Numerous light rare earth elements(LREE)minerals containing Fe and P were processed by sulfuric acid roasting method,and the leaching solution mainly comprises LREE sulfate,Fe2(SO4)3,H3PO4,and H2SO4,however,the solubi...Numerous light rare earth elements(LREE)minerals containing Fe and P were processed by sulfuric acid roasting method,and the leaching solution mainly comprises LREE sulfate,Fe2(SO4)3,H3PO4,and H2SO4,however,the solubility data of LREE sulfates in this system is few.This work studies the solubility of LREE sulfates in independent LREE sulfate system RE2(SO4)3-Fe2(SO4)3-H3 PO4-H2SO4(RE=La,Ce,Pr or Nd)and mixed LREE sulfates system(La,Ce,Pr,Nd)2(SO4)3-Fe2(SO4)3-H3 PO4-H2SO4 at different temperature(25-65℃)and concentrations of Fe2(SO4)3(Fe2 O3,0-50.13 g/L),H2SO4(0.5 mol/L),and H3 PO4(P2 O5,20.34 g/L)based on the industrial operating condition at low liquid and solid ratio 2:1.The solubility of each LREE sulfate in the independent system(La2 O3,12.25-20.88 g/L;CeO2,41.93-62.35 g/L;Pr6 O11,37.34-56.69 g/L;Nd2 O3,26.60-37.63 g/L)is much higher than that of the mixed system(La2 O3,6.95-11.03 g/L;CeO2,10.63-21.51 g/L;Pr6 O11,11.56-20.36 g/L;Nd2 O3,12.36-19.79 g/L)under the same other conditions.The results also indicate that,in the two systems,both Fe and the temperature have negative effects on the solubility of LREE sulfates.That may occur due to the complication reactions between the complexes of RESO4+and Fe(SO4)2-.However,the influence degree of temperature and iron concentration on the LREE sulfates solubility varies in the two systems and among different LREE species.This research is of theoretical significance for optimizing the conditions of the sulfuric acid process for recovering the LREE from the mixed LREE bearing minerals as well as the single LREE containing secondary rare earth scraps.展开更多
Seven new rare earth transition metal sulfates were synthesized by hydrothermal reactions under conditions slightly above the critical point of water. Their crystal structures were determined from single crystal X-ray...Seven new rare earth transition metal sulfates were synthesized by hydrothermal reactions under conditions slightly above the critical point of water. Their crystal structures were determined from single crystal X-ray data. The compositions of the new compounds can be represented by two general formulae : REM (OH) 3 (SO4) and RE2M (OH) 3 (SO4) 2F (H2O) with RE = Gd, Tb, Dy ; M = Ni, Cu. Three different crystal structure types were found for the formula REM (OH) 3 (SO4). The structures of the new compounds all feature infinite chains of REOn coordination polyhedra, which are connected to chains of CuO6 or NiO6 octabedra. The limited size range of the rare earth cations observed in these compounds is most likely because of interactions between the octabedral chains and the chains of REOn polyhedra. The new compounds are closely related to the known yttrium transition metal sulfates.展开更多
The precipitation of the water-leaching solution of Baotou mixed rare earth(RE) concentrate roasted with sulfuric acid using ammonium bicarbonate for producing RE carbonate produces a mass of ammonia-nitrogen wastewat...The precipitation of the water-leaching solution of Baotou mixed rare earth(RE) concentrate roasted with sulfuric acid using ammonium bicarbonate for producing RE carbonate produces a mass of ammonia-nitrogen wastewater because of the relatively low solubility of rare earth sulfate.To solve the serious problem of ammonia-nitrogen pollution,new precipitators need to be developed urgently so as to meet the requirements of environmental protection and impurities content of the product(SO_(4)^(2-)<1.8 wt% in RE carbonates products).In this paper,we studied the effects of feeding modes on the behavior of SO_(4)^(2-) during the preparation of light RE carbonate(RE=La,Ce,Pr,Nd) from their sulfate solutions using Mg(HCO_(3))_(2) as a precipitant.The results indicate that the contents of SO_(4)^(2-) in the La and Ce precipitates using positive feeding mode exceed 16 wt% because of the formation of La_(2)(CO_(3))2.15(-SO_(4))0.85·4 H_(2)O and Ce_(2)(CO_(3))_(2).15(SO_(4))0.85·3H_(2)O,while those of the Pr and Nd precipitates are 4 wt%-5 wt% since they exist in the form of n-carbonate.The precipitates prepared using synchronous feeding mode are all RE carbonate with only 4 wt%-5 wt% of SO_(4)^(2-) enclosed in the precipitation.The content of SO_(4)^(2-) in the RE carbonate obtained using reverse feeding mode is the lowest.Among them,the content of SO_(4)^(2-) in La precipitate is only 1.40 wt%.Both synchronous and reverse feeding modes can effectively reduce the content of SO_(4)^(2-)in RE carbonate,which provides theoretical guidance for the preparation of qualified light RE carbonate products by Mg(HCO3)2 precipitation method.展开更多
Weathered crust elution-deposited rare earth ore is an important resource of rare earths, including grantic weathered crust elution-deposited rare earth ore and volcanic weathered crust elution-deposited rare earth or...Weathered crust elution-deposited rare earth ore is an important resource of rare earths, including grantic weathered crust elution-deposited rare earth ore and volcanic weathered crust elution-deposited rare earth ore. The development condition of the weathered crust, weathering degree and mineral composition of these ores will be different because of the differences between their parent rocks and weathered crust causes of mineralogy path. Therefore, mineral properties and leaching characteristics of volcanic weathered crust elution-deposited rare earth ore from Chongzuo(CZ), Guangxi province were investigated. It was found that the CZ rare earth ore was a typical mid-yttrium and rich-europium ore, with the overall rare earth(REE) grade in ion-exchangeable phase of 0.15%. Partide size classification showed that finer particle had a higher REE grade. Column leaching tests showed that the leaching efficiency of REE was above 94% with leaching agent concentration of 0.20 mol/L, liquid-solid ratio of 4:3, flow rate of 0.60 mL/min, and initial pH value around 5.67. Compared to ammonium sulfate leaching, magnesium sulfate leaching was advantaged by nearly zero ammonia nitrogen emission while their REE leaching was almost equivalent.展开更多
This study described a hydrometallurgical method to investigate the separation of rare earth elements(REEs)from rare earth polishing powder wastes(REPPWs)containing large amounts of rare earth oxides with a major ...This study described a hydrometallurgical method to investigate the separation of rare earth elements(REEs)from rare earth polishing powder wastes(REPPWs)containing large amounts of rare earth oxides with a major phase of CeO2 and minor phases of La2O3,Pr2O3,and Nd2O3 using a process devised by the authors.The suggested approach consisted of five processes:the synthesis of NaR E(SO4)2·xH2O from rare earth oxides in Na2SO4-H2SO4-H2 O solutions(Process 1),the conversion of NaR E(SO4)2·xH2O into RE(OH)3 using NaO H(Process 2),and the oxidation of Ce(OH)3 into Ce(OH)4 using air with O2 injection(Process 3),followed by Processes 4 and 5 for separation of REEs by acid leaching using HCl and H2SO4,respectively.To confirm the high yield of NaR E(SO4)2·xH2O in Process 1,experiments were carried out under various Na2SO4 concentrations(0.4–2.5 mol/L),sulfuric acid concentrations(6–14 mol/L),and reaction temperatures(95–125 oC).In addition,the effect of the pH value on the separation of Ce(OH)4 in HCl-H2 O solutions with Ce(OH)4,La-,Pr-,and Nd(OH)3 in Process 4 was also investigated.On the basis of above results,the possibility of effective separation of REEs from REPPWs could be confirmed.展开更多
Three CeO_2 samples with different morphologies, i.e., cubes, rods, and spindles, were synthesized and investigated for 2-chloroethyl ethyl sulfide(2-CEES) degradation. The samples were characterized using scanning ...Three CeO_2 samples with different morphologies, i.e., cubes, rods, and spindles, were synthesized and investigated for 2-chloroethyl ethyl sulfide(2-CEES) degradation. The samples were characterized using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, the Brunauer-Emmett-Teller method, and temperature-programmed CO_2 desorption. It was found that morphologies of CeO_2 could strongly affect the surface properties and the 2-CEES degradation activities. The surface basicity and the continuous 2-CEES degradation activity of spindle-like CeO_2 were much better than those of the other CeO_2 samples, although all the samples had identical chemical compositions. That was benefited by the largest surface area, abundant microcracks, and surface oxygen vacancies of the spindle-like CeO_2.展开更多
基金Project supported by the National Natural Science Foundation of China(51674037)GRINM Youth Foundation。
文摘Numerous light rare earth elements(LREE)minerals containing Fe and P were processed by sulfuric acid roasting method,and the leaching solution mainly comprises LREE sulfate,Fe2(SO4)3,H3PO4,and H2SO4,however,the solubility data of LREE sulfates in this system is few.This work studies the solubility of LREE sulfates in independent LREE sulfate system RE2(SO4)3-Fe2(SO4)3-H3 PO4-H2SO4(RE=La,Ce,Pr or Nd)and mixed LREE sulfates system(La,Ce,Pr,Nd)2(SO4)3-Fe2(SO4)3-H3 PO4-H2SO4 at different temperature(25-65℃)and concentrations of Fe2(SO4)3(Fe2 O3,0-50.13 g/L),H2SO4(0.5 mol/L),and H3 PO4(P2 O5,20.34 g/L)based on the industrial operating condition at low liquid and solid ratio 2:1.The solubility of each LREE sulfate in the independent system(La2 O3,12.25-20.88 g/L;CeO2,41.93-62.35 g/L;Pr6 O11,37.34-56.69 g/L;Nd2 O3,26.60-37.63 g/L)is much higher than that of the mixed system(La2 O3,6.95-11.03 g/L;CeO2,10.63-21.51 g/L;Pr6 O11,11.56-20.36 g/L;Nd2 O3,12.36-19.79 g/L)under the same other conditions.The results also indicate that,in the two systems,both Fe and the temperature have negative effects on the solubility of LREE sulfates.That may occur due to the complication reactions between the complexes of RESO4+and Fe(SO4)2-.However,the influence degree of temperature and iron concentration on the LREE sulfates solubility varies in the two systems and among different LREE species.This research is of theoretical significance for optimizing the conditions of the sulfuric acid process for recovering the LREE from the mixed LREE bearing minerals as well as the single LREE containing secondary rare earth scraps.
基金Foundation ite m:Project supported by R.A.Welch Foundation
文摘Seven new rare earth transition metal sulfates were synthesized by hydrothermal reactions under conditions slightly above the critical point of water. Their crystal structures were determined from single crystal X-ray data. The compositions of the new compounds can be represented by two general formulae : REM (OH) 3 (SO4) and RE2M (OH) 3 (SO4) 2F (H2O) with RE = Gd, Tb, Dy ; M = Ni, Cu. Three different crystal structure types were found for the formula REM (OH) 3 (SO4). The structures of the new compounds all feature infinite chains of REOn coordination polyhedra, which are connected to chains of CuO6 or NiO6 octabedra. The limited size range of the rare earth cations observed in these compounds is most likely because of interactions between the octabedral chains and the chains of REOn polyhedra. The new compounds are closely related to the known yttrium transition metal sulfates.
基金Project supported by the National Natural Science Foundation of China(51674037,51674036)Guangxi Science and Technology Major Project(Guike-AA18242022)。
文摘The precipitation of the water-leaching solution of Baotou mixed rare earth(RE) concentrate roasted with sulfuric acid using ammonium bicarbonate for producing RE carbonate produces a mass of ammonia-nitrogen wastewater because of the relatively low solubility of rare earth sulfate.To solve the serious problem of ammonia-nitrogen pollution,new precipitators need to be developed urgently so as to meet the requirements of environmental protection and impurities content of the product(SO_(4)^(2-)<1.8 wt% in RE carbonates products).In this paper,we studied the effects of feeding modes on the behavior of SO_(4)^(2-) during the preparation of light RE carbonate(RE=La,Ce,Pr,Nd) from their sulfate solutions using Mg(HCO_(3))_(2) as a precipitant.The results indicate that the contents of SO_(4)^(2-) in the La and Ce precipitates using positive feeding mode exceed 16 wt% because of the formation of La_(2)(CO_(3))2.15(-SO_(4))0.85·4 H_(2)O and Ce_(2)(CO_(3))_(2).15(SO_(4))0.85·3H_(2)O,while those of the Pr and Nd precipitates are 4 wt%-5 wt% since they exist in the form of n-carbonate.The precipitates prepared using synchronous feeding mode are all RE carbonate with only 4 wt%-5 wt% of SO_(4)^(2-) enclosed in the precipitation.The content of SO_(4)^(2-) in the RE carbonate obtained using reverse feeding mode is the lowest.Among them,the content of SO_(4)^(2-) in La precipitate is only 1.40 wt%.Both synchronous and reverse feeding modes can effectively reduce the content of SO_(4)^(2-)in RE carbonate,which provides theoretical guidance for the preparation of qualified light RE carbonate products by Mg(HCO3)2 precipitation method.
基金supported by National Science and Technology Support Program of China(2015BAB16B01)Science and Technology Support Program of Guangxi(1598007-41)
文摘Weathered crust elution-deposited rare earth ore is an important resource of rare earths, including grantic weathered crust elution-deposited rare earth ore and volcanic weathered crust elution-deposited rare earth ore. The development condition of the weathered crust, weathering degree and mineral composition of these ores will be different because of the differences between their parent rocks and weathered crust causes of mineralogy path. Therefore, mineral properties and leaching characteristics of volcanic weathered crust elution-deposited rare earth ore from Chongzuo(CZ), Guangxi province were investigated. It was found that the CZ rare earth ore was a typical mid-yttrium and rich-europium ore, with the overall rare earth(REE) grade in ion-exchangeable phase of 0.15%. Partide size classification showed that finer particle had a higher REE grade. Column leaching tests showed that the leaching efficiency of REE was above 94% with leaching agent concentration of 0.20 mol/L, liquid-solid ratio of 4:3, flow rate of 0.60 mL/min, and initial pH value around 5.67. Compared to ammonium sulfate leaching, magnesium sulfate leaching was advantaged by nearly zero ammonia nitrogen emission while their REE leaching was almost equivalent.
文摘This study described a hydrometallurgical method to investigate the separation of rare earth elements(REEs)from rare earth polishing powder wastes(REPPWs)containing large amounts of rare earth oxides with a major phase of CeO2 and minor phases of La2O3,Pr2O3,and Nd2O3 using a process devised by the authors.The suggested approach consisted of five processes:the synthesis of NaR E(SO4)2·xH2O from rare earth oxides in Na2SO4-H2SO4-H2 O solutions(Process 1),the conversion of NaR E(SO4)2·xH2O into RE(OH)3 using NaO H(Process 2),and the oxidation of Ce(OH)3 into Ce(OH)4 using air with O2 injection(Process 3),followed by Processes 4 and 5 for separation of REEs by acid leaching using HCl and H2SO4,respectively.To confirm the high yield of NaR E(SO4)2·xH2O in Process 1,experiments were carried out under various Na2SO4 concentrations(0.4–2.5 mol/L),sulfuric acid concentrations(6–14 mol/L),and reaction temperatures(95–125 oC).In addition,the effect of the pH value on the separation of Ce(OH)4 in HCl-H2 O solutions with Ce(OH)4,La-,Pr-,and Nd(OH)3 in Process 4 was also investigated.On the basis of above results,the possibility of effective separation of REEs from REPPWs could be confirmed.
基金supported by the National Key Research and Development Program of China(2016YFC0205001)
文摘Three CeO_2 samples with different morphologies, i.e., cubes, rods, and spindles, were synthesized and investigated for 2-chloroethyl ethyl sulfide(2-CEES) degradation. The samples were characterized using scanning electron microscopy, transmission electron microscopy, X-ray diffraction, X-ray photoelectron spectroscopy, the Brunauer-Emmett-Teller method, and temperature-programmed CO_2 desorption. It was found that morphologies of CeO_2 could strongly affect the surface properties and the 2-CEES degradation activities. The surface basicity and the continuous 2-CEES degradation activity of spindle-like CeO_2 were much better than those of the other CeO_2 samples, although all the samples had identical chemical compositions. That was benefited by the largest surface area, abundant microcracks, and surface oxygen vacancies of the spindle-like CeO_2.