CN107365909B - Extraction separation method - Google Patents
Extraction separation method Download PDFInfo
- Publication number
- CN107365909B CN107365909B CN201610316320.7A CN201610316320A CN107365909B CN 107365909 B CN107365909 B CN 107365909B CN 201610316320 A CN201610316320 A CN 201610316320A CN 107365909 B CN107365909 B CN 107365909B
- Authority
- CN
- China
- Prior art keywords
- organic phase
- phase
- extraction
- graphene aerogel
- back extraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/38—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds containing phosphorus
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/28—Amines
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/306—Ketones or aldehydes
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/402—Mixtures of acyclic or carbocyclic compounds of different types
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
- C22B3/40—Mixtures
- C22B3/408—Mixtures using a mixture of phosphorus-based acid derivatives of different types
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
- C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
- C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
- C22B60/026—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries liquid-liquid extraction with or without dissolution in organic solvents
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
- C22B60/02—Obtaining thorium, uranium, or other actinides
- C22B60/0291—Obtaining thorium, uranium, or other actinides obtaining thorium
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses an extraction separation method. The method comprises the following steps: adsorbing the organic phase on the graphene aerogel until the adsorption is saturated, and removing the organic phase on the surface of the graphene aerogel to prepare a graphene aerogel immobilized organic phase; placing the graphene aerogel fixed organic phase in a feed liquid water phase to be extracted, extracting target metal ions in the feed liquid water phase until extraction is balanced, and separating the graphene aerogel fixed organic phase from the extracted water phase; and (3) placing the separated graphene aerogel fixed organic phase into a back extraction water phase, performing back extraction, and recovering target metal ions. The method greatly improves the extraction capacity, relieves the loss of the extracting agent and greatly reduces the generation of organic waste liquid.
Description
Technical Field
The invention relates to an extraction separation method.
Background
Liquid-liquid extraction is a separation technology with wide application and strong practicability, and plays an important role in various fields such as chemical industry, environment, medicine, nuclear industry, analysis and the like. Liquid-liquid extraction refers to a process in which after two completely or partially immiscible liquid phases are brought into contact, the solute in one liquid phase enters the other liquid phase through physical or chemical action, or redistributes among the two phases, and then the two phases are separated. In practical operation, the two phases are usually an aqueous phase and an organic phase extractant immiscible with the aqueous phase, and the physical properties require that the organic phase and the aqueous phase have larger density difference and lower water solubility.
The density difference between the organic phase and the aqueous phase is the principle basis for realizing liquid-liquid extraction phase separation, while the higher water solubility can cause part of the extractant to flow to the aqueous phase in the phase separation process, thus leading to extractant loss and simultaneously increasing the treatment difficulty of aqueous phase waste liquid, and the selection range of the extractant is greatly reduced by the above requirements. In addition, most of the extracting agents need to add a large amount of organic diluent to adjust the physical properties of the organic phase, including density and viscosity, in the extraction process so as to meet the dynamic requirements of phase separation, and the saturated extraction capacity of the organic phase is reduced while a large amount of organic waste liquid is generated. Many extraction systems are prone to three-phase formation due to diluent addition and limited extraction capacity.
Disclosure of Invention
The invention aims to solve the technical problems that the saturated extraction capacity of an organic phase is reduced and the amount of organic waste liquid is increased due to the addition of a diluent in the traditional liquid-liquid extraction method, and the selection of an extracting agent is limited to a certain extent, and the problem that the extracting agent is easy to partially flow to a water phase, so that the treatment difficulty of the water phase waste liquid is increased is solved, and the extraction separation method of the graphene aerogel immobilized organic phase is provided. The extraction separation method of the invention can avoid the phase mixing and phase splitting process of the organic phase and the water phase, improve the saturated extraction capacity of the organic phase and reduce the amount of organic waste liquid.
The invention provides an extraction separation method for fixing an organic phase by utilizing graphene aerogel, which comprises the following steps:
(1) adsorbing the organic phase on the graphene aerogel until the adsorption is saturated, and removing the organic phase on the surface of the graphene aerogel to prepare a graphene aerogel immobilized organic phase;
(2) placing the graphene aerogel fixed organic phase in a feed liquid water phase to be extracted, extracting target metal ions in the feed liquid water phase until extraction is balanced, and separating the graphene aerogel fixed organic phase from the extracted water phase;
(3) and (3) placing the graphene aerogel fixed organic phase obtained by separation in the step (2) into a back extraction aqueous phase, performing back extraction until the back extraction is balanced, and recovering target metal ions.
In the step (1), the method for adsorbing the organic phase on the graphene aerogel is a conventional method in the art, and preferably comprises the following steps: the organic phase is immersed or dripped on the graphene aerogel.
Wherein the organic phase comprises an extractant and a diluent. Wherein, the volume percentage of the extractant in the organic phase is conventional in the field, preferably 50-100%, and more preferably 100%. When the volume percentage of the extracting agent in the organic phase is 100%, the extraction capacity of the organic phase can be improved to the maximum extent and the use of the organic diluent can be reduced to the maximum extent.
Wherein the extracting agent is one or more of extracting agents conventionally used in the field aiming at target metal ions, preferably tributyl phosphate (TBP), diisoamyl methyl phosphonate (DAMP), di (1-methyl) heptyl methyl phosphonate (DMHMP), trioctyl phosphine oxide (TOPO), methyl isobutyl ketone (MIBK), trioctyl/decyl tertiary amine (N235/7301), 2-ethylhexyl phosphate (P-507), di (2-ethylhexyl) phosphate (P204), N, one or more of N-di-sec-octylacetamide (N503), tetraoctyl-3-oxypentanediol-1, 5-diamide (TODGA) and a mixture of linear trialkyl phosphine oxides (Cyanex 923).
Wherein, the diluent is a diluent which is conventionally used in the field aiming at a target extraction system, and preferably one or more of n-dodecane, kerosene, trichloromethane and toluene.
The graphene aerogel is a hydrophobic microporous material with a space network structure, which is prepared by taking graphene or graphene oxide as a raw material through a sol-gel method or a vapor deposition method. Preferably, the graphene aerogel is prepared by a sol-gel method; more preferably, the graphene aerogel is prepared by adopting the following method: adopting a commercially available graphene oxide dispersion liquid (GO) and water as a solvent, regulating the concentration of the graphene oxide dispersion liquid to be 2mg/mL, adding ethylenediamine according to the mass ratio of 1:5 (the regulated graphene oxide dispersion liquid is ethylenediamine), uniformly stirring, and carrying out a water bath reaction at 85 ℃ for 24 hours; cooling to remove water after forming hydrogel, washing twice with 1mol/L HCl solution, adding diluted ethanol (the volume ratio of water to ethanol is 5:1, and the ethanol used before dilution is 95% ethanol), soaking for 6-8 hours, adding diluted ethanol, soaking and washing for three times, and taking about 24 hours; then freezing for 2-3 hours at-80 ℃, and then freeze-drying for 4 days.
The commercially available graphene oxide dispersion liquid is purchased from Nanjing Xiancheng nanometer material science and technology Limited company or is prepared by commercially available graphite powder. Among them, when the graphene oxide dispersion is prepared by itself from a commercially available graphite powder, the raw material graphite powder is commercially available and is preferably purchased from chemical reagents ltd.
The reagents used in the present invention include ethylenediamine, acid, alcohol, tributyl phosphate (TBP), n-dodecane, a mixture of linear trialkylphosphine oxides (Cyanex923), etc., all of which are conventional reagents, preferably available from national pharmaceutical group chemical Co., Ltd.
In step (1), when the adsorption saturation is reached, the saturation adsorption amount of the graphene aerogel is preferably 0.17mL/mg, that is, 0.17mL of organic phase is adsorbed per mg of graphene aerogel.
In step (1), the method for removing the organic phase on the surface of the graphene aerogel is a method conventional in the art, and preferably filter paper adsorption.
In the step (2), the separation is performed conventionally in the art, and preferably, the graphene aerogel fixed organic phase after extraction equilibrium is taken out from the extraction aqueous phase.
In the step (2), the time required for reaching the extraction equilibrium is preferably 1 to 8 hours.
In the step (3), the time required for the back extraction equilibrium is preferably 2 to 7 hours.
In the steps (2) and (3), the extraction and the back extraction are preferably carried out with stirring, and the stirring is preferably magnetic stirring. The rotating speed of the magnetic stirring is conventional in the field, preferably 100-1000 r/min, more preferably 200-400 r/min; wherein, the stirring is preferably accompanied by heating, the heating is a conventional operation in the field, and the heating temperature is preferably 15-70 ℃, more preferably 15-50 ℃.
In the step (2), the target metal ion is any kind of metal ion, preferably one or more of target metals commonly treated in the fields related to chemical engineering, environmental protection, pharmacy and nuclear fuel circulation, more preferably one or more of alkaline earth metal, rare earth metal ion, actinide metal ion and transition metal ion, and further more preferably, the element of the target metal ion is one or more of strontium (Sr), cesium (Cs), lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), rolled (Gd), dysprosium (Dy), thorium (Th), uranium (U), plutonium (Pu), americium (Am), curium (Cm), zirconium (Zr), niobium (Nb), ruthenium (Ru) and rhodium (Rh). Wherein strontium (Sr) belongs to alkaline earth metals, lanthanum (La), cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), rolled (Gd) and dysprosium (Dy) belong to rare earth metals, thorium (Th), uranium (U), plutonium (Pu), americium (Am) and curium (Cm) belong to actinides, and zirconium (Zr), niobium (Nb), ruthenium (Ru) and rhodium (Rh) belong to transition metals.
In the steps (2) and (3), the volume ratio of the feed liquid aqueous phase to the graphene aerogel fixed organic phase and the volume ratio of the strip aqueous phase to the graphene aerogel fixed organic phase are within the conventional scope of the field, and the volume ratio of the feed liquid aqueous phase to the graphene aerogel fixed organic phase is preferably not less than 3, and more preferably 3-5. Because of the inherent volume of the aerogel, when the volume of the aerogel after the aerogel adsorbs the organic phase in a saturated mode is still equal to the inherent macroscopic volume of the aerogel, only when the volume of the feed liquid water phase or the back extraction water phase is more than or equal to three times of the volume of the graphene aerogel fixed organic phase, the contact area and the extraction capacity of the graphene aerogel fixed organic phase can be fully utilized.
In the step (3), the back extraction water phase is water or an acidic aqueous solution. The acidic aqueous solution is conventional in the art, and the acidic substance adopted in the acidic aqueous solution is preferably one or more of hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid and ferrous sulfamate. The concentration of the acidic aqueous solution is preferably 0.001 to 1 mol/L.
According to the invention, the hydrophobic property of the graphene aerogel and the characteristic of large specific surface area of micropores of a spatial network structure have a strong adsorption function on an organic solution, so that the method is suitable for any water-oil two-phase extraction system.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The reagents and raw materials used in the present invention (except for the finished aerogel) are commercially available.
On the basis of the common knowledge in the field, the above preferred conditions can be combined randomly to obtain the preferred embodiments of the invention.
The positive progress effects of the invention are as follows:
based on the hydrophobicity of graphene, aerogel is used as a support structure to adsorb an organic phase, and then the organic phase is placed in a water phase to be extracted and back-extracted, so that the phase mixing and phase splitting processes of two phases in the traditional liquid-liquid extraction method are avoided, and the limitation of density difference of the two phases is avoided, therefore, the saturated extraction capacity of the organic phase is improved by infinitely increasing the proportion of an extracting agent in the organic phase, and meanwhile, the use of an organic reagent and the generation of waste liquid are reduced; the extraction separation method of the invention has high recovery rate (even more than 98.8 percent) of metal ions and has good separation effect on separating one metal ion from a plurality of metal ions.
Drawings
Fig. 1 is a schematic diagram of the operation process of the extraction separation method using a graphene aerogel-immobilized organic phase according to the present invention.
FIG. 2 is a graph showing the change in the concentration of uranium ions in the aqueous phase of the feed liquid with the contact time in example 1.
FIG. 3 is a graph of the concentration of uranium ions in the strip phase as a function of contact time in example 1.
FIG. 4 is a graph showing the concentration of metal ions in the aqueous phase of the feed in example 2 as a function of contact time.
Detailed Description
The invention is further illustrated by the following examples, which are not intended to limit the scope of the invention. The experimental methods without specifying specific conditions in the following examples were selected according to the conventional methods and conditions, or according to the commercial instructions.
The specific operation process of the extraction separation method using a graphene aerogel immobilized organic phase according to the embodiment of the present invention is shown in fig. 1, and includes the following steps: filling or attaching the organic phase 3 to the graphene aerogel 1 rich in the microporous structure 2 until the adsorption is saturated, and removing the organic phase 3 on the surface of the graphene aerogel 1 to prepare a graphene aerogel immobilized organic phase; then, placing the graphene aerogel fixed organic phase in a feed liquid water phase 4 to be extracted, extracting target metal ions in the feed liquid water phase until extraction is balanced, and separating the graphene aerogel fixed organic phase from an extracted water phase; placing the separated graphene aerogel fixed organic phase in a back extraction water phase 5, performing back extraction, and recovering target metal ions; stirring 6 is also accompanied in the extraction and stripping processes.
In the embodiment of the invention, the used graphene aerogel is prepared by a sol-gel method, specifically by the following method: adopting a commercially available graphene oxide dispersion liquid (GO) and water as a solvent, regulating the concentration of the graphene oxide dispersion liquid to be 2mg/mL, adding ethylenediamine according to the mass ratio of 1:5 (the regulated graphene oxide dispersion liquid is ethylenediamine), uniformly stirring, and carrying out a water bath reaction at 85 ℃ for 24 hours; cooling to remove water after forming hydrogel, washing twice with 1mol/L HCl solution, adding diluted ethanol (the volume ratio of water to ethanol is 5:1, and the ethanol used before dilution is 95% ethanol), soaking for 6-8 hours, adding diluted ethanol, soaking and washing for three times, and taking about 24 hours; then freezing for 2-3 hours at-80 ℃, and then freeze-drying for 4 days.
In the following examples, the ratios are volume ratios.
Example 1
Taking n-dodecane as an organic diluent and tributyl phosphate (TBP) as an extractant, and preparing organic solutions with TBP volume concentrations of 5%, 30%, 45% and 60% respectively as organic phases; preparing 3mol/L nitric acid aqueous solution with initial uranium concentration of 52.27mg/mL as a feed liquid water phase; preparing 0.001mol/L nitric acid aqueous solution as a back extraction aqueous phase; the ratio of the graphene aerogel fixed organic phase to the feed liquid water phase to the back extraction water phase is 1:5: 5;
(1) dropwise adding the prepared organic phase on 6mg of hydrophobic graphene aerogel material until the adsorption is saturated, wherein the volume of the adsorbed organic phase is 1 mL; removing the surface organic phase to prepare a graphene aerogel fixed organic phase;
(2) placing the mixed solution into 5mL of feed liquid water phase, carrying out extraction balance operation under the stirring condition of 200r/min, and detecting the relation between the concentration of uranium in the feed liquid water phase and the contact time; after the graphene aerogel is fixed with the organic phase and is extracted and balanced, detecting that the relation between the uranium concentration of the feed liquid water phase and the contact time in the extraction operation is shown in figure 2;
(3) taking out the graphene aerogel fixed organic phase after extraction balance, placing the graphene aerogel fixed organic phase in 5mL of back extraction water phase, carrying out back extraction balance operation under the stirring condition of 200r/min, recycling uranium ions and detecting the relation between the concentration of uranium and contact time in the back extraction water phase; after the stripping is balanced, the relation between the uranium concentration of the stripping aqueous phase and the contact time in the stripping operation is detected as shown in figure 3;
detection shows that extraction balance is achieved after 8 hours in extraction operation, the extraction capacity of the organic phase uranium is increased along with the increase of the content of TBP in the organic phase, and the larger the percentage of an extracting agent occupying the organic phase is, the larger the extraction capacity is; the counter-extraction balance is reached after the contact time is 2 hours in the counter-extraction operation, and the extraction amount of uranium is increased along with the increase of the content of the extractant in the organic phase.
Example 2
Pure tributyl phosphate (TBP) is directly adopted as an organic phase without using an organic diluent; preparing 3mol/L nitric acid aqueous solution with initial uranium concentration of 0.48mg/mL and initial concentrations of other metals of strontium and cesium of 0.10 and 0.11mg/mL as feed liquid water phase; preparing a nitric acid aqueous solution with the concentration of 0.001mol/L as a back extraction aqueous phase; the ratio of the graphene aerogel fixed organic phase to the material liquid aqueous phase to the back extraction aqueous phase is 1: 3: 3;
(1) dropwise adding pure TBP on 6mg of hydrophobic graphene aerogel material until adsorption is saturated, wherein the volume of the adsorbed TBP is 1mL, and removing a surface organic phase to prepare a graphene aerogel immobilized organic phase;
(2) placing the mixed solution into a 3mL feed liquid water phase, carrying out extraction balance operation under the stirring condition of 150r/min, detecting the relation between the concentration of uranium, strontium and cesium in the feed liquid water phase and the contact time, and after extraction balance, detecting that the relation between the uranium concentration of the feed liquid water phase and the contact time in the extraction operation is shown in figure 4;
(3) taking out the graphene aerogel fixed organic phase after extraction balance, placing the graphene aerogel fixed organic phase in 3mL of back extraction aqueous phase, carrying out back extraction balance operation under the stirring condition of 150r/min, and recovering uranium ions;
in this embodiment, only one kind of uranium ions is recovered, and the remaining ions, namely strontium and cesium, remain in the extracted aqueous phase, and the separation process of the two ions depends on the difference in the distribution ratio of the three kinds of ions in the selected extractant to realize separation. In the extraction process of adding the feed liquid water phase into the fixed organic phase, uranium ions are combined with an extracting agent in the fixed organic phase and extracted into the organic phase, and strontium and cesium are not combined with the extracting agent or are combined with the extracting agent weakly and are left in the water phase, so that the separation effect is achieved.
Detection shows that under the condition, the extraction balance of uranium is achieved within 1 hour; the extraction recovery rate of uranium is 96.7%, and the separation coefficients of uranium, strontium and cesium are both more than 107The recovery rate of metal ions extracted by utilizing the graphene aerogel fixed organic phase is high, and for a system containing various metal ions, the separation coefficient among the metal ions is very high.
Example 3
An extractant straight-chain trialkyl phosphine oxide mixture (Cyanex923) is directly adopted as an organic phase without using an organic diluent; preparing 1mol/L nitric acid aqueous solution with initial lanthanum concentration of 0.07mg/mL as a feed liquid water phase; preparing a nitric acid aqueous solution with the concentration of 1mol/L as a back extraction aqueous phase; the ratio of the graphene aerogel fixed organic phase to the material liquid aqueous phase to the back extraction aqueous phase is 1: 3: 3;
(1) dropwise adding the Cyanex923 to a 6mg hydrophobic graphene aerogel material until the adsorption is saturated, wherein the volume of the adsorbed Cyanex923 is 1mL, removing a surface organic phase, and preparing a graphene aerogel immobilized organic phase
(2) Placing the mixed solution into 3mL of feed liquid water phase, carrying out extraction balance operation under the stirring condition of 200r/min, and detecting the relation between the lanthanum concentration in the feed liquid water phase and the contact time;
(3) taking out the graphene aerogel fixed organic phase after extraction balance, placing the graphene aerogel fixed organic phase in 3mL of back extraction water phase, carrying out back extraction balance operation under the stirring condition of 200r/min, and recovering lanthanum ions;
detection shows that under the condition, the lanthanum concentration of the feed liquid water phase reaches balance after the contact time of the extraction operation reaches 1 hour; the extraction recovery rate of lanthanum is 98.8%, and the detection result shows that the graphene aerogel immobilized organic phase has high recovery rate when being used for extracting and separating target ions.
Example 4
Taking n-dodecane as an organic diluent and tributyl phosphate (TBP) as an extractant to prepare an organic solution with the TBP volume concentration of 60 percent as an organic phase; preparing 3mol/L nitric acid aqueous solution with initial thorium concentration of 50.48mg/mL as a feed liquid water phase; preparing a nitric acid aqueous solution with the concentration of 0.005mol/L as a back extraction aqueous phase; the ratio of the graphene aerogel fixed organic phase to the material liquid aqueous phase to the back extraction aqueous phase is 1: 3: 3;
(1) dropwise adding the prepared organic phase on 6mg of hydrophobic graphene aerogel material until the adsorption is saturated, wherein the volume of the adsorbed organic phase is 1 mL; removing the surface organic phase to prepare a graphene aerogel fixed organic phase;
(2) placing the mixture into 3mL of aqueous phase feed liquid, carrying out extraction balance operation under the stirring condition of 200r/min, and detecting the concentration of thorium in the extracted aqueous phase after balance;
(3) taking out the graphene aerogel fixed organic phase after extraction balance, placing the graphene aerogel fixed organic phase in 3mL of back extraction aqueous phase, carrying out back extraction balance operation under the stirring condition of 200r/min, and recovering thorium ions;
under the condition, the extraction equilibrium is still the extraction water phase and the graphene aerogel fixed organic phase, no third phase exists, and the thorium concentration in the extraction water phase is 27g/L through detection.
Example 5
In this example, the process conditions and steps of the extraction separation method were the same as those in example 1, except that: in the organic phase, the volume concentration of the extractant tributyl phosphate (TBP) was 50%.
Example 6
In this example, the process conditions and steps of the extraction separation method were the same as those in example 1, except that: the volume concentration of the extractant tributyl phosphate (TBP) in the organic phase was 100%.
Example 7
In this example, the process conditions and steps of the extraction separation method were the same as those in example 1, except that: the back extraction water phase is ferrous sulfamate water solution with the concentration of 0.03 mol/L.
Example 8
In this example, the process conditions and steps of the extraction separation method were the same as those in example 3, except that: the feed liquid water phase is 0.001mol/L nitric acid water solution with initial strontium concentration of 0.05 mg/mL.
Example 9
In this example, the process conditions and steps of the extraction separation method were the same as those in example 3, except that: the stirring speed in the extraction and back extraction processes is 1000 r/min.
Example 10
In this example, the process conditions and steps of the extraction separation method were the same as those in example 3, except that: the stirring speed in the extraction and back extraction processes is 400 r/min.
Example 11
In this example, the process conditions and steps of the extraction separation method were the same as those in example 3, except that: heating is also carried out during the stirring process, and the heating range is from room temperature to 70 ℃.
Example 12
In this example, the process conditions and steps of the extraction separation method were the same as those in example 3, except that: heating is also carried out during the stirring process, and the heating range is from room temperature to 50 ℃.
Comparative example 1
Taking n-dodecane as an organic diluent and tributyl phosphate (TBP) as an extractant to prepare an organic solution with the TBP volume concentration of 30 percent as an organic phase; preparing 3mol/L nitric acid aqueous solution with initial thorium concentration of 50.48mg/mL as a feed liquid water phase; the ratio of the organic phase to the feed liquid water phase is 1: 3;
mixing the prepared organic phase and the feed liquid water phase according to a ratio of 1:3(1mL:3mL), oscillating for 2 minutes through a vortex oscillator, centrifuging for one minute under the condition of 3000rpm of a centrifuge, and detecting the concentration of thorium in the extracted water phase;
under the condition, a third phase is generated in the extraction system after centrifugal phase separation, and the thorium concentration in the extracted water phase is detected to be 38 g/L. While the equilibrated organic phase has separated into a light and a heavy phase.
Compared to example 4, the extraction capacity was halved and the trouble of three phases could not be eliminated.
Claims (10)
1. An extraction separation method is characterized in that: the extraction separation method comprises the following steps:
taking n-dodecane as an organic diluent and tributyl phosphate as an extractant to prepare an organic solution with TBP volume concentration of 5%, 30%, 45%, 50%, 60% or 100% as an organic phase; preparing 3mol/L nitric acid aqueous solution with initial uranium concentration of 52.27mg/mL as a feed liquid water phase; preparing 0.001mol/L nitric acid aqueous solution as a back extraction aqueous phase; the ratio of the graphene aerogel fixed organic phase to the feed liquid water phase to the back extraction water phase is 1:5: 5;
(1) dropwise adding the prepared organic phase on 6mg of hydrophobic graphene aerogel material until the adsorption is saturated, wherein the volume of the adsorbed organic phase is 1 mL; removing the surface organic phase to prepare a graphene aerogel fixed organic phase;
(2) placing the mixture into 5mL of feed liquid water phase, and carrying out extraction balance operation under the stirring condition of 200 r/min;
(3) and taking out the graphene aerogel fixed organic phase after extraction balance, placing the graphene aerogel fixed organic phase in 5mL of back extraction water phase, carrying out back extraction balance operation under the stirring condition of 200r/min, and recovering uranium ions.
2. An extraction separation method is characterized in that: the extraction separation method comprises the following steps:
taking n-dodecane as an organic diluent and tributyl phosphate as an extractant to prepare an organic solution with TBP volume concentration of 5%, 30%, 45% or 60% as an organic phase; preparing 3mol/L nitric acid aqueous solution with initial uranium concentration of 52.27mg/mL as a feed liquid water phase; preparing a ferrous sulfamate aqueous solution with the concentration of 0.03mol/L as a back extraction aqueous phase; the ratio of the graphene aerogel fixed organic phase to the feed liquid water phase to the back extraction water phase is 1:5: 5;
(1) dropwise adding the prepared organic phase on 6mg of hydrophobic graphene aerogel material until the adsorption is saturated, wherein the volume of the adsorbed organic phase is 1 mL; removing the surface organic phase to prepare a graphene aerogel fixed organic phase;
(2) placing the mixture into 5mL of feed liquid water phase, and carrying out extraction balance operation under the stirring condition of 200 r/min;
(3) and taking out the graphene aerogel fixed organic phase after extraction balance, placing the graphene aerogel fixed organic phase in 5mL of back extraction water phase, carrying out back extraction balance operation under the stirring condition of 200r/min, and recovering uranium ions.
3. An extraction separation method is characterized in that: the extraction separation method comprises the following steps:
pure tributyl phosphate is directly adopted as an organic phase without using an organic diluent; preparing 3mol/L nitric acid aqueous solution with initial uranium concentration of 0.48mg/mL and initial concentrations of other metals of strontium and cesium of 0.10 and 0.11mg/mL as feed liquid water phase; preparing a nitric acid aqueous solution with the concentration of 0.001mol/L as a back extraction aqueous phase; the ratio of the graphene aerogel fixed organic phase to the material liquid aqueous phase to the back extraction aqueous phase is 1: 3: 3;
(1) dropwise adding pure TBP on 6mg of hydrophobic graphene aerogel material until adsorption is saturated, wherein the volume of the adsorbed TBP is 1mL, and removing a surface organic phase to prepare a graphene aerogel immobilized organic phase;
(2) placing the mixture into 3mL of feed liquid water phase, and carrying out extraction balance operation under the stirring condition of 150 r/min;
(3) and taking out the graphene aerogel fixed organic phase after extraction balance, placing the graphene aerogel fixed organic phase in 3mL of back extraction water phase, carrying out back extraction balance operation under the stirring condition of 150r/min, and recovering uranium ions.
4. An extraction separation method is characterized in that: the extraction separation method comprises the following steps:
directly adopting a linear trialkyl phosphine oxide mixture as an extracting agent as an organic phase without using an organic diluent; preparing 1mol/L nitric acid aqueous solution with initial lanthanum concentration of 0.07mg/mL as a feed liquid water phase; preparing a nitric acid aqueous solution with the concentration of 1mol/L as a back extraction aqueous phase; the ratio of the graphene aerogel fixed organic phase to the material liquid aqueous phase to the back extraction aqueous phase is 1: 3: 3;
(1) dropwise adding Cyanex923 to a 6mg hydrophobic graphene aerogel material until the adsorption is saturated, wherein the volume of the adsorbed Cyanex923 is 1mL, and removing a surface organic phase to prepare a graphene aerogel immobilized organic phase;
(2) placing the mixture into 3mL of feed liquid water phase, and carrying out extraction balance operation under the stirring condition of 200 r/min;
(3) and taking out the graphene aerogel fixed organic phase after extraction balance, placing the graphene aerogel fixed organic phase in 3mL of back extraction water phase, carrying out back extraction balance operation under the stirring condition of 200r/min, and recovering lanthanum ions.
5. The extractive separation process of claim 4, wherein: the stirring process is accompanied by heating, and the heating range is from room temperature to 70 ℃.
6. The extractive separation process of claim 4, wherein: the stirring process is accompanied by heating, and the heating range is from room temperature to 50 ℃.
7. An extraction separation method is characterized in that: the extraction separation method comprises the following steps:
directly adopting a linear trialkyl phosphine oxide mixture as an extracting agent as an organic phase without using an organic diluent; preparing 0.001mol/L nitric acid aqueous solution with initial strontium concentration of 0.05mg/mL as a feed liquid aqueous phase; preparing a nitric acid aqueous solution with the concentration of 1mol/L as a back extraction aqueous phase; the ratio of the graphene aerogel fixed organic phase to the material liquid aqueous phase to the back extraction aqueous phase is 1: 3: 3;
(1) dropwise adding Cyanex923 to a 6mg hydrophobic graphene aerogel material until the adsorption is saturated, wherein the volume of the adsorbed Cyanex923 is 1mL, and removing a surface organic phase to prepare a graphene aerogel immobilized organic phase;
(2) placing the mixture into 3mL of feed liquid water phase, and carrying out extraction balance operation under the stirring condition of 200 r/min;
(3) and taking out the graphene aerogel fixed organic phase after extraction balance, placing the graphene aerogel fixed organic phase into 3mL of back extraction water phase, carrying out back extraction balance operation under the stirring condition of 200r/min, and recovering strontium ions.
8. An extraction separation method is characterized in that: the extraction separation method comprises the following steps:
directly adopting a linear trialkyl phosphine oxide mixture as an extracting agent as an organic phase without using an organic diluent; preparing 1mol/L nitric acid aqueous solution with initial lanthanum concentration of 0.07mg/mL as a feed liquid water phase; preparing a nitric acid aqueous solution with the concentration of 1mol/L as a back extraction aqueous phase; the ratio of the graphene aerogel fixed organic phase to the material liquid aqueous phase to the back extraction aqueous phase is 1: 3: 3;
(1) dropwise adding Cyanex923 to a 6mg hydrophobic graphene aerogel material until the adsorption is saturated, wherein the volume of the adsorbed Cyanex923 is 1mL, and removing a surface organic phase to prepare a graphene aerogel immobilized organic phase;
(2) placing the mixture into 3mL of feed liquid water phase, and carrying out extraction balance operation under the stirring condition of 400 r/min;
(3) and taking out the graphene aerogel fixed organic phase after extraction balance, placing the graphene aerogel fixed organic phase in 3mL of back extraction water phase, carrying out back extraction balance operation under the stirring condition of 400r/min, and recovering lanthanum ions.
9. An extraction separation method is characterized in that: the extraction separation method comprises the following steps:
directly adopting a linear trialkyl phosphine oxide mixture as an extracting agent as an organic phase without using an organic diluent; preparing 1mol/L nitric acid aqueous solution with initial lanthanum concentration of 0.07mg/mL as a feed liquid water phase; preparing a nitric acid aqueous solution with the concentration of 1mol/L as a back extraction aqueous phase; the ratio of the graphene aerogel fixed organic phase to the material liquid aqueous phase to the back extraction aqueous phase is 1: 3: 3;
(1) dropwise adding Cyanex923 to a 6mg hydrophobic graphene aerogel material until the adsorption is saturated, wherein the volume of the adsorbed Cyanex923 is 1mL, and removing a surface organic phase to prepare a graphene aerogel immobilized organic phase;
(2) placing the mixture into 3mL of feed liquid water phase, and carrying out extraction balance operation under the stirring condition of 1000 r/min;
(3) and taking out the graphene aerogel fixed organic phase after extraction balance, placing the graphene aerogel fixed organic phase in 3mL of back extraction water phase, carrying out back extraction balance operation under the stirring condition of 1000r/min, and recovering lanthanum ions.
10. An extraction separation method is characterized in that: the extraction separation method comprises the following steps:
taking n-dodecane as an organic diluent and tributyl phosphate as an extractant to prepare an organic solution with TBP volume concentration of 60% as an organic phase; preparing 3mol/L nitric acid aqueous solution with initial thorium concentration of 50.48mg/mL as a feed liquid water phase; preparing a nitric acid aqueous solution with the concentration of 0.005mol/L as a back extraction aqueous phase; the ratio of the graphene aerogel fixed organic phase to the material liquid aqueous phase to the back extraction aqueous phase is 1: 3: 3;
(1) dropwise adding the prepared organic phase on 6mg of hydrophobic graphene aerogel material until the adsorption is saturated, wherein the volume of the adsorbed organic phase is 1 mL; removing the surface organic phase to prepare a graphene aerogel fixed organic phase;
(2) placing the mixture into 3mL of aqueous phase feed liquid, and carrying out extraction balance operation under the stirring condition of 200 r/min;
(3) and taking out the graphene aerogel fixed organic phase after extraction balance, placing the graphene aerogel fixed organic phase in 3mL of back extraction water phase, carrying out back extraction balance operation under the stirring condition of 200r/min, and recovering thorium ions.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610316320.7A CN107365909B (en) | 2016-05-12 | 2016-05-12 | Extraction separation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610316320.7A CN107365909B (en) | 2016-05-12 | 2016-05-12 | Extraction separation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107365909A CN107365909A (en) | 2017-11-21 |
| CN107365909B true CN107365909B (en) | 2021-03-19 |
Family
ID=60304600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610316320.7A Active CN107365909B (en) | 2016-05-12 | 2016-05-12 | Extraction separation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107365909B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108085493B (en) * | 2017-11-29 | 2019-10-25 | 中铝广西国盛稀土开发有限公司 | A method of impurity in rare earth chloride liquid is removed using batch process |
| CN108048654B (en) * | 2017-11-29 | 2019-08-30 | 中铝广西国盛稀土开发有限公司 | A method of continuously removing impurity in rare earth chloride liquid using extraction tank |
| CN110540191B (en) * | 2018-05-29 | 2021-09-14 | 厦门稀土材料研究所 | Polyamine-functionalized three-dimensional graphene-based aerogel and preparation method and application thereof |
| CN109207732B (en) * | 2018-09-26 | 2020-06-09 | 绍兴文理学院 | Rare earth extraction system and method for rare earth tricolor fluorescent powder wastewater for lamp |
| CN109207731B (en) * | 2018-09-26 | 2020-06-09 | 绍兴文理学院 | Rare earth extraction system and method for erbium-containing wastewater |
| CN111876598B (en) * | 2019-12-10 | 2022-03-22 | 核工业北京化工冶金研究院 | Method for separating uranium and niobium through co-extraction |
| CN111450808A (en) * | 2020-04-13 | 2020-07-28 | 东华理工大学 | Phosphonic acid functionalized polymer/graphene nanoribbon composite aerogel and preparation method and application thereof |
| CN114807602B (en) * | 2022-05-19 | 2023-02-21 | 哈尔滨工业大学（威海） | Extraction solvent and extraction method for separating zirconium and hafnium |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102500133A (en) * | 2011-10-15 | 2012-06-20 | 东南大学 | Application method of graphene sponge |
| CN102492853B (en) * | 2011-12-19 | 2015-07-01 | 云南民族大学 | P-NBR type reagent and application of p-NBR type reagent in solid-phase extraction of platinum |
| CN104250005B (en) * | 2014-09-11 | 2016-07-06 | 中国科学院上海应用物理研究所 | A kind of graphene aerogel and its preparation method and application |
| CN104611560A (en) * | 2015-01-26 | 2015-05-13 | 江西理工大学 | Method for enriching rare earth from rare-earth leaching mother liquor |
| CN104593594B (en) * | 2015-01-26 | 2017-11-03 | 江西理工大学 | The method of rare earth is enriched with a kind of leaching mother liquor from rare earth |
-
2016
- 2016-05-12 CN CN201610316320.7A patent/CN107365909B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107365909A (en) | 2017-11-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107365909B (en) | Extraction separation method | |
| US7731870B2 (en) | Purex method and its uses | |
| CN104894372B (en) | Method for extracting and separating trivalent lanthanum and trivalent actinium ion | |
| US8999168B2 (en) | Supported liquid inorganic membranes for nuclear waste separation | |
| RU2663882C1 (en) | Method for recycling nuclear waste, including uranium (vi) purification from at least one actinide (iv) by producing actinide (iv) complex | |
| Xu et al. | Separation of zirconium and hafnium by solvent extraction using mixture of DIBK and P204 | |
| Zhao et al. | Effects of some parameters on mass-transfer efficiency of a ϕ20 mm annular centrifugal contactor for nuclear solvent extraction processes | |
| Misra et al. | Studies on the simultaneous removal of dissolved DBP and TBP as well as uranyl ions from aqueous solutions by using Micellar-Enhanced Ultrafiltration Technique | |
| CN102776373A (en) | Method for extracting and separating uranyl ions from water phase containing zirconium ions and lanthanide ions | |
| CN108085490A (en) | The method of extracts composition and enriching lithium | |
| CN107958717A (en) | It is a kind of that trivalent actinium series and the method for lanthanide ion are separated based on cooperative effect | |
| US3077378A (en) | Separation of europium from other lanthanide rare earths by solvent extraction | |
| US3326811A (en) | Processing of irradiated nuclear fuels | |
| Formiga et al. | Cerium separation from light rare earth concentrate by liquid-liquid extraction | |
| JP2018123373A (en) | Selective separation method of metal element and separation unit | |
| US5395532A (en) | Method for extracting metals from aqueous waste streams for long term storage | |
| Basuki et al. | Separation factor of Y/Dy emulsion on membrane process using nitric acid and D2EHPA solvent | |
| Kopunec et al. | Extraction of rare earth elements with organophosphorus extractants as carriers in supported liquid membranes | |
| Boudry et al. | Adaptation of the Purex process to the reprocessing of fast reactor fuels | |
| Miura et al. | Direct extraction of uranium and plutonium from oxide fuel using TBP-HNO {sub 3} complex for super-DIREX process | |
| Manohar et al. | Removal of dissolved Tri n-butyl phosphate from aqueous streams of reprocessing origin: engineering scale studies | |
| CN116065021B (en) | Ion exchange separation and purification method of single rare earth element samarium | |
| Ganz et al. | Application of Kapton nuclear track microfilters in liquid-liquid extraction of actinoide elements | |
| Xu et al. | Study on treatment of uranium-containing wastewater with the TBP emulsion liquid membrane | |
| Chen et al. | Separation of trivalent americium and europium by purified Cyanex 301 immobilized in macro porous polymer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |