This paper focuses on the preparation of rare earth oxide products from rare earth chloride solutions during the rare earth extraction and separation processes,as well as the recycling of magnesium chloride solutions....This paper focuses on the preparation of rare earth oxide products from rare earth chloride solutions during the rare earth extraction and separation processes,as well as the recycling of magnesium chloride solutions.It proposes the idea of introducing spray pyrolysis technology into the rare earth extraction and separation processes.This paper briefly describes the development history of chloride spray pyrolysis technology,focusing on the research status and application progress of rare earth chloride solution and magnesium chloride solution spray pyrolysis technology,as well as spray pyrolysis equipment.The paper also analyzes the challenges and technical intricacies associated with applying spray pyrolysis technology to chloride solutions in the rare earth extraction and separation processes.Additionally,it explores future trends and proposes strategies to facilitate the full recycling of acids and bases,streamline the process flow,and enhance the prospects for green and low-carbon rare earth metallurgy.展开更多
Rare earth elements(REEs)are irreplaceable materials supporting low-carbon technology and equip-ment,and their commercial demand and strategic position are becoming increasingly prominent.With the continuous depletion...Rare earth elements(REEs)are irreplaceable materials supporting low-carbon technology and equip-ment,and their commercial demand and strategic position are becoming increasingly prominent.With the continuous depletion of rare earth(RE)resources,developing high-efficiency beneficiation and eco-friendly metallurgical processes has attracted widespread attention.This paper reviews the major minerals exploited for RE production and their deposits,as well as the beneficiation and metallurgical processes of RE minerals.Bastnaesite,monazite,mixed RE ores,and ion-adsorption clays are the main raw materials in the world to date.RE-bearing ores(except ion-adsorption minerals)are generally beneficiated by flotation,gravity and magnetic separation techniques.The mainstream metallurgical processes for bastnaesite,monazite and mixed RE concentrates are oxidation roasting-HCl leaching,caustic soda decomposition and high-temperature concentrated sulfuric acid roasting,respectively.Ion-adsorption clays are directly processed by in situ leaching-precipitation/solvent extraction.To achieve the sustainable development of RE resources,it is essential to further explore innovative techniques to achievecomprehensive utilization and cleaner production.展开更多
A sintered Nd-Y-Fe-B magnet was designed and manufactured by the multi-main-phase process.Unevenly distributed Y in the magnet decreases the adverse magnetic weakening effect of Y on the coercivity.Grain boundary diff...A sintered Nd-Y-Fe-B magnet was designed and manufactured by the multi-main-phase process.Unevenly distributed Y in the magnet decreases the adverse magnetic weakening effect of Y on the coercivity.Grain boundary diffusion process(GBDP)was conducted to further enhance the coercivity of the Nd-Y-Fe-B magnet.The coercivity increases significantly from 884 to 1741 kA/m after GBDP with Pr_(60)Tb_(10)Cu_(30)alloy.The mechanism of the coercivity enhancement is discussed based on the microstructure analysis.Micromagnetic simulation reveals that when the diffused Tb-rich shell thickness is lower than 12 nm the c-plane shell(perpendicular to the c-axis)is much more effective in enhancing the coercivity than the side plane shell(parallel to the c-axis).But when the Tb-rich shell thickness is above12 nm the side plane shell contributes more to the coercivity enhancement.The results in this work can help to design and manufacture Nd-Fe-B magnets with low cost and high magnetic properties.展开更多
In order to better understand the leaching process of rare earth （RE） and aluminum （Al） from the weathered crust elutiondepositedRE ore, the mass transfer of RE and Al in column leaching was investigated using the...In order to better understand the leaching process of rare earth （RE） and aluminum （Al） from the weathered crust elutiondepositedRE ore, the mass transfer of RE and Al in column leaching was investigated using the chromatographic plate theory. Theresults show that a higher initial ammonium concentration in a certain range can enhance the mass transfer process. pH of leachingagent in the range of 2 to 8 almost has no effect on the mass transfer efficiency of RE, but plays a positive role in the mass transferefficiency of Al under strong acidic condition （pH〈4）. There is an optimum flow rate that makes the highest mass transfer efficiency.The optimum leaching condition of RE is the leaching agent pH of 4？8, ammonium concentration of 0.4 mol/L and flow rate of0.5 mL/min. The mass transfer efficiencies of RE and Al both follow the order： （NH4）2SO4〈NH4Cl〈NH4NO3, implying thecomplexing ability of anion.展开更多
Mineral liberation analyser(MLA) was applied to quantitatively analyze the rare earth ore from Weishan in Shandong. Mineralogy parameters, such as mineral composition, occurrence states of rare earth elements(REEs) an...Mineral liberation analyser(MLA) was applied to quantitatively analyze the rare earth ore from Weishan in Shandong. Mineralogy parameters, such as mineral composition, occurrence states of rare earth elements(REEs) and valuable elements, mineral embedded grain size distribution, mineral association and liberation, are obtained. Results show that the contents of REEs and other valuable elements mainly contained in the ore were La 1.02 wt%, Ce 4.29 wt%, Pr 0.34 wt%, Nd 0.84 wt%, Sr 3.4 wt%and Ba 26.53 wt%, respectively. The REEs mainly occur in bastnaesite and carbocernaite in the form of independent mineral and the contents of bastnaesite and carbocernaite in the ore were 5.96 wt% and12.30 wt%, respectively. 67.34% of strontium occurs in carbocernaite and the rest occurs in celestobarite and strontianite mineral. 92.71% of barium occurs in barite. Liberation of main rare-earth minerals such as bastnaesite and carbocernaite is more than 80% when the grinding fineness is78.42% passing 74 μm. The research results could be employed to provide detailed basic theoretical data for further improvement of the beneficiation process flow and the processing index of rare earth ore, the recycling of other valuable minerals and the comprehensive utilization of tailings.展开更多
There is a wide diversity of landforms in China. The topography of three major ter- races, decreasing in height stepwise from west to east, was formed by the early Miocene. With the commencement of the Great Northern ...There is a wide diversity of landforms in China. The topography of three major ter- races, decreasing in height stepwise from west to east, was formed by the early Miocene. With the commencement of the Great Northern Hemisphere Glaciations （GHGs） and the glacial-interglacial cycles in the Pleistocene, thick loess deposits accumulated in north China, and fluvial terraces were formed and lakes expanded and contracted in eastern and central China. The earliest evidence of hominins in China is dated to ~1.7 Ma; they occupied the monsoon-dominated region for a long interval, until the late Pleistocene, ~50 ka. In this study, we investigated a large area rich in the relics and artifacts of early man. The results indicate that the early humans occupied riverine areas, especially medium-sized fluvial basins, and lake shores. Even in the relatively recent geological past, the occupation and abandonment of settlements were directly forced by the shifting of sand dune fields in the desert-loess transi- tional zone, which in turn was closely associated with variations in the monsoon climate and vegetation patterns. Our observations indicate that landforms were one of the main determi- nants of early human behavior, in that loess tableland, large alluvial plains, desert-Gobi areas, and the Tibetan Plateau, were not suitable environments for early human settlement. We infer that the early humans in China adapted their behavior to specific landforms and landform processes. The monsoon climate, which shapes the large-scale step-like pattern of fluvial landforms, promotes vegetation coverage and dominates soil formation, provides a crucial context for early human adaptation. The adaptation of early humans to earth surface proc- esses in East Asia is investigated for the first time in this study. Future investigations will provide further information that will increase our understanding of the linkage between early human behavior and landform processes in East Asia.展开更多
Due to large deserts on Earth surface a thorough understanding of climate change, landscape evolution and geomorphological processes having occurred in deserts is crucial for Earth System Science. The landscapes in de...Due to large deserts on Earth surface a thorough understanding of climate change, landscape evolution and geomorphological processes having occurred in deserts is crucial for Earth System Science. The landscapes in deserts are, however, diverse and different over the globe with regard to their geomorphological nature, human activities and geological histories. In the last decades a great number of efforts have been put to the investigation of the initial timing of the occurrence of arid climate, e. g. in northwestern China. Silty sediments in the downwind directions have been used to deduce the histories of deserts. In general, there is a lack of knowledge about processes and landscapes in Chinese drylands between the initial Miocene silt sedimentation at desert margins and the late Quaternary multiple occurrences of wetter climate with assumed large lakes in many of the deserts in northern China. The geomorphological concept of three primary triggering factors, i.e., the sediment supply, sediment availability and transport capacity of wind, and additionally the underground geology need to be fully considered for a better understanding of the environmental histories of sand seas which should not be viewed as equivalent for deserts because sand seas cover between 〈 1% and ca. 45% of the desert areas in various continents dependent on a complex interaction between various processes of both exogenous and endogenous origins.展开更多
Pumice,the most widely distributed volcanic rock in Okinawa Trough,is loose and porous.Since its formation,it has definitely suffered from the denudation of the sea to different degrees.In order to truly reveal the ge...Pumice,the most widely distributed volcanic rock in Okinawa Trough,is loose and porous.Since its formation,it has definitely suffered from the denudation of the sea to different degrees.In order to truly reveal the geochemical features of pumice,we choose the method of mineral separation.Firstly,the phenocryst is separated from glass.Then the phenocryst is divided into light and heavy mineral compositions.By ICP-MS(inductively coupled plasma mass spectrometry) analytical technology,the contents of trace and rare earth elements in the whole pumice,the glass and the heavy and light mineral compositions are determined respectively.By researching the elemental geochemical features,the magma dynamic processes are found.It shows that the initial magma for the pumice in Okinawa Trough came from the depleted mantle,from which the N-MORB(normal type of mid-ocean ridge basalt) is formed,homologous with the local basalts.But they are formed in different periods of magma crystal fractionation.Featured with sufficient crystal fractionation for pumice,it is found that the earlier crystallizing minerals are olivine,plagioclase and pyroxene.The pumice magma,formed from the depleted mantle,was mixed with additional subduction-related materials(components),and contaminated with the mass from upper crust when it rose up into the crust.As the Okinawa Trough is a back-arc basin in its early back-arc spreading stage,its magmatism has a series of its own unique characteristics,different from not only the mid-ocean ridge expansion,but also the mature back-arc basin.展开更多
Specific gravity segregation that occurs during the smelting process always leads to the low composition homogeneity and poor performance stability of the magnesium-rare earth(Mg-RE)alloys.In this study,the segregatio...Specific gravity segregation that occurs during the smelting process always leads to the low composition homogeneity and poor performance stability of the magnesium-rare earth(Mg-RE)alloys.In this study,the segregation behavior of Mg-Gd alloy was investigated by sampling from different locations in the ingot fabricated in a resistance furnace without a pouring process.The combined application of induction-heating and mechanical stirring with various speeds(0-130 r/min)was applied to promote the distribution homogeneity of Gd atoms.In the resistance-heating fabricated ingot,Gd content at the bottom section reaches 407%of that at the top.The coarse dendrites surrounded by the network-like eutectic structures are responsible for the brittle fracture with a poor elongation of 3.7%.By the combined employment of the induction heating and mechanical stirring with the speed of 87 r/min at 740℃for 40 s,the variation of the Gd content within the whole ingot can be reduced to be the minimum of 0.23 wt%.Corresponding formation and regulating models of segregation were also proposed.However,the cooling rate of the melt is reduced by the continuous increase of the stirring speed to 130 r/min,which results in the grain coarsening and lower homogeneity of the ingot.展开更多
Rare earth elements (REE) were used to study the temporal and spatial processes of soil erosion from different depths and sections of a slope. Two simulated rainfall events were applied to a prepared plot with a slope...Rare earth elements (REE) were used to study the temporal and spatial processes of soil erosion from different depths and sections of a slope. Two simulated rainfall events were applied to a prepared plot with a slope of 22°. The total runoff and sediment yield were collected every minute during the rainfall events. During the first twenty minutes of the first rainfall event, the average rate of rill erosion and the accumulated sediment yield due to rill erosion was 0.5 and 0.3 times higher than for sheet erosion. During this time, most of the erosion occurred on the lower one third of the plot. After 20 min, rill erosion became the dominant process on the slope. The average acceleration in the rate of rill erosion, the rate of rill erosion and the accumulated sediment yield due to rill erosion were 42, 6 and 4 times higher than that of sheet erosion, respectively. During the first 35 minutes of the second rainfall event, the average acceleration in the rate of rill erosion was 6～9 times higher than that of sheet erosion. Afterwards, the slope became nearly stable with little change in either rill or sheet erosion rates. Initially, most of the rill erosion occurred in the lower third of the slope but later the preexisting rillhead in the middle section of the slope became reactivated and erosion in this section of the slope increased rapidly. These results indicate that REE tracer technology is a valuable tool for quantifying spatial and temporal changes in erosion from a soil slope.展开更多
In order to intensify the leaching process of rare earth（RE） and reduce the impurities in the leachate, ammonium chloride（NH4Cl） and ammonium nitrate（NH4NO3） were mixed as a compound leaching agent to treat the ...In order to intensify the leaching process of rare earth（RE） and reduce the impurities in the leachate, ammonium chloride（NH4Cl） and ammonium nitrate（NH4NO3） were mixed as a compound leaching agent to treat the weathered crust elution-deposited RE ore. Effects of molar ratio of NH~＋_4Cl and NH_4NO_3, ammonium（NH_4） concentration, leaching agent pH and flow rate on the leaching process of RE were studied and evaluated by the chromatographic plate theory. Leaching process of the main impurity aluminium（Al） was also discussed in detail. Results showed that a higher initial ammonium concentration in a certain range could enhance the mass transfer process of RE and Al by providing a driving force to overcome the resistance of diffusion. pH almost had no effects on the mass transfer efficiency of RE and Al in the range of 4 to 8. The relationship between the flow rate and height equivalent to a theoretical plate（HETP） could fit well with the Van Deemter equation, and the flow rate at the lowest HETP was determined. The optimum conditions of column leaching for RE and Al were 1：1（molar ratio） of NH_4Cl and NH_4NO_3, 0.2 mol/L of ammonium concentration, pH 4–8 of leaching agent and 0.5 mL /min of flow rate. Under this condition, the mass transfer efficiency of RE was improved, but no change was observed for Al compared with the most widely used ammonium sulfate. Moreover, the significant difference value（around 20 mL） of retention volume at the peak concentration between RE and Al provided a possibility for their separation. It suggested the potential application of the novel compound leaching agent（NH_4Cl/NH_4NO_3）. It was found that the relative concentration of RE in the leachate could be easily obtained by monitoring the pH of leachate.展开更多
On the basis of the description of the rare-earth countercurrent extraction process, the on-line detecting method and equipments of rare-earth elements and the application in the process of the rare-earth countercurre...On the basis of the description of the rare-earth countercurrent extraction process, the on-line detecting method and equipments of rare-earth elements and the application in the process of the rare-earth countercurrent extraction are summarized. The procedure simulation of the computer, the automation control method and its current application are also mentioned in the process of rare-earth countercurrent extraction. The method of soft sensor is proposed. Optimal control method based on object-oriented rare-earth countercurrent extraction process and integrated automation system composed of process management system and process control system are presented, which are the developing direction of the automation of rare-earth countercurrent extraction process.展开更多
The phase-transformation in sol-gel preparation of barium hexaferrite and the formation of barium hexaferrite doped with La 3+ were studied by chemical p hase analysis, X-ray diffraction and infrared spectrometry an...The phase-transformation in sol-gel preparation of barium hexaferrite and the formation of barium hexaferrite doped with La 3+ were studied by chemical p hase analysis, X-ray diffraction and infrared spectrometry analysis. The expe rimental results show that phase transformation reactions of FeCO 3, Fe 2O 3 and BaFe 2O 4, barium hexaferrite and γ-Fe 2O 3 take place in the heat tr eatment of gel. While the doping lanthanide ion replace barium ion, an equivalen t quantity of Fe 3+ are reduced to Fe 2+ to maintain the charge equili brium.展开更多
Rare earth carbonate precipitation is mainly amorphous,of large volume and difficult to filter.To prepare crystalline rare earth carbonate,mother liquor of heavy rare earth was taken as research object,and the experim...Rare earth carbonate precipitation is mainly amorphous,of large volume and difficult to filter.To prepare crystalline rare earth carbonate,mother liquor of heavy rare earth was taken as research object,and the experimental scheme was designed based on the response surface central composite design(CCD)method.The concentration of mother liquor,aging time and seed crystal dosage were taken as independent variables,and the particle size of rare earth carbonate was taken as the response value to establish a quadratic polynomial numerical model to optimize the reactive-crystallization process of rare earth carbonate.The results show that these three factors have significant effect on the particle size of rare earth carbonate,and the influence order is mother liquid concentration>aging time>seed crystal dosage.Moreover,the interaction between mother liquor concentration and seed crystal dosage has a significant effect on the size of rare earth carbonate particles.The optimal parameters predicted by the model are as follows:the concentration of mother liquid is 1.75 g/L,seed crystal dosage is 13.56 wt%,and aging time is 8 h.Under these conditions,the predicted particle size is 28.74μm,and the experiment particle size is 28.23μm,between both,the relative error is 0.73%,which indicates that the established response surface model has a good prediction effect and a certain practical significance to guide the reactive-crystallization process of rare earth carbonate.The obtained rare earth carbonate has a crystallinity of 97.82%,uniform particles size,and low-hydrated crystals with a tengerite structure.展开更多
In order to explore the eff ect of a small amount of rare earth addition in ultra-cleaned pipeline steel and the influence of the cooling process on the tensile and impact properties,three API X80 pipeline steels were...In order to explore the eff ect of a small amount of rare earth addition in ultra-cleaned pipeline steel and the influence of the cooling process on the tensile and impact properties,three API X80 pipeline steels were fabricated by varying RE addition and the cooling process at the same time.Three microstructures with different features for a low C high Nb microalloyed high-strength pipeline steel and the corresponding mechanical properties were investigated.The results showed that even in the ultra-cleaned steel with O and S contents less than 10 ppm,the addition of RE would still cause an increase in the volume fraction of inclusions consisting of complicated RE oxysulfide and RE sulfide.More inclusions formed in the 112 ppm RE steel were harmful to the low temperature toughness,while few inclusions formed in the 47 ppm RE steel had almost no influence on the low temperature toughness.The two RE additions had no effect on strength of the steels.As the finishing cooling temperature was increased and the cooling rate was decreased within a certain range,the volume fractions of polygonal ferrite and quasi-polygonal ferrite as well as the number density and size of martensite–austenite islands were increased.Under such combined effect,the strength of the steels had almost no change.As the finishing cooling temperature was increased from 481 to 584℃and the cooling rate was reduced from 20 to 13℃/s,for the steel with 112 ppm addition of RE,there was an obvious decrease in the low temperature toughness.The reduced value(about 33 J)of the USE of steel consisted of two parts including the influence(about 18 J)of more inclusions formed due to 112 ppm addition of RE and the eff ect(about 15 J)of the lower high-angle grain boundaries.展开更多
A leaching experiment on simulated rare earth ore pillars with uneven grade distribution was conducted because of the readsorption of rare earth elements in the in situ leaching process of ion-adsorption-type rare ear...A leaching experiment on simulated rare earth ore pillars with uneven grade distribution was conducted because of the readsorption of rare earth elements in the in situ leaching process of ion-adsorption-type rare earth ore.Results show that the readsorption of rare earth elements in the barren layer is the main reason for the decrease in rare earth concentration in the leachate,decrease in rare earth recovery and extension of the leaching process.This limitation could be affected by the concentration of rare earth of the influent flow passing through the barren ore layer,and pH value of leaching agents shows minimal effect during leaching.The magnesium sulfate leaching process requires higher liquid-tosolid ratio than the ammonium sulfate leaching process.The former also has lower peak value of rare earth concentration and more significant tailing in the leaching curve.The readsorption of rare earth elements in the barren layer is more severe in magnesium sulfate leaching than in ammonium sulfate leaching.Thus,areas without ore belts should be avoided when magnesium sulfate is used for leaching.展开更多
Improving the seepage of leaching solution in the ore body and strengthening the mass transfer process of rare earth ions during in-situ leaching are two critical methods to improve the leaching efficiency of rare ear...Improving the seepage of leaching solution in the ore body and strengthening the mass transfer process of rare earth ions during in-situ leaching are two critical methods to improve the leaching efficiency of rare earth.In this study,2 wt%MgSO_(4)solution was used for the indoor simulated column leaching experiment on rare earth samples and an electric field was applied at both ends of the samples.Then the effects of different intensities,initial application time and duration of the electric field on the rare earth leaching system and its mechanism were investigated.The results show that compared with the single MgSO_(4)solution leaching,applying an electric field with a strength of 6 V/cm can save the leaching time of 30 min and increase the flow velocity of the rare earth leachate by 26.98%.Under the optimal conditions of applying an electric field with a strength of 6 V/cm for 20 min to the leaching system after10 min of the rare earth leachate flowing out,the leaching efficiency of sample increases from 81.20% to 86.05% with the increase of 4.85%.The mechanism analysis shows that when a direct current electric field is applied to the rare earth leaching system,rare earth ions rapidly change from disorderly movement with the seepage into faster and directional movement.In addition,the seepage of the leaching solution is also improved due to the increase of the cross-sectional area of the seepage channel,the polarized water molecules migrate directionally by force from the negative pole,and the movement of the hydrogen is generated by the electrolytic water.More impo rtantly,based on the principle of in-situ leaching process,the layout of injection holes and deflector holes in this process provides a natural site for the electrode layout of the electric field.With the simple equipme nt and the ope ration,the rare earth leaching process with the applied electric field has high feasibility in industrial application.展开更多
The solidified microstructure of immiscible alloys strongly depends on the nucleation, diffusional growth, especially the coalescence of the second phase droplets in the miscibility gap. A numerical model based on the...The solidified microstructure of immiscible alloys strongly depends on the nucleation, diffusional growth, especially the coalescence of the second phase droplets in the miscibility gap. A numerical model based on the discrete multi-particle approach was developed to simulate the nucleation and coalescence mode of the second phase droplets during the earth-based processing of immiscible alloys (in this case, the effect of gravity cannot be neglected). The cooling rate is the major factor influencing the coalescence mode. Under the super-rapid or rapid solidification condition (>104K/s), Brownian collision is the dominant coalescence mode. Marangoni collision becomes the dominant mode under the sub-rapid solidification condition (>102K/s). In the conventional slow cooling scope(101K/s), Stokes collision becomes the dominant coalescence mode, correspondingly, leading to a serious phase segregation.展开更多
Development and application of new ceramic die materials is one of the important topics in the field of die research. The composition, processing technology, mechanical property and engineering performance of the cera...Development and application of new ceramic die materials is one of the important topics in the field of die research. The composition, processing technology, mechanical property and engineering performance of the ceramic materials such as cermet, ZTA, TZP, TZP/Al2O3, TZP/TiC/Al2O3, PSZ and Sialon, etc., with rare earth yttrium, lanthanum and cerium, and so on working as additives, were investigated and analyzed in the present study. Problems existed in the research and application of rare earth ceramic die materials were discussed. Rare earth additives can effectively improve the mechanical property and engineering performance of ceramic die materials. Thus, it will have further perspectives of wider application. More attention should be paid in the future to the toughening and strengthening of the ceramic die materials, the adding forms and kinds of rare earth elements and acting mechanisms of rare earth additives in ceramic die materials.展开更多
P507 （HEH [EHP]） is an important extractant for the separation of rare earth and is widely used in industry. Since the complexes of heavy rare earth ions with saponified P507 are so stable that the rare earth ions a...P507 （HEH [EHP]） is an important extractant for the separation of rare earth and is widely used in industry. Since the complexes of heavy rare earth ions with saponified P507 are so stable that the rare earth ions are difficult to be exchanged and stripped by H^＋ ions. Thus, the cycled extractant loads certain amount of heavy rare earth ion after stripped by acid. This amount of rare earth ions loaded in blank organic phase is named as the ＂cycling loaded rare earth ions （CLREs）＂. In the separation process of Tm^3＋, Yb^3 ＋, and Lu^3 ＋ , the amount of CLREs carl be more than 10% of the normal capacity of saponifiedorganic phase. In fact, CLREs affect the separation efficiency and decrease the purity of the products. Based on the extracting-stripping equilibrium and mass balance, the influence of different process parameters on the amount of CLREs was studied by computer simulation. The results indicate that higher acid consumption and more stripping stages are required to eliminate CLREs. For an industrial practice, however, the acid consumption and the number of stripping stage can be designed by choosing an economic process and controlling CLREs at a reasonable level.展开更多
基金supported by the National Key Research and Development Program of China(2022YFB3504501)the National Natural Science Foundation of China(52274355)。
文摘This paper focuses on the preparation of rare earth oxide products from rare earth chloride solutions during the rare earth extraction and separation processes,as well as the recycling of magnesium chloride solutions.It proposes the idea of introducing spray pyrolysis technology into the rare earth extraction and separation processes.This paper briefly describes the development history of chloride spray pyrolysis technology,focusing on the research status and application progress of rare earth chloride solution and magnesium chloride solution spray pyrolysis technology,as well as spray pyrolysis equipment.The paper also analyzes the challenges and technical intricacies associated with applying spray pyrolysis technology to chloride solutions in the rare earth extraction and separation processes.Additionally,it explores future trends and proposes strategies to facilitate the full recycling of acids and bases,streamline the process flow,and enhance the prospects for green and low-carbon rare earth metallurgy.
基金Project supported by the National Key R&D Program of China(2022YFC2905800,2021YFC2901000)the National Natural Science Foundation of China(52174242,52130406).
文摘Rare earth elements(REEs)are irreplaceable materials supporting low-carbon technology and equip-ment,and their commercial demand and strategic position are becoming increasingly prominent.With the continuous depletion of rare earth(RE)resources,developing high-efficiency beneficiation and eco-friendly metallurgical processes has attracted widespread attention.This paper reviews the major minerals exploited for RE production and their deposits,as well as the beneficiation and metallurgical processes of RE minerals.Bastnaesite,monazite,mixed RE ores,and ion-adsorption clays are the main raw materials in the world to date.RE-bearing ores(except ion-adsorption minerals)are generally beneficiated by flotation,gravity and magnetic separation techniques.The mainstream metallurgical processes for bastnaesite,monazite and mixed RE concentrates are oxidation roasting-HCl leaching,caustic soda decomposition and high-temperature concentrated sulfuric acid roasting,respectively.Ion-adsorption clays are directly processed by in situ leaching-precipitation/solvent extraction.To achieve the sustainable development of RE resources,it is essential to further explore innovative techniques to achievecomprehensive utilization and cleaner production.
基金Project supported by the National Natural Science Foundation of China(51901087)China Postdoctoral Science Foundation(2021M701504)。
文摘A sintered Nd-Y-Fe-B magnet was designed and manufactured by the multi-main-phase process.Unevenly distributed Y in the magnet decreases the adverse magnetic weakening effect of Y on the coercivity.Grain boundary diffusion process(GBDP)was conducted to further enhance the coercivity of the Nd-Y-Fe-B magnet.The coercivity increases significantly from 884 to 1741 kA/m after GBDP with Pr_(60)Tb_(10)Cu_(30)alloy.The mechanism of the coercivity enhancement is discussed based on the microstructure analysis.Micromagnetic simulation reveals that when the diffused Tb-rich shell thickness is lower than 12 nm the c-plane shell(perpendicular to the c-axis)is much more effective in enhancing the coercivity than the side plane shell(parallel to the c-axis).But when the Tb-rich shell thickness is above12 nm the side plane shell contributes more to the coercivity enhancement.The results in this work can help to design and manufacture Nd-Fe-B magnets with low cost and high magnetic properties.
基金Projects(51274152,41472071)supported by the National Natural Science Foundation of ChinaProject(T201506)supported by the Program for Excellent Young Scientific and Technological Innovation Team of Hubei Provincial Department of Education,China
文摘In order to better understand the leaching process of rare earth （RE） and aluminum （Al） from the weathered crust elutiondepositedRE ore, the mass transfer of RE and Al in column leaching was investigated using the chromatographic plate theory. Theresults show that a higher initial ammonium concentration in a certain range can enhance the mass transfer process. pH of leachingagent in the range of 2 to 8 almost has no effect on the mass transfer efficiency of RE, but plays a positive role in the mass transferefficiency of Al under strong acidic condition （pH〈4）. There is an optimum flow rate that makes the highest mass transfer efficiency.The optimum leaching condition of RE is the leaching agent pH of 4？8, ammonium concentration of 0.4 mol/L and flow rate of0.5 mL/min. The mass transfer efficiencies of RE and Al both follow the order： （NH4）2SO4〈NH4Cl〈NH4NO3, implying thecomplexing ability of anion.
基金Project supported by the National Natural Sciences Foundation of China(51734001,41472071)
文摘Mineral liberation analyser(MLA) was applied to quantitatively analyze the rare earth ore from Weishan in Shandong. Mineralogy parameters, such as mineral composition, occurrence states of rare earth elements(REEs) and valuable elements, mineral embedded grain size distribution, mineral association and liberation, are obtained. Results show that the contents of REEs and other valuable elements mainly contained in the ore were La 1.02 wt%, Ce 4.29 wt%, Pr 0.34 wt%, Nd 0.84 wt%, Sr 3.4 wt%and Ba 26.53 wt%, respectively. The REEs mainly occur in bastnaesite and carbocernaite in the form of independent mineral and the contents of bastnaesite and carbocernaite in the ore were 5.96 wt% and12.30 wt%, respectively. 67.34% of strontium occurs in carbocernaite and the rest occurs in celestobarite and strontianite mineral. 92.71% of barium occurs in barite. Liberation of main rare-earth minerals such as bastnaesite and carbocernaite is more than 80% when the grinding fineness is78.42% passing 74 μm. The research results could be employed to provide detailed basic theoretical data for further improvement of the beneficiation process flow and the processing index of rare earth ore, the recycling of other valuable minerals and the comprehensive utilization of tailings.
基金Foundation： National Natural Science Foundation of China, No.41472138, No.41401220, No.41472026 The CAS Strate- gic Priority Research Program Grant B, No.XDPB05 The Ministry of Science and Technology of China, No.2016YFA0600503
文摘There is a wide diversity of landforms in China. The topography of three major ter- races, decreasing in height stepwise from west to east, was formed by the early Miocene. With the commencement of the Great Northern Hemisphere Glaciations （GHGs） and the glacial-interglacial cycles in the Pleistocene, thick loess deposits accumulated in north China, and fluvial terraces were formed and lakes expanded and contracted in eastern and central China. The earliest evidence of hominins in China is dated to ~1.7 Ma; they occupied the monsoon-dominated region for a long interval, until the late Pleistocene, ~50 ka. In this study, we investigated a large area rich in the relics and artifacts of early man. The results indicate that the early humans occupied riverine areas, especially medium-sized fluvial basins, and lake shores. Even in the relatively recent geological past, the occupation and abandonment of settlements were directly forced by the shifting of sand dune fields in the desert-loess transi- tional zone, which in turn was closely associated with variations in the monsoon climate and vegetation patterns. Our observations indicate that landforms were one of the main determi- nants of early human behavior, in that loess tableland, large alluvial plains, desert-Gobi areas, and the Tibetan Plateau, were not suitable environments for early human settlement. We infer that the early humans in China adapted their behavior to specific landforms and landform processes. The monsoon climate, which shapes the large-scale step-like pattern of fluvial landforms, promotes vegetation coverage and dominates soil formation, provides a crucial context for early human adaptation. The adaptation of early humans to earth surface proc- esses in East Asia is investigated for the first time in this study. Future investigations will provide further information that will increase our understanding of the linkage between early human behavior and landform processes in East Asia.
基金the National Natural Science Foundation of China(grant no.:41430532)the Alexander von Humboldt Stiftung/Foundation,Germany for support
文摘Due to large deserts on Earth surface a thorough understanding of climate change, landscape evolution and geomorphological processes having occurred in deserts is crucial for Earth System Science. The landscapes in deserts are, however, diverse and different over the globe with regard to their geomorphological nature, human activities and geological histories. In the last decades a great number of efforts have been put to the investigation of the initial timing of the occurrence of arid climate, e. g. in northwestern China. Silty sediments in the downwind directions have been used to deduce the histories of deserts. In general, there is a lack of knowledge about processes and landscapes in Chinese drylands between the initial Miocene silt sedimentation at desert margins and the late Quaternary multiple occurrences of wetter climate with assumed large lakes in many of the deserts in northern China. The geomorphological concept of three primary triggering factors, i.e., the sediment supply, sediment availability and transport capacity of wind, and additionally the underground geology need to be fully considered for a better understanding of the environmental histories of sand seas which should not be viewed as equivalent for deserts because sand seas cover between 〈 1% and ca. 45% of the desert areas in various continents dependent on a complex interaction between various processes of both exogenous and endogenous origins.
基金financially supported by the National Basic Research Program(973 Program)of China(No.2013CB29702)the China Ocean Mineral Resources Research and Development Association(DY125-11-R-05,DY125-12-R-03)
文摘Pumice,the most widely distributed volcanic rock in Okinawa Trough,is loose and porous.Since its formation,it has definitely suffered from the denudation of the sea to different degrees.In order to truly reveal the geochemical features of pumice,we choose the method of mineral separation.Firstly,the phenocryst is separated from glass.Then the phenocryst is divided into light and heavy mineral compositions.By ICP-MS(inductively coupled plasma mass spectrometry) analytical technology,the contents of trace and rare earth elements in the whole pumice,the glass and the heavy and light mineral compositions are determined respectively.By researching the elemental geochemical features,the magma dynamic processes are found.It shows that the initial magma for the pumice in Okinawa Trough came from the depleted mantle,from which the N-MORB(normal type of mid-ocean ridge basalt) is formed,homologous with the local basalts.But they are formed in different periods of magma crystal fractionation.Featured with sufficient crystal fractionation for pumice,it is found that the earlier crystallizing minerals are olivine,plagioclase and pyroxene.The pumice magma,formed from the depleted mantle,was mixed with additional subduction-related materials(components),and contaminated with the mass from upper crust when it rose up into the crust.As the Okinawa Trough is a back-arc basin in its early back-arc spreading stage,its magmatism has a series of its own unique characteristics,different from not only the mid-ocean ridge expansion,but also the mature back-arc basin.
基金Project supported by Key Research&Development Project of Guangdong Province(2020B010186002)National Natural Science Foundation of China(U2037601)Science and Technology Project of Sichuan Province(2020YFG0213)。
文摘Specific gravity segregation that occurs during the smelting process always leads to the low composition homogeneity and poor performance stability of the magnesium-rare earth(Mg-RE)alloys.In this study,the segregation behavior of Mg-Gd alloy was investigated by sampling from different locations in the ingot fabricated in a resistance furnace without a pouring process.The combined application of induction-heating and mechanical stirring with various speeds(0-130 r/min)was applied to promote the distribution homogeneity of Gd atoms.In the resistance-heating fabricated ingot,Gd content at the bottom section reaches 407%of that at the top.The coarse dendrites surrounded by the network-like eutectic structures are responsible for the brittle fracture with a poor elongation of 3.7%.By the combined employment of the induction heating and mechanical stirring with the speed of 87 r/min at 740℃for 40 s,the variation of the Gd content within the whole ingot can be reduced to be the minimum of 0.23 wt%.Corresponding formation and regulating models of segregation were also proposed.However,the cooling rate of the melt is reduced by the continuous increase of the stirring speed to 130 r/min,which results in the grain coarsening and lower homogeneity of the ingot.
文摘Rare earth elements (REE) were used to study the temporal and spatial processes of soil erosion from different depths and sections of a slope. Two simulated rainfall events were applied to a prepared plot with a slope of 22°. The total runoff and sediment yield were collected every minute during the rainfall events. During the first twenty minutes of the first rainfall event, the average rate of rill erosion and the accumulated sediment yield due to rill erosion was 0.5 and 0.3 times higher than for sheet erosion. During this time, most of the erosion occurred on the lower one third of the plot. After 20 min, rill erosion became the dominant process on the slope. The average acceleration in the rate of rill erosion, the rate of rill erosion and the accumulated sediment yield due to rill erosion were 42, 6 and 4 times higher than that of sheet erosion, respectively. During the first 35 minutes of the second rainfall event, the average acceleration in the rate of rill erosion was 6～9 times higher than that of sheet erosion. Afterwards, the slope became nearly stable with little change in either rill or sheet erosion rates. Initially, most of the rill erosion occurred in the lower third of the slope but later the preexisting rillhead in the middle section of the slope became reactivated and erosion in this section of the slope increased rapidly. These results indicate that REE tracer technology is a valuable tool for quantifying spatial and temporal changes in erosion from a soil slope.
基金Project supported by the National Natural Science Foundation of China(51274152 and 41472071)the Program for Excellent Young Scientific and Technological Innovation Team of Hubei Provincial Department of Education,China(T201506)
文摘In order to intensify the leaching process of rare earth（RE） and reduce the impurities in the leachate, ammonium chloride（NH4Cl） and ammonium nitrate（NH4NO3） were mixed as a compound leaching agent to treat the weathered crust elution-deposited RE ore. Effects of molar ratio of NH~＋_4Cl and NH_4NO_3, ammonium（NH_4） concentration, leaching agent pH and flow rate on the leaching process of RE were studied and evaluated by the chromatographic plate theory. Leaching process of the main impurity aluminium（Al） was also discussed in detail. Results showed that a higher initial ammonium concentration in a certain range could enhance the mass transfer process of RE and Al by providing a driving force to overcome the resistance of diffusion. pH almost had no effects on the mass transfer efficiency of RE and Al in the range of 4 to 8. The relationship between the flow rate and height equivalent to a theoretical plate（HETP） could fit well with the Van Deemter equation, and the flow rate at the lowest HETP was determined. The optimum conditions of column leaching for RE and Al were 1：1（molar ratio） of NH_4Cl and NH_4NO_3, 0.2 mol/L of ammonium concentration, pH 4–8 of leaching agent and 0.5 mL /min of flow rate. Under this condition, the mass transfer efficiency of RE was improved, but no change was observed for Al compared with the most widely used ammonium sulfate. Moreover, the significant difference value（around 20 mL） of retention volume at the peak concentration between RE and Al provided a possibility for their separation. It suggested the potential application of the novel compound leaching agent（NH_4Cl/NH_4NO_3）. It was found that the relative concentration of RE in the leachate could be easily obtained by monitoring the pH of leachate.
文摘On the basis of the description of the rare-earth countercurrent extraction process, the on-line detecting method and equipments of rare-earth elements and the application in the process of the rare-earth countercurrent extraction are summarized. The procedure simulation of the computer, the automation control method and its current application are also mentioned in the process of rare-earth countercurrent extraction. The method of soft sensor is proposed. Optimal control method based on object-oriented rare-earth countercurrent extraction process and integrated automation system composed of process management system and process control system are presented, which are the developing direction of the automation of rare-earth countercurrent extraction process.
文摘The phase-transformation in sol-gel preparation of barium hexaferrite and the formation of barium hexaferrite doped with La 3+ were studied by chemical p hase analysis, X-ray diffraction and infrared spectrometry analysis. The expe rimental results show that phase transformation reactions of FeCO 3, Fe 2O 3 and BaFe 2O 4, barium hexaferrite and γ-Fe 2O 3 take place in the heat tr eatment of gel. While the doping lanthanide ion replace barium ion, an equivalen t quantity of Fe 3+ are reduced to Fe 2+ to maintain the charge equili brium.
基金Project supported by the National Natural Science Foundation of China(51674125,51604128,51874150)the Doctoral Scientific Research Foundation of Jiangxi University of Science and Technology(jxxjbs19020)+2 种基金Jiangxi Provincial Department of Education Science and Technology Research Project(GJJ190486)Outstanding Doctoral Dissertation Project Fund of JXUST(YB2016001)Jiangxi Outstanding Young Talents Program(20192BCB23017)。
文摘Rare earth carbonate precipitation is mainly amorphous,of large volume and difficult to filter.To prepare crystalline rare earth carbonate,mother liquor of heavy rare earth was taken as research object,and the experimental scheme was designed based on the response surface central composite design(CCD)method.The concentration of mother liquor,aging time and seed crystal dosage were taken as independent variables,and the particle size of rare earth carbonate was taken as the response value to establish a quadratic polynomial numerical model to optimize the reactive-crystallization process of rare earth carbonate.The results show that these three factors have significant effect on the particle size of rare earth carbonate,and the influence order is mother liquid concentration>aging time>seed crystal dosage.Moreover,the interaction between mother liquor concentration and seed crystal dosage has a significant effect on the size of rare earth carbonate particles.The optimal parameters predicted by the model are as follows:the concentration of mother liquid is 1.75 g/L,seed crystal dosage is 13.56 wt%,and aging time is 8 h.Under these conditions,the predicted particle size is 28.74μm,and the experiment particle size is 28.23μm,between both,the relative error is 0.73%,which indicates that the established response surface model has a good prediction effect and a certain practical significance to guide the reactive-crystallization process of rare earth carbonate.The obtained rare earth carbonate has a crystallinity of 97.82%,uniform particles size,and low-hydrated crystals with a tengerite structure.
基金financially supported by the National Key Research and Development Program of China(Grant No.2017YFB0304901)。
文摘In order to explore the eff ect of a small amount of rare earth addition in ultra-cleaned pipeline steel and the influence of the cooling process on the tensile and impact properties,three API X80 pipeline steels were fabricated by varying RE addition and the cooling process at the same time.Three microstructures with different features for a low C high Nb microalloyed high-strength pipeline steel and the corresponding mechanical properties were investigated.The results showed that even in the ultra-cleaned steel with O and S contents less than 10 ppm,the addition of RE would still cause an increase in the volume fraction of inclusions consisting of complicated RE oxysulfide and RE sulfide.More inclusions formed in the 112 ppm RE steel were harmful to the low temperature toughness,while few inclusions formed in the 47 ppm RE steel had almost no influence on the low temperature toughness.The two RE additions had no effect on strength of the steels.As the finishing cooling temperature was increased and the cooling rate was decreased within a certain range,the volume fractions of polygonal ferrite and quasi-polygonal ferrite as well as the number density and size of martensite–austenite islands were increased.Under such combined effect,the strength of the steels had almost no change.As the finishing cooling temperature was increased from 481 to 584℃and the cooling rate was reduced from 20 to 13℃/s,for the steel with 112 ppm addition of RE,there was an obvious decrease in the low temperature toughness.The reduced value(about 33 J)of the USE of steel consisted of two parts including the influence(about 18 J)of more inclusions formed due to 112 ppm addition of RE and the eff ect(about 15 J)of the lower high-angle grain boundaries.
基金financially supported by the National Natural Science Foundation of China (No.5177041221)。
文摘A leaching experiment on simulated rare earth ore pillars with uneven grade distribution was conducted because of the readsorption of rare earth elements in the in situ leaching process of ion-adsorption-type rare earth ore.Results show that the readsorption of rare earth elements in the barren layer is the main reason for the decrease in rare earth concentration in the leachate,decrease in rare earth recovery and extension of the leaching process.This limitation could be affected by the concentration of rare earth of the influent flow passing through the barren ore layer,and pH value of leaching agents shows minimal effect during leaching.The magnesium sulfate leaching process requires higher liquid-tosolid ratio than the ammonium sulfate leaching process.The former also has lower peak value of rare earth concentration and more significant tailing in the leaching curve.The readsorption of rare earth elements in the barren layer is more severe in magnesium sulfate leaching than in ammonium sulfate leaching.Thus,areas without ore belts should be avoided when magnesium sulfate is used for leaching.
基金Projects supported by the National Key R&D Program of China(2020YFC1909000)Self-deployed Projects of Ganjiang Innovation Academy,Chinese Academy of Sciences(E055A001,E055A002)+1 种基金Key Research Programs of the Chinese Academy of Sciences(ZDRW-CN-2021-3)National Natural Science Foundation of China(52174113,51874148)。
文摘Improving the seepage of leaching solution in the ore body and strengthening the mass transfer process of rare earth ions during in-situ leaching are two critical methods to improve the leaching efficiency of rare earth.In this study,2 wt%MgSO_(4)solution was used for the indoor simulated column leaching experiment on rare earth samples and an electric field was applied at both ends of the samples.Then the effects of different intensities,initial application time and duration of the electric field on the rare earth leaching system and its mechanism were investigated.The results show that compared with the single MgSO_(4)solution leaching,applying an electric field with a strength of 6 V/cm can save the leaching time of 30 min and increase the flow velocity of the rare earth leachate by 26.98%.Under the optimal conditions of applying an electric field with a strength of 6 V/cm for 20 min to the leaching system after10 min of the rare earth leachate flowing out,the leaching efficiency of sample increases from 81.20% to 86.05% with the increase of 4.85%.The mechanism analysis shows that when a direct current electric field is applied to the rare earth leaching system,rare earth ions rapidly change from disorderly movement with the seepage into faster and directional movement.In addition,the seepage of the leaching solution is also improved due to the increase of the cross-sectional area of the seepage channel,the polarized water molecules migrate directionally by force from the negative pole,and the movement of the hydrogen is generated by the electrolytic water.More impo rtantly,based on the principle of in-situ leaching process,the layout of injection holes and deflector holes in this process provides a natural site for the electrode layout of the electric field.With the simple equipme nt and the ope ration,the rare earth leaching process with the applied electric field has high feasibility in industrial application.
文摘The solidified microstructure of immiscible alloys strongly depends on the nucleation, diffusional growth, especially the coalescence of the second phase droplets in the miscibility gap. A numerical model based on the discrete multi-particle approach was developed to simulate the nucleation and coalescence mode of the second phase droplets during the earth-based processing of immiscible alloys (in this case, the effect of gravity cannot be neglected). The cooling rate is the major factor influencing the coalescence mode. Under the super-rapid or rapid solidification condition (>104K/s), Brownian collision is the dominant coalescence mode. Marangoni collision becomes the dominant mode under the sub-rapid solidification condition (>102K/s). In the conventional slow cooling scope(101K/s), Stokes collision becomes the dominant coalescence mode, correspondingly, leading to a serious phase segregation.
基金Project supported by National Natural Science Foundation of China (50405047)Natural Science foundation of Shandong Province (Y2005F04)Jinan Young Star Plan of Science and Technology (08108)
文摘Development and application of new ceramic die materials is one of the important topics in the field of die research. The composition, processing technology, mechanical property and engineering performance of the ceramic materials such as cermet, ZTA, TZP, TZP/Al2O3, TZP/TiC/Al2O3, PSZ and Sialon, etc., with rare earth yttrium, lanthanum and cerium, and so on working as additives, were investigated and analyzed in the present study. Problems existed in the research and application of rare earth ceramic die materials were discussed. Rare earth additives can effectively improve the mechanical property and engineering performance of ceramic die materials. Thus, it will have further perspectives of wider application. More attention should be paid in the future to the toughening and strengthening of the ceramic die materials, the adding forms and kinds of rare earth elements and acting mechanisms of rare earth additives in ceramic die materials.
文摘P507 （HEH [EHP]） is an important extractant for the separation of rare earth and is widely used in industry. Since the complexes of heavy rare earth ions with saponified P507 are so stable that the rare earth ions are difficult to be exchanged and stripped by H^＋ ions. Thus, the cycled extractant loads certain amount of heavy rare earth ion after stripped by acid. This amount of rare earth ions loaded in blank organic phase is named as the ＂cycling loaded rare earth ions （CLREs）＂. In the separation process of Tm^3＋, Yb^3 ＋, and Lu^3 ＋ , the amount of CLREs carl be more than 10% of the normal capacity of saponifiedorganic phase. In fact, CLREs affect the separation efficiency and decrease the purity of the products. Based on the extracting-stripping equilibrium and mass balance, the influence of different process parameters on the amount of CLREs was studied by computer simulation. The results indicate that higher acid consumption and more stripping stages are required to eliminate CLREs. For an industrial practice, however, the acid consumption and the number of stripping stage can be designed by choosing an economic process and controlling CLREs at a reasonable level.
