Physicochemical properties of arsenic-bearing lime-ferrate sludge and its leaching behaviors

Physicochemical properties and leaching behaviors of two typical arsenic-bearing lime?ferrate sludges(ABLFS),waste acid residue(WAR)and calcium arsenate residue(CAR),are comprehensively described.The chemical composition,morphological features,phase composition and arsenic occurrence state of WAR and CAR are analyzed by ICP?AES,SEM?EDS,XRD,XPS and chemical phase analysis.The toxicity leaching test and three-stage BCR sequential extraction procedure are utilized to investigate arsenic leaching behaviors.The results show that the contents of arsenic in WAR and CAR are2.5%and21.2%and mainly present in the phases of arsenate and arsenic oxides dispersed uniformly or agglomerated in amorphous particles.The leaching concentrations of arsenic excess119and1063times of TCLP standard regulatory level with leaching rates of47.66%and50.15%for WAR and CAR,respectively.About90%of extracted arsenic is in the form of acid soluble and reducible,which is the reason of high arsenic leaching toxicity and environmental activity of ABLFS.This research provides comprehensive information on harmless disposal of ABLFS from industrial wastewater treatment of lime?ferrate process.

Physicochemical and environmental properties of arsenic sulfide sludge from copper and lead-zinc smelter

Physicochemical properties of arsenic sulfide sludge(ASS) from copper smelter(ASS-I) and lead-zinc smelter(ASS-II) were examined by XRD, Raman spectroscopy, SEM-EDS, TG-DTA, XPS and chemical phase analysis method. The toxicity characteristic leaching procedure(TCLP), Chinese standard leaching tests(CSLT), three-stage sequential extraction procedure(BCR) and batch leaching experiments(BLE) were used to investigate the environmental stability. The ASSs from different smelters had obviously different physicochemical and environmental properties. The phase composition and micrograph analysis indicate that ASS-I mainly consists of super refined flocculent particles including amorphous arsenic sulfide adhered with amorphous sulfur and that ASS-II mainly consists of amorphous arsenic sulfide. The valence state of arsenic in both sludges is trivalent, but the valence composition of sulfur is quite different. The ASSs have thermal instability properties. The results of TCLP and CSLT indicate that the concentrations of As and Pd in the leaching solution exceed the standard limits. More than 5% and 90% of arsenic are in the form of acid soluble and oxidizable fractions, respectively, which explains the high arsenic leaching toxicity and environmental activity of ASS. This research provides comprehensive information for the disposal of ASS from copper and lead-zinc smelter.

Recovery of valuable metals from zinc leaching residue by sulfate roasting and water leaching

Zinc leaching residue(ZLR),produced from traditional zinc hydrometallurgy process,is not only a hazardous waste but also a potential valuable solid.The combination of sulfate roasting and water leaching was employed to recover the valuable metals from ZLR.The ZLR was initially roasted with ferric sulfate at640°C for1h with ferric sulfate/zinc ferrite mole ratio of1.2.In this process,the valuable metals were efficiently transformed into water soluble sulfate,while iron remains as ferric oxide.Thereafter,water leaching was conducted to extract the valuable metals sulfate for recovery.The recovery rates of zinc,manganese,copper,cadmium and iron were92.4%,93.3%,99.3%,91.4%and1.1%,respectively.A leaching toxicity test for ZLR was performed after water leaching.The results indicated that the final residue was effectively detoxified and all of the heavy metal leaching concentrations were under the allowable limit.

Separation and recovery of copper in Cu-As-bearing copper electrorefining black slime by oxidation acid leaching and sulfide precipitation

A new hydrometallurgical route for separation and recovery of Cu from Cu-As-bearing copper electrorefining black slime was developed. The proposed process comprised oxidation acid leaching of Cu-As-bearing slime and selective sulfide precipitation of Cu from the leachate. The effects of various process parameters on the leaching and precipitation of Cu and As were investigated. At the first stage, Cu extraction of 95.2% and As extraction of 97.6% were obtained at 80 ℃ after 4 h with initial H2 SO4 concentration of 1.0 mol/L and liquid-to-solid ratio of 10 mL/g. In addition, the leaching kinetics of Cu and As was successfully reproduced by the Avrami model, and the apparent activation energies were found to be 33.6 and 35.1 kJ/mol for the Cu and As leaching reaction, respectively, suggesting a combination of chemical reaction and diffusion control. During the selective sulfide precipitation, about 99.4% Cu was recovered as CuS, while only 0.1% As was precipitated under the optimal conditions using sulfide-to-copper ratio of 2.4:1, time of 1.5 h and temperature of 25 ℃.

Stabilization of ferric arsenate sludge with mechanochemically prepared FeS2/Fe composites

FeS2/Fe composites were mechanochemically prepared with iron powder and pyrite for the stabilization of ferrite arsenate sludge(FAS).The effects of preparation parameters on stabilization performance were investigated.The results show that the optimum conditions are FeS2/Fe molar ratio of 5:5,milling time of 2 h,ball-to-material mass ratio of 15:1 and milling with stainless steel ball.Then,the composites were characterized by XRD,SEM,FTIR,etc.The physicochemical properties of FeS2/Fe mixture change dramatically,which is responsible for its excellent performance.Finally,the stabilization process of FAS was optimized.When the FAS is mixed with composites at mass ratio of 4:1 and milled for 30 min,the As leaching concentration of FAS can be reduced from 639.15 to 4.74 mg/L with the stabilization ratio of 99.2%.

Interaction mechanism between arsenate and fayalite-type copper slag at high temperatures

The interaction mechanism between sodium arsenate and fayalite-type copper slag at 1200℃was investigated through XRD,XPS,HRTEM,TCLP and other technical means and methods.The results indicated that the proportions of sodium arsenate in the slag and flue gas phases were approximately 30%and 70%,respectively.The addition of sodium arsenate depolymerized the fayalite structure and changed it from a crystalline state to an amorphous state.The fayalite structural changes indicated that the[AsO_(4)]tetrahedron in sodium arsenate combined with the[SiO_(4)]tetrahedron and[FeO_(4)]tetrahedron through bridging oxygen to form a silicate glass structure.The TCLP test results of the samples before and after the high temperature reaction of fayalite and sodium arsenate showed that after high temperature reaction,fayalite could effectively reduce the leaching toxicity of sodium arsenate,reducing the leaching concentration of arsenic from 3025.52 to 12.8 mg/L before and after reaction,respectively.

Isothermal reduction kinetics of zinc calcine under carbon monoxide

The reduction kinetics of zinc calcine under a CO atmosphere was evaluated by isothermal reductive roasting in a temperature range of 600-800℃.The extent of reaction of zinc calcine was measured using thermogravimetry(TG),and the decomposition mechanism of zinc ferrite in zinc calcine was analyzed based on variations in the soluble zinc and ferrous contents.The results indicate that the reaction was controlled by the nucleation of the products,with an apparent activation energy of 65.28 k J/mol.The partial pressure of CO affected the reaction rate more strongly than the CO intensity(defined as PCO/(PCO+PCO2)).The generation rate of zinc oxide was higher than that of ferrous oxide;therefore,the nucleation of ferrous oxide is the rate-determining step of the reaction.

Microstructure and magnetic properties of FeAs with coarse-grain and nanocrystalline structure

The microstructure and magnetic properties of iron arsenide(FeAs) with coarse-grain and nanocrystalline structure were investigated. Coarse-grain FeAs was synthesized through high-energy ball milling and heat treatment. Nanocrystalline FeAs was obtained by ball milling of coarse-grain FeAs. The results suggest that the reduced grain size of FeAs(from >100 to 32.4 nm) is accompanied by the introduction of internal strains up to 0.568% with ball milling time from 0 to 32 h. The magnetic properties of FeAs show that the coercivity is reduced from 29.2 to 15.6 kA/m and the magnetization is increased over time of milling. The low coercivity is mainly due to the small grain size stemmed from ball milling, while the increase of magnetization is primarily caused by the change of lattice parameters of FeAs and the emergence of superparamagnetic phase at the same time.

Preparation of Fe-As alloys by mechanical alloying and vacuum hot-pressed sintering:microstructure evolution,mechanical properties,and mechanisms

Arsenic materials have attracted great attention due to their unique properties.However,research concerning iron-arsenic(Fe-As) alloys is very scarce due to the volatility of As at low temperature and the high melting point of Fe.Herein,a new Fe-As alloy was obtained by mechanical alloying(MA) followed by vacuum hot-pressed sintering(VHPS).Moreover,a systematic study was carried out on the microstructural evolution,phase composition,leaching toxicity of As,and physical and mechanical properties of Fe-As alloys with varying weight fractions of As(20%,25%,30%,35%,45%,55%,65%,and 75%).The results showed that pre-alloyed metallic powders(PAMPs) have a fine grain size and specific supersaturated solid solution after MA,which could effectively improve the mechanical properties of Fe-As alloys by VHPS.A high density(> 7.350 g·cm^(-3)),low toxicity,and excellent mechanical properties could be obtained for FeAs alloys sintered via VHPS by adding an appropriate amount of As,which is more valuable than commercial Fe-As products.The Fe-25% As alloy with low toxicity and a relatively high density(7.635 g·cm^(-3)) provides an ultra-high compressive strength(1989.19 MPa),while the Fe-65% As alloy owns the maximum Vickers hardness(HVo.5 899.41).After leaching by the toxicity characteristic leaching procedure(TCLP),these alloys could still maintain good mechanical performance,and the strengthening mechanisms of Fe-As alloys before and after leaching were clarified.Changes in the grain size,micro structure,and phase distribution induced significant differences in the compressive strength and hardness.

New function of the Yb^(3+) ion as an efficient emitter of persistent luminescence in the short-wave infrared

The trivalent ytterbium(Yb^(3+))ion has been extensively used as an emitter in short-wave infrared(SWIR)lasers,a sensitizer to activate other lanthanide ions for up-conversion luminescence,and a spectral converter in Ln^(3+)-Yb^(3+)doubly doped quantum cutting phosphors.Here we report a new function of the Yb^(3+)ion—as an efficient emitting center for SWIR persistent luminescence.We have developed the first real SWIR persistent phosphor,MgGeO3:Yb^(3+),which exhibits very-long persistent luminescence at around 1000 nm for longer than 100 h.The MgGeO3:Yb^(3+)phosphor is spectrally transparent to visible/near-infrared light(~400–900 nm)and is a promising ultraviolet-to-SWIR spectral convertor.The MgGeO3:Yb^(3+)phosphor also exhibits a photostimulated persistent luminescence capability,where the SWIR persistent emission in an ultraviolet-light pre-irradiated sample can be rejuvenated by low-energy light(white or red light)stimulation.The MgGeO3:Yb^(3+)phosphor is expected to have promising applications in biomedical imaging,night-vision surveillance and photovoltaics.