CN107365909A - A kind of extraction separating method - Google Patents
A kind of extraction separating method Download PDFInfo
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- CN107365909A CN107365909A CN201610316320.7A CN201610316320A CN107365909A CN 107365909 A CN107365909 A CN 107365909A CN 201610316320 A CN201610316320 A CN 201610316320A CN 107365909 A CN107365909 A CN 107365909A
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- 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
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- 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
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- 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
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- 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
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- C22B3/402—Mixtures of acyclic or carbocyclic compounds of different types
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- 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
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- 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
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- 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
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- 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
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Abstract
The invention discloses a kind of extraction separating method.This method comprises the following steps：By organic phase absorption on graphene aerogel, until adsorption saturation, then the organic phase on graphene aerogel surface is removed, graphene aerogel is made and fixes organic phase；Described graphene aerogel is fixed into organic phase to be placed in feed liquid aqueous phase to be extracted, carries out the extraction of wherein target metal ions, to extraction equilibrium, graphene aerogel is fixed into organic phase and raffinate aqueous phase separation；Isolated graphene aerogel is fixed into organic phase to be placed in strip aqueous, is stripped, reclaims target metal ions, you can.This method drastically increases loading capacity, alleviates the loss of extractant and significantly reduces the generation of organic liquid waste.
Description
Technical field
The present invention relates to a kind of extraction separating method.
Background technology
Liquid-liquid extraction is one and is widely used the isolation technics very strong with practicality, chemical industry, environment,
Critical role is occupied in each fields such as medicine, nuclear industry and analysis.Liquid-liquid extraction refers to two completely not
Dissolve each other or the contact of the liquid phase of partial miscibility after, solute in a liquid phase enters by physically or chemically effect
Another liquid phase, or redistributed in two-phase, the process for then again being separated two-phase.In reality
In operating process, two-phase is usually aqueous phase and immiscible organic extractant phase agent therewith, in physical property
It is required that organic phase has larger density contrast and relatively low water solubility with aqueous phase.
The density contrast of organic phase and aqueous phase is the basis for realizing liquid-liquid extraction split-phase, and higher water
Dissolubility can then cause the part extractant in phase process to flow to aqueous phase, cause extractant to be lost in while increase
The intractability of aqueous phase waste liquid, requirements above all greatly reduce the range of choice of extractant.In addition,
In extraction process, most of extractants are required for adding substantial amounts of organic diluent to adjust the thing of organic phase
Rationality matter, including density and viscosity, to meet the power demand of split-phase, reducing the extraction of organic phase saturation
Also the generation of a large amount of organic liquid wastes is caused while capacity.Addition and extraction of many extraction systems because of diluent
The limited generation for easily causing three-phase for the amount of trying to please.
The content of the invention
The technical problems to be solved by the invention are, in order to overcome diluent in traditional liquid-liquid extraction method
Addition cause organic phase saturation loading capacity reduce, organic waste liquid measure increase the problem of, and extraction
There is a definite limitation and its easily partly flow to aqueous phase in the selection of agent, and cause the intractability of aqueous phase waste liquid
The problem of increasing, and the extraction separating method that a kind of graphene aerogel fixes organic phase is provided.The present invention
Extraction separating method can remove the mixed phase and phase process of organic phase and aqueous phase from, improve the full of organic phase
And loading capacity, reduce organic waste liquid measure.
The invention provides a kind of extraction separating method that organic phase is fixed using graphene aerogel, and it is wrapped
Include following steps：
(1) by organic phase absorption on graphene aerogel, until adsorption saturation, then remove graphene
The organic phase on aeroge surface, graphene aerogel is made and fixes organic phase；
(2) described graphene aerogel is fixed into organic phase to be placed in feed liquid aqueous phase to be extracted, entered
The extraction of row wherein target metal ions, to extraction equilibrium, graphene aerogel is fixed into organic phase and extraction
Remaining aqueous phase separation；
(3) the isolated graphene aerogel of step (2) is fixed into organic phase to be placed in strip aqueous,
Back extraction, to stripping equilibria, reclaim target metal ions, you can.
It is this area routine side by method of the organic phase absorption on graphene aerogel in step (1)
Method, preferably：Organic phase is impregnated or is added dropwise on graphene aerogel.
Wherein, described organic phase includes extractant and diluent.Wherein, described extractant accounts for described
Organic phase percent by volume it is conventional for this area, preferably 50%~100%, be more preferably 100%.
When the percent by volume that extractant accounts for described organic phase is 100%, can improve to greatest extent
Machine phase loading capacity and the use for reducing organic diluent to greatest extent.
Wherein, described extractant is to be directed to the conventional use of extractant of target metal ions in this area,
One kind in extractant is commonly used preferably in chemical industry, environmental protection, pharmacy, nuclear fuel cycle and analysis field
Or it is several, it is more preferably tributyl phosphate (TBP), diisoamyl methylphosphonate (DAMP), methyl
Phosphonic acids two (1- methyl) heptyl ester (DMHMP), trioctylphosphine oxide (TOPO), methyl iso-butyl ketone (MIBK)
(MIBK), three pungent/decyl tertiary amines (N235/7301), 2- ethylhexyl phosphoric acid 2- ethylhexyls
(P-507), di-(2-ethylhexyl)phosphoric acid ester (P204), N, N- DOAA di sec octylacetamides (N503),
Four octyl- 3- oxygen pentanediol -1,5- diamides (TODGA) and straight chain trialkyl phosphine mixture
(Cyanex923) one or more in.
Wherein, described diluent is to be directed to the conventional use of diluent of target extraction system in this area,
One or more preferably in n-dodecane, kerosene, chloroform and toluene.
Wherein, described graphene aerogel is that one kind graphene or graphene oxide make raw material, is passed through
The more micropore materials of the hydrophobicity with space net structure that sol-gel process or vapour deposition process are prepared
Material.It is preferred that described graphene aerogel is made using sol-gel process；More preferably, it is described
Graphene aerogel is made using following methods：Using commercially available graphene oxide dispersion (GO), solvent
For water, it is 2mg/mL by graphene oxide dispersion Concentration Modulation, is in mass ratio 1:5 (after modulation
Graphene oxide dispersion：Ethylenediamine) add after ethylenediamine stirs, the water-bath under the conditions of 85 DEG C
React 24h；Water is outwelled in cooling after into hydrogel, is washed twice with 1mol/L HCl solutions, is added dilution
(water and ethanol are 5 by volume to ethanol:1 is diluted, and ethanol used is the second of 95% concentration before dilution
Alcohol) soak 6~8 hours, alcohol,diluted washing by soaking is added three times altogether, about with 24 hours time；
Then freeze 2~3 hours, then be freeze-dried 4 days in -80 DEG C of conditions.
Wherein, described commercially available graphene oxide dispersion, it is limited to be purchased from Nanjing Xian Feng nano material science and technology
Company is voluntarily prepared by commercially available graphite powder.Wherein, graphite oxide is voluntarily prepared by commercially available graphite powder
During alkene dispersion liquid, its raw graphite powder is commercially available, is preferably purchased from the limited public affairs of Chinese medicines group chemical reagent
Department.
Agents useful for same of the present invention include ethylenediamine, acid, alcohol, tributyl phosphate (TBP), n-dodecane,
Straight chain trialkyl phosphine mixture (Cyanex923) etc. is conventional reagent, is preferably purchased from traditional Chinese medicines
Chemical reagent Co., Ltd of group.
In step (1), when reaching described adsorption saturation, the saturation of described graphene aerogel is inhaled
Attached amount is preferably 0.17mL/mg, i.e., per mg graphene aerogels absorption 0.17mL organic phases.
In step (1), the method for the organic phase on described removing graphene aerogel surface is this area
Conventional method, preferably Adsorption of Filter Paper.
In step (2), described is separated into this area routine operation, preferably by after extraction equilibrium
Graphene aerogel fix organic phase fished for out from raffinate aqueous phase.
In step (2), when reaching extraction equilibrium, the required time is preferably 1~8 hour.
In step (3), when reaching stripping equilibria, the required time is preferably 2~7 hours.
In step (2) and (3), in described extraction and described back extraction, stirred it is preferred that also accompanying by
Mix, described stirring is preferably magnetic agitation.The rotating speed of described magnetic agitation is that this area is conventional,
Preferably 100~1000r/min, it is more preferably 200~400r/min；Wherein, described stirring compared with
Heating is also accompanied by goodly, and described is heated to be this area routine operation, and the temperature of described heating is preferably
It it is more preferably 15 DEG C~50 DEG C for 15 DEG C~70 DEG C.
In step (2), described target metal ions are the metal ion of any kind, preferably
The metal target often handled in chemical industry, environmental protection, pharmacy, nuclear fuel cycle association area, it is more preferably alkali
One or more in earth metal, rare earth ion, actinide metal ion and transition metal ions, enter
One step, the elements of described target metal ions is more preferably strontium (Sr), caesium (Cs), lanthanum (La),
Cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), roll (Gd), dysprosium (Dy),
Thorium (Th), uranium (U), plutonium (Pu), americium (Am), curium (Cm), zirconium (Zr), niobium (Nb),
One or more in ruthenium (Ru) and rhodium (Rh).Wherein, strontium (Sr) belongs to alkaline-earth metal, lanthanum (La),
Cerium (Ce), praseodymium (Pr), neodymium (Nd), samarium (Sm), europium (Eu), roll (Gd) and dysprosium (Dy)
Belong to rare earth metal, thorium (Th), uranium (U), plutonium (Pu), americium (Am) and curium (Cm) belong to
Actinide metals, zirconium (Zr), niobium (Nb), ruthenium (Ru) and rhodium (Rh) belong to transition metal.
In step (2) and (3), described feed liquid aqueous phase is fixed organic with described graphene aerogel
The volume ratio that the volume ratio of phase, described strip aqueous fix organic phase with described graphene aerogel is equal
In the general category of this area, both are preferably >=3 respectively, are more preferably 3~5.Because aeroge is intrinsic
Volume, volume after its saturation the adsorbs organic phase macroscopical volume intrinsic still equal to aeroge, only
When the volume of feed liquid aqueous phase or strip aqueous is more than or equal to the volume of graphene aerogel fixation organic phase
Three times, graphene aerogel can be just made full use of to fix the contact area and loading capacity of organic phase.
In step (3), described strip aqueous is water or acidic aqueous solution.Described acidic aqueous solution
It is conventional for this area, the acidic materials used in described acidic aqueous solution be preferably hydrochloric acid, sulfuric acid,
One or more in phosphoric acid, nitric acid and ferrous sulfamate.The concentration of described acidic aqueous solution is preferable
Ground is 0.001~1mol/L.
In the present invention, because of the hydrophobic property of graphene aerogel and more micropores of space net structure are big compares table
Area features have very powerful adsorption function to organic solution, therefore, this method be applied to any water-
Oily two-phase extraction system.
On the basis of common sense in the field is met, above-mentioned each optimum condition, it can be combined, produce this hair
Bright each preferred embodiments.
Agents useful for same and raw material of the present invention are commercially available (in addition to finished product aeroge).
On the basis of common sense in the field is met, above-mentioned each optimum condition, it can be combined, produce this hair
Bright each preferred embodiment.
The positive effect of the present invention is：
Hydrophobicity of the invention based on graphene, supporting construction absorption organic phase is made using aeroge, then put
Extracted and be stripped in aqueous phase, eliminate the mixed phase of two-phase and split-phase mistake in traditional liquid-liquid extraction method
Journey, do not limited by two-phase density contrast, thus by infinitely increase accounting of the extractant in organic phase come
Organic phase saturation loading capacity is improved, while reduces the use of organic reagent and the generation of waste liquid；The present invention
Extraction separating method it is very high (even as high as more than 98.8%) for the rate of recovery of metal ion, for
A metal ion species are separated from various metals ion also has good separating effect.
Brief description of the drawings
Fig. 1 is the operating process for the extraction separating method that the present invention fixes organic phase using graphene aerogel
Schematic diagram.
Fig. 2 is the curve map that the concentration of uranium ion in feed liquid aqueous phase in embodiment 1 changes with time of contact.
Fig. 3 is the curve map that the concentration of uranium ion in strip aqueous in embodiment 1 changes with time of contact.
Fig. 4 is the curve map that the concentration of metal ion in feed liquid aqueous phase in embodiment 2 changes with time of contact.
Embodiment
The present invention is further illustrated below by the mode of embodiment, but is not therefore limited the present invention to
Among described scope of embodiments.The experimental method of unreceipted actual conditions in the following example, according to normal
Rule method and condition, or selected according to catalogue.
The involved extract and separate that organic phase is fixed using graphene aerogel in embodiments of the invention
The specific operation process of method is as shown in figure 1, it comprises the following steps：Organic phase 3 is filled or adhered to
On the graphene aerogel 1 rich in microcellular structure 2, until adsorption saturation, then remove graphene airsetting
The organic phase 3 on the surface of glue 1, graphene aerogel is made and fixes organic phase；Then, by described graphite
Alkene aeroge is fixed organic phase and is placed in feed liquid aqueous phase 4 to be extracted, and carries out the extraction of wherein target metal ions,
To extraction equilibrium, graphene aerogel is fixed into organic phase and raffinate aqueous phase separation；By isolated stone
Black alkene aeroge is fixed organic phase and is placed in strip aqueous 5, is stripped, and reclaims target metal ions, you can；
Also with stirring 6 in shown extraction and the stripping process.
In embodiments of the invention, the graphene aerogel used uses sol-gel process, specific to use
Following methods are made：Using commercially available graphene oxide dispersion (GO), solvent is water, by graphite oxide
Alkene dispersion liquid concentration is modulated to 2mg/mL, is in mass ratio 1:5 (graphene oxide after modulation disperses
Liquid：Ethylenediamine) add after ethylenediamine stirs, the water-bath 24h under the conditions of 85 DEG C；Into water-setting
Water is outwelled in cooling after glue, is washed twice with 1mol/L HCl solutions, is added alcohol,diluted (water and ethanol
It is 5 by volume:1 is diluted, and ethanol used is the ethanol of 95% concentration before dilution) immersion is 6~8 small
When, alcohol,diluted washing by soaking is added three times altogether, about with 24 hours time；Then in -80 DEG C of conditions
Freezing 2~3 hours, then be freeze-dried 4 days.
In following embodiments, described comparing refers to volume ratio.
Embodiment 1
Using n-dodecane as organic diluent, tributyl phosphate (TBP) is extractant, prepares TBP
Volumetric concentration is respectively 5%, 30%, 45%, 60% organic solution, as organic phase；Prepare initial
Uranium concentration is 52.27mg/mL 3mol/L aqueous solution of nitric acid, as feed liquid aqueous phase；Prepare 0.001mol/L
Aqueous solution of nitric acid is as strip aqueous；Graphene aerogel fixes organic phase, feed liquid aqueous phase, strip aqueous
Be in a ratio of 1:5:5；
(1) organic phase prepared is added dropwise on 6mg hydrophobicity graphene aerogel materials, to suction
Attached saturation, organic phase volume of absorption is 1mL；Surface organic phase is removed, graphene aerogel is made and consolidates
Determine organic phase；
(2) it is placed on again in 5mL feed liquid aqueous phases, it is flat that extraction is carried out under 200r/min stirring conditions
Weighing apparatus operation, detects the concentration of uranium and the relation of time of contact in feed liquid aqueous phase；Treat that graphene aerogel is fixed
After organic extractant phase balance, the relation of the uranium concentration of feed liquid aqueous phase and time of contact in extracting operation are detected
As shown in Figure 2；
(3) graphene aerogel after extraction equilibrium is fixed into organic phase taking-up and is placed in 5mL strip aqueous
In, stripping equilibria operation is carried out under 200r/min stirring conditions, uranium ion is reclaimed and detects strip aqueous
The concentration of middle uranium and the relation of time of contact；To stripping equilibria, strip aqueous in back extraction operation is detected
Uranium concentration and the relation of time of contact it is as shown in Figure 3；
After testing, extraction equilibrium is reached in extracting operation after 8 hours, the loading capacity of organic phase uranium is with having
TBP content increases and increased in machine phase, and the percentage that extractant accounts for organic phase is bigger, loading capacity
It is bigger；Reach stripping equilibria after 2 hours times of contact in back extraction operation, the extraction quantity of uranium is with organic phase
Extract the increase of agent content and increase.
Embodiment 2
Organic diluent is not used, organic phase is directly used as using pure phosphoric acid tributyl (TBP)；Match somebody with somebody
It is 0.48mg/mL to make initial uranium concentration, and the initial concentration of other Preparation of Metallic Strontium and caesium is 0.10,0.11mg/mL
3mol/L aqueous solution of nitric acid, as feed liquid aqueous phase；Configuration concentration is that 0.001mol/L nitric acid is water-soluble
Liquid is as strip aqueous；Graphene aerogel fixes being in a ratio of for organic phase and feed liquid aqueous phase and strip aqueous
1：3：3；
(1) pure TBP is added dropwise on 6mg hydrophobicity graphene aerogel materials, to adsorption saturation,
The TBP volumes of absorption are 1mL, remove surface organic phase, and graphene aerogel is made and fixes organic phase；
(2) it is placed on again in 3mL feed liquid aqueous phases, it is flat that extraction is carried out under 150r/min stirring conditions
Weighing apparatus operation, detects uranium, strontium, the concentration of caesium and the relation of time of contact in feed liquid aqueous phase, balance to be extracted
Afterwards, detect that the uranium concentration of feed liquid aqueous phase and the relation of time of contact are as shown in Figure 4 in extracting operation；
(3) graphene aerogel after extraction equilibrium is fixed into organic phase taking-up and is placed in 3mL strip aqueous
In, stripping equilibria operation is carried out under 150r/min stirring conditions, reclaims uranium ion；
In the present embodiment, the only uranium ion of recovery is a kind of, and remaining ion strontium and caesium are then retained in raffinate
In aqueous phase, both separation processes are exactly that the distribution ratio by these three ions in selected extractant is different
Realize separation.Fixation it is organic it is congenial have an extraction process of feed liquid aqueous phase, uranium ion is with being fixed with phase
Extractant is combined, and extracts into organic phase, and strontium and caesium are not combined with extractant or combination is very weak, then are retained in
In aqueous phase, therefore reach separating effect.
After testing, under the conditions of this, 1 hour extraction equilibrium for reaching uranium；The recovery of extraction of uranium is 96.7%,
The separation of uranium and strontium and caesium is all higher than 107, organic phase extracting metals are fixed using graphene aerogel
The ion rate of recovery is high, and for containing various metals ionic system, having very high separation between each metal ion
Coefficient.
Embodiment 3
Organic diluent is not used, directly uses extractant straight chain trialkyl phosphine mixture
(Cyanex923) it is used as organic phase；Prepare the 1mol/L nitric acid aqueous solutions that initial la concn is 0.07mg/mL
Solution, as feed liquid aqueous phase；Configuration concentration is 1mol/L aqueous solution of nitric acid as strip aqueous；Stone
Black alkene aeroge fixation organic phase and feed liquid aqueous phase and strip aqueous are in a ratio of 1：3：3；
(1) Cyanex923 is added dropwise on 6mg hydrophobicity graphene aerogel materials, it is full to adsorbing
With, the Cyanex923 volumes of absorption are 1mL, remove surface organic phase, graphene aerogel is made and consolidates
Determine organic phase
(2) it is placed on again in 3mL feed liquid aqueous phases, it is flat that extraction is carried out under 200r/min stirring conditions
Weighing apparatus operation, detects the relation of la concn and time of contact in feed liquid aqueous phase；
(3) graphene aerogel after extraction equilibrium is fixed into organic phase taking-up and is placed in 3mL strip aqueous
In, stripping equilibria operation is carried out under 200r/min stirring conditions, reclaims lanthanum ion；
After testing, under the conditions of this, after extracting operation time of contact up to 1 hour, the la concn of feed liquid aqueous phase
Reach balance；The recovery of extraction of lanthanum is 98.8%, and it is organic that testing result shows that graphene aerogel is fixed
The extract and separate for mutually carrying out object ion has the very high rate of recovery.
Embodiment 4
Using n-dodecane as organic diluent, tributyl phosphate (TBP) is extractant, prepares TBP
Volumetric concentration is 60% organic solution, as organic phase；It is 50.48mg/mL to prepare initial thorium concentration
3mol/L aqueous solution of nitric acid, as feed liquid aqueous phase；Configuration concentration is that 0.005mol/L nitric acid is water-soluble
Liquid is as strip aqueous；Graphene aerogel fixes being in a ratio of for organic phase and feed liquid aqueous phase and strip aqueous
1：3：3；
(1) organic phase prepared is added dropwise on 6mg hydrophobicity graphene aerogel materials, to suction
Attached saturation, organic phase volume of absorption is 1mL；Surface organic phase is removed, graphene aerogel is made and consolidates
Determine organic phase；
(2) it is placed on again in 3mL aqueous phase liquids, it is flat that extraction is carried out under 200r/min stirring conditions
Weighing apparatus operation, detect the concentration of thorium in raffinate aqueous phase after balancing；
(3) graphene aerogel after extraction equilibrium is fixed into organic phase taking-up and is placed in 3mL strip aqueous
In, stripping equilibria operation is carried out under 200r/min stirring conditions, reclaims thorium ion；
It is still the organic phase that raffinate aqueous phase and graphene aerogel are fixed under the conditions of this, after extraction equilibrium, no
Third phase be present, after testing, the thorium concentration in raffinate aqueous phase is 27g/L.
Embodiment 5
In the present embodiment, with embodiment 1, difference exists the process conditions and step of extraction separating method
In：In organic phase, the volumetric concentration of extractant tributyl phosphate (TBP) is 50%.
Embodiment 6
In the present embodiment, with embodiment 1, difference exists the process conditions and step of extraction separating method
In：The volumetric concentration of extractant tributyl phosphate (TBP) is 100% in organic phase.
Embodiment 7
In the present embodiment, with embodiment 1, difference exists the process conditions and step of extraction separating method
In：Strip aqueous is the ferrous sulfamate aqueous solution that concentration is 0.03mol/L.
Embodiment 8
In the present embodiment, with embodiment 3, difference exists the process conditions and step of extraction separating method
In：Feed liquid aqueous phase is the aqueous solution of nitric acid for the 0.001mol/L that initial strontium concentration is 0.05mg/mL.
Embodiment 9
In the present embodiment, with embodiment 3, difference exists the process conditions and step of extraction separating method
In：Stir speed (S.S.) is 1000r/min in extraction and stripping process.
Embodiment 10
In the present embodiment, with embodiment 3, difference exists the process conditions and step of extraction separating method
In：Stir speed (S.S.) is 400r/min in extraction and stripping process.
Embodiment 11
In the present embodiment, with embodiment 3, difference exists the process conditions and step of extraction separating method
In：Heating is also accompanied by whipping process, heating scope is room temperature to 70 DEG C.
Embodiment 12
In the present embodiment, with embodiment 3, difference exists the process conditions and step of extraction separating method
In：Heating is also accompanied by whipping process, heating scope is room temperature to 50 DEG C.
Comparative example 1
Using n-dodecane as organic diluent, tributyl phosphate (TBP) is extractant, prepares TBP
Volumetric concentration is 30% organic solution, as organic phase；It is 50.48mg/mL to prepare initial thorium concentration
3mol/L aqueous solution of nitric acid, as feed liquid aqueous phase；Organic phase is in a ratio of 1 with feed liquid aqueous phase:3；
By the organic phase prepared and feed liquid aqueous phase by 1:3(1mL:3mL) mix, pass through vortex oscillation
Device vibrates 2 minutes, then with centrifuge 3000rpm pelleted by centrifugation split-phase one minute, detects in raffinate aqueous phase
The concentration of thorium；
Under the conditions of this, extraction system generates third phase after centrifuging split-phase, after testing, in raffinate aqueous phase
Thorium concentration is 38g/L.And the organic phase after balancing has split into weight two-phase.
Compared to embodiment 4, loading capacity halves, and can not eliminate the puzzlement of three-phase.
Claims (10)
- A kind of 1. extraction separating method, it is characterised in that：Described extraction separating method includes following step Suddenly：(1) organic phase absorption to adsorption saturation, then is removed into graphene gas on graphene aerogel The organic phase of gel surface, graphene aerogel is made and fixes organic phase；(2) graphene aerogel of step (1) is fixed into organic phase to be placed in feed liquid aqueous phase to be extracted, The extraction of target metal ions is carried out, to extraction equilibrium, graphene aerogel is fixed into organic phase and raffinate Aqueous phase separation；(3) the isolated graphene aerogel of step (2) is fixed into organic phase to be placed in strip aqueous, Back extraction, to stripping equilibria, reclaim target metal ions, you can.
- 2. extraction separating method as claimed in claim 1, it is characterised in that：In step (1), institute The method adsorbed organic phase on graphene aerogel stated is dipping or is added dropwise；The method of the organic phase on the removing graphene aerogel surface described in step (1) is Adsorption of Filter Paper；Described in step (2) be separated into by after extraction equilibrium graphene aerogel fix organic phase from Taken out in raffinate aqueous phase.
- 3. extraction separating method as claimed in claim 1, it is characterised in that：Described graphene gas Gel is made by sol-gel process or vapour deposition process, it is preferred that described graphene aerogel is adopted It is made with sol-gel process.
- 4. extraction separating method as claimed in claim 1, it is characterised in that described organic phase bag Extractant and diluent are included, the percent by volume that described extractant accounts for described organic phase is 50%~100%；Described strip aqueous is water or acidic aqueous solution, and the acidic materials of described acidic aqueous solution are salt One or more in acid, sulfuric acid, phosphoric acid, nitric acid and ferrous sulfamate；Described acidic aqueous solution Concentration be 0.001~1mol/L.
- 5. extraction separating method as claimed in claim 4, it is characterised in that：Described extractant accounts for The percent by volume of described organic phase is 100%.
- 6. extraction separating method as claimed in claim 4, it is characterised in that：Described extractant is Tributyl phosphate, diisoamyl methylphosphonate, methylphosphonic acid two (1- methyl) heptyl ester, oxidation trioctylphosphine Phosphine, methyl iso-butyl ketone (MIBK), three pungent/decyl tertiary amines, 2- ethylhexyl phosphoric acid 2- ethylhexyls, two (2- Ethylhexyl) phosphate, N, N- DOAA di sec octylacetamides, four octyl- 3- oxygen pentanediol -1,5- diamides and straight One or more in chain trialkyl phosphine mixture；Described diluent is the one or more in n-dodecane, kerosene, chloroform and toluene.
- 7. extraction separating method as claimed in claim 1, it is characterised in that：Described metal target The element of ion is the one or more in alkaline-earth metal, rare earth metal, actinide metals and transition metal, Preferably strontium, caesium, lanthanum, cerium, praseodymium, neodymium, samarium, europium, roll, dysprosium, thorium, uranium, plutonium, americium, curium, One or more in zirconium, niobium, ruthenium and rhodium.
- 8. extraction separating method as claimed in claim 1, it is characterised in that：Described in step (2) Feed liquid aqueous phase and described graphene aerogel fix the volume ratio of organic phase, described in step (3) Strip aqueous and described graphene aerogel fix organic phase volume ratio be not less than 3, preferably For 3~5.
- 9. extraction separating method as claimed in claim 1, it is characterised in that：Described graphene gas The saturated extent of adsorption of gel is 0.17mL/mg；The time needed for extraction equilibrium described in reaching is 1~8h；The time needed for stripping equilibria described in reaching is 2~7h.
- 10. extraction separating method as claimed in claim 1, it is characterised in that：Described extraction and institute The back extraction stated accompanies by stirring, it is preferred that described stirring also accompanies by heating；Wherein, described stirring is magnetic agitation, and the speed of described stirring is 100~1000r/min, Preferably 200~400r/min；The temperature of described heating is 15 DEG C~70 DEG C, preferably 15 DEG C~50 DEG C.
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| CN114807602A (en) * | 2022-05-19 | 2022-07-29 | 哈尔滨工业大学（威海） | Extraction solvent and extraction method for separating zirconium and hafnium |
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