To address the inefficient utilization of electrolytic manganese residue(EMR)caused by its high inert content,this study developed a multifunctional solid waste cementitious material by replacing 50-60%of ordinary Por...To address the inefficient utilization of electrolytic manganese residue(EMR)caused by its high inert content,this study developed a multifunctional solid waste cementitious material by replacing 50-60%of ordinary Portland cement(PO 42.5)with wet-ground electrolytic manganese residue(WEMR),wetground granulated blast-furnace slag(WGBFS),and carbide slag(CS).The mechanical properties,hydration characteristics,microstructure,and carbon emissions of the material were systematically investigated with varying WEMR dosages.The experimental results demonstrates that the wet-grinding process significantly refines the particle size and enhances the reactivity of both EMR and GBFS.As the WEMR dosage increases,the 28-day compressive strength initially rise and then declines.Optimal mechanical performance was achieved with 24%WEMR and 6%CS,yielding a 28-day compressive strength of 48.2 MPa.Advanced analytical techniques,including XRD,TG-DTG,SEM,and MIP,were employed to examine the hydration products.The findings reveal that the wet-grinding-alkali-sulfur synergistic activation system in the multi-solid waste cementitious material effectively utilize EMR to generate abundant hydration products such as AFt and C-(A)-S-H.Additionally,the fine particles of WEMR fill the pores in the mortar,further enhancing compressive strength.The cost and carbon emissions of this multifunctional system are only 65.97%and 46.9% of those of PO 42.5,respectively.This study provides a feasible approach for the efficient utilization of EMR,contributing to sustainable construction practices.展开更多
The effects of calcination temperature and mechanical ball milling on the physicochemical properties of electrolytic manganese residue(EMR),mineral phase transition,pozzolanic activity,and pore structure were studied....The effects of calcination temperature and mechanical ball milling on the physicochemical properties of electrolytic manganese residue(EMR),mineral phase transition,pozzolanic activity,and pore structure were studied.The experimental results show that the strength activity index(SAI)of 20%EMR mixed mortar at 28 days is 90.54%,95.40%,and 90.73%,respectively,after pretreatment with EMR at 800℃calcined for 3,5,and 8 min.This is mainly attributed to the high temperature decomposition of gypsum dihydrate to form activated calcium oxide.In addition,high temperature and mechanical force destroys the Si-O chemical bond and promotes the formation of calcium silicate gel structure.Due to the existence of a large number of gypsum phases in EMR mixed mortar,a large number of ettringite,C-S-H,aluminosilicate,C-A-S-H,and AFm are formed,which strongly verifies the volcanic activity of EMR.The leaching test shows that high temperature calcination has a significant effect on the stabilization of NH_(3)-N.However,the curing effect of Mn^(2+)is significant only in the calcination at 1000℃,but both Mn^(2+)and NH_(3)-N in the calcined EMR are higher than the emission standard.The encapsulation effect of EMR composite mortar provided by hydration products,and the buffering capacity of the Si-Al system for solidification of heavy metals and strong alkalis are conducive to the stability of Mn^(2+)and NH_(3)-N.After the EMR mixed mortar is aged for 3 days,Mn and NH_(3)-N are completely lower than the emission standard.In general,the EMR mixed mortar can meet the requirements for green building use.展开更多
This study introduced a low-temperature thermochemical method for the treatment of EMR in the presence of carbide slag(CS)to achieve an economical and efficient harmless effect.The experimental results indicate that,u...This study introduced a low-temperature thermochemical method for the treatment of EMR in the presence of carbide slag(CS)to achieve an economical and efficient harmless effect.The experimental results indicate that,under suitable conditions,the NH_(4)^(+)and Mn^(2+)contents in EMR decrease notably with the increasing CS content,accompanied by an increase in pH value.Furthermore,the concentration of NH_(4)^(+)in EMR considerably decreases with the increasing liquid-to-solid ratio,eventually stabilizing.Similarly,the pH value first increases and then decreases,ultimately stabilizing.At a CS content of 12%and a liquid-to-solid ratio of 0.7,the leaching concentrations of NH_(4)^(+)and Mn^(2+)in EMR(127.7 mg/kg and 0.15 mg/L,respectively)fall below the standard detection limit(2 mg/L),with the pH measuring 8.26,meeting the conditions outlined in the GB 8978.NH_(4)^(+)is converted to NH_(3),while Mn^(2+)is transformed into solid precipitates such as Mn(OH)_(2),Mn_(2)O_(3),MnO_(2),Ca_(3)Mn_(2)O_(7),and Ca_(2)MnO_(4).The majority of manganese ions exist in trivalent or tetravalent states and remain stable over time.The cost of using CS as a reagent for treating 1 ton of EMR is merely$1.01.The high OH^(-)concentration provided by CS enables the effective removal of NH_(4)^(+)from EMR and the solidification of Mn^(2+)during thermal reactions.展开更多
To investigate the feasibility of applying electrolytic manganese residue(EMR)in cementitious materials,an approach combining high-temperature activation(200,400,600,800 and 1000℃)and mechanical grinding(5 min)was ad...To investigate the feasibility of applying electrolytic manganese residue(EMR)in cementitious materials,an approach combining high-temperature activation(200,400,600,800 and 1000℃)and mechanical grinding(5 min)was adopted to stimulate the EMR activity.We analyzed the effect of calcination temperature on the performance of EMR with the aid of X-ray diffraction(XRD),specific surface area test(BET)and pozzolanic activity test,explored the effects of EMR activation temperature and content(0%,10%,15% and 20%)on the setting time,soundness,drying shrinkage,compressive strength,hydration products of cement-EMR mixed slurry,and assessed the effect of cement hydration on the solidification of harmful NH_(4)^(+)-N and Mn^(2+) in EMR.The research results show that high-temperature calcination can lead to the dehydration,decomposition or crystalline phase transformation of the inert sulfate and other substances in EMR,mechanical grinding can improve its particle distribution,and the coupling of the two can effectively enhance the pozzolanic activity of EMR.The decomposition and recombination of aluminum-silica phase at 800℃ optimized the EMR activity,and the strength activity index(SAI)of EMR at 28 d reached up to 95%.Appropriate calcination temperature and EMR content can ensure the workability of the mixed slurry,and when the EMR calcination temperature was 400-1000℃,the setting time of the mixed slurry under different EMR contents satisfied the specification requirements.When the calcination temperature was 600-1000℃ and EMR content was less than 20%,the soundness of the mixed slurry satisfied the specification requirements.The compressive strength of the mixed slurry increased and then decreased with the increase of activated EMR content,when the EMR content was 10%,the compressive strength of all specimens was optimal and higher than the baseline group;when the activation temperature was 800℃,the C-S-H gel in the mixed slurry interconnected with the rod-like Aft and blocked Ca(OH)_(2),and the 28 d compressive strength was increased by 14%compared with that of the baseline group.The solidification rate of Mn^(2+) in EMR by cement hydration was higher than 99%,and that of NH_(4)^(+)-N was higher than 97%.The leaching toxicity after solidification can meet the requirements of toxic emission.The results of the study may provide theoretical basis for the feasibility of the application of EMR in cementitious materials.展开更多
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;the...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.展开更多
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 e...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.展开更多
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,...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.展开更多
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 hydrat...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.展开更多
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 thi...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.展开更多
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 c...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.展开更多
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 synthesi...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.展开更多
With growing concerns regarding electromagnetic pollution,low-cost,environmentally friendly,and high-performance electromagnetic wave absorption(EWA)materials have attracted significant attention.This paper reports on...With growing concerns regarding electromagnetic pollution,low-cost,environmentally friendly,and high-performance electromagnetic wave absorption(EWA)materials have attracted significant attention.This paper reports on the synthesis of porous Fe_(3)O_(4)/C composites that incorporate dielectric and magnetic loss mechanisms via the carbothermal reduction method and optimization of waste ratio to enhance EWA performance.The Fe_(3)O_(4)/C composites with 10wt%soybean residues(Fe_(3)O_(4)/C-10),demonstrated the best EWA performance,achieving the minimum reflection loss of−56.4 dB and a bandwidth of 2.14 GHz at a thickness of 2.23 mm.This enhanced EWA performance is primarily attributable to improved impedance matching and the synergistic effect between dielectric and magnetic losses.Furthermore,radar cross-sectional simulations confirmed the practical feasibility of the porous Fe_(3)O_(4)/C composites.This study proposes a viable strategy for utilizing soybean residue and electrolytic manganese residue,highlighting their potential applications in EWA.展开更多
In addressing the challenges of solid waste disposal, this study proposed to utilize electrolytic manganese residue to produce building insulation materials. The research focused on the factors such as precursor mater...In addressing the challenges of solid waste disposal, this study proposed to utilize electrolytic manganese residue to produce building insulation materials. The research focused on the factors such as precursor material ratio, alkali activator ratio, foaming agent and foam stabilizer on the target insulation materials properties. The findings indicated that SiO_(2)/Al_(2)O_(3) molar ratio, SiO_(2)/Na_(2)O molar ratio, and liquid/solid mass ratio impact the mechanical properties of the samples. The best mechanical performance of building structural material samples was characterized by a compressive strength of 11.15 MPa and a density of 1476 kg/m3. The optimal properties for building insulation materials were a thermal conductivity of 0.131–0.104 W/(m·K), compressive strength of 1.49–0.69 MPa, and density of 533–433 kg/m^(3), with a cost of 1722–1294 CNY/m^(3). This research provides a new approach for large-scale electrolytic manganese residue utilization while enhancing insulation performance and reducing energy consumption in buildings, with promising prospects for further engineering development.展开更多
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 ...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.展开更多
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 benz...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.展开更多
We considered adding different amounts(1%,2%,3%,and 4%)of EMR to prepare manganese residue polymer magnesium phosphate cement composite(EMR-PMPC).The influence mechanism of EMR doping on the early macroscopic and micr...We considered adding different amounts(1%,2%,3%,and 4%)of EMR to prepare manganese residue polymer magnesium phosphate cement composite(EMR-PMPC).The influence mechanism of EMR doping on the early macroscopic and microscopic pore structure properties of composites was studied by combining macroscopic and microscopic testing methods.The experimental results show that the addition of EMR can improve the working performance of the slurry and enhance the strength in the later stage,the 28 d compressive strength value of the slurry doped with EMR can reach 49.5 MPa.The Mn element and NH4_(+)^(-)N in EMR react with MgO in the raw material to produce Struvite and Mn(OH)_(2)and Mn_(3)(PO_(4))·6H_(2)O gel,the hydration products coexist with each other and lap each other to form a dense microfine structure and effectively refine the pores.The hydration process consists of five stages,mainly concentrated in the first 10 h or less to exothermic mainly,infrared spectral absorption band is mainly composed of O-H bond,H-O-H bond,PO_(4)bond and metal oxygen bond 3 parts,EMR makes the wave number of the absorption band from the ground wave number to the high wave number.EMR doping T_(2)spectral relaxation time will lag behind,the pore size distribution changes.The total porosity and bound fluid saturation decrease with increasing,the free fluid saturation shows the opposite trend,the permeability decreases and then increases.展开更多
基金Funded by the Guangxi Key Research and Development Program(Nos.GK AB24010020,and GK AB23026071)the Key Project of Guangxi Natural Science Foundation(No.2025GXNSFDA090046)the Guangxi Science and Technology Base and Talent Special Project(No.GK AD24010062)。
文摘To address the inefficient utilization of electrolytic manganese residue(EMR)caused by its high inert content,this study developed a multifunctional solid waste cementitious material by replacing 50-60%of ordinary Portland cement(PO 42.5)with wet-ground electrolytic manganese residue(WEMR),wetground granulated blast-furnace slag(WGBFS),and carbide slag(CS).The mechanical properties,hydration characteristics,microstructure,and carbon emissions of the material were systematically investigated with varying WEMR dosages.The experimental results demonstrates that the wet-grinding process significantly refines the particle size and enhances the reactivity of both EMR and GBFS.As the WEMR dosage increases,the 28-day compressive strength initially rise and then declines.Optimal mechanical performance was achieved with 24%WEMR and 6%CS,yielding a 28-day compressive strength of 48.2 MPa.Advanced analytical techniques,including XRD,TG-DTG,SEM,and MIP,were employed to examine the hydration products.The findings reveal that the wet-grinding-alkali-sulfur synergistic activation system in the multi-solid waste cementitious material effectively utilize EMR to generate abundant hydration products such as AFt and C-(A)-S-H.Additionally,the fine particles of WEMR fill the pores in the mortar,further enhancing compressive strength.The cost and carbon emissions of this multifunctional system are only 65.97%and 46.9% of those of PO 42.5,respectively.This study provides a feasible approach for the efficient utilization of EMR,contributing to sustainable construction practices.
基金Funded by the National Natural Science Foundation of China(No.52178216)the Gansu Provincial Science and Technology Programme(No.23JRRA813)。
文摘The effects of calcination temperature and mechanical ball milling on the physicochemical properties of electrolytic manganese residue(EMR),mineral phase transition,pozzolanic activity,and pore structure were studied.The experimental results show that the strength activity index(SAI)of 20%EMR mixed mortar at 28 days is 90.54%,95.40%,and 90.73%,respectively,after pretreatment with EMR at 800℃calcined for 3,5,and 8 min.This is mainly attributed to the high temperature decomposition of gypsum dihydrate to form activated calcium oxide.In addition,high temperature and mechanical force destroys the Si-O chemical bond and promotes the formation of calcium silicate gel structure.Due to the existence of a large number of gypsum phases in EMR mixed mortar,a large number of ettringite,C-S-H,aluminosilicate,C-A-S-H,and AFm are formed,which strongly verifies the volcanic activity of EMR.The leaching test shows that high temperature calcination has a significant effect on the stabilization of NH_(3)-N.However,the curing effect of Mn^(2+)is significant only in the calcination at 1000℃,but both Mn^(2+)and NH_(3)-N in the calcined EMR are higher than the emission standard.The encapsulation effect of EMR composite mortar provided by hydration products,and the buffering capacity of the Si-Al system for solidification of heavy metals and strong alkalis are conducive to the stability of Mn^(2+)and NH_(3)-N.After the EMR mixed mortar is aged for 3 days,Mn and NH_(3)-N are completely lower than the emission standard.In general,the EMR mixed mortar can meet the requirements for green building use.
基金Funded by the Guangxi Key Research and Development Program(Guike AB23026071 and Guike AB24010020)the Guangxi Science and Technology Base and Talent Project(Guike AD24010062)the Guangxi Beibu Gulf Engineering Research Center for Green Marine Materials。
文摘This study introduced a low-temperature thermochemical method for the treatment of EMR in the presence of carbide slag(CS)to achieve an economical and efficient harmless effect.The experimental results indicate that,under suitable conditions,the NH_(4)^(+)and Mn^(2+)contents in EMR decrease notably with the increasing CS content,accompanied by an increase in pH value.Furthermore,the concentration of NH_(4)^(+)in EMR considerably decreases with the increasing liquid-to-solid ratio,eventually stabilizing.Similarly,the pH value first increases and then decreases,ultimately stabilizing.At a CS content of 12%and a liquid-to-solid ratio of 0.7,the leaching concentrations of NH_(4)^(+)and Mn^(2+)in EMR(127.7 mg/kg and 0.15 mg/L,respectively)fall below the standard detection limit(2 mg/L),with the pH measuring 8.26,meeting the conditions outlined in the GB 8978.NH_(4)^(+)is converted to NH_(3),while Mn^(2+)is transformed into solid precipitates such as Mn(OH)_(2),Mn_(2)O_(3),MnO_(2),Ca_(3)Mn_(2)O_(7),and Ca_(2)MnO_(4).The majority of manganese ions exist in trivalent or tetravalent states and remain stable over time.The cost of using CS as a reagent for treating 1 ton of EMR is merely$1.01.The high OH^(-)concentration provided by CS enables the effective removal of NH_(4)^(+)from EMR and the solidification of Mn^(2+)during thermal reactions.
基金Funded by the Science and Technology Program of Gansu Province(No.25CXGA070)。
文摘To investigate the feasibility of applying electrolytic manganese residue(EMR)in cementitious materials,an approach combining high-temperature activation(200,400,600,800 and 1000℃)and mechanical grinding(5 min)was adopted to stimulate the EMR activity.We analyzed the effect of calcination temperature on the performance of EMR with the aid of X-ray diffraction(XRD),specific surface area test(BET)and pozzolanic activity test,explored the effects of EMR activation temperature and content(0%,10%,15% and 20%)on the setting time,soundness,drying shrinkage,compressive strength,hydration products of cement-EMR mixed slurry,and assessed the effect of cement hydration on the solidification of harmful NH_(4)^(+)-N and Mn^(2+) in EMR.The research results show that high-temperature calcination can lead to the dehydration,decomposition or crystalline phase transformation of the inert sulfate and other substances in EMR,mechanical grinding can improve its particle distribution,and the coupling of the two can effectively enhance the pozzolanic activity of EMR.The decomposition and recombination of aluminum-silica phase at 800℃ optimized the EMR activity,and the strength activity index(SAI)of EMR at 28 d reached up to 95%.Appropriate calcination temperature and EMR content can ensure the workability of the mixed slurry,and when the EMR calcination temperature was 400-1000℃,the setting time of the mixed slurry under different EMR contents satisfied the specification requirements.When the calcination temperature was 600-1000℃ and EMR content was less than 20%,the soundness of the mixed slurry satisfied the specification requirements.The compressive strength of the mixed slurry increased and then decreased with the increase of activated EMR content,when the EMR content was 10%,the compressive strength of all specimens was optimal and higher than the baseline group;when the activation temperature was 800℃,the C-S-H gel in the mixed slurry interconnected with the rod-like Aft and blocked Ca(OH)_(2),and the 28 d compressive strength was increased by 14%compared with that of the baseline group.The solidification rate of Mn^(2+) in EMR by cement hydration was higher than 99%,and that of NH_(4)^(+)-N was higher than 97%.The leaching toxicity after solidification can meet the requirements of toxic emission.The results of the study may provide theoretical basis for the feasibility of the application of EMR in cementitious materials.
基金supported by the National Key R&D Program of China(No.2018YFC0213405)。
文摘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.
基金the National Natural Science Foundation of China(Nos.51104008 and 51034008)China Postdoctoral Science Foundation Funded Project(No.20100480202)+1 种基金the Research Fund for the Doctoral Program of Higher Education of China (No.20100006120010)the Fundamental Research Funds for the Central Universities(No.FRF-TP-12- 026A)
文摘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.
基金the National High Technology Research and Development Program (‘863’ Program) of China (No. 2008AA031206)Key Scientific and Technological Projects of Chongqing (No. CSTC2007AB4019)
文摘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.
基金Project(21376273)supported by the National Natural Science Foundation of ChinaProject(2010FJ1011)supported by the Research Fund of Science and Technology of Hunan Province,China
文摘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.
基金supported by the Key Research and Development Program of Guangxi Province,China (No.AB23075174)the National Natural Science Foundation of China (No.52174386)the Science and Technology Plan Project of Sichuan Province,China (No.2022YFS0459).
文摘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.
基金Project(2018YFC1903500)supported by the National Key Research and Development Program of ChinaProject(52174386)supported by the National Natural Science Foundation of ChinaProject(2021YFH0058)supported by the Science and Technology Plan Project of Sichuan Province,China。
文摘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.
基金supported by the National Natural Science Foundation of China(52164036,U1960201,51764007)the Guizhou Province Graduate Research Fund(YJSKYJJ(2021)003).
文摘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.
基金supported by the National Natural Science Foundation of China(No.52471221)the Natural Science Foundation of Hunan Province,China(No.2024JJ7145)the National Sustainable Development Agenda Innovation Demonstration Zone Hunan special project,China(No.2022sfq09).
文摘With growing concerns regarding electromagnetic pollution,low-cost,environmentally friendly,and high-performance electromagnetic wave absorption(EWA)materials have attracted significant attention.This paper reports on the synthesis of porous Fe_(3)O_(4)/C composites that incorporate dielectric and magnetic loss mechanisms via the carbothermal reduction method and optimization of waste ratio to enhance EWA performance.The Fe_(3)O_(4)/C composites with 10wt%soybean residues(Fe_(3)O_(4)/C-10),demonstrated the best EWA performance,achieving the minimum reflection loss of−56.4 dB and a bandwidth of 2.14 GHz at a thickness of 2.23 mm.This enhanced EWA performance is primarily attributable to improved impedance matching and the synergistic effect between dielectric and magnetic losses.Furthermore,radar cross-sectional simulations confirmed the practical feasibility of the porous Fe_(3)O_(4)/C composites.This study proposes a viable strategy for utilizing soybean residue and electrolytic manganese residue,highlighting their potential applications in EWA.
基金supported by the National Natural Science Foundation of China(No.52076070,No.52008166)the Natural Science Foundation of Hunan Province(No.2021JJ30256,No.2022JJ30139).
文摘In addressing the challenges of solid waste disposal, this study proposed to utilize electrolytic manganese residue to produce building insulation materials. The research focused on the factors such as precursor material ratio, alkali activator ratio, foaming agent and foam stabilizer on the target insulation materials properties. The findings indicated that SiO_(2)/Al_(2)O_(3) molar ratio, SiO_(2)/Na_(2)O molar ratio, and liquid/solid mass ratio impact the mechanical properties of the samples. The best mechanical performance of building structural material samples was characterized by a compressive strength of 11.15 MPa and a density of 1476 kg/m3. The optimal properties for building insulation materials were a thermal conductivity of 0.131–0.104 W/(m·K), compressive strength of 1.49–0.69 MPa, and density of 533–433 kg/m^(3), with a cost of 1722–1294 CNY/m^(3). This research provides a new approach for large-scale electrolytic manganese residue utilization while enhancing insulation performance and reducing energy consumption in buildings, with promising prospects for further engineering development.
基金financially supported by the Open-Up and Innovation Funds of Hubei Three Gorges Laboratory (No.SK211004)。
文摘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.
基金supported by National Natural Science Foundation of China(52174386,21806132)the National Key Research and Development Program of China(2018YFC1903500)+1 种基金the Science and Technology Plan Project of Sichuan Province(2021YFH0058)the Key Research and Development Program of Guangxi Province(AB18126088)。
文摘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.
基金Funden by the National Natural Science Foundation of China(Nos.51868044 and 52178216)the Basic Research Program of Qinghai Province(No.2022-ZJ-921)+2 种基金“the Innovation Star”Project for Excellent Postgraduates in Gansu Province(No.2022-CXZX-450)the Hongliu First-class Discipline Construction Program of Lanzhou University of TechnologyScience and Technology Project of Gansu Provincial Department of Transportation(No.2022-23)。
文摘We considered adding different amounts(1%,2%,3%,and 4%)of EMR to prepare manganese residue polymer magnesium phosphate cement composite(EMR-PMPC).The influence mechanism of EMR doping on the early macroscopic and microscopic pore structure properties of composites was studied by combining macroscopic and microscopic testing methods.The experimental results show that the addition of EMR can improve the working performance of the slurry and enhance the strength in the later stage,the 28 d compressive strength value of the slurry doped with EMR can reach 49.5 MPa.The Mn element and NH4_(+)^(-)N in EMR react with MgO in the raw material to produce Struvite and Mn(OH)_(2)and Mn_(3)(PO_(4))·6H_(2)O gel,the hydration products coexist with each other and lap each other to form a dense microfine structure and effectively refine the pores.The hydration process consists of five stages,mainly concentrated in the first 10 h or less to exothermic mainly,infrared spectral absorption band is mainly composed of O-H bond,H-O-H bond,PO_(4)bond and metal oxygen bond 3 parts,EMR makes the wave number of the absorption band from the ground wave number to the high wave number.EMR doping T_(2)spectral relaxation time will lag behind,the pore size distribution changes.The total porosity and bound fluid saturation decrease with increasing,the free fluid saturation shows the opposite trend,the permeability decreases and then increases.
