CN109628769A - A method of using light rare earth elements in ion liquid microemulsion extraction acid solution - Google Patents
A method of using light rare earth elements in ion liquid microemulsion extraction acid solution Download PDFInfo
- Publication number
- CN109628769A CN109628769A CN201910107617.6A CN201910107617A CN109628769A CN 109628769 A CN109628769 A CN 109628769A CN 201910107617 A CN201910107617 A CN 201910107617A CN 109628769 A CN109628769 A CN 109628769A
- Authority
- CN
- China
- Prior art keywords
- rare earth
- extraction
- light rare
- microemulsion
- liquid
- 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.)
- Granted
Links
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
- 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
- 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
- C22B3/409—Mixtures at least one compound being an organo-metallic compound
-
- 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
Landscapes
- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Geology (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geochemistry & Mineralogy (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
A method of using light rare earth elements in ion liquid microemulsion extraction acid solution, belonging to field of rare earth hydrometallurgy and ion liquid abstraction technical field.The method is to mix ion liquid microemulsion and light rare earth material liquid for the ratio of 1:2~1:8 with O/A, is extracted in oscillator, and the revolving speed of oscillator is 200~400r/min, 5~30min of extraction time, 25~45 DEG C of extraction temperature；After the completion of extraction, it is centrifuged to obtain the organic phase of supported rare earth and raffinate, 1000~2000r/min of centrifugal rotational speed, 5~10min of centrifugation time.The present invention is added to ionic liquid in microemulsion, it can replace organic phase or other ingredients, the problems such as to effectively compensate for complex process caused by using conventional organic solvents, organic phase loss and environmental pollution, be a kind of friendly and economical profitable RE extraction separation process of green environment.
Description
Technical field
The invention belongs to field of rare earth hydrometallurgy and ion liquid abstraction technical field, and in particular to a kind of to use ion
The method that liquid microemulsion extracts light rare earth elements in acid solution.
Background technique
Rare earth element is the IIIth B race in the periodic table of elements, lanthanide series and yttrium, scandium totally 17 of the atomic number by 57~71
The general name of a element.Rare earth is widely used in metallurgical engineering, space flight and aviation, electronics because of its unique physics and chemical property
The fields such as information, petrochemical industry, environmental protection.It is the indispensable pass in the fields such as Modern High-Tech's industry and national defence sophisticated weapons
Key material.
The separation method of rare earth element mainly has fractionation crystallization, step-by-step precipitation method, ion exchange chromatography, extraction chromatography
Method, solvent extraction etc..Relative to other extracting process, solvent extraction is because treating capacity is big, and continuous production is in actual production
It has a clear superiority.But the usual extraction yield of Conventional solvents extraction is low, and extraction time is long, is stripped so that causing secondary pollution is not
It is evitable, and easily there is the problems such as third phase in solvent extraction.Microemulsion is usually by organic solvent, water, surfactant
The isotropism of (adding cosurfactant sometimes) composition, transparent, thermodynamically stable dispersion.It is extracted in metal ion
Separation aspect shows good prospect.It must be II type of Winsor extracting microemulsion system used in separating metal ions, i.e.,
The biphase-equilibrium system of W/O microemulsion and water phase.Compared with traditional solvent extraction, microemulsion have nanoscale chondritic,
The special property of quick coarse separation speed and higher solubilising power etc..
Ionic liquid refer to be in a liquid state at a temperature of room temperature or near room temperature only by forming ion from molecular substance
The cation of liquid is generally organic cation, and anion can be inorganic anion or organic anion.It is in recent years green
The completely new medium and soft functional material to grow up under colour chemistry frame, with fusing point is low, liquid temperature range is wide, is not easy to wave
The peculiar properties such as hair, solvability strong, designability, electrochemical window mouth width.
Summary of the invention
The purpose of the present invention is be added ionic liquid after there is only every advantages of microemulsion, can also replace microemulsion in
Consumption of organic solvent provide a kind of using in ion liquid microemulsion extraction acid solution so as to improve the influence to environment
The method of light rare earth elements.Purpose is to be transferred to rare earth element in ionic liquid from acid solution by liquid-liquid extraction, is led to
Centrifuge separation is crossed, realizes rare earth from the extraction in aqueous solution.
A kind of ion liquid microemulsion extraction system, the ion liquid microemulsion are by surfactant, help surface living
Property agent, organic solvent, extractant, ionic liquid, water phase are mixed according to the mass ratio of 75:50:75:18:4.5:14.2, institute
Stating water phase is hydrochloric acid；The surfactant is that OP-4 and OP-7 is mixed, and wherein OP-4 and OP-7 mass ratio are 3:2.
Refer to the volume ratio of organic phase and water phase compared to O/A in the present invention, middle finger ion liquid microemulsion of the present invention with
The volume ratio of light rare earth material liquid.
Ion liquid microemulsion system is prepared in the present invention, using OP-4 and OP-7 as surfactant, OP-4 and OP-7 matter
For amount than being 3:2, surfactant (OP-4 and OP-7) and cosurfactant mass ratio are 3:2, surfactant (OP-4 and
It OP-7) is 1:1 with organic solvent mass ratio, OP-4 and ionic liquid mass ratio are 10:1, and OP-4 is with extractant mass ratio
2.5:1, the mass ratio that water phase hydrochloric acid occupies whole system is 6%.
The full name of OP-4 is Nonyl pheno (4) ether in the present invention, and the full name of OP-7 is Nonyl pheno (7)
Ether is commercially available.
Preferably, the cosurfactant is benzyl alcohol or n-amyl alcohol.
Preferably, the organic solvent is kerosene.
Preferably, the extractant is di-(2-ethylhexyl)phosphoric acid or 2- ethylhexyl phosphonic acids single 2-ethyl base ester.
Preferably, the ionic liquid is 1- octyl -3- methyl imidazolium tetrafluoroborate.
Di-(2-ethylhexyl)phosphoric acid hereinafter referred to as P204 in the present invention, 2- ethylhexyl phosphonic acids single 2-ethyl base ester with
Lower abbreviation P507.
1- octyl -3- methyl imidazolium tetrafluoroborate in the present invention, following shorthand [OMIM] BF4。
Preferably, the concentration of the hydrochloric acid is 2~6mol/L.
It is a further object of the present invention to provide light rare earth members in a kind of above-mentioned ion liquid microemulsion extraction acid solution
The method of element, the method be by above-mentioned ion liquid microemulsion and light rare earth material liquid with O/A for 1:2~1:8 ratio into
Row mixing, extracts in oscillator, and the revolving speed of oscillator is 200~400r/min, 5~30min of extraction time, extraction temperature 25
~45 DEG C；After the completion of extraction, it is centrifuged to obtain the organic phase of supported rare earth and raffinate, centrifugal rotational speed is 1000~
2000r/min, centrifugation time are 5~10min；The light rare earth material liquid is that light rare earth concentration is 0.001~0.1mol/L, pH
For 1~5 solution.
Preferably, the light rare earth material liquid is re chloride, rare earth nitrate solution or rare earth sulfate solution.
Preferably, the light rare earth elements be La, Ce, Pr or Nd, after the completion of extraction in the organic phase of supported rare earth with
Ionic species exists.
The organic phase Yu water phase (raffinate) of supported rare earth can all have rare earth ion in the present invention, and the rare earth ion of water phase is got over
Few, rare earth ion is more in the organic phase of supported rare earth, and extraction yield is higher.
Compared with prior art, the invention has the following advantages that
By the characteristic for the existing ionic liquid of microemulsion that ionic liquid forms, and there is the property of microemulsion.Not only it can be reduced
The problems such as volatility caused by organic solvent is big in microemulsion, strong toxicity, easily pollutes the environment, moreover it is possible to solve ionic liquid
The drawbacks of large viscosity.
Since ionic liquid is not volatile, ionic mobility is high, chemical property is stable, is easy to the advantages that being recycled, structure
The application range that ion liquid microemulsion greatly expands microemulsion is built, can be applicable to and prepare functional nanomaterials, medicine
With extraction and separation field.The present invention is added to ionic liquid in microemulsion, can replace organic phase or other ingredients, thus
The problems such as effectively compensating for complex process caused by using conventional organic solvents, organic phase loss and environmental pollution is a kind of green
The friendly and economical profitable RE extraction separation process in colour circle border.
Specific embodiment
Following non-limiting embodiments can with a person of ordinary skill in the art will more fully understand the present invention, but not with
Any mode limits the present invention.
Test method described in following embodiments is unless otherwise specified conventional method；The reagent and material, such as
Without specified otherwise, commercially obtain.
During present invention process, after the completion of extraction and separation process, rare earth concentration can refer to GB/ in raffinate solution
T14635-2008 rare earth metal and its compound chemical analysis method, by EDTA titration measuring, in ion liquid microemulsion
Rare earth concentration can be obtained by minusing.
The extraction yield E of rare earth is calculated as follows:
C in formulat、CeTo extract the rare earth concentration in forward and backward water phase, mol/L.
Embodiment 1
Ion liquid microemulsion system is prepared, using OP-4 and OP-7 as surfactant, OP-4 and OP-7 mass ratio are 3:
2, surfactant (OP-4 and OP-7) and cosurfactant benzyl alcohol mass ratio are 3:2, surfactant (OP-4 and OP-
It 7) is 1:1, OP-4 and [OMIM] BF with kerosene mass ratio4Mass ratio is that 10:1, OP-4 and P204 mass ratio are 2.5:1, water phase
The mass ratio that hydrochloric acid occupies whole system is 6%, and the concentration of hydrochloric acid is 6mol/L；
Seven water of lanthanum chloride for weighing 0.3714g, is put into beaker and is dissolved in water, and adds salt acid for adjusting pH, then constant volume is to 100mL
In volumetric flask, being configured to concentration is 0.01mol/L, the light rare earth material liquid La that pH is 33+Solution is the light rare earth of the present embodiment
Material liquid；
Above-mentioned light rare earth material liquid is mixed with ion liquid microemulsion and is extracted, is 1:2, as ion compared to O/A
The volume ratio of liquid microemulsion and light rare earth material liquid is 1:2.It being extracted in oscillator, the revolving speed of oscillator is 200r/min,
Extraction time 15min, 25 DEG C of extraction temperature.After the completion of extraction, mixed solution be centrifuged to obtain supported rare earth organic phase and
Raffinate, centrifugal rotational speed 2000r/min, centrifugation time 5min.Water phase rare earth concentration is measured, is computed, extraction yield is
86.36%.
Embodiment 2
Ion liquid microemulsion system is prepared, using OP-4 and OP-7 as surfactant, OP-4 and OP-7 mass ratio are 3:
2, surfactant (OP-4 and OP-7) and cosurfactant benzyl alcohol mass ratio are 3:2, surfactant (OP-4 and OP-
It 7) is 1:1 with kerosene mass ratio, it is 2.5:1, water phase that OP-4, which is 10:1, OP-4 and P204 mass ratio with [OMIM] BF4 mass ratio,
The mass ratio that hydrochloric acid occupies whole system is 6%, and the concentration of hydrochloric acid is 6mol/L；
Seven water of cerium chloride for weighing 0.0373g, is put into beaker and is dissolved in water, and adds salt acid for adjusting pH, then constant volume is to 100mL
In volumetric flask, being configured to concentration is 0.001mol/L, the Ce that pH is 33+Solution is the light rare earth material liquid of the present embodiment；
Above-mentioned light rare earth material liquid is mixed with ion liquid microemulsion and is extracted, is 1:4, as ion compared to O/A
The volume ratio of liquid microemulsion and light rare earth material liquid is 1:4.It being extracted in oscillator, the revolving speed of oscillator is 300r/min,
Extraction time 15min, 35 DEG C of extraction temperature.After the completion of extraction, mixed solution be centrifuged to obtain supported rare earth organic phase and
Raffinate, centrifugal rotational speed 2000r/min, centrifugation time 5min.Water phase rare earth concentration is measured, is computed, extraction yield is
90.1%.
Embodiment 3
Ion liquid microemulsion system is prepared, using OP-4 and OP-7 as surfactant, OP-4 and OP-7 mass ratio are 3:
2, surfactant (OP-4 and OP-7) and cosurfactant benzyl alcohol mass ratio are 3:2, surfactant (OP-4 and OP-
It 7) is 1:1 with kerosene mass ratio, it is 2.5:1, water phase that OP-4, which is 10:1, OP-4 and P204 mass ratio with [OMIM] BF4 mass ratio,
The mass ratio that hydrochloric acid occupies whole system is 6%, and the concentration of hydrochloric acid is 6mol/L；
The neodymia for weighing 0.0168g, the nitric acid of water and 16mol/L is added into the beaker containing neodymia, and is put into water
Heating, which is sufficiently stirred, in bath makes it dissolve, and bonus point analyses pure ammonium hydroxide and adjusts pH, then constant volume is configured to Nd into 100mL volumetric flask3+
Concentration is 0.001mol/L, the Nd that pH is 43+Solution is the light rare earth material liquid of the present embodiment；
Above-mentioned light rare earth material liquid is mixed with ionic liquid and is extracted, is 1:4 compared to O/A, as ionic liquid is micro-
Lotion and the volume ratio of light rare earth material liquid are 1:4.It is extracted in oscillator, the revolving speed of oscillator is 300r/min, when extraction
Between 15min, 35 DEG C of extraction temperature.After the completion of extraction, mixed solution is centrifuged to obtain supported rare earth organic phase and raffinate,
Centrifugal rotational speed is 2000r/min, centrifugation time 10min.Water phase rare earth concentration is measured, is computed, extraction yield 77.14%.
Claims (9)
1. a kind of ion liquid microemulsion extraction system, which is characterized in that the ion liquid microemulsion be by surfactant,
Cosurfactant, organic solvent, extractant, ionic liquid, water phase are mixed according to the mass ratio of 75:50:75:18:4.5:14.2
It closes, the water phase is hydrochloric acid；The surfactant is that OP-4 and OP-7 is mixed, wherein OP-4 and OP-7 mass ratio
For 3:2.
2. system according to claim 1, which is characterized in that the cosurfactant is benzyl alcohol or n-amyl alcohol.
3. system according to claim 1, which is characterized in that the organic solvent is kerosene.
4. system according to claim 1, which is characterized in that the extractant is di-(2-ethylhexyl)phosphoric acid or 2- second
Base base phosphonic acids single 2-ethyl base ester.
5. system according to claim 1, which is characterized in that the ionic liquid is 1- octyl -3- methylimidazole tetrafluoro
Borate.
6. system according to claim 1, which is characterized in that the concentration of the hydrochloric acid is 2~6mol/L.
7. the method for light rare earth elements in ion liquid microemulsion extraction acid solution described in claim 1, which is characterized in that
The method be by ion liquid microemulsion described in claim 1 and light rare earth material liquid with O/A for 1:2~1:8 ratio into
Row mixing, extracts in oscillator, and the revolving speed of oscillator is 200~400r/min, 5~30min of extraction time, extraction temperature 25
~45 DEG C；After the completion of extraction, it is centrifuged to obtain the organic phase of supported rare earth and raffinate, centrifugal rotational speed is 1000~
2000r/min, centrifugation time are 5~10min；The light rare earth material liquid is that light rare earth concentration is 0.001~0.1mol/L, pH
For 1~5 solution.
8. the method according to the description of claim 7 is characterized in that the light rare earth material liquid is re chloride, nitric acid
Earth solution or rare earth sulfate solution.
9. being extracted the method according to the description of claim 7 is characterized in that the light rare earth elements is La, Ce, Pr or Nd
Exist in the form of an ion in the organic phase of supported rare earth after the completion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910107617.6A CN109628769B (en) | 2019-02-02 | 2019-02-02 | Method for extracting light rare earth elements in acidic solution by adopting ionic liquid microemulsion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910107617.6A CN109628769B (en) | 2019-02-02 | 2019-02-02 | Method for extracting light rare earth elements in acidic solution by adopting ionic liquid microemulsion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109628769A true CN109628769A (en) | 2019-04-16 |
| CN109628769B CN109628769B (en) | 2021-04-06 |
Family
ID=66064983
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910107617.6A Active CN109628769B (en) | 2019-02-02 | 2019-02-02 | Method for extracting light rare earth elements in acidic solution by adopting ionic liquid microemulsion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109628769B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113106271A (en) * | 2021-04-06 | 2021-07-13 | 中国科学院过程工程研究所 | Method for purifying rare earth element gadolinium with high purity by using carboxylic acid functionalized ionic liquid |
| CN114015901A (en) * | 2021-11-15 | 2022-02-08 | 山东大学 | O/W emulsion and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242934A (en) * | 2013-04-02 | 2013-08-14 | 华南理工大学 | Ionic liquid/vegetable oil microemulsion type biological lubricant base oil and preparation method thereof |
| CN104498960A (en) * | 2014-11-30 | 2015-04-08 | 蔡明建 | Preparation method of corrosion inhibitor for novel ionic liquid oil field water |
| CN106048221A (en) * | 2016-08-22 | 2016-10-26 | 东北大学 | Method for extracting light rare earth elements in acidic solution by using ionic liquid [OMIM] BF4 |
| CN108975391A (en) * | 2018-07-26 | 2018-12-11 | 四川理工学院 | A kind of synthetic method of metal oxide nano microballoon |
-
2019
- 2019-02-02 CN CN201910107617.6A patent/CN109628769B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103242934A (en) * | 2013-04-02 | 2013-08-14 | 华南理工大学 | Ionic liquid/vegetable oil microemulsion type biological lubricant base oil and preparation method thereof |
| CN104498960A (en) * | 2014-11-30 | 2015-04-08 | 蔡明建 | Preparation method of corrosion inhibitor for novel ionic liquid oil field water |
| CN106048221A (en) * | 2016-08-22 | 2016-10-26 | 东北大学 | Method for extracting light rare earth elements in acidic solution by using ionic liquid [OMIM] BF4 |
| CN108975391A (en) * | 2018-07-26 | 2018-12-11 | 四川理工学院 | A kind of synthetic method of metal oxide nano microballoon |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113106271A (en) * | 2021-04-06 | 2021-07-13 | 中国科学院过程工程研究所 | Method for purifying rare earth element gadolinium with high purity by using carboxylic acid functionalized ionic liquid |
| CN114015901A (en) * | 2021-11-15 | 2022-02-08 | 山东大学 | O/W emulsion and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109628769B (en) | 2021-04-06 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102618736B (en) | Extraction separation method of rare-earth element | |
| CN105536536B (en) | A kind of extraction system for extracting lithium isotope | |
| CN103801194B (en) | A kind of extractant and its application for being used to separate lithium isotope | |
| CN105536537A (en) | Method for extracting lithium isotope | |
| US10428405B2 (en) | Extractant and method for extracting and separating yttrium | |
| Yin et al. | Effect of complexing agent lactic acid on the extraction and separation of Pr (III)/Ce (III) with di-(2-ethylhexyl) phosphoric acid | |
| CN108456792B (en) | A kind of rare earth extraction separation extractant and preparation method thereof and extraction separating method | |
| CN106048221B (en) | One kind uses ionic liquid [OMIM] BF4The method for extracting LREE in acid solution | |
| CN109260950A (en) | A kind of method for separating and concentrating of lithium isotope | |
| CN109628769A (en) | A method of using light rare earth elements in ion liquid microemulsion extraction acid solution | |
| Grenthe et al. | Stability Relationships Among the Rare Earth Acetylacetonates | |
| CN108854535A (en) | Separate the shunting extraction process of lithium isotope | |
| CN103397184B (en) | Method for separating uranium and iron from tertiary amine organic phase by back extraction | |
| CN109680166B (en) | Process for recovering rare earth from ionic rare earth ore leaching mother liquor by centrifugal extraction method | |
| RU2319666C2 (en) | Method of extractive separation of rare-earth elements | |
| CN104263970A (en) | Lithium ion extracting agent | |
| CN107958717B (en) | Method for separating trivalent actinide and lanthanide ions based on synergistic effect | |
| CN103320629A (en) | Method for extracting cerium (IV) from sulfur phosphorus mixed acid system and preparing cerous phosphate nano material | |
| CN109761953B (en) | Fluorine-containing crown ether compound and application thereof | |
| CN108085490A (en) | The method of extracts composition and enriching lithium | |
| CN109022837B (en) | Method for preparing rod-like rare earth oxalate powder based on reverse microemulsion method | |
| CN110306059B (en) | Method for recycling rare earth in cerium-doped lutetium yttrium silicate waste | |
| CN106148697A (en) | A kind of rare earth synergistic extractant system and utilize the method that this synergistic extractant system extracts separation of rare earth elements from nitric rare earth feed liquid | |
| CN116726702A (en) | Hydrophobic deep eutectic solvent for extracting and separating boron isotopes and application thereof | |
| CN109750160B (en) | Mixed extracting agent and method for separating rare earth yttrium |
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 |