Enhanced recovery of high-purity Fe powder from iron-rich electrolytic manganese residue by slurry electrolysis

Iron-rich electrolytic manganese residue(IREMR)is an industrial waste produced during the processing of electrolytic metal manganese,and it contains certain amounts of Fe and Mn resources and other heavy metals.In this study,the slurry electrolysis technique was used to recover high-purity Fe powder from IREMR.The effects of IREMR and H2SO4 mass ratio,current density,reaction temper-ature,and electrolytic time on the leaching and current efficiencies of Fe were studied.According to the results,high-purity Fe powder can be recovered from the cathode plate,and the slurry electrolyte can be recycled.The leaching efficiency,current efficiency,and purity of Fe reached 92.58%,80.65%,and 98.72wt%,respectively,at a 1:2.5 mass ratio of H2SO4 and IREMR,reaction temperature of 60℃,electric current density of 30 mA/cm^(2),and reaction time of 8 h.In addition,vibrating sample magnetometer(VSM)analysis showed that the coercivity of electrolytic iron powder was 54.5 A/m,which reached the advanced magnetic grade of electrical pure-iron powder(DT4A coercivity standard).The slurry electrolytic method provides fundamental support for the industrial application of Fe resource recovery in IRMER.

Synthesis of zeolite A and zeolite X from electrolytic manganese residue,its characterization and performance for the removal of Cd^(2+)from wastewater

Electrolytic manganese residue(EMR)can cause serious environmental and biological hazards.In order to solve the problem,zeolite A(EMRZA)and zeolite X(EMRZX)were synthesized by EMR.The pure phase zeolites were synthesized by alkaline melting and hydrothermal two-step process,which had high crystallinity and excellent crystal control.And the optimum conditions for synthesis of zeolite were investigated:NaOH-EMR mass ratio=1.2,L/S=10,hydrothermal temperature=90℃,and hydrothermal time=6 h.Then,EMRZA and EMRZX showed excellent adsorption of Cd^(2+).When T=25℃,time=120min,pH=6,C0=518 mg·L^(-1),and quantity of absorbent=1.5 g·L^(-1),the adsorption capacities of EMRZA and EMRZX reached 314.2 and 289,5 mg·g^(-1),respectively,In addition,after three repeated adsorption-desorption cycles,EMRZA and EMRZX retained 80%and 74%of the initial zeolites removal rates,respectively.Moreover,adsorption results followed quasi-second-order kinetics and monolayer adsorption,which was regulated by a combination of chemisorption and intra-particle diffusion mechanisms.The adsorption mechanism was ions exchange between Cd^(2+)and Na+.In summary,it has been confirmed that EMRZA and EMRZX can be reused as highly efficient adsorbents to treat Cd^(2+)-contaminated wastewater.

Sulfur resource recovery based on electrolytic manganese residue calcination and manganese oxide ore desulfurization for the clean production of electrolytic manganese

An environmentally friendly and resource-conserving route to the clean production of electrolytic manganese was developed,in which the electrolytic manganese residue(EMR)was initially calcined for cement buffering;then the generated SO2-containing flue gas was managed using manganese oxide ore and anolyte(MOOA)desulfurization;at last,the desulfurized slurry was introduced to the electrolytic manganese production(EMP).Results showed that 4.0 wt%coke addition reduced the sulfur of calcined EMR to 0.9%,thereby satisfying the cement-buffer requirement.Pilot-scale desulfurization showed that about 7.5 vol%of high SO2 containing flue gas can be cleaned to less than 0.1 vol%through a five-stage countercurrent MOOA desulfurization.The desulfurized slurry had 42.44 g·L-Mn2+and 1.92 g·L-1 S2 O62-,which was suitable for electrowinning after purification,and the purity of manganese product was 99.93%,satisfy the National Standard of China YB/T051-2015.This new integrated technology fulfilled 99.7%of sulfur reutilization from the EMR and 94.1%was effectively used to the EMP.The MOOA desulfurization linked the EMP a closed cycle without any pollutant discharge,which promoted the cleaner production of EMP industry.

Crystallization Characteristic of Glass-ceramic Made from Electrolytic Manganese Residue

Electrolytic manganese residue （EMR） is a waste from electrolytic manganese industry that contains high concentration of toxic substances. Since the EMR disposal in landfill sites has a serious environmental impact, new ways of EMR utilization are being sought. Considering the melting of EMR to a glass at high temperature was a relatively less energy-intensive process, EMR was first made into a base glass and then the ground base glass was heat-treated in a certain procedure to make a glass-ceramic and the crystallization process was studied. It was determined by X-ray diffraction （XRD） that the primary crystalline phases of the EMR glass-ceramic were diopside and anorthite, which formed the surface crystallization mechanism with a crystallization activation energy of 429 kJ/mol. Scanning electron microscopy （SEM） observation showed that a layer of small spherical particles with an average size of about 0.5 ~tm were covered on the glass matrix surface, and among them there were some big particles. The low melting temperature and crystallization activation energy make it promising to reuse EMR for glass-ceramic production.

Preparation of MnO_2 and calcium silicate hydrate from electrolytic manganese residue and evaluation of adsorption properties

Electrolytic manganese residue(EMR), a high volume byproduct resulting from the electrolytic manganese industry, was used as a cheap and abundant chemical source for preparing MnO2 and EMR-made calcium silicate hydrate(EMR-CSH). The MnO2 is successfully synthesized from the metal cations extracted from EMR, which can effectively recycle the manganese in the EMR. By the combination of XRD, SEM and EDX analysis, the as-prepared MnO2 is found to exhibit a single-phase with the purity of 90.3%. Furthermore, EMR-CSH is synthesized from EMR via hydrothermal method. Based on the detailed analyses using XRD, FT-IR, FE-SEM, EDX and BET surface area measurement, the product synthesized under the optimum conditions(p H 12.0 and 100 °C) is identified to be a calcium silicate hydrate with a specific surface area of 205 m2/g incorporating the slag-derived metals(Al and Mg) in its structure. The as-synthesized material shows good adsorption properties for removal of Mn2+ and phosphate ions diluted in water, making it a promising candidate for efficient bulk wastewater treatment. This conversion process, which enables us to fabricate two different kinds of valuable materials from EMR at low cost and through convenient preparation steps, is surely beneficial from the viewpoint of the chemical and economical use of EMR.

Cooperative removal of Mn^(2+),NH_(4)^(+)-N,PO_(4)^(3-)-P and F−from electrolytic manganese residue leachate and phosphogypsum leachate

Electrolytic manganese residue leachate(EMRL)contains plenty of Mn^(2+) and NH_(4)^(+)-N,and phosphogypsum leachate(PGL)contains large amounts of PO_(4)^(3-)-P and F^(-).Traditional methods of EMRL and PGL discharge could seriously damage the ecological environment.In this study,an innovative method for cooperative removal Mn^(2+),NH_(4)^(+)-N,PO_(4)^(3-)-P,F^(-)from PG and POFT was studied.The result showed that Mn^(2+),PO_(4)^(3-)-P and F^(-)were mainly removed in forms of Mg_(3)Si_(4)O_(10)(OH)_(2),Mn_(3)O_(4),Mn_(3)(PO_(4))_(2),Mg_(3)(PO_(4))_(2),CaSO_(4)·2H_(2)O,MnF_(2),MnOOH and Ca_(2)P_(2)O_(7)·2H_(2)O,when LG-MgO was used to adjust the pH value of the system to 9.5,and the volume ratio of EMRL and PGL was 1:4,as well as reaction for 1 h at 25℃.NH_(4)^(+)-N was mainly removed by struvite precipitate,when the molar ratio of N:Mg:P was 1:3:2.4.The concentrations of Mn^(2+),NH_(4)^(+)-N and F^(-)were lower than the integrated wastewater discharge standard.The concentration of PO_(4)^(3-)-P decreased from 254.20 mg/L to 3.21 mg/L.This study provided a new method for EMRL and PGL cooperative harmless treatment.

Enhanced Mn^(2+)solidification and NH_(4)^(+)-N removal from electrolytic manganese metal residue via surfactants

Electrolytic manganese metal residue(EMMR)harmless treatment has always lacked a low-cost and quick processing technology.In this study,surfactants,namely tetradecyl trimethylammonium chloride(TTC),sodium dodecyl benzene sulfonate(SDBS),sodium lignin sulfonate(SLS),and octadecyl trimethylammonium chloride(OTC),were used in the solidification of Mn^(2+)and removal of NH_(4)^(+)-N from EMMR.The Mn^(2+)and NH_(4)^(+)-N concentrations under different reaction conditions,Mn^(2+)solidification and NH_(4)^(+)-N removal mechanisms,and leaching behavior were studied.The results revealed that the surfactants could enhance the Mn^(2+)solidification and NH_(4)^(+)-N removal from EMMR,and the order of enhancement was as follows:TTC>SDBS>OTC>SLS.The NH_(4)^(+)-N and Mn^(2+)concentrations were 12.3 and 0.05 mg·L^(-1)with the use of 60.0 mg·kg^(-1)TTC under optimum conditions(solid–liquid ratio of 1.5:1,EMMR to BRM mass ratio of 100:8,temperature of 20℃,and reaction duration of 12 h),which met the integrated wastewater discharge standard(GB8978-1996).Mn^(2+)was mainly solidified as Mn(OH)_(2),MnOOH and MnSiO_(3),and NH_(4)^(+)-N in EMMR was mostly removed in the form of ammonia.The results of this study could provide a new idea for cost-effective EMMR harmless treatment.

A novel electrolytic-manganese-residues-and-serpentine-based composite(S-EMR) for enhanced Cd(Ⅱ) and Pb(Ⅱ) adsorption in aquatic environment

Electrolytic manganese residue(EMR) is the waste slag generated from the electrolysis manganese industry.As a promising exploitable adsorbent,EMR has become a hot research topic.However,EMR’s low adsorption capacity has limited its applications as an efficient adsorbent.In this study,the EMR was mixed with serpentine and calcined(at 800℃ for 2 h) to prepare a composite adsorbent(S-EMR) with its specific surface area of 11.998 m^(2)·g^(-1)(increased compared to the original EMR) and improved adsorption capacities for Cd^(2+)(98.05 mg·g^(-1)) and Pb^(2+)(565.81 mg·g^(-1)).Kinetic studies have shown that the pseudo-first-order kinetics(PSO)model could best describe the adsorption kinetics of S-EMR for Cd^(2+)/Pb^(2+),implying that the chemisorption process is the rate-limiting step.The effects of different interfering ions on S-EMR’ s adsorption for Cd^(2+)/Pb^(2+)may be due to the difference in their electronegativity.Results of response surface methodology tests showed that pH had the highest influence on adsorption,and the removal efficiency of S-EMR reached 99.92% for Cd(Ⅱ) and 94.00%for Pb(Ⅱ).X-ray photoelectron spectroscopy(XPS) analyses revealed that chemical precipitation was the predominant mechanism for Cd^(2+)/Pb^(2+)removal,and the adsorption mechanisms were associated with ion exchange and electrostatic attraction.The results showed that S-EMR could be used as an effective adsorbent for the removal of Cd(Ⅱ)/Pb(Ⅱ) from water bodies,rendering dual benefits of pollution control and resource recovery.

Phase Transitions Relating to the Pozzolanic Activity of Electrolytic Manganese Residue During Calcination

Electrolytic manganese residue （EMR） is generated from electrolytic manganese metal （EMM） indus- try, and its disposal is currently a serious problem in China. The EMR were calcined in the interval 100-900 ℃ to enhance their pozzolanic activity and characterized by the differential thermal analysis-thermogravimetry （TG- DTA）, X-ray diffraction （XRD）, infra-red （IR） and chemical analysis techniques with the aim to correlate phase transitions and structural features with the pozzolanic activity of calcined EMR. From the phase analysis and compressive strength results, it is found that the EMR calcined within 700--800℃ had the best pozzolanic activity due to the decomposition of poorly-crystallized CaSO4 under the reducing ambient created by the decomposition of （NH4）2SO4. The appearance of reactive CaO mainly contributes to the good pozzolanic activity of EMR cal- cined within 700--800℃. The crystallinity of MnaO4 increases leading an unfavourable effect on the pozzolanic behaviour of EMR calcined at 900℃. The developed pozzolanic material containing 30% （mass fraction） EMR possesses compressive strength properties at a level similar to 42.5# normal Portland cement, in the range of 41.5--50.5 MPa. Besides, leaching results show that EMR blend cement pastes have excellent effect on the solidi- fication of heavy metals.