Enlarging the steric hindrance to the molecular structures of extractants is a common way to improve their selectivity.To improve the separation factor of thorium(Ⅳ)and cerium(Ⅳ),cyclic groups having large steric hi...Enlarging the steric hindrance to the molecular structures of extractants is a common way to improve their selectivity.To improve the separation factor of thorium(Ⅳ)and cerium(Ⅳ),cyclic groups having large steric hindrance such as phenyl,cyclohexyl,and benzyl were introduced into theα-aminophosphonate extractant molecules.Bis(2-ethylhexyl)((phenylamino)methyl)phosphonate(PAMP),bis(2-ethylhexyl)((cyclohexylamino)methyl)phosphonate(CAMP),and bis(2-ethylhexyl)((benzylamine)methyl)phosphate(BAMP)were synthesized and applied in the separation and recovery of thorium(Ⅳ)and cerium(Ⅳ)from sulfuric acid solution.The separation ability between cerium(Ⅳ)and thorium(Ⅳ)descends in the order of CAMP>BAMP≈Cextrant230>DEHAMP>>PAMP,which is consistent with the decreasing order of steric hindrance.Nearly non-extraction of both cerium(Ⅳ)and thorium(Ⅳ)and the lowest separation ability for PAMP will be due to the conjugation of the lone pair of the amino N atom and benzene ring in PAMP.Furthermore,the extraction of REs(Ⅲ)by CAMP is lower than that of thorium(Ⅳ).Thermodynamic parameters(ΔG^(0),ΔH^(0),ΔS^(0))and extraction equilibrium constants were determined.An extraction process was developed to separate and retrieve thorium(Ⅳ)and cerium(Ⅳ)from a bastnaesite leaching solution.The final product purity of CeO2and ThO2is 99%and 98.4%,respectively,and the yields are 90.2%and 97.6%,respectively.展开更多
The acid leaching residue(ALR)of ionic rare earth(IRE)concentrates containing radioactive elements such as thorium(Th)is classified as low-level radioactive waste.ALR holds valuable strategic resources such as rare ea...The acid leaching residue(ALR)of ionic rare earth(IRE)concentrates containing radioactive elements such as thorium(Th)is classified as low-level radioactive waste.ALR holds valuable strategic resources such as rare earth and Th,while improper long-term heaping storage of ALR poses a substantial environmental risk.This paper proposes a comprehensive process involving low-temperature roasting,hydrochloric acid leaching,single extractant enrichment,and stepwise stripping to recover rare earth elements and thorium from ALR.The achieved leaching efficiencies are 80.11%of LnY,99.43%of Sc(Ⅲ),and 98.67%of Th(Ⅳ)after the carbonization of the organic phase in the ALR through low-temperature roasting.Despite large amounts of acid and impurities present in the leachate,2-ethylhexyl phosphonic acid mono 2-ethylhexyl ester(HEHEHP)still exhibits nearly 100%extraction efficiency for Sc(Ⅲ)and Th(Ⅳ).The effective separation of LnY,Th(Ⅳ),and Sc(Ⅲ)was achieved by implementing fractional extraction enrichment of Th(Ⅳ)and Sc(Ⅲ),followed by Th(Ⅳ)removal through H_(2)SO_(4)and Sc(Ⅲ)removal via NaOH from the loaded organic phase.This scheme successfully achieves a recovery of RE and Th and offers a viable solution for the safe disposal of ALR.展开更多
This work was conducted to determine the practicability of using a new adsorbent 4-ethyl thiosemicarbazide intercalated, organophilic calcined hydrotalcite （ETSC-OHTC） for the removal of uranium （U（Ⅵ））, and tho...This work was conducted to determine the practicability of using a new adsorbent 4-ethyl thiosemicarbazide intercalated, organophilic calcined hydrotalcite （ETSC-OHTC） for the removal of uranium （U（Ⅵ））, and thorium （Th（Ⅳ）） from water and wastewater. The FTIR analysis helped in realizing the involvement of nitrogen and sulphur atoms of ETSC in binding the metal ions through complex formation. Parameters like adsorbent dosage, solution pH, initial metal ions concentration, contact time and ionic strength, that influence adsorption phenomenon, were studied. The optimum pH for maximum adsorption of U（VI） and Th（IV） was found to be in the range 4.0-6.0. The contact time required for reaching equilibrium was 4 hr. The pseudo second-order kinetic model was the best fit to represent the kinetic data. Analysis of the equilibrium adsorption data using Langmuir, Freundlich and Sips models showed that the Freundlich model was well suited to describe the metal ions adsorption. The KF values were 25.43 and 29.11 mg/g for U（Ⅵ） and Th（Ⅳ）, respectively, at 30℃. The adsorbent can be regenerated effectively from U（Ⅵ） and Th（Ⅳ） loaded ones using 0.01 mol/L HC1. The new adsorbent was quite stable for many cycles, without much reduction in its adsorption capacity towards the metals.展开更多
In the present work,a novelα-aminophosphonate extractant(Cextrant 230)was synthesized for the extraction and recovery of cerium and thorium from sulphate medium.The introduction of amine group into the phosphate mole...In the present work,a novelα-aminophosphonate extractant(Cextrant 230)was synthesized for the extraction and recovery of cerium and thorium from sulphate medium.The introduction of amine group into the phosphate molecule would enhance the extraction of Ce(Ⅳ)and Th(Ⅳ).The effects of extractant concentration,H_(2)SO_(4)concentration and temperature on the metal extraction were investigated in detail.It was found that the extraction of Ce(Ⅳ),Th(Ⅳ)and REs(La,Gd,Yb)in sulphate medium decreased in the following order:Ce(Ⅳ)〉Th(Ⅳ)〉REs(Ⅲ).A solvent extraction process to extract and recover cerium and thorium from bastnasite leaching was proposed,in which the purities of cerium and thorium products reached 99.9%and 99%with yield of 92%and 98%,respectively.展开更多
Thorium-234 and particle composition （organic matter, biogenic silica, carbonate and lithogenic component） were examined in the East China Sea （ECS） and the northern South China Sea （NSCS） in order to constrain ...Thorium-234 and particle composition （organic matter, biogenic silica, carbonate and lithogenic component） were examined in the East China Sea （ECS） and the northern South China Sea （NSCS） in order to constrain the particle types scavenging thorium isotopes. Good positive correlations between particulate organic matter （POM） or carbonate and thorium-234 in suspended particulate matter （SPM） indicates that POM and carbonate are efficient to scavenge thorium-234. No relationship between biogenic silica and thorium-234 suggests that geochemical behavior of thorium-234 may be not influenced by biogenic silica. A simple model was used to evaluate the affinity of thorium-234 to different particle components. The results show that POM is the most efficient scavenger for thorium-234 in the ECS and the NSCS, followed by carbonate. The authors＇ results lend support to the utility of thorium-234 as a proxy of POC and carbonate in the upper layer. However, the strong dependence of thorium scavenging on particle composition challenges thorium-230 as a constant flux proxy.展开更多
The Bayan Obo deposit in northern China is an ultra-large Fe–REE–Nb deposit.The occurrences,and geochemical characteristics of thorium in iron ores from the Bayan Obo Main Ore Body were examined using chemical analy...The Bayan Obo deposit in northern China is an ultra-large Fe–REE–Nb deposit.The occurrences,and geochemical characteristics of thorium in iron ores from the Bayan Obo Main Ore Body were examined using chemical analysis,field emission scanning electron microscopy,energy dispersive spectrometer,and automatic mineral analysis software.Results identified that 91.69%of ThO2 in the combined samples was mainly distributed in rare earth minerals(bastnaesite,huanghoite,monazite;56.43%abundance in the samples),iron minerals(magnetite,hematite,pyrite;20.97%),niobium minerals(aeschynite;14.29%),and gangue minerals(aegirine,riebeckite,mica,dolomite,apatite,fluorite;4.22%).An unidentified portion(4.09%)of ThO2 may occur in other niobium minerals(niobite,ilmenorutile,pyrochlore).Only a few independent minerals of thorium occur in the iron ore samples.Thorium mainly occurs in rare earth minerals in the form of isomorphic substitution.Analyses of the geochemical characteristics of the major elements indicate that thorium mineralization in the Main Ore Body was related to alkali metasomatism,which provided source material and favorable porosity for hydrothermal mineralization.Trace elements such as Sc,Nb,Zr,and Ta have higher correlation coefficients with thorium,which resulted from being related to the relevant minerals formed during thorium mineralization.In addition,correlation analysis of ThO2 and TFe,and REO and TFe in the six types of iron ore samples showed that ThO2 did not always account for the highest distribution rate in rare earth minerals,and the main occurrence minerals of ThO2 were closely related to iron ore types.展开更多
Axial gas-liquid separators have been adopted in fission gas removal systems for the development of thorium molten salt reactors. In our previous study, we observed an unsteady flow phenomenon in which the flow patter...Axial gas-liquid separators have been adopted in fission gas removal systems for the development of thorium molten salt reactors. In our previous study, we observed an unsteady flow phenomenon in which the flow pattern is directly dependent on the backpressure in a gas-liquid separator; however, the underlying flow mechanism is still unknown. In order to move a step further in clarifying how the flow pattern evolves with a variation in backpressure, a large eddy simulation(LES) was adopted to study the flow field evolution. In the simulation, an artificial boundary was applied at the separator outlet under the assumption that the backpressure increases linearly. The numerical results indicate that the unsteady flow feature is captured by the LES approach, and the flow transition is mainly due to the axial velocity profile redistribution induced by the backpressure variation. With the increase in backpressure,the axial velocity near the downstream orifice transits from negative to positive. This change in the axial velocity sign forces the unstable spiral vortex to become a stable rectilinear vortex.展开更多
Ion-absorbed rare earth ores radioactive residues(IREORR)are a class of waste residue from the production of rare earth elements(REEs).Because of its radioactive dose,IREORR are usually stored in waste warehouses.IREO...Ion-absorbed rare earth ores radioactive residues(IREORR)are a class of waste residue from the production of rare earth elements(REEs).Because of its radioactive dose,IREORR are usually stored in waste warehouses.IREORR are difficult to be disposed of.However,it contains relatively high concentrations of REEs,which can be considered as a valuable secondary resource.In this paper,a novel process is developed for the separation of thorium(Th)and recovery of REEs from IREORR hydrochloric acid leachate with primary amine N1923 and Cyanex?572,respectively.The effects of sulfate concentration,extractant concentration and pH on N1923 extraction in hydrochloric acid solution were investigated in detail.The results show that the extraction capacity of N1923 can be improved by adding sulfate to the solution and increasing the concentration of N1923.Acidity has little effect on the extraction of Th when pH is higher than 1.As for the stripping,REEs are more easily stripped from loaded organic phase than Th,and nitric acid is a better stripping agent than hydrochloric acid.Combined with the extraction of Cyanex■572 for REEs,a fractional extraction experiment for separating Th and enriching of REEs was performed.The yield of Th is higher than 99.9%and the concentration of REEs is enriched to 183.84 g/L.展开更多
The based membrane extraction of Th 4+ and Yb 3+ was studied in HBTMPP heptane using a hollow fibber membrane. The separation method of Th 4+ and Yb 3+ was proposed by kinetics competition. The se...The based membrane extraction of Th 4+ and Yb 3+ was studied in HBTMPP heptane using a hollow fibber membrane. The separation method of Th 4+ and Yb 3+ was proposed by kinetics competition. The separation operation of Th 4+ and Yb 3+ mixture was carried out by two successive extraction and stripping simultaneously. The concentration ratio of Th 4+ to Yb 3+ is 16 74 in the stripping solution. The recovery and purity of Th 4+ are 71 6% and 95 74% respectively.展开更多
A calixarene derivative, 5,11,17,23-tetra（diethoxyphosphoryl）-25,26,27,28-tetraacetoxycalix[4]arene （L）, was studied for the extraction and separation of thorium and rare earths in nitrate medium. Thorium was extr...A calixarene derivative, 5,11,17,23-tetra（diethoxyphosphoryl）-25,26,27,28-tetraacetoxycalix[4]arene （L）, was studied for the extraction and separation of thorium and rare earths in nitrate medium. Thorium was extracted into the organic phase by a complex of Th（NO3）4·L with the logarithm of the equilibrium constant of 2.77. Thermodynamic functions, AH, AG and AS were calculated to be -2.49, -15.55 kJ/mol and 44.53 J/（mol·K）, respectively. The results indicated that this calixarene derivative might be used to separate thorium from rare earths and the separation factors were larger than 26. However, the salting-out agents affected the separation.展开更多
Dissolved and particulate thorium-234, particulate organic carbon in the upper 150 m of water columns from five stations in the Prydz Bay, the Southern Ocean were determined during the 22nd Chinese National Antarctic ...Dissolved and particulate thorium-234, particulate organic carbon in the upper 150 m of water columns from five stations in the Prydz Bay, the Southern Ocean were determined during the 22nd Chinese National Antarctic Research Expedition （from November 2005 to March 2006 ）. The disequilibria between thorium-234 and its parent uranium-238 in upper layer was used to derive the averaged residence time of thorium-234, which decreased along with the latitude to the south and a minimum value, 1 - 8 d for particulate thorium-234 and 29 - 48 d for dissolved thorium-234, appeared at the medium latitude station, and the export fluxes of thorium-234 were calculated too and ＇a maximum value, 0. 35 -0. 63 Bq/（m^3 · d） for the particulate thorium-234 and 0. 44 -0. 65 Bq/ （m^3 ·d） for the dissolved thorium-234, appeared at the same station. The export fluxes of particulate organic carbon at different water columns were derived by two methods with irreversible scavenging model, and the averaged values were 104. 7 mmol/ （ m2 · d ） （ E method） and 120. 6 mmol/（ m2·d ） （ B method ）, respectively, indicating that a relatively high new production would exist in summer in the Prydz Bay where it will play a potential significant role in sequestering the absorption CO2 to deeper ocean.展开更多
A low-level β counting-or spectrum apparatus used for the detection of the β radiation of thorium-234 and α spectrum of thorium- 228 simultaneously and an easy operating procedure for the enrichment, radiochemical ...A low-level β counting-or spectrum apparatus used for the detection of the β radiation of thorium-234 and α spectrum of thorium- 228 simultaneously and an easy operating procedure for the enrichment, radiochemical separating, sampling and measurement of thorium-234 and uranium-238 in the ocean are developed based on the requirements of analyzing export productivity in the eupho- ric zone via thorium-234 - uranium-238 radioactivity disequilibrium. The detecting efficiency both of 13 and α radiation is higher than 20%. The background of βradiation is less than 0. 5 min ^-1 , and the energy resolution of ct detector is better than 1%. Total recycle ratio of thorium-234 is about 75%. Using the above apparatus and procedure, the radioactivities of dissolved thorium-234 and uranium-238, particle thorium-234 and uranium-238 in seawater of the South China Sea, the Southern Ocean and the Arctic Ocean were analyzed.展开更多
This work presents the results of computer simulation of neutronic processes in a high-temperature gas-cooled thorium reactor for 30 different options of core loading.To guarantee stable and long-term reactor operatio...This work presents the results of computer simulation of neutronic processes in a high-temperature gas-cooled thorium reactor for 30 different options of core loading.To guarantee stable and long-term reactor operation(7-10 years),the quantity of fuel compact dispersion phase and starting fuel composition was selected.It is demonstrated that it is possible in principle to substitute the near-axial recirculation zone of the reactor core by a long magnetic trap with a high-temperature plasma column for generating thermonuclear neutrons.The distribution of neutron yield along the length of the plasma source is also presented.Such a thorium reactor,with a near-axial source of extra neutrons,can be applied for researching thermophysical and neutronic characteristics of dispersion thorium fuel to improve its properties.The results of the work are of great interest from the perspective of future advancement of the thermonuclear power industry,by means of creation of a hybrid installation based on a thorium reactor with a long plasma column as a source of additional neutrons.展开更多
In order to lower the usage of expensive Cyanex 923 and increase the extraction capacity of the system of Cextrant 230,the synergistic extraction of thorium from chloride media by a mixture of Cextrant 230 and Cyanex ...In order to lower the usage of expensive Cyanex 923 and increase the extraction capacity of the system of Cextrant 230,the synergistic extraction of thorium from chloride media by a mixture of Cextrant 230 and Cyanex 923 was investigated.The maximum synergistic enhancement coefficient(R)of 1.53 is obtained at 1:1 molar ratio of Cextrant 230/Cyanex 923.The syne rgistic extracted species of Th^(4+)is determined as ThCl_(4)·2Cextrant 230·Cyanex 923.The synergistic extraction of Th^(4+)is an entropy-driven exothermic process.The loading capacity of 0.60 mol/L mixed extractant for thorium is about 17.10 g/L(calculated as ThO_(2)),and the loaded thorium in the organic phase can be effectively stripped by distilled water.For comparison,rare earth cations are barely extracted under the similar conditions,suggesting that the mixtures can be applied to separate thorium from rare earths.A cascade extraction process was developed based on the synergistic extraction system to separate thorium from the hydrochloric acid leaching of bastnaesite.The content of thorium in the leaching solution decreases obviously from 19.90 mg/L to1.4μg/L by 3 stages of extraction,which is superior to sole Cextrant 230 or Cyanex 923.The introduction of Cextrant 230 into the extraction system not only lowers the usage of Cyanex 923 but also enhances the selective extraction of thorium at low acidity,implying that the synergistic extraction system can selectively extract thorium more efficiently and economically than the sole systems.展开更多
Retention behavior of U(VI) and Th(IV) as their 2, 6-pyridine dicarboxylic acid (PDCA) complexes on reversed phase and ion exchange (cation, anion and mixed ion exchange) columns was studied and based on the results, ...Retention behavior of U(VI) and Th(IV) as their 2, 6-pyridine dicarboxylic acid (PDCA) complexes on reversed phase and ion exchange (cation, anion and mixed ion exchange) columns was studied and based on the results, a simple ion chromatography method for the determination of trace level thorium in uranium oxide using 0.075mM 2, 6-pyridine dicarboxylic acid (PDCA) and 1M KNO3 in 1.2M HNO3 as eluent (flow rate 1 mL/min)was proposed. The advantage of the developed method is that the separation of uranium matrix is not required prior to the ion chromatographic determination of trace Th. Separation was carried out on a mixed ion exchange stationary phase and a 10?4 M arsenazo (III) solution was used as post column reagent for detecting the separated metal ions. The separation of Th from uranium using PDCA in the present investigation is attributed through cation exchange mechanism. A calibration plot was constructed by following the standard addition method over the concentration range of 0.25 to 10 ppm of Th in the presence of uranium matrix, which resulted in a linear regression coefficient of 0.9978. The precision of the method was better than 5% and the LOD for Th was found to be 0.1ppm (S/N=3). The method has been validated by comparing the results with the results obtained from ICP-MS analysis where the This separated from the uranium matrix. The proposed method is simple, rapid, accurate and cost effective compared to techniques like ICP-MS or ICP-AES and is suitable for the routine kind of analysis.展开更多
We present the thorium distribution on the lunar surface derived from observations by the Chang’E-2 gamma-ray spectrometer(CE-2 GRS). This new map shows a similar thorium distribution to previous observations. In com...We present the thorium distribution on the lunar surface derived from observations by the Chang’E-2 gamma-ray spectrometer(CE-2 GRS). This new map shows a similar thorium distribution to previous observations. In combination with this new thorium map and impact cratering model, we investigate the origination of thorium on the Moon’s highlands, which was previously thought to be contributed from Imbrium ejecta. We found that the Imbrium ejecta has a small contribution(~20%–30%) to the thorium on the lunar highlands but most thorium is likely to be indigenous before the deposition of the Imbrium ejecta. This new thorium map also confirms that the eastern highlands have a relatively higher thorium concentration than the western highlands. We propose that the thin crust and large basins on the eastern highlands are responsible for this difference in thorium.展开更多
Density functional theory(DFT) calculations are performed to investigate the electronic and structural properties of the stoichiometric thorium oxide clusters(ThO2)n-/0(n = 1~5). Generalized Koopmans' theorem is a...Density functional theory(DFT) calculations are performed to investigate the electronic and structural properties of the stoichiometric thorium oxide clusters(ThO2)n-/0(n = 1~5). Generalized Koopmans' theorem is applied to predict the vertical detachment energies(VDEs)which are used to simulate the anionic photoelectron spectra(PES). Molecular orbital analyses are performed as well to analyze the chemical bonding in these thorium oxide clusters. The results show that the ground states of(ThO2)_n-/0(n = 1~5) clusters prefer the low-spin structures. With increasing of the cluster size(n), the structure parameters of(ThO2)n-/0(n = 1~5) gradually evolve toward bulk thorium oxide species. It shows that both the coordination number and the average bond length increase gradually in(ThO2)n-/0(n = 1~5) to approach that of ThO2 bulk. What's more, the vibration frequencies of Th=O double bonds are found to be decreasing along with the increased cluster size.展开更多
Herein, we assess the129I transmutation capability of a 2250-MWt single-fluid double-zone thorium molten salt reactor(SD-TMSR) by considering two methods. One is realized by loading an appropriate amount of129I before...Herein, we assess the129I transmutation capability of a 2250-MWt single-fluid double-zone thorium molten salt reactor(SD-TMSR) by considering two methods. One is realized by loading an appropriate amount of129I before the startup of the reactor, and the amount of129I during operation is kept constant by online feeding129I.The other adopts only an initial loading of129I before startup, and no other129I is fed online during operation.The investigation first focuses on the effect of the loading of I on the Th-233U isobreeding performance. The results indicate that a233U isobreeding mode can be achieved for both scenarios for a 60-year operation when the initial molar proportion of LiI is maintained within 0.40% and 0.87%, respectively. Then, the transmutation performances for the two scenarios are compared by changing the amount of injected iodine into the core. It is found that the scenario that adopts an initial loading of129I shows a slightly better transmutation performance in comparison with the scenario that adopts online feeding of129I when the net233U productions for the two scenarios are kept equal. The initial loading of129I scenario with LiI = 0.87% molar proportion is recommended for129I transmutation in the SD-TMSR,and can transmute 1.88 t of129I in the233U isobreeding mode over 60 years.展开更多
Supercritical Fluid Extraction (SFE) is emerging as a powerful technique in the extraction of metal ions. In the present study, the extraction of nitrates of uranium and thorium was carried out using supercritical car...Supercritical Fluid Extraction (SFE) is emerging as a powerful technique in the extraction of metal ions. In the present study, the extraction of nitrates of uranium and thorium was carried out using supercritical carbon dioxide (Sc-CO2) modified with various organophosphorous compounds such as dialkylalkyl phosphonates, trialkyl phosphates and trialkyl phosphine oxides in the presence of co-solvents such as methanol, dichlormethane and n-hexane. The influence of ligand and co-solvent on the extraction of the metal nitrates was studied in detail. These studies have established that co-solvent plays an important role in the extraction as well as fractionation of uranium and thorium nitrates. Polar co-solvent, methanol provided faster extraction without fractionation whereas the non-polar solvent, e.g. n-hexane provided some fractionation of metal nitrates though the extraction kinetics was slower.展开更多
In this study uranium and thorium contents and depositional characteristics of ay rhan bituminous shales（ BS）, west of Ankara（central Anatolia）, are investigated. Samples used were collected from boreholes opened ...In this study uranium and thorium contents and depositional characteristics of ay rhan bituminous shales（ BS）, west of Ankara（central Anatolia）, are investigated. Samples used were collected from boreholes opened by Park Holding Ltd. A total of 25 samples were taken from bituminous shale levels in boreholes drilled at 6 different locations in the study area. The H rka formation which hosts bituminous shale deposits is a volcanosedimentary sequence and all lithofacies indicate that a lacustrine environment where the water level was continuously changed. In addition to hydrocarbon generation potential, bituminous shales also accumulate significant amount of radioactive elements such as uranium and thorium. The average uranium and thorium concentrations of BS（1.83/2.62 ppm） are much lower than averages of UC, NASK and PAAS（uranium： 2.70/2.66/3.10 ppm; thorium： 8.50/12.30/14.60 ppm）. Low uranium contents in comparison to those of similar lacustrine environments might be attributed to that waters of depositional environment of BS contain low concentration of dissolved uranium and redox conditions were of oxic and dioxic character. Correlation data indicate that U and Th have a similar source and are associated predominantly with clays and phosphates and dominantly with organic material. Radioactive elements in the basin might be derived from Paleozoic granites and metamorphites（e.g. gneiss, schist） which comprise the basement and volcanism which was active in the region throughout the Miocene period. These elements are probably associated with uraniferous phosphate minerals（e.g. autunite, torbernite） which occur in granite, gneiss and schist. BS with average TOC content of 10.96 % shows very good/perfect source rock potential. Positive correlations between Gamma-Ray values and U, Th and K concentrations imply that radioactivity might be originated from these three elements.展开更多
基金Project supported by the National Natural Science Foundation of China(92262301)。
文摘Enlarging the steric hindrance to the molecular structures of extractants is a common way to improve their selectivity.To improve the separation factor of thorium(Ⅳ)and cerium(Ⅳ),cyclic groups having large steric hindrance such as phenyl,cyclohexyl,and benzyl were introduced into theα-aminophosphonate extractant molecules.Bis(2-ethylhexyl)((phenylamino)methyl)phosphonate(PAMP),bis(2-ethylhexyl)((cyclohexylamino)methyl)phosphonate(CAMP),and bis(2-ethylhexyl)((benzylamine)methyl)phosphate(BAMP)were synthesized and applied in the separation and recovery of thorium(Ⅳ)and cerium(Ⅳ)from sulfuric acid solution.The separation ability between cerium(Ⅳ)and thorium(Ⅳ)descends in the order of CAMP>BAMP≈Cextrant230>DEHAMP>>PAMP,which is consistent with the decreasing order of steric hindrance.Nearly non-extraction of both cerium(Ⅳ)and thorium(Ⅳ)and the lowest separation ability for PAMP will be due to the conjugation of the lone pair of the amino N atom and benzene ring in PAMP.Furthermore,the extraction of REs(Ⅲ)by CAMP is lower than that of thorium(Ⅳ).Thermodynamic parameters(ΔG^(0),ΔH^(0),ΔS^(0))and extraction equilibrium constants were determined.An extraction process was developed to separate and retrieve thorium(Ⅳ)and cerium(Ⅳ)from a bastnaesite leaching solution.The final product purity of CeO2and ThO2is 99%and 98.4%,respectively,and the yields are 90.2%and 97.6%,respectively.
基金supported by the National Key Research and Development Program of China(2020YFC1909001)the Natural Science Foundation of Jiangxi Province(20202BABL214024)。
文摘The acid leaching residue(ALR)of ionic rare earth(IRE)concentrates containing radioactive elements such as thorium(Th)is classified as low-level radioactive waste.ALR holds valuable strategic resources such as rare earth and Th,while improper long-term heaping storage of ALR poses a substantial environmental risk.This paper proposes a comprehensive process involving low-temperature roasting,hydrochloric acid leaching,single extractant enrichment,and stepwise stripping to recover rare earth elements and thorium from ALR.The achieved leaching efficiencies are 80.11%of LnY,99.43%of Sc(Ⅲ),and 98.67%of Th(Ⅳ)after the carbonization of the organic phase in the ALR through low-temperature roasting.Despite large amounts of acid and impurities present in the leachate,2-ethylhexyl phosphonic acid mono 2-ethylhexyl ester(HEHEHP)still exhibits nearly 100%extraction efficiency for Sc(Ⅲ)and Th(Ⅳ).The effective separation of LnY,Th(Ⅳ),and Sc(Ⅲ)was achieved by implementing fractional extraction enrichment of Th(Ⅳ)and Sc(Ⅲ),followed by Th(Ⅳ)removal through H_(2)SO_(4)and Sc(Ⅲ)removal via NaOH from the loaded organic phase.This scheme successfully achieves a recovery of RE and Th and offers a viable solution for the safe disposal of ALR.
文摘This work was conducted to determine the practicability of using a new adsorbent 4-ethyl thiosemicarbazide intercalated, organophilic calcined hydrotalcite （ETSC-OHTC） for the removal of uranium （U（Ⅵ））, and thorium （Th（Ⅳ）） from water and wastewater. The FTIR analysis helped in realizing the involvement of nitrogen and sulphur atoms of ETSC in binding the metal ions through complex formation. Parameters like adsorbent dosage, solution pH, initial metal ions concentration, contact time and ionic strength, that influence adsorption phenomenon, were studied. The optimum pH for maximum adsorption of U（VI） and Th（IV） was found to be in the range 4.0-6.0. The contact time required for reaching equilibrium was 4 hr. The pseudo second-order kinetic model was the best fit to represent the kinetic data. Analysis of the equilibrium adsorption data using Langmuir, Freundlich and Sips models showed that the Freundlich model was well suited to describe the metal ions adsorption. The KF values were 25.43 and 29.11 mg/g for U（Ⅵ） and Th（Ⅳ）, respectively, at 30℃. The adsorbent can be regenerated effectively from U（Ⅵ） and Th（Ⅳ） loaded ones using 0.01 mol/L HC1. The new adsorbent was quite stable for many cycles, without much reduction in its adsorption capacity towards the metals.
基金Project supported by National Basic Research Program of China(973 program,2012CBA01206)the National Natural Science Foundation of China(21521092,51222404)the Strategic Priority Research Program of CAS(XDA02030100)
文摘In the present work,a novelα-aminophosphonate extractant(Cextrant 230)was synthesized for the extraction and recovery of cerium and thorium from sulphate medium.The introduction of amine group into the phosphate molecule would enhance the extraction of Ce(Ⅳ)and Th(Ⅳ).The effects of extractant concentration,H_(2)SO_(4)concentration and temperature on the metal extraction were investigated in detail.It was found that the extraction of Ce(Ⅳ),Th(Ⅳ)and REs(La,Gd,Yb)in sulphate medium decreased in the following order:Ce(Ⅳ)〉Th(Ⅳ)〉REs(Ⅲ).A solvent extraction process to extract and recover cerium and thorium from bastnasite leaching was proposed,in which the purities of cerium and thorium products reached 99.9%and 99%with yield of 92%and 98%,respectively.
基金The National Natural Science Foundation of China under contract Nos 40606022 and 90411016 the National Key Basic Research Special Foundation Program of China under contract No 2005CB422305
文摘Thorium-234 and particle composition （organic matter, biogenic silica, carbonate and lithogenic component） were examined in the East China Sea （ECS） and the northern South China Sea （NSCS） in order to constrain the particle types scavenging thorium isotopes. Good positive correlations between particulate organic matter （POM） or carbonate and thorium-234 in suspended particulate matter （SPM） indicates that POM and carbonate are efficient to scavenge thorium-234. No relationship between biogenic silica and thorium-234 suggests that geochemical behavior of thorium-234 may be not influenced by biogenic silica. A simple model was used to evaluate the affinity of thorium-234 to different particle components. The results show that POM is the most efficient scavenger for thorium-234 in the ECS and the NSCS, followed by carbonate. The authors＇ results lend support to the utility of thorium-234 as a proxy of POC and carbonate in the upper layer. However, the strong dependence of thorium scavenging on particle composition challenges thorium-230 as a constant flux proxy.
基金supported by the National Basic Research Program of China (973 Program) (2012CBA01200)Northern Rare Earth Science and Technology Project (BFXT-2015D-0002) and (2016H1928)
文摘The Bayan Obo deposit in northern China is an ultra-large Fe–REE–Nb deposit.The occurrences,and geochemical characteristics of thorium in iron ores from the Bayan Obo Main Ore Body were examined using chemical analysis,field emission scanning electron microscopy,energy dispersive spectrometer,and automatic mineral analysis software.Results identified that 91.69%of ThO2 in the combined samples was mainly distributed in rare earth minerals(bastnaesite,huanghoite,monazite;56.43%abundance in the samples),iron minerals(magnetite,hematite,pyrite;20.97%),niobium minerals(aeschynite;14.29%),and gangue minerals(aegirine,riebeckite,mica,dolomite,apatite,fluorite;4.22%).An unidentified portion(4.09%)of ThO2 may occur in other niobium minerals(niobite,ilmenorutile,pyrochlore).Only a few independent minerals of thorium occur in the iron ore samples.Thorium mainly occurs in rare earth minerals in the form of isomorphic substitution.Analyses of the geochemical characteristics of the major elements indicate that thorium mineralization in the Main Ore Body was related to alkali metasomatism,which provided source material and favorable porosity for hydrothermal mineralization.Trace elements such as Sc,Nb,Zr,and Ta have higher correlation coefficients with thorium,which resulted from being related to the relevant minerals formed during thorium mineralization.In addition,correlation analysis of ThO2 and TFe,and REO and TFe in the six types of iron ore samples showed that ThO2 did not always account for the highest distribution rate in rare earth minerals,and the main occurrence minerals of ThO2 were closely related to iron ore types.
基金supported by the National Natural Science Foundation of China(Nos.11535009 and 51406114)
文摘Axial gas-liquid separators have been adopted in fission gas removal systems for the development of thorium molten salt reactors. In our previous study, we observed an unsteady flow phenomenon in which the flow pattern is directly dependent on the backpressure in a gas-liquid separator; however, the underlying flow mechanism is still unknown. In order to move a step further in clarifying how the flow pattern evolves with a variation in backpressure, a large eddy simulation(LES) was adopted to study the flow field evolution. In the simulation, an artificial boundary was applied at the separator outlet under the assumption that the backpressure increases linearly. The numerical results indicate that the unsteady flow feature is captured by the LES approach, and the flow transition is mainly due to the axial velocity profile redistribution induced by the backpressure variation. With the increase in backpressure,the axial velocity near the downstream orifice transits from negative to positive. This change in the axial velocity sign forces the unstable spiral vortex to become a stable rectilinear vortex.
基金supported by the National Key R&D Program of China(2017YFE0106900)Science and Technology Major Project of Ganzhou(2018)Fujian Program for High-Level Entrepreneurial and Innovative Talents Introduction and Science and Technology Service Network Initiative from Chinese Academy of Sciences。
文摘Ion-absorbed rare earth ores radioactive residues(IREORR)are a class of waste residue from the production of rare earth elements(REEs).Because of its radioactive dose,IREORR are usually stored in waste warehouses.IREORR are difficult to be disposed of.However,it contains relatively high concentrations of REEs,which can be considered as a valuable secondary resource.In this paper,a novel process is developed for the separation of thorium(Th)and recovery of REEs from IREORR hydrochloric acid leachate with primary amine N1923 and Cyanex?572,respectively.The effects of sulfate concentration,extractant concentration and pH on N1923 extraction in hydrochloric acid solution were investigated in detail.The results show that the extraction capacity of N1923 can be improved by adding sulfate to the solution and increasing the concentration of N1923.Acidity has little effect on the extraction of Th when pH is higher than 1.As for the stripping,REEs are more easily stripped from loaded organic phase than Th,and nitric acid is a better stripping agent than hydrochloric acid.Combined with the extraction of Cyanex■572 for REEs,a fractional extraction experiment for separating Th and enriching of REEs was performed.The yield of Th is higher than 99.9%and the concentration of REEs is enriched to 183.84 g/L.
文摘The based membrane extraction of Th 4+ and Yb 3+ was studied in HBTMPP heptane using a hollow fibber membrane. The separation method of Th 4+ and Yb 3+ was proposed by kinetics competition. The separation operation of Th 4+ and Yb 3+ mixture was carried out by two successive extraction and stripping simultaneously. The concentration ratio of Th 4+ to Yb 3+ is 16 74 in the stripping solution. The recovery and purity of Th 4+ are 71 6% and 95 74% respectively.
基金Project supported by National Basic Research Program of China (2012CBA01206)National Natural Science Foundation of China (51074148,51222404,91026024)
文摘A calixarene derivative, 5,11,17,23-tetra（diethoxyphosphoryl）-25,26,27,28-tetraacetoxycalix[4]arene （L）, was studied for the extraction and separation of thorium and rare earths in nitrate medium. Thorium was extracted into the organic phase by a complex of Th（NO3）4·L with the logarithm of the equilibrium constant of 2.77. Thermodynamic functions, AH, AG and AS were calculated to be -2.49, -15.55 kJ/mol and 44.53 J/（mol·K）, respectively. The results indicated that this calixarene derivative might be used to separate thorium from rare earths and the separation factors were larger than 26. However, the salting-out agents affected the separation.
基金The Scientific Research Foundation of Third Institute of Oceanography,State Oceanic Administration under contract NoTIO2007003the Natural Science Foundation of Fujian Province of China under contract No2006J0287+1 种基金the National Natural Science Foundation of China fromkey program under contract No 40531007 and from general program under contract Nos40406014 and 40276001the State Social Commonweal Foundationof China under contract No 2004DIB5178
文摘Dissolved and particulate thorium-234, particulate organic carbon in the upper 150 m of water columns from five stations in the Prydz Bay, the Southern Ocean were determined during the 22nd Chinese National Antarctic Research Expedition （from November 2005 to March 2006 ）. The disequilibria between thorium-234 and its parent uranium-238 in upper layer was used to derive the averaged residence time of thorium-234, which decreased along with the latitude to the south and a minimum value, 1 - 8 d for particulate thorium-234 and 29 - 48 d for dissolved thorium-234, appeared at the medium latitude station, and the export fluxes of thorium-234 were calculated too and ＇a maximum value, 0. 35 -0. 63 Bq/（m^3 · d） for the particulate thorium-234 and 0. 44 -0. 65 Bq/ （m^3 ·d） for the dissolved thorium-234, appeared at the same station. The export fluxes of particulate organic carbon at different water columns were derived by two methods with irreversible scavenging model, and the averaged values were 104. 7 mmol/ （ m2 · d ） （ E method） and 120. 6 mmol/（ m2·d ） （ B method ）, respectively, indicating that a relatively high new production would exist in summer in the Prydz Bay where it will play a potential significant role in sequestering the absorption CO2 to deeper ocean.
基金This project was supported by the State Social Commonweal Grant(project name:the comprehensive investigation of Nansha Islands waters)the Natural Science Foundation of Fujian Province of China under contract No.2006J0287+2 种基金This study was also supported,in part,by the National Natural Science Foundation of China from key program under contract No.40531007general program under contract Nos 40406014 and 40276001State Social Commonweal Grant under contract No.2004DIB5178.
文摘A low-level β counting-or spectrum apparatus used for the detection of the β radiation of thorium-234 and α spectrum of thorium- 228 simultaneously and an easy operating procedure for the enrichment, radiochemical separating, sampling and measurement of thorium-234 and uranium-238 in the ocean are developed based on the requirements of analyzing export productivity in the eupho- ric zone via thorium-234 - uranium-238 radioactivity disequilibrium. The detecting efficiency both of 13 and α radiation is higher than 20%. The background of βradiation is less than 0. 5 min ^-1 , and the energy resolution of ct detector is better than 1%. Total recycle ratio of thorium-234 is about 75%. Using the above apparatus and procedure, the radioactivities of dissolved thorium-234 and uranium-238, particle thorium-234 and uranium-238 in seawater of the South China Sea, the Southern Ocean and the Arctic Ocean were analyzed.
文摘This work presents the results of computer simulation of neutronic processes in a high-temperature gas-cooled thorium reactor for 30 different options of core loading.To guarantee stable and long-term reactor operation(7-10 years),the quantity of fuel compact dispersion phase and starting fuel composition was selected.It is demonstrated that it is possible in principle to substitute the near-axial recirculation zone of the reactor core by a long magnetic trap with a high-temperature plasma column for generating thermonuclear neutrons.The distribution of neutron yield along the length of the plasma source is also presented.Such a thorium reactor,with a near-axial source of extra neutrons,can be applied for researching thermophysical and neutronic characteristics of dispersion thorium fuel to improve its properties.The results of the work are of great interest from the perspective of future advancement of the thermonuclear power industry,by means of creation of a hybrid installation based on a thorium reactor with a long plasma column as a source of additional neutrons.
基金Project supported by the National Key Research and Development Project of China(2022YFC2905201)the Science and Technology Service Network Initiative Program of the Chinese Academy of Sciences(KFJ-STSQYZD-2021-18-001)+3 种基金the Research Projects of Ganjiang Innovation Academy,Chinese Academy of Sciences(E055C002)Jiangxi"Double Thous and Plan"(jxsq.2020101005)Jiangxi Province Natural Science Foundation(20212BAB213033)Ganzhou Science and Technology Program(2022CXRC9671)。
文摘In order to lower the usage of expensive Cyanex 923 and increase the extraction capacity of the system of Cextrant 230,the synergistic extraction of thorium from chloride media by a mixture of Cextrant 230 and Cyanex 923 was investigated.The maximum synergistic enhancement coefficient(R)of 1.53 is obtained at 1:1 molar ratio of Cextrant 230/Cyanex 923.The syne rgistic extracted species of Th^(4+)is determined as ThCl_(4)·2Cextrant 230·Cyanex 923.The synergistic extraction of Th^(4+)is an entropy-driven exothermic process.The loading capacity of 0.60 mol/L mixed extractant for thorium is about 17.10 g/L(calculated as ThO_(2)),and the loaded thorium in the organic phase can be effectively stripped by distilled water.For comparison,rare earth cations are barely extracted under the similar conditions,suggesting that the mixtures can be applied to separate thorium from rare earths.A cascade extraction process was developed based on the synergistic extraction system to separate thorium from the hydrochloric acid leaching of bastnaesite.The content of thorium in the leaching solution decreases obviously from 19.90 mg/L to1.4μg/L by 3 stages of extraction,which is superior to sole Cextrant 230 or Cyanex 923.The introduction of Cextrant 230 into the extraction system not only lowers the usage of Cyanex 923 but also enhances the selective extraction of thorium at low acidity,implying that the synergistic extraction system can selectively extract thorium more efficiently and economically than the sole systems.
文摘Retention behavior of U(VI) and Th(IV) as their 2, 6-pyridine dicarboxylic acid (PDCA) complexes on reversed phase and ion exchange (cation, anion and mixed ion exchange) columns was studied and based on the results, a simple ion chromatography method for the determination of trace level thorium in uranium oxide using 0.075mM 2, 6-pyridine dicarboxylic acid (PDCA) and 1M KNO3 in 1.2M HNO3 as eluent (flow rate 1 mL/min)was proposed. The advantage of the developed method is that the separation of uranium matrix is not required prior to the ion chromatographic determination of trace Th. Separation was carried out on a mixed ion exchange stationary phase and a 10?4 M arsenazo (III) solution was used as post column reagent for detecting the separated metal ions. The separation of Th from uranium using PDCA in the present investigation is attributed through cation exchange mechanism. A calibration plot was constructed by following the standard addition method over the concentration range of 0.25 to 10 ppm of Th in the presence of uranium matrix, which resulted in a linear regression coefficient of 0.9978. The precision of the method was better than 5% and the LOD for Th was found to be 0.1ppm (S/N=3). The method has been validated by comparing the results with the results obtained from ICP-MS analysis where the This separated from the uranium matrix. The proposed method is simple, rapid, accurate and cost effective compared to techniques like ICP-MS or ICP-AES and is suitable for the routine kind of analysis.
基金supported by the National Natural Science Foundation of China(11773087)the Science and Technology Development Fund of Macao(079/2018/A2)
文摘We present the thorium distribution on the lunar surface derived from observations by the Chang’E-2 gamma-ray spectrometer(CE-2 GRS). This new map shows a similar thorium distribution to previous observations. In combination with this new thorium map and impact cratering model, we investigate the origination of thorium on the Moon’s highlands, which was previously thought to be contributed from Imbrium ejecta. We found that the Imbrium ejecta has a small contribution(~20%–30%) to the thorium on the lunar highlands but most thorium is likely to be indigenous before the deposition of the Imbrium ejecta. This new thorium map also confirms that the eastern highlands have a relatively higher thorium concentration than the western highlands. We propose that the thin crust and large basins on the eastern highlands are responsible for this difference in thorium.
基金supported by Hunan Police Academy Research Innovation Team-Key Technologies of Road Traffic Safety Law Enforcementthe Key Laboratory of Impression Evidence Examination and Identification Technology,Ministry of Public Security,People’s Republic of China
文摘Density functional theory(DFT) calculations are performed to investigate the electronic and structural properties of the stoichiometric thorium oxide clusters(ThO2)n-/0(n = 1~5). Generalized Koopmans' theorem is applied to predict the vertical detachment energies(VDEs)which are used to simulate the anionic photoelectron spectra(PES). Molecular orbital analyses are performed as well to analyze the chemical bonding in these thorium oxide clusters. The results show that the ground states of(ThO2)_n-/0(n = 1~5) clusters prefer the low-spin structures. With increasing of the cluster size(n), the structure parameters of(ThO2)n-/0(n = 1~5) gradually evolve toward bulk thorium oxide species. It shows that both the coordination number and the average bond length increase gradually in(ThO2)n-/0(n = 1~5) to approach that of ThO2 bulk. What's more, the vibration frequencies of Th=O double bonds are found to be decreasing along with the increased cluster size.
基金supported by the Chinese TMSR Strategic Pioneer Science and Technology Project(No.XDA02010000)the Frontier Science Key Program of the Chinese Academy of Sciences(No.QYZDY-SSW-JSC016)
文摘Herein, we assess the129I transmutation capability of a 2250-MWt single-fluid double-zone thorium molten salt reactor(SD-TMSR) by considering two methods. One is realized by loading an appropriate amount of129I before the startup of the reactor, and the amount of129I during operation is kept constant by online feeding129I.The other adopts only an initial loading of129I before startup, and no other129I is fed online during operation.The investigation first focuses on the effect of the loading of I on the Th-233U isobreeding performance. The results indicate that a233U isobreeding mode can be achieved for both scenarios for a 60-year operation when the initial molar proportion of LiI is maintained within 0.40% and 0.87%, respectively. Then, the transmutation performances for the two scenarios are compared by changing the amount of injected iodine into the core. It is found that the scenario that adopts an initial loading of129I shows a slightly better transmutation performance in comparison with the scenario that adopts online feeding of129I when the net233U productions for the two scenarios are kept equal. The initial loading of129I scenario with LiI = 0.87% molar proportion is recommended for129I transmutation in the SD-TMSR,and can transmute 1.88 t of129I in the233U isobreeding mode over 60 years.
文摘Supercritical Fluid Extraction (SFE) is emerging as a powerful technique in the extraction of metal ions. In the present study, the extraction of nitrates of uranium and thorium was carried out using supercritical carbon dioxide (Sc-CO2) modified with various organophosphorous compounds such as dialkylalkyl phosphonates, trialkyl phosphates and trialkyl phosphine oxides in the presence of co-solvents such as methanol, dichlormethane and n-hexane. The influence of ligand and co-solvent on the extraction of the metal nitrates was studied in detail. These studies have established that co-solvent plays an important role in the extraction as well as fractionation of uranium and thorium nitrates. Polar co-solvent, methanol provided faster extraction without fractionation whereas the non-polar solvent, e.g. n-hexane provided some fractionation of metal nitrates though the extraction kinetics was slower.
基金supported by Ankara University Scientific Research Projects Coordination Unit(Project No:09B4343013)
文摘In this study uranium and thorium contents and depositional characteristics of ay rhan bituminous shales（ BS）, west of Ankara（central Anatolia）, are investigated. Samples used were collected from boreholes opened by Park Holding Ltd. A total of 25 samples were taken from bituminous shale levels in boreholes drilled at 6 different locations in the study area. The H rka formation which hosts bituminous shale deposits is a volcanosedimentary sequence and all lithofacies indicate that a lacustrine environment where the water level was continuously changed. In addition to hydrocarbon generation potential, bituminous shales also accumulate significant amount of radioactive elements such as uranium and thorium. The average uranium and thorium concentrations of BS（1.83/2.62 ppm） are much lower than averages of UC, NASK and PAAS（uranium： 2.70/2.66/3.10 ppm; thorium： 8.50/12.30/14.60 ppm）. Low uranium contents in comparison to those of similar lacustrine environments might be attributed to that waters of depositional environment of BS contain low concentration of dissolved uranium and redox conditions were of oxic and dioxic character. Correlation data indicate that U and Th have a similar source and are associated predominantly with clays and phosphates and dominantly with organic material. Radioactive elements in the basin might be derived from Paleozoic granites and metamorphites（e.g. gneiss, schist） which comprise the basement and volcanism which was active in the region throughout the Miocene period. These elements are probably associated with uraniferous phosphate minerals（e.g. autunite, torbernite） which occur in granite, gneiss and schist. BS with average TOC content of 10.96 % shows very good/perfect source rock potential. Positive correlations between Gamma-Ray values and U, Th and K concentrations imply that radioactivity might be originated from these three elements.
