the apparent activation energy of 1.574×105 J/mol, and at the late-mid stage, the oxidation of the samples obeys the parabolic law with the apparent activation energy of 2.693×105 J/mol. With the increase of TiN content, mass gain of the materials increases significantly.

Study on non-metallic inclusions in Al killed high strength alloy steel refined by high basicity and high Al_2O_3 content slag

Laboratory and industrial studies were carried out to investigate non-metallic inclusions in high strength alloy steel refined by high basicity and high Al_2O_3 slag.It was found that the steel/slag reaction time largely affected non-metallic inclusions.With the reaction time increased from 30 min to 90 min in laboratory study,MgO-Al_2O_3 spinels were gradually changed into CaO-MgO-Al_2O_3 system inclusions surrounded by softer CaO-Al_2O_3 surface layers.By using high basicity slag which contained as much as 41%Al_2O_3 in the laboratory study,ratio of low melting temperature CaO-MgO-Al_2O_3 system inclusions was remarkably increased to above 80%.In the industrial experiment,during the secondary refining,the inclusions changed in order of 'Al_2O_3→MgO-Al_2O_3→CaO-MgO-Al_2O_3'.Through the LF and RH refining,most inclusions could be transferred to lower melting temperature CaO-Al_2O_3 and CaO-MgO-Al_2O_3 system inclusions.

Optimization of operating parameters and kinetics for chloride leaching of lead from melting furnace slag

The feasibility and kinetics of lead recovery from the slag of traditional lead melting furnace using chloride leaching were investigated.The effects of operating parameters such as leaching time,NaCl concentration,FeCl3concentration,liquid/solid ratio,stirring rate,temperature,and particle size on recovery of lead were studied and the optimization was done through the response surface methodology(RSM)based on central composite design(CCD)model.The optimum conditions were achieved as follows:leaching time60min,80°C,stirring rate800r/min,NaCl concentration200g/L,FeCl3concentration80g/L,liquid/solid ratio16,and particle size less than106μm.More than96%of lead was effectively recovered in optimum condition.Based on analysis of variance,the reaction temperature,liquid/solid ratio,and NaCl concentration were determined as the most effective parameters on leaching process,respectively.Kinetics study revealed that chloride leaching of galena is a first-order reaction and the diffusion through solid reaction product and chemical reaction control the mechanism.The activation energy of chloride leaching of galena was determined using Arrhenius model as27.9kJ/mol.

Green evaluation of microwave-assisted leaching process of high titanium slag on life cycle assessment

A greenness evaluation index and system of microwave-assisted leaching method were established.The effects of the life cycle assessment variables,such as the resource consumption,environment impact,cost,time and quality,were investigated,and the concept of green degree was applied in the production of synthetic rutile.An analytic hierarchy process was utilized to assess matrix of greenness evaluation.The Gauss-Seidel iterative matrix method was employed to solve the assessment matrix and obtain the weights and membership functions of all evaluation indexes.A fuzzy decision-making method was applied to build the greenness evaluation model,and then the scores of green degree in microwave-assisted leaching process was obtained.The greenness evaluation model was applied to the life cycle assessment of the microwave-assisted leaching process.The results show that the microwave-assisted leaching process has advantages over the conventional ones,with respect to energy-consumption,processing time and environmental protection.

Vaporization behavior of lead from the FeO-CaO-SiO_2-Al_2O_3 slag system

Vaporization behavior （1163-1463 K） of lead in the slag system of FeO-CaO-SiO2-Al2O3 with CaC% was examined. A thermodynamic estimation with the principle of Gibbs free energy minimization showed that the major vapor species from the sample of the FeO-CaO-SiO2-Al2O3 system＋PbO＋CaCl2 were metallic Pb, PbCl, PbCl2, and FeCl2, at the experimental temperature range. The experimental results show that the mole ratio of vaporized Cl in lead chlorides to vaporized Pb, simply expressed as Cl/Pb decreases with increasing temperature. The larger Cl/Pb means a larger ratio of gaseous PbCl2, since metallic Pb and PbCl vapors are formed in a similar reduction atmosphere. The evaporation is initially rapid and becomes steady after holding for 10 min. Gaseous PbCl2 is mainly formed during the heating period, and at the holding stage, it reacts with FeO to produce gaseous FeCl2 With regard to slag composition, FeO content and basicity significantly affect the evaporation of lead. High FeO content and high basicity promotes the formation of metallic Pb and PbCI, whereas, it prohibits PbCl2 evaporation.

Iron extraction from lead slag by bath smelting

A new bath smelting process was proposed to recover iron for solid wastes reduction.99.79%of iron metallization,99.61%of iron recovery,pig iron with93.58%Fe,0.021%S,0.11%P,1.38%C,0.22%Si,0.01%Pb and0.031%Zn were achievedafter the wastes were smelted at1575°C for20min under C/Fe molar ratio of1.6and basicity of1.2.The produced pig iron could beused in steel-making.This study provides a way for recycling iron from smelting slag and hydrometallurgical residue.

Development of Steel Slag-Based Solidification/Stabilization Materials for High Moisture Content Soil

To solve the problems of high moisture content,high viscosity,and poor engineering mechanical properties of soil,this paper using with steel slag(SS)and desulfurization ash(DS)as initial raw materials,realizing the coop-erative treatment of solid waste and solidification of silt soil.The synergistic utilization of SS and DS can reduce the production cost of curing agent and promote its own consumption.According to blended cement of various SS contents and inspected compressive strength performances,the most suitable raw materials ratio was selected.The best formula for this curing agent is cement:steel slag=3:7 with 5%DS,and its 28-day compressive strength can reach 30 MPa.The experiment shows that the effect of DS and Na_(2)SO_(4) reagent with the same quality on early compressive strength improvement of cement and SS system is not much different.In this study,the mineral composition and microstructure of different gel system blocks were characterized by XRD,SEM and EDX,and a large number of webbed structures were found in the SEM test,which was not seen in previous studies.Besides,unconfined compressive strength(UCS),water resistance,and toxic characteristic leaching procedure(TCLP)were used to evaluate silt solidified soil properties.The results demonstrated that the solidified silt could meet not only the standard of general subgrade;but also has a partial stabilization effect of heavy metal ions.

Recovery of iron from lead-zinc metallurgical slags by bath smelting

The recovery of iron from iron sinking slag and lead smelter slag was investigated by desulfurization-reduction bath smelting. The effects of lead smelter slag(LSS) to iron sinking slag(ISS) mass ratio and temperature were investigated in desulfurization experiments. The X-ray diffraction(XRD) and X-ray fluorescence(XRF) analyses show that the optimum conditions are LSS:ISS of 3:7 and temperature of 1350°C. The composition of desulfurization products is mainly Zn Fe2O4, and the desulfurization rate of 99.66% is obtained under optimum conditions. The thermogravimetric(TG) and differential scanning calorimeter(DSC) analyses demonstrate that reductant is necessary for decomposition and reduction of zinc ferrite in desulfurization product. The effects of reductant, temperature and feeding modes on iron enrichment were investigated in reduction experiments. The scanning electron microscope(SEM) and energy dispersive spectrometer(EDS) determination show that the iron content of reduction product is up to 99.36% under optimum conditions of coke as reductant, reduction temperature of 1450°C and the feeding mode of premixing.

Roasting and leaching behaviors of vanadium and chromium in calcification roasting–acid leaching of high-chromium vanadium slag

Calcification roasting–acid leaching of high-chromium vanadium slag(HCVS)was conducted to elucidate the roasting and leaching behaviors of vanadium and chromium.The effects of the purity of Ca O,molar ratio between Ca O and V_2O_5(n(Ca O)/n(V_2O_5)),roasting temperature,holding time,and the heating rate used in the oxidation–calcification processes were investigated.The roasting process and mechanism were analyzed by X-ray diffraction(XRD),scanning electron microscopy(SEM),and thermogravimetry–differential scanning calorimetry(TG–DSC).The results show that most of vanadium reacted with Ca O to generate calcium vanadates and transferred into the leaching liquid,whereas almost all of the chromium remained in the leaching residue in the form of(Fe_(0.6)Cr_(0.4))_2O_3.Variation trends of the vanadium and chromium leaching ratios were always opposite because of the competitive reactions of oxidation and calcification between vanadium and chromium with Ca O.Moreover,Ca O was more likely to combine with vanadium,as further confirmed by thermodynamic analysis.When the HCVS with Ca O added in an n(Ca O)/n(V_2O_5)ratio of 0.5 was roasted in an air atmosphere at a heating rate of 10°C/min from room temperature to 950°C and maintained at this temperature for 60 min,the leaching ratios of vanadium and chromium reached91.14%and 0.49%,respectively;thus,efficient extraction of vanadium from HCVS was achieved and the leaching residue could be used as a new raw material for the extraction of chromium.Furthermore,the oxidation and calcification reactions of the spinel phases occurred at 592and 630°C for n(Ca O)/n(V_2O_5)ratios of 0.5 and 5,respectively.

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.

Influence of TiO2 on the melting property and viscosity of Cr-containing high-Ti melting slag

A study on the melting and viscosity properties of the chromium-containing high-titanium melting slag(CaO–SiO2–MgO–Al2O3–TiO2–Cr2O3) with TiO2 contents ranging from 38.63 wt% to 42.63 wt% was conducted. The melting properties were investigated with a meltingpoint apparatus, and viscosity was measured using the rotating cylinder method. The FactSage 7.1 software and X-ray diffraction, in combination with scanning electron microscopy–energy-dispersive spectroscopy(SEM–EDS), were used to characterize the phase equilibrium and microstructure of chromium-containing high-titanium melting slags. The results indicated that an increase in the TiO2 content led to a decrease in the viscosity of the chromium-containing high-titanium melting slag. In addition, the softening temperature, hemispheric temperature, and flowing temperature decreased with increasing TiO2 content. The amount of crystallized anosovite and sphene phases gradually increased with increasing TiO2 content, whereas the amount of perovskite phase decreased. SEM observations revealed that the distribution of the anosovite phase was dominantly influenced by TiO2.

Research on the Low-carbon Cementitious Materials:Effect of Triisopropanolamine on the Hydration of Phosphorous Slag and Steel Slag

Cement,phosphorous slag(PS),and steel slag(SS)were used to prepare low-carbon cementitious materials,and triisopropanolamine(TIPA)was used to improve the mechanical properties by controlling the hydration process.The experimental results show that,by using 0.06%TIPA,the compressive strength of cement containing 60%PS or 60%SS could be enhanced by 12%or 18%at 28 d.The presence of TIPA significantly affected the hydration process of PS and SS in cement.In the early stage,TIPA accelerated the dissolution of Al in PS,and the formation of carboaluminate hydrate was facilitated,which could induce the hydration;TIPA promoted the dissolution of Fe in SS,and the formation of Fe-monocarbonate,which was precipitated on the surface of SS,resulting in the postponement of hydration,especially for the high SS content.In the later stage,under the continuous solubilization effect of TIPA,the hydration of PS and SS could refine the pore structure.It was noted that compared with portland cement,the carbon emissions of cement-PS-TIPA and cement-SS-TIPA was reduced by 52%and 49%,respectively.

Early Intervention on the Properties of Steel Slag at High Temperature by Modifier Compound with Tailings: A Feasible Way for Comprehensive Utilization of Solid Wastes

Steel slag, a by-product of the steel production industry reaches 10%–15% of crude steel output (Motz and Geiseler, 2001). Their main application lies in the field of building materials due to some containing cementitious components, such as dicalcium silicate (C2S) and tricalcium silicate (C3S) (Waligora et al., 2010). However, blended cements with steelmaking slag show low early hydration activity, low compressive strength and bad durability because steel slag generates above 1600 ℃ with the tense and large grain size crystals, consisting of low content of C2S and C3S and high proportions of f-CaO and f-MgO compared with cement clinker.