TiO_(2)is the dominant and most widely researched photocatalyst for environmental remediation,however,the drawbacks,such as only responding to UV light(<5%of sunlight),low charge separation efficiency,and difficult...TiO_(2)is the dominant and most widely researched photocatalyst for environmental remediation,however,the drawbacks,such as only responding to UV light(<5%of sunlight),low charge separation efficiency,and difficulties in recycling,have severely hindered its practical application.Herein,we synthesized magnetically separable Fe_(3)O_(4)@MoS_(2)@mesoporous TiO_(2)(FMmT)photocatalysts via a simple,green,and template-free solvothermal method combined with ultrasonic hydrolysis.It is found that FMmT possesses a high specific surface area(55.09 m2·g−1),enhanced visible-light responsiveness(~521 nm),and remarkable photogenerated charge separation efficiency.In addition,the photocatalytic degradation efficiencies of FMmT for methylene blue(MB),rhodamine B(RhB),and tetracycline(TC)are 99.4%,98.5%,and 89.3%within 300 min,respectively.The corresponding degradation rates are 4.5,4.3,and 3.1 times higher than those of pure TiO_(2)separately.Owing to the high saturation magnetization(43.1 A·m^(2)·kg^(−1)),FMmT can achieve effective recycling with an applied magnetic field.The improved photocatalytic activity is closely related to the effective transport of photogenerated electrons by the active interlayer MoS_(2) and the electron–hole separation caused by the MoS_(2)@TiO_(2)heterojunction.Meanwhile,the excellent light-harvesting ability and abundant reactive sites of the mesoporous TiO_(2)shell further boost the photocatalytic efficiency of FMmT.This work provides a new approach and some experimental basis for the design and performance improvement of magnetic photocatalysts by innovatively incorporating MoS2 as the active interlayer and integrating it with a mesoporous shell.展开更多
Availability of magnetic materials is most crucial for modern Europe,as they are integral to energy conversion across the renewable energy and electric mobility sectors.Unfortunately,there is still no circular economy...Availability of magnetic materials is most crucial for modern Europe,as they are integral to energy conversion across the renewable energy and electric mobility sectors.Unfortunately,there is still no circular economy to reuse and capture value for these types of materials.With the prediction that the need for NdFeB Rare Earth(RE)magnets will double in the next 10 years,this problem becomes even more urgent.As the quality of the recollected materials varies significantly,the development of a classification system for recyclate grades of EOL NdFeB magnets in combination with an eco-labelling system for newly produced RE permanent magnets is proposed to clearly identify different magnet types and qualities.It categorises the NdFeB magnets by technical pre-processing requirements,facilitating use of the highly effective HPMS process(Hydrogen Processing of Magnetic Scrap)for re-processing extracted materials directly from NdFeB alloy.The proposed measures will have a great impact to overcome existing low recycling rates due to poor collection,high leakages of collected materials into non-suitable channels,and inappropriate interface management between logistics,mechanical pre-processing and metallurgical metals recovery.展开更多
Environmental friendly recycling process for Nd-Fe-B sintered magnet sludges generated in the manufacturing process, which contain large amount of rare earth, including Nd, Pr and Dy, is badly needed so far. In presen...Environmental friendly recycling process for Nd-Fe-B sintered magnet sludges generated in the manufacturing process, which contain large amount of rare earth, including Nd, Pr and Dy, is badly needed so far. In present study, we have developed an effective route to obtain recycled sintered magnets from Nd-Fe-B sintered magnet sludges by calcium reduction-diffusion(RD) process. Compared to conventional recycling process, our research is focused on recovering most of the useful elements, including Nd, Pr, Dy, Co, and Fe together instead of just rare earth elements. To improve the recycling efficiency and reduce pollution, the co-precipitating parameters were simulated and calculated using MATLAB software. Most of useful elements were recovered by a co-precipitation method, and the obtained composite powders were then directly fabricated as recycled Nd-Fe-B powders by a calcium reduction-diffusion(RD) method. The recovery rates are 98%, 99%, 99%, 93%, and 99%, for Nd, Pr, Dy, Co, and Fe, respectively. The amount of useful elements contained in the recovered composite powders is greater than99.71 wt%. The process of RD for synthesizing NdFeB and subsequently removing CaO was thoroughly investigated. Furthermore, the recycled Nd-Fe-B magnet exhibits a remanence of 1.1 T, a coercivity of1053 kA/m, and an energy product of 235.6 kJ/m~3, respectively, indicating that recycled Nd-Fe-B sintered magnet was successfully recovered from the severely contaminated sludges via an effective recycling route.展开更多
The main difficulty for the recovery of Nd-Fe-B bonded magnet wastes is how to completely remove the epoxy resins.In this study,chemical reaction and physical dissolution were combined to remove the epoxy resins by ad...The main difficulty for the recovery of Nd-Fe-B bonded magnet wastes is how to completely remove the epoxy resins.In this study,chemical reaction and physical dissolution were combined to remove the epoxy resins by adding ammonia-water and mixed organic solvents.Ammonia-water can react with the epoxy functional group of epoxy resin to generate polyols.Mixed organic solvents of alcohol,dimethyl formamide(DMF),and tetrahydrofuran(THF) can dissolve the generated polyols and residual epoxy resins.Under the optimum processing conditions,the epoxy resins in the waste magnetic powders are substantially removed.The oxygen and carbon contents in the recycled magnetic powder are reduced from 13500 × 10^(-6) to 1600 × 10^(-6) and from 19500 × 10^(-6) to 2100 × 10^(-6) with the reduction ratio of88.1% and 89.2%,respectively.The recycled magnetic powder presents improved magnetic properties with MS of 1.306 × 10^(-1) A·m^(2)/g,Mr of 0.926 × 10^(-1) A·m^(2)/g,Hcj of 1.170 T,and(BH)max of 125.732 kJ/m^(3),which reach 99.8%,99.4%,95.9%,and 96.9% of the original magnetic powders,respectively.展开更多
In this work,the recycled Nd-Fe-B powders and regenerated Nd-Fe-B sintered magnets with low impurity content were successfully prepared from Nd-Fe-B magnet sludge via reduction diffusion(RD)method followed by a chemo-...In this work,the recycled Nd-Fe-B powders and regenerated Nd-Fe-B sintered magnets with low impurity content were successfully prepared from Nd-Fe-B magnet sludge via reduction diffusion(RD)method followed by a chemo-selective dissolution washing proc ess.The chemo-selective dissolution effect of various solution(deionized water,dilute acetic acid solution,NH_(4)Cl-methanol solution) was evaluated by impurity content and magnetic properties of the recycled Nd-Fe-B powder.The NH_(4)Cl-methanol solution can selectively remove impurities with minimal damage to the magnetic phase.Besides,the optimal NH_(4)Cl concentration and liquid-to-solid ratio were investigated.As a consequence,the contents of Ca,O,and H after optimal washing process are reduced to 0.07 wt%,0.31 wt% and 0.22 wt%,respectively.Hence,M_(3) Tis increased to 146.72 emu/g,which is 33% higher than that of the initial sludge.Then,the regenerated Nd-Fe-B sintered magnets with properties of B_(r)=11.66 kG,H_(cj)=16.49 kOe,and(BH)_(m)=31.78 MGOe were successfully prepared by mixing with 40 wt% Nd4Fe14B alloy powders.Compared with the corresponding regenerated magnets washed with deionized water,the remanence and coercivity are increased by 18% and 59%,respectively.展开更多
NdFeB magnets currently dominate the magnet market. Supply risks of certain rare earth metals(REM), e.g. Nd and Dy, impose efficient recycling schemes that are applicable to different types and compositions of these...NdFeB magnets currently dominate the magnet market. Supply risks of certain rare earth metals(REM), e.g. Nd and Dy, impose efficient recycling schemes that are applicable to different types and compositions of these magnets with minimum use of chemicals and waste generation. In this study, a hydrometallurgical method was studied that could be adjusted to recover not only REM, but also other valuable metals(e.g.Co, Ni and Cu) that co-existed in the magnet. The magnet powders were completely dissolved in a dilute sulfuric acid solution giving more than 98% of dissolved iron in the ferrous state. Chemical oxidation of Fe-(2+) into Fe-(3+) by the addition of MnO 2 required only 1 h at ambient temperature. It was then possible to precipitate more than 99% of this ferric iron by adjusting the pH of the solution above 3 with either Ca(OH)2 or MnO additions. However, the addition of Ca(OH)2 resulted in the formation of gypsum and up to ca. 23% REM losses, possibly via co-precipitation into the gypsum. MnO elevated the Mn-(2+) concentration in the solution. However, it was found to be problematic that subsequent direct electrolysis removed Mn and Co. Low anodic current efficiencies(ACE) resulted in high energy consumption(EC), while incomplete Mn and Co removals and undesired REM losses were reported. Pre-electrolysis removals of REM and/or Co by oxalate and/or sulfide precipitation were proven to be successful and selective, but this enlarged the flowsheet considerably with only minor improvement of the Mn removal, ACE and EC.展开更多
基金financially supported by the National Key R & D Projects (Nos. 2021YFC1910504, 2019YFC1907101, 2019YFC1907103, and 2017YFB0702304)the Key R & D Project in Ningxia Hui Autonomous Region, China (No. 2020BCE01001)+6 种基金the Key and Normal Projects National Natural Science Foundation of China (Nos. U2002212 and 51672024)the Xijiang Innovation and Entrepreneurship Team (No. 2017A0109004)the Fundamental Research Funds for the Central Universities (Nos. FRF-BD-20-24A, FRF-TP-20-031A1, FRF-IC-19-017Z, FRF-GF-19-032B, and 06500141)the Integration of Green Key Process Systems MIIT, Natural Science Foundation of Beijing Municipality (No. 2214073)the Guangdong Basic and Applied Research Foundation, China (No. 2020A1515110408)the Foshan Science and Technology Innovation Special Foundation, China (No. BK21BE002)the Postdoctor Research Foundation of Shunde Graduate School of University of Science and Technology Beijing (No. 2020BH004)
文摘TiO_(2)is the dominant and most widely researched photocatalyst for environmental remediation,however,the drawbacks,such as only responding to UV light(<5%of sunlight),low charge separation efficiency,and difficulties in recycling,have severely hindered its practical application.Herein,we synthesized magnetically separable Fe_(3)O_(4)@MoS_(2)@mesoporous TiO_(2)(FMmT)photocatalysts via a simple,green,and template-free solvothermal method combined with ultrasonic hydrolysis.It is found that FMmT possesses a high specific surface area(55.09 m2·g−1),enhanced visible-light responsiveness(~521 nm),and remarkable photogenerated charge separation efficiency.In addition,the photocatalytic degradation efficiencies of FMmT for methylene blue(MB),rhodamine B(RhB),and tetracycline(TC)are 99.4%,98.5%,and 89.3%within 300 min,respectively.The corresponding degradation rates are 4.5,4.3,and 3.1 times higher than those of pure TiO_(2)separately.Owing to the high saturation magnetization(43.1 A·m^(2)·kg^(−1)),FMmT can achieve effective recycling with an applied magnetic field.The improved photocatalytic activity is closely related to the effective transport of photogenerated electrons by the active interlayer MoS_(2) and the electron–hole separation caused by the MoS_(2)@TiO_(2)heterojunction.Meanwhile,the excellent light-harvesting ability and abundant reactive sites of the mesoporous TiO_(2)shell further boost the photocatalytic efficiency of FMmT.This work provides a new approach and some experimental basis for the design and performance improvement of magnetic photocatalysts by innovatively incorporating MoS2 as the active interlayer and integrating it with a mesoporous shell.
文摘Availability of magnetic materials is most crucial for modern Europe,as they are integral to energy conversion across the renewable energy and electric mobility sectors.Unfortunately,there is still no circular economy to reuse and capture value for these types of materials.With the prediction that the need for NdFeB Rare Earth(RE)magnets will double in the next 10 years,this problem becomes even more urgent.As the quality of the recollected materials varies significantly,the development of a classification system for recyclate grades of EOL NdFeB magnets in combination with an eco-labelling system for newly produced RE permanent magnets is proposed to clearly identify different magnet types and qualities.It categorises the NdFeB magnets by technical pre-processing requirements,facilitating use of the highly effective HPMS process(Hydrogen Processing of Magnetic Scrap)for re-processing extracted materials directly from NdFeB alloy.The proposed measures will have a great impact to overcome existing low recycling rates due to poor collection,high leakages of collected materials into non-suitable channels,and inappropriate interface management between logistics,mechanical pre-processing and metallurgical metals recovery.
基金Project supported by the Beijing Municipal Natural Science Foundation(2172012)the International S&T Cooperation Program of China(2015DFG52020)the National High Technology Research and Development Program of China(2012AA063201)
文摘Environmental friendly recycling process for Nd-Fe-B sintered magnet sludges generated in the manufacturing process, which contain large amount of rare earth, including Nd, Pr and Dy, is badly needed so far. In present study, we have developed an effective route to obtain recycled sintered magnets from Nd-Fe-B sintered magnet sludges by calcium reduction-diffusion(RD) process. Compared to conventional recycling process, our research is focused on recovering most of the useful elements, including Nd, Pr, Dy, Co, and Fe together instead of just rare earth elements. To improve the recycling efficiency and reduce pollution, the co-precipitating parameters were simulated and calculated using MATLAB software. Most of useful elements were recovered by a co-precipitation method, and the obtained composite powders were then directly fabricated as recycled Nd-Fe-B powders by a calcium reduction-diffusion(RD) method. The recovery rates are 98%, 99%, 99%, 93%, and 99%, for Nd, Pr, Dy, Co, and Fe, respectively. The amount of useful elements contained in the recovered composite powders is greater than99.71 wt%. The process of RD for synthesizing NdFeB and subsequently removing CaO was thoroughly investigated. Furthermore, the recycled Nd-Fe-B magnet exhibits a remanence of 1.1 T, a coercivity of1053 kA/m, and an energy product of 235.6 kJ/m~3, respectively, indicating that recycled Nd-Fe-B sintered magnet was successfully recovered from the severely contaminated sludges via an effective recycling route.
基金Project supported by the National Key Research and Development Program of China (YFC1903405)Major Science and Technology Projects of Anhui Province (201903a07020002)+1 种基金the Beijing Municipal Natural Science Foundation (2172012)Program of Top Disciplines Construction in Beijing(PXM2019014204500031),China。
文摘The main difficulty for the recovery of Nd-Fe-B bonded magnet wastes is how to completely remove the epoxy resins.In this study,chemical reaction and physical dissolution were combined to remove the epoxy resins by adding ammonia-water and mixed organic solvents.Ammonia-water can react with the epoxy functional group of epoxy resin to generate polyols.Mixed organic solvents of alcohol,dimethyl formamide(DMF),and tetrahydrofuran(THF) can dissolve the generated polyols and residual epoxy resins.Under the optimum processing conditions,the epoxy resins in the waste magnetic powders are substantially removed.The oxygen and carbon contents in the recycled magnetic powder are reduced from 13500 × 10^(-6) to 1600 × 10^(-6) and from 19500 × 10^(-6) to 2100 × 10^(-6) with the reduction ratio of88.1% and 89.2%,respectively.The recycled magnetic powder presents improved magnetic properties with MS of 1.306 × 10^(-1) A·m^(2)/g,Mr of 0.926 × 10^(-1) A·m^(2)/g,Hcj of 1.170 T,and(BH)max of 125.732 kJ/m^(3),which reach 99.8%,99.4%,95.9%,and 96.9% of the original magnetic powders,respectively.
基金Project supported by the National Key R&D Program of China (2021YFB3500801)the National Natural Science Foundation of China(52271161)+5 种基金the Science and Technology Program of Anhui Province(201903a07020002)General Program of Science and Technology Development Project of Beijing Municipal Education Commission (KM202010005009)"QiHang Programme"for Faculty of Materials and Manufacturing,BJUT (QH202211)Program of Top Disciplines Construction in Beijing (PXM2019_014204_500031)Key Laboratory of Ionic Rare Earth Resources and Environment,Ministry of Natural Resources of the People’s Republic of China (2022IRERE302)the State Key Laboratory of Rare Earth Permanent Magnetic Materials Opening Foundation(SKLREPM170F02)。
文摘In this work,the recycled Nd-Fe-B powders and regenerated Nd-Fe-B sintered magnets with low impurity content were successfully prepared from Nd-Fe-B magnet sludge via reduction diffusion(RD)method followed by a chemo-selective dissolution washing proc ess.The chemo-selective dissolution effect of various solution(deionized water,dilute acetic acid solution,NH_(4)Cl-methanol solution) was evaluated by impurity content and magnetic properties of the recycled Nd-Fe-B powder.The NH_(4)Cl-methanol solution can selectively remove impurities with minimal damage to the magnetic phase.Besides,the optimal NH_(4)Cl concentration and liquid-to-solid ratio were investigated.As a consequence,the contents of Ca,O,and H after optimal washing process are reduced to 0.07 wt%,0.31 wt% and 0.22 wt%,respectively.Hence,M_(3) Tis increased to 146.72 emu/g,which is 33% higher than that of the initial sludge.Then,the regenerated Nd-Fe-B sintered magnets with properties of B_(r)=11.66 kG,H_(cj)=16.49 kOe,and(BH)_(m)=31.78 MGOe were successfully prepared by mixing with 40 wt% Nd4Fe14B alloy powders.Compared with the corresponding regenerated magnets washed with deionized water,the remanence and coercivity are increased by 18% and 59%,respectively.
基金Project supported by the European Community’s Seventh Framework Programme([FP7/2007-2013])under grant Agreement No.607411(MC-ITN EREAN:European Rare Earth Magnet Recycling Network)the Hercules Foundation(Project ZW09-09)
文摘NdFeB magnets currently dominate the magnet market. Supply risks of certain rare earth metals(REM), e.g. Nd and Dy, impose efficient recycling schemes that are applicable to different types and compositions of these magnets with minimum use of chemicals and waste generation. In this study, a hydrometallurgical method was studied that could be adjusted to recover not only REM, but also other valuable metals(e.g.Co, Ni and Cu) that co-existed in the magnet. The magnet powders were completely dissolved in a dilute sulfuric acid solution giving more than 98% of dissolved iron in the ferrous state. Chemical oxidation of Fe-(2+) into Fe-(3+) by the addition of MnO 2 required only 1 h at ambient temperature. It was then possible to precipitate more than 99% of this ferric iron by adjusting the pH of the solution above 3 with either Ca(OH)2 or MnO additions. However, the addition of Ca(OH)2 resulted in the formation of gypsum and up to ca. 23% REM losses, possibly via co-precipitation into the gypsum. MnO elevated the Mn-(2+) concentration in the solution. However, it was found to be problematic that subsequent direct electrolysis removed Mn and Co. Low anodic current efficiencies(ACE) resulted in high energy consumption(EC), while incomplete Mn and Co removals and undesired REM losses were reported. Pre-electrolysis removals of REM and/or Co by oxalate and/or sulfide precipitation were proven to be successful and selective, but this enlarged the flowsheet considerably with only minor improvement of the Mn removal, ACE and EC.