In response to the fact that the presence of manganese dithionate(MnS_(2)O_(6))leads to a series of adverse impacts,especially lower purity of manganese sulfate(MnSO_(4))and disruption of its recovery,advanced oxidati...In response to the fact that the presence of manganese dithionate(MnS_(2)O_(6))leads to a series of adverse impacts,especially lower purity of manganese sulfate(MnSO_(4))and disruption of its recovery,advanced oxidation methods such as ozonation system are used to manage MnS_(2)O_(6)in the leaching solution,replacing conventional methods.To ascertain the conversion rate and kinetics of MnS_(2)O_(6)during the ozonation process,we explored the factors influencing its removal rate,including ozone dosage,manganese dithionate concentration,sulfuric acid concentration,and reaction temperature.Batch experiments were conducted to determine the reaction rate constant of ozone(k)and activation energy(Ea)obtained from intermittent experimental data fitting,revealing a least-squares exponential conversion relationship between k and the MnS_(2)O_(6)removal amount,wherein an increase in the aforementioned factors led to an enhanced MnS_(2)O_(6)conversion rate,exceeding 99.3%.The formation mechanism of the ozone products proposed during the experiment was summarized and proposed as follows:1)Mn^(2+)was directly oxidized to MnO_(2),and 2)SO_(4)2−was obtained by the catalytic oxidation of S_(2)O_(6)^(2−)with HO•from O3 decomposition.According to the kinetics analysis,the pre-exponential factor and total activation energy of the ozonation kinetics equation were 1.0×10^(23) s^(−1) and 177.28 kJ/mol,respectively.Overall,the present study demonstrates that O_(3) as an oxidizing agent can effectively facilitate MnS_(2)O_(6)disproportionation while preventing the release of the secondary pollutant,SO_(2)gas.展开更多
The Qujiashan manganese deposit is located in the Longmen-Daba fold belt along the northern margin of the Yangtze Block. The layered ore bodies are distributed within the purple-red calcareous shale. Qujiashan is a hi...The Qujiashan manganese deposit is located in the Longmen-Daba fold belt along the northern margin of the Yangtze Block. The layered ore bodies are distributed within the purple-red calcareous shale. Qujiashan is a high-grade w(MnO)=8.92% to 18.76%) manganese deposit with low-phosphorus w(P2O5)=0.08% to 0.16%) content. It also has a low total REEs contents(with an average of 101.3×10-6), and has inconspicuous Ce(0.81 to 1.29) and Eu(1.00 to 1.25) anomalies. lg(Ce/Ce*) values are from-0.02 to 0.11. The ores have high SiO2/Al2O3 and Al/(Al + Fe + Mn) ratios. In figures of Fe–Mn–[(Ni+Cu+Co)×10] and lgU–lgTh, all samples show that hydrothermal exhalative fluids played an important role during mineralisation. The δ13CPDB and δ18OSMOW values of eight ore samples are from-20.7‰ to-8.2‰(with an average of-12.4‰) and from 14.3‰ to 18.7‰(with an average of 17.0‰), respectively. These carbon and oxygen isotopic features indicate that hydrothermal fluids derived from deep earth are participation in the metallogenic process, which is also supported by high paleo-seawater temperatures varying from 47.08 to 73.98 °C. Therefore, the geological and geochemical evidences show that the Qujiashan deposit formed from submarine exhalative hydrothermal sedimentation.展开更多
The hot compressive deformation behaviors of ZHMn34-2-2-1 manganese brass are investigated on Thermecmastor-Z thermal simulator over wide processing domain of temperatures （923–1073 K） and strain rates （0.01–10 s...The hot compressive deformation behaviors of ZHMn34-2-2-1 manganese brass are investigated on Thermecmastor-Z thermal simulator over wide processing domain of temperatures （923–1073 K） and strain rates （0.01–10 s^–1）. The true stress–strain curves exhibit a single peak stress, after which the stress monotonously decreases until a steady state stress occurs, indicating a typical dynamic recrystallization. The analysis of deviation between strain-dependent Arrhenius type constitutive and experimental data revealed that the material parameters （n, A, and Q） for the ZHMn34-2-2-1 manganese brass are not constants but varies as functions of the deformation conditions. A revised strain-independent sine hyperbolic constitutive was proposed, which considered the coupled effects of strain rate temperature and strain on material parameters. The correlation coefficient and the average absolute relative error are used to evaluate the accuracy of the established constitutive model. The quantitative results indicate that the proposed constitutive model can precisely characterize the hot deformation behavior of ZHMn34-2-2-1 manganese brass.展开更多
According to the statistic analysis,the reserve of manganese in electrolytic manganese residue deposit is over 780 kt. The average contents of available manganese and ammonium reach 3.90% and 1.68% (mass fraction),res...According to the statistic analysis,the reserve of manganese in electrolytic manganese residue deposit is over 780 kt. The average contents of available manganese and ammonium reach 3.90% and 1.68% (mass fraction),respectively. Large amount of manganese compounds and ammonium sulfate are detruded without any treatment or recovery. The compositions of the main elements in electrolytic manganese residue were analyzed comprehensively based on the extensive research data. According to the new development of electrolytic manganese residue comprehensively used in recent years,a water washing residue-twice precipitation process was also proposed. The experimental results indicate that manganese dioxide silicon dioxide and calcium sulfate are presented as amorphous state in the manganese residues. The recovery rates of manganese and nitrogen reach up to 99.5% and 94.5 %,respectively. The recovery process can be easily implemented,environment-friendly and fitting for industrial production.展开更多
The kinetics of reductive leaching of manganese from a low-grade manganese oxide ore were studied using cellulose as reductant in dilute sulfuric acid medium.It was found that when the stirring speed was higher than 2...The kinetics of reductive leaching of manganese from a low-grade manganese oxide ore were studied using cellulose as reductant in dilute sulfuric acid medium.It was found that when the stirring speed was higher than 200 r/min,the effect of gas film diffusion on manganese extraction efficiency could be neglected,and the kinetic behavior was investigated under the condition of elimination of external diffusion influence on the leaching process.Effects of leaching temperature,mass ratio of cellulose and ore,and the sulfuric acid concentration on manganese extraction efficiency were discussed.The kinetic data were analyzed based on the shrinking core model,which indicated that the leaching process was dominated by both ash layer diffusion and chemical reaction at the initial stage,with the progress of leaching reaction,the rate-controlling step switched to the ash layer diffusion.It was also concluded that the sulfuric acid concentration had the most significant influence on the leaching rate,the reaction orders with respect to the sulfuric acid concentration were 2.102 in the first 60 min,and 3.642 in the later 90 min,while the reaction orders for mass ratio of cellulose and ore were 0.660 and 0.724,respectively.An Arrhenius relationship was used to relate the temperature to the rate of leaching,from which apparent activation energies were calculated to be 46.487 kJ/mol and 62.290 kJ/mol at the two stages,respectively.Finally,the overall leaching rate equations for the manganese dissolution reaction with cellulose in sulphuric acid solution were developed.The morphological changes and mineralogical forms of the ore before and after the chemical treatment were discussed with the support of SEM and XRD analyses.展开更多
Developing high-performance lithium ion batteries(LIBs)using manganese oxides as anodes is attractive due to their high theoretical capacity and abundant resources.Herein,we report a facile synthesis of hierarchical s...Developing high-performance lithium ion batteries(LIBs)using manganese oxides as anodes is attractive due to their high theoretical capacity and abundant resources.Herein,we report a facile synthesis of hierarchical spherical MnO2 containing coherent amorphous/crystalline domained by a simple yet effective redox precipitation reaction at room temperature.Further,flower-like CoMn2O4 constructed by single-crystalline spinel nanosheets has been fabricated using MnO2 as precursor.This mild methodology avoids undesired particle aggregation and loss of active surface area in conventional hydrothermal or solid-state processes.Moreover,both MnO2 and CoMn2O4 nanosheets manifest superior lithium-ion storage properties,rendering them promising applications in LIBs and other energy-related fields.展开更多
Pelletization is one of useful processes for the agglomeration of iron ore or concentrates. However, manganese ore fines are mainly agglomerated by sintering due to its high combined water which adversely affects the ...Pelletization is one of useful processes for the agglomeration of iron ore or concentrates. However, manganese ore fines are mainly agglomerated by sintering due to its high combined water which adversely affects the roasting performance of pellets. In this work, high pressure roll grinding(HPRG) process and optimization of temperature elevation system were investigated to improve the strength of fired manganese ore pellets. It is shown that the manganese ore possesses good ballability after being pretreated by HPRG twice, and good green balls were produced under the conditions of blending 2.0% bentonite in the feed, balling for 7 min at 16.00% moisture. High quality roasted pellets with the compressive strength of 2711 N per pellet were manufactured through preheating at 1050 °C for 10 min and firing at 1335 °C for 15 min by controlling the cracks formation. The fired manganese pellets keep the strength by the solid interconnection of recrystallized pyrolusite grains and the binding of manganite liquid phase which filled the pores and clearance among minerals. The product pellets contain high Mn grade and low impurities, and can be used to smelt ferromanganese, which provides a possible way to use imported manganese ore fines containing high combined water to produce high value ferromanganese.展开更多
An analytical method, using sector field inductively coupled plasma mass spectrometry （SF-ICP-MS） for rapid simultaneous determination of Be, Na, Mg, Si, Ca, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, As, Sn, Sb, Pb and Bi in e...An analytical method, using sector field inductively coupled plasma mass spectrometry （SF-ICP-MS） for rapid simultaneous determination of Be, Na, Mg, Si, Ca, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, As, Sn, Sb, Pb and Bi in electrolytic manganese metal, was described. At the beginning, the samples were decomposed by HNO3 and H2504, and then analyzed by SF-ICP-MS. Most of the spectral interferences could be avoided by measuring in different mass resolution modes. The matrix effects due to the excess of sulfuric acid and Mn were evaluated. Correction of matrix effects was conducted by using the internal standard elements. The optimum condition for the determination was investigated and discussed. The detection limit is in the range of 0.001-0.169 gg/L. The current method is applied to the determination of trace impurities in electrolytic manganese metal. And experiments show that good results can be obtained much faster, more accurately and conveniently by current method.展开更多
Reduction roasting-acid leaching process was utilized to process high-iron-content manganese oxide ore using black charcoal as reductant. The results indicate that, compared with the traditional reductant of anthracit...Reduction roasting-acid leaching process was utilized to process high-iron-content manganese oxide ore using black charcoal as reductant. The results indicate that, compared with the traditional reductant of anthracite, higher manganese extraction efficiency is achieved at lower roasting temperature and shorter residence time. The effects of roasting parameters on the leaching efficiency of Mn and Fe were studied, and the optimal parameters are determined as follows: roasting temperature is 650 °C, residence time is 40 min, and black charcoal dosage is 10%(mass fraction). Under these conditions, the leaching efficiency of Mn reaches 82.37% while that of Fe is controlled below 7%. XRD results show that a majority of MnO2 and Fe2O3 in the raw ore are reduced to MnO and Fe3O4, respectively.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
A series of Ag,Cu and Co-doped manganese oxide octahedral molecular sieves(OMS-2) were synthesized and evaluated to remove nitrogen oxides(NOx) from cigarette mainstream smoke.The three kinds of catalysts were added t...A series of Ag,Cu and Co-doped manganese oxide octahedral molecular sieves(OMS-2) were synthesized and evaluated to remove nitrogen oxides(NOx) from cigarette mainstream smoke.The three kinds of catalysts were added to cigarettes for studying the capabilities of reducing NOx from cigarette mainstream smoke.The catalysis and reduction of NO in laboratory were studied.A mechanism for NOx catalytic reduction from burning cigarettes with the catalysts adding to cigarettes was described.The catalysts show excellent catalytic activity for NOx removal,especially the Ag-doped OMS-2 catalyst.0.5%(mass fraction) Ag-doped OMS-2 catalyst has the best ability to remove NOx from cigarette mainstream smoke.The use of Ag-doped OMS-2 as catalyst for removing carcinogenic compounds from cigarette smoke will be an effective strategy to protect the environment and public health.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
Grainy electrolytic manganese dioxide was prepared by electrodeposition in a 0.9 mol/L MnSO4 and 2.5 mol/LH2SO4 solution. The structure, particle size and appearance of the grainy electrolytic manganese dioxide were d...Grainy electrolytic manganese dioxide was prepared by electrodeposition in a 0.9 mol/L MnSO4 and 2.5 mol/LH2SO4 solution. The structure, particle size and appearance of the grainy electrolytic manganese dioxide were determined by powder X-ray diffraction, laser particle size analysis and scanning electron micrographs measurements. Current density has important effects on cell voltage, anodic current efficiency and particle size of the grainy electrolytic manganese dioxide, and the optimum current density is 30 A/dm2. The grainy electrolytic manganese dioxide electrodeposited under the optimum conditions consists of γ-MnO2 with an orthorhombic lattice structure; the grainy electrolytic manganese dioxide has a spherical or sphere-like appearance and a narrow particle size distribution with an average particle diameter of 7.237 μm.展开更多
The pollution of iron,manganese and nitrate in groundwater is a huge threat to human beings.In this study,column experiments of ceramic,manganese sand,ceramic sand,volcanic rock,quartz sand were conducted.Iron and man...The pollution of iron,manganese and nitrate in groundwater is a huge threat to human beings.In this study,column experiments of ceramic,manganese sand,ceramic sand,volcanic rock,quartz sand were conducted.Iron and manganese contents of influent were 3.3 mg/L and 2.1 mg/L.When the biofilm became mature,the highest iron and manganese removal rate achieved by manganese sand as a filter material.Quartz did a little worse than manganese sand,but other three filter material could not reach展开更多
The characteristic of groundwater belongs to low iron but high manganese in Shenyang Hunnan New Developed Area.The first stage engineering of The WTP of Shenyang Hunnan industry Area were designed according the techno...The characteristic of groundwater belongs to low iron but high manganese in Shenyang Hunnan New Developed Area.The first stage engineering of The WTP of Shenyang Hunnan industry Area were designed according the technology of aerated-contact oxidation,and the water quality couldn’t reach to the standard after the WTP putted into production,1996.展开更多
A new densification method of chemical manganese dioxide(CMD) NaMnO 4 densification has been developed. This MnO 2 produced by NaMnO 4 oxidation possessed γ type structure. After the crude MnO 2 was densified, ...A new densification method of chemical manganese dioxide(CMD) NaMnO 4 densification has been developed. This MnO 2 produced by NaMnO 4 oxidation possessed γ type structure. After the crude MnO 2 was densified, the tap density of the MnO 2 powder could be increased from 1.2 to 2.0 g/cm 3. The discharge capacity is higher than that densified by other oxidizers.展开更多
Implementation of manganese–bismuth(MnBi)alloys as high-performance permanent magnets is a challenge for physicists and engineers because the ferromagnetic low-temperature phase(LTP)is not exclusively obtained.In thi...Implementation of manganese–bismuth(MnBi)alloys as high-performance permanent magnets is a challenge for physicists and engineers because the ferromagnetic low-temperature phase(LTP)is not exclusively obtained.In this work,melting powered by four commercial magnetrons of 2000–2500 W in a microwave furnace is demonstrated as a new route to alloy MnBi.Under an argon atmosphere,microwave heating transferred to pieces of broken Bi ingots and Mn flakes for 2 h gave rise to products of inhomogeneous composition and morphology.Scanning electron micrographs were classified into three regions according to morphology and elemental composition.Cubic-like clusters characterized as Mn precipitated over light solidified Bi-rich regions,and the MnBi phase was formed in homogeneous regions with a balanced composition between Mn and Bi.A ferromagnetic hysteresis loop was obtained in the ground powder with a coercivity of 40 kA/m.Subsequent annealing at 553 K under a pressure of 414 kPa for 12 h enhanced the MnBi phase with extended regions of balanced composition.It follows that the coercivity was increased to 60 kA/m.However,remanent magnetization was slightly reduced.This MnBi alloyed by microwave radiation can be further used in rare-earth-free magnets.展开更多
Monodispersed manganese ferrite （MnFe2O4） nanocrystals could be successfully synthesized in large quantities via a facile synthetic technique based on the pyrolysis of organometallic compound precursor, in which oct...Monodispersed manganese ferrite （MnFe2O4） nanocrystals could be successfully synthesized in large quantities via a facile synthetic technique based on the pyrolysis of organometallic compound precursor, in which octadecene was used as solvent, and oleic acid and oleylamine were used as capping ligands. MnFe204 nanocrystals were obtained with size in a tunable range of 4- 15 nm and their morphologies could be tuned from spherical to triangle-shaped by varying the surfactants. The phase structure, morphology, and size of the products were characterized in detail by X-ray diffraction （XRD） and transmission electron microscopy （TEM）. Magnetic properties of MnFe2O4 nanocrystals with different morphologies were measured using a superconducting quantum interference device （SQUID）. Both monodisperse MnFe204 nanocrystals with spherical and triangle-shapes are superparamagnetic at room temperature while ferromagnetic at 2 K. The pyrolysis method may provide an effective route to synthesize other spinel ferrites or metal oxides nanocrystals.展开更多
China’s manganese resources are usually associated with the valuable elements such as silver, lead, zinc, cobalt, nickel, scandium, etc which should be comprehensively recovered during the manganese beneficiation. A ...China’s manganese resources are usually associated with the valuable elements such as silver, lead, zinc, cobalt, nickel, scandium, etc which should be comprehensively recovered during the manganese beneficiation. A manganese ore from western China contains Mn 23.18%, Co 0.073%, Ni 0.21% and Sc 0.013%. The mineralogy composition of ore and the occurrence of associated elements of Sc, Co as well as Ni are studied in this paper. According to the results, the manganese minerals in this ore are mainly lithiophorite and a little secondary pyrolusite. The lithiophorite in this ore is rich in aluminum and actually it is the generic name for the multi-mineral aggregates mixed by silicon, aluminum and iron, which is quite different with the ordinary psilomelane. There is not any Sc, Ni or Co mineral in this ore and more than 98% of Sc, Ni and Ni exists in lithiophorite and pyrolusite. The distribution of Sc, Co and Ni in lithiophorite is further studied by EPMA and the results indicate that Sc and Co in lithiophorite is sparse and dispersed distribution while Ni usually distributes in the argillaceous lithiophorite and is local enrichment. Reduction-sulfuric acid leaching tests show that the dissolution of Sc and Co happens before lithiophorite dissolves; the dissolution rate of Sc and Co is almost the same, which is significantly higher than the dissolution rate of manganese. However, the dissolution rate of Ni is extremely low with the dissolution of manganse, which indicates that Ni is hard to dissolve and its dissolution rate obviously lags behind that of Mn, Sc and Co. The conclusion can be drawn that Sc and Co exist in the lithiophorite crystals as interface adsorption while Ni exists in the clay (kaolinite) mixed up with lithiophorite as interface adsorption. The conclusion indicates that Sc and Co can dissolve before the dissolution of manganese at a high dissolution rate in the hydrometallurgical process while Ni is also into the solution through desorption from the interface of clay but its dissolution rate is rather slow because of the insoluble nature of clay.展开更多
The amino acid Schiff base complex (Sal-AMBA-Mn) was prepared with p-amino-methylbenzoic acid, salicylaldehyde and Mn(OAc)2·4H2O. Its structures was characterized with IR and UV spectra. Oxygenation mechanism of ...The amino acid Schiff base complex (Sal-AMBA-Mn) was prepared with p-amino-methylbenzoic acid, salicylaldehyde and Mn(OAc)2·4H2O. Its structures was characterized with IR and UV spectra. Oxygenation mechanism of the complex in N, N-dimethylformamide solution was investigated. The results show that lower temperature is in favor of the oxygenation, and energy, enthalpy and entropy are -3.8 kJ/mol, -4.2 J/mol and -161.44 J/(mol·K), respectively. In the presence of the manganese complex, dehydroepiandrosterone acetate is effectively oxidized by molecular oxygen and the corresponding enone 7-ketodehydroepiandrosterone acetate is obtained. The yield is 62.1% when the oxidation is carried out under the reaction conditions of 60 ℃, 2 MPa of O2 pressure, C5H5N as a solvent and molar ratio of the substrate to the complex of 1:10.展开更多
基金Project(2022M710619)supported by the Postdoctoral Science Foundation of ChinaProjects(2020YFH0213,2020YFG0039)supported by the Sichuan Science and Technology Program,China+1 种基金Projects(XJ2024001501,KCXTD2023-4)supported by the Basic Scientific Foundation and Innovation Team Funds of China West Normal UniversityProject(CSPC202403)supported by the Open Project Program of Chemical Synthesis and Pollution Control Key Laboratory of Sichuan Province,China。
文摘In response to the fact that the presence of manganese dithionate(MnS_(2)O_(6))leads to a series of adverse impacts,especially lower purity of manganese sulfate(MnSO_(4))and disruption of its recovery,advanced oxidation methods such as ozonation system are used to manage MnS_(2)O_(6)in the leaching solution,replacing conventional methods.To ascertain the conversion rate and kinetics of MnS_(2)O_(6)during the ozonation process,we explored the factors influencing its removal rate,including ozone dosage,manganese dithionate concentration,sulfuric acid concentration,and reaction temperature.Batch experiments were conducted to determine the reaction rate constant of ozone(k)and activation energy(Ea)obtained from intermittent experimental data fitting,revealing a least-squares exponential conversion relationship between k and the MnS_(2)O_(6)removal amount,wherein an increase in the aforementioned factors led to an enhanced MnS_(2)O_(6)conversion rate,exceeding 99.3%.The formation mechanism of the ozone products proposed during the experiment was summarized and proposed as follows:1)Mn^(2+)was directly oxidized to MnO_(2),and 2)SO_(4)2−was obtained by the catalytic oxidation of S_(2)O_(6)^(2−)with HO•from O3 decomposition.According to the kinetics analysis,the pre-exponential factor and total activation energy of the ozonation kinetics equation were 1.0×10^(23) s^(−1) and 177.28 kJ/mol,respectively.Overall,the present study demonstrates that O_(3) as an oxidizing agent can effectively facilitate MnS_(2)O_(6)disproportionation while preventing the release of the secondary pollutant,SO_(2)gas.
基金Project(41663006)supported by the National Natural Science Foundation of ChinaProject(1212011220725)supported by the Geological Survey Project of the China Geological Survey
文摘The Qujiashan manganese deposit is located in the Longmen-Daba fold belt along the northern margin of the Yangtze Block. The layered ore bodies are distributed within the purple-red calcareous shale. Qujiashan is a high-grade w(MnO)=8.92% to 18.76%) manganese deposit with low-phosphorus w(P2O5)=0.08% to 0.16%) content. It also has a low total REEs contents(with an average of 101.3×10-6), and has inconspicuous Ce(0.81 to 1.29) and Eu(1.00 to 1.25) anomalies. lg(Ce/Ce*) values are from-0.02 to 0.11. The ores have high SiO2/Al2O3 and Al/(Al + Fe + Mn) ratios. In figures of Fe–Mn–[(Ni+Cu+Co)×10] and lgU–lgTh, all samples show that hydrothermal exhalative fluids played an important role during mineralisation. The δ13CPDB and δ18OSMOW values of eight ore samples are from-20.7‰ to-8.2‰(with an average of-12.4‰) and from 14.3‰ to 18.7‰(with an average of 17.0‰), respectively. These carbon and oxygen isotopic features indicate that hydrothermal fluids derived from deep earth are participation in the metallogenic process, which is also supported by high paleo-seawater temperatures varying from 47.08 to 73.98 °C. Therefore, the geological and geochemical evidences show that the Qujiashan deposit formed from submarine exhalative hydrothermal sedimentation.
基金Project(2012ZX04010-081) supported by the National Science and Technology Major Project of the Ministry of Science and Technology of China
文摘The hot compressive deformation behaviors of ZHMn34-2-2-1 manganese brass are investigated on Thermecmastor-Z thermal simulator over wide processing domain of temperatures （923–1073 K） and strain rates （0.01–10 s^–1）. The true stress–strain curves exhibit a single peak stress, after which the stress monotonously decreases until a steady state stress occurs, indicating a typical dynamic recrystallization. The analysis of deviation between strain-dependent Arrhenius type constitutive and experimental data revealed that the material parameters （n, A, and Q） for the ZHMn34-2-2-1 manganese brass are not constants but varies as functions of the deformation conditions. A revised strain-independent sine hyperbolic constitutive was proposed, which considered the coupled effects of strain rate temperature and strain on material parameters. The correlation coefficient and the average absolute relative error are used to evaluate the accuracy of the established constitutive model. The quantitative results indicate that the proposed constitutive model can precisely characterize the hot deformation behavior of ZHMn34-2-2-1 manganese brass.
基金Project(2008AA031202) supported by the National High Technology Research and Development Program of ChinaProject(0992007-6) supported by Major Science & Technology of Guangxi ProvinceProject(CSTC2008AB7127) supported by Major Science & Technology of Chongqing
文摘According to the statistic analysis,the reserve of manganese in electrolytic manganese residue deposit is over 780 kt. The average contents of available manganese and ammonium reach 3.90% and 1.68% (mass fraction),respectively. Large amount of manganese compounds and ammonium sulfate are detruded without any treatment or recovery. The compositions of the main elements in electrolytic manganese residue were analyzed comprehensively based on the extensive research data. According to the new development of electrolytic manganese residue comprehensively used in recent years,a water washing residue-twice precipitation process was also proposed. The experimental results indicate that manganese dioxide silicon dioxide and calcium sulfate are presented as amorphous state in the manganese residues. The recovery rates of manganese and nitrogen reach up to 99.5% and 94.5 %,respectively. The recovery process can be easily implemented,environment-friendly and fitting for industrial production.
基金Project(2010FJ1011)supported by the Major Project of Science and Technology of Hunan Province,China
文摘The kinetics of reductive leaching of manganese from a low-grade manganese oxide ore were studied using cellulose as reductant in dilute sulfuric acid medium.It was found that when the stirring speed was higher than 200 r/min,the effect of gas film diffusion on manganese extraction efficiency could be neglected,and the kinetic behavior was investigated under the condition of elimination of external diffusion influence on the leaching process.Effects of leaching temperature,mass ratio of cellulose and ore,and the sulfuric acid concentration on manganese extraction efficiency were discussed.The kinetic data were analyzed based on the shrinking core model,which indicated that the leaching process was dominated by both ash layer diffusion and chemical reaction at the initial stage,with the progress of leaching reaction,the rate-controlling step switched to the ash layer diffusion.It was also concluded that the sulfuric acid concentration had the most significant influence on the leaching rate,the reaction orders with respect to the sulfuric acid concentration were 2.102 in the first 60 min,and 3.642 in the later 90 min,while the reaction orders for mass ratio of cellulose and ore were 0.660 and 0.724,respectively.An Arrhenius relationship was used to relate the temperature to the rate of leaching,from which apparent activation energies were calculated to be 46.487 kJ/mol and 62.290 kJ/mol at the two stages,respectively.Finally,the overall leaching rate equations for the manganese dissolution reaction with cellulose in sulphuric acid solution were developed.The morphological changes and mineralogical forms of the ore before and after the chemical treatment were discussed with the support of SEM and XRD analyses.
基金Project(JCYJ20170817110251498)supported by the Basic Research Project of the Science and Technology Innovation Commission of Shenzhen,ChinaProject(2016TQ03C919)supported by the Guangdong Special Support for the Science and Technology Leading Young Scientist,ChinaProject(21603094)supported by the National Natural Science Foundation of China
文摘Developing high-performance lithium ion batteries(LIBs)using manganese oxides as anodes is attractive due to their high theoretical capacity and abundant resources.Herein,we report a facile synthesis of hierarchical spherical MnO2 containing coherent amorphous/crystalline domained by a simple yet effective redox precipitation reaction at room temperature.Further,flower-like CoMn2O4 constructed by single-crystalline spinel nanosheets has been fabricated using MnO2 as precursor.This mild methodology avoids undesired particle aggregation and loss of active surface area in conventional hydrothermal or solid-state processes.Moreover,both MnO2 and CoMn2O4 nanosheets manifest superior lithium-ion storage properties,rendering them promising applications in LIBs and other energy-related fields.
基金Project(2011GH561685)supported by the China Torch Program
文摘Pelletization is one of useful processes for the agglomeration of iron ore or concentrates. However, manganese ore fines are mainly agglomerated by sintering due to its high combined water which adversely affects the roasting performance of pellets. In this work, high pressure roll grinding(HPRG) process and optimization of temperature elevation system were investigated to improve the strength of fired manganese ore pellets. It is shown that the manganese ore possesses good ballability after being pretreated by HPRG twice, and good green balls were produced under the conditions of blending 2.0% bentonite in the feed, balling for 7 min at 16.00% moisture. High quality roasted pellets with the compressive strength of 2711 N per pellet were manufactured through preheating at 1050 °C for 10 min and firing at 1335 °C for 15 min by controlling the cracks formation. The fired manganese pellets keep the strength by the solid interconnection of recrystallized pyrolusite grains and the binding of manganite liquid phase which filled the pores and clearance among minerals. The product pellets contain high Mn grade and low impurities, and can be used to smelt ferromanganese, which provides a possible way to use imported manganese ore fines containing high combined water to produce high value ferromanganese.
基金Project(21075138)supported by the National Natural Science Foundation of ChinaProject(cstc2013jcyjA10088)supported by Chongqing Natural Science Foundation,ChinaProject(KJ121311)supported by Scientific and Technological Research Program of Chongqing Municipal Education Commission,China
文摘An analytical method, using sector field inductively coupled plasma mass spectrometry （SF-ICP-MS） for rapid simultaneous determination of Be, Na, Mg, Si, Ca, Ti, V, Cr, Fe, Co, Ni, Cu, Zn, As, Sn, Sb, Pb and Bi in electrolytic manganese metal, was described. At the beginning, the samples were decomposed by HNO3 and H2504, and then analyzed by SF-ICP-MS. Most of the spectral interferences could be avoided by measuring in different mass resolution modes. The matrix effects due to the excess of sulfuric acid and Mn were evaluated. Correction of matrix effects was conducted by using the internal standard elements. The optimum condition for the determination was investigated and discussed. The detection limit is in the range of 0.001-0.169 gg/L. The current method is applied to the determination of trace impurities in electrolytic manganese metal. And experiments show that good results can be obtained much faster, more accurately and conveniently by current method.
基金Project(2013JSJJ028)supported by the Teachers’Research Fund of Central South University,ChinaProject supported by Co-Innovation Center for Clean and Efficient Utilization of Strategic Mineral Resources,China
文摘Reduction roasting-acid leaching process was utilized to process high-iron-content manganese oxide ore using black charcoal as reductant. The results indicate that, compared with the traditional reductant of anthracite, higher manganese extraction efficiency is achieved at lower roasting temperature and shorter residence time. The effects of roasting parameters on the leaching efficiency of Mn and Fe were studied, and the optimal parameters are determined as follows: roasting temperature is 650 °C, residence time is 40 min, and black charcoal dosage is 10%(mass fraction). Under these conditions, the leaching efficiency of Mn reaches 82.37% while that of Fe is controlled below 7%. XRD results show that a majority of MnO2 and Fe2O3 in the raw ore are reduced to MnO and Fe3O4, respectively.
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.
文摘A series of Ag,Cu and Co-doped manganese oxide octahedral molecular sieves(OMS-2) were synthesized and evaluated to remove nitrogen oxides(NOx) from cigarette mainstream smoke.The three kinds of catalysts were added to cigarettes for studying the capabilities of reducing NOx from cigarette mainstream smoke.The catalysis and reduction of NO in laboratory were studied.A mechanism for NOx catalytic reduction from burning cigarettes with the catalysts adding to cigarettes was described.The catalysts show excellent catalytic activity for NOx removal,especially the Ag-doped OMS-2 catalyst.0.5%(mass fraction) Ag-doped OMS-2 catalyst has the best ability to remove NOx from cigarette mainstream smoke.The use of Ag-doped OMS-2 as catalyst for removing carcinogenic compounds from cigarette smoke will be an effective strategy to protect the environment and public health.
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.
文摘Grainy electrolytic manganese dioxide was prepared by electrodeposition in a 0.9 mol/L MnSO4 and 2.5 mol/LH2SO4 solution. The structure, particle size and appearance of the grainy electrolytic manganese dioxide were determined by powder X-ray diffraction, laser particle size analysis and scanning electron micrographs measurements. Current density has important effects on cell voltage, anodic current efficiency and particle size of the grainy electrolytic manganese dioxide, and the optimum current density is 30 A/dm2. The grainy electrolytic manganese dioxide electrodeposited under the optimum conditions consists of γ-MnO2 with an orthorhombic lattice structure; the grainy electrolytic manganese dioxide has a spherical or sphere-like appearance and a narrow particle size distribution with an average particle diameter of 7.237 μm.
文摘The pollution of iron,manganese and nitrate in groundwater is a huge threat to human beings.In this study,column experiments of ceramic,manganese sand,ceramic sand,volcanic rock,quartz sand were conducted.Iron and manganese contents of influent were 3.3 mg/L and 2.1 mg/L.When the biofilm became mature,the highest iron and manganese removal rate achieved by manganese sand as a filter material.Quartz did a little worse than manganese sand,but other three filter material could not reach
文摘The characteristic of groundwater belongs to low iron but high manganese in Shenyang Hunnan New Developed Area.The first stage engineering of The WTP of Shenyang Hunnan industry Area were designed according the technology of aerated-contact oxidation,and the water quality couldn’t reach to the standard after the WTP putted into production,1996.
文摘A new densification method of chemical manganese dioxide(CMD) NaMnO 4 densification has been developed. This MnO 2 produced by NaMnO 4 oxidation possessed γ type structure. After the crude MnO 2 was densified, the tap density of the MnO 2 powder could be increased from 1.2 to 2.0 g/cm 3. The discharge capacity is higher than that densified by other oxidizers.
基金Project(ThEP-60-PIP-WU3)supported by the Thailand Center of Excellence in Physics。
文摘Implementation of manganese–bismuth(MnBi)alloys as high-performance permanent magnets is a challenge for physicists and engineers because the ferromagnetic low-temperature phase(LTP)is not exclusively obtained.In this work,melting powered by four commercial magnetrons of 2000–2500 W in a microwave furnace is demonstrated as a new route to alloy MnBi.Under an argon atmosphere,microwave heating transferred to pieces of broken Bi ingots and Mn flakes for 2 h gave rise to products of inhomogeneous composition and morphology.Scanning electron micrographs were classified into three regions according to morphology and elemental composition.Cubic-like clusters characterized as Mn precipitated over light solidified Bi-rich regions,and the MnBi phase was formed in homogeneous regions with a balanced composition between Mn and Bi.A ferromagnetic hysteresis loop was obtained in the ground powder with a coercivity of 40 kA/m.Subsequent annealing at 553 K under a pressure of 414 kPa for 12 h enhanced the MnBi phase with extended regions of balanced composition.It follows that the coercivity was increased to 60 kA/m.However,remanent magnetization was slightly reduced.This MnBi alloyed by microwave radiation can be further used in rare-earth-free magnets.
基金Project(2010QZZD008) supported by the Prospect Key Projects of Fundamental Research Funds for the Central UniversitiesProject(2007FJ3008) supported by the Hunan Provincial Key Science and Technology Program of China
文摘Monodispersed manganese ferrite （MnFe2O4） nanocrystals could be successfully synthesized in large quantities via a facile synthetic technique based on the pyrolysis of organometallic compound precursor, in which octadecene was used as solvent, and oleic acid and oleylamine were used as capping ligands. MnFe204 nanocrystals were obtained with size in a tunable range of 4- 15 nm and their morphologies could be tuned from spherical to triangle-shaped by varying the surfactants. The phase structure, morphology, and size of the products were characterized in detail by X-ray diffraction （XRD） and transmission electron microscopy （TEM）. Magnetic properties of MnFe2O4 nanocrystals with different morphologies were measured using a superconducting quantum interference device （SQUID）. Both monodisperse MnFe204 nanocrystals with spherical and triangle-shapes are superparamagnetic at room temperature while ferromagnetic at 2 K. The pyrolysis method may provide an effective route to synthesize other spinel ferrites or metal oxides nanocrystals.
文摘China’s manganese resources are usually associated with the valuable elements such as silver, lead, zinc, cobalt, nickel, scandium, etc which should be comprehensively recovered during the manganese beneficiation. A manganese ore from western China contains Mn 23.18%, Co 0.073%, Ni 0.21% and Sc 0.013%. The mineralogy composition of ore and the occurrence of associated elements of Sc, Co as well as Ni are studied in this paper. According to the results, the manganese minerals in this ore are mainly lithiophorite and a little secondary pyrolusite. The lithiophorite in this ore is rich in aluminum and actually it is the generic name for the multi-mineral aggregates mixed by silicon, aluminum and iron, which is quite different with the ordinary psilomelane. There is not any Sc, Ni or Co mineral in this ore and more than 98% of Sc, Ni and Ni exists in lithiophorite and pyrolusite. The distribution of Sc, Co and Ni in lithiophorite is further studied by EPMA and the results indicate that Sc and Co in lithiophorite is sparse and dispersed distribution while Ni usually distributes in the argillaceous lithiophorite and is local enrichment. Reduction-sulfuric acid leaching tests show that the dissolution of Sc and Co happens before lithiophorite dissolves; the dissolution rate of Sc and Co is almost the same, which is significantly higher than the dissolution rate of manganese. However, the dissolution rate of Ni is extremely low with the dissolution of manganse, which indicates that Ni is hard to dissolve and its dissolution rate obviously lags behind that of Mn, Sc and Co. The conclusion can be drawn that Sc and Co exist in the lithiophorite crystals as interface adsorption while Ni exists in the clay (kaolinite) mixed up with lithiophorite as interface adsorption. The conclusion indicates that Sc and Co can dissolve before the dissolution of manganese at a high dissolution rate in the hydrometallurgical process while Ni is also into the solution through desorption from the interface of clay but its dissolution rate is rather slow because of the insoluble nature of clay.
基金Project(76132020) supported by the Post-Doctoral Science Fund of Central South University
文摘The amino acid Schiff base complex (Sal-AMBA-Mn) was prepared with p-amino-methylbenzoic acid, salicylaldehyde and Mn(OAc)2·4H2O. Its structures was characterized with IR and UV spectra. Oxygenation mechanism of the complex in N, N-dimethylformamide solution was investigated. The results show that lower temperature is in favor of the oxygenation, and energy, enthalpy and entropy are -3.8 kJ/mol, -4.2 J/mol and -161.44 J/(mol·K), respectively. In the presence of the manganese complex, dehydroepiandrosterone acetate is effectively oxidized by molecular oxygen and the corresponding enone 7-ketodehydroepiandrosterone acetate is obtained. The yield is 62.1% when the oxidation is carried out under the reaction conditions of 60 ℃, 2 MPa of O2 pressure, C5H5N as a solvent and molar ratio of the substrate to the complex of 1:10.
