CN113388736B - Method for separating rare earth element from rare earth solution - Google Patents
Method for separating rare earth element from rare earth solution Download PDFInfo
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 107
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title claims abstract description 34
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 41
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims abstract description 28
- -1 rare earth ions Chemical class 0.000 claims description 61
- 239000003960 organic solvent Substances 0.000 claims description 9
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 5
- 229910052691 Erbium Inorganic materials 0.000 claims description 5
- 229910052693 Europium Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- 229910052689 Holmium Inorganic materials 0.000 claims description 5
- 229910052765 Lutetium Inorganic materials 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- 229910052771 Terbium Inorganic materials 0.000 claims description 5
- 229910052775 Thulium Inorganic materials 0.000 claims description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims description 5
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 5
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 5
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 5
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 5
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 5
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 5
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 5
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 5
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 5
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910052706 scandium Inorganic materials 0.000 claims description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 4
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 3
- 238000000926 separation method Methods 0.000 abstract description 38
- 238000000605 extraction Methods 0.000 abstract description 29
- HNNQYHFROJDYHQ-UHFFFAOYSA-N 3-(4-ethylcyclohexyl)propanoic acid 3-(3-ethylcyclopentyl)propanoic acid Chemical compound CCC1CCC(CCC(O)=O)C1.CCC1CCC(CCC(O)=O)CC1 HNNQYHFROJDYHQ-UHFFFAOYSA-N 0.000 abstract description 21
- 239000000126 substance Substances 0.000 abstract description 12
- 239000012074 organic phase Substances 0.000 abstract description 9
- 229910052747 lanthanoid Inorganic materials 0.000 abstract description 7
- 150000002602 lanthanoids Chemical class 0.000 abstract description 7
- 230000009467 reduction Effects 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 106
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 45
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 30
- 238000002156 mixing Methods 0.000 description 23
- 238000006243 chemical reaction Methods 0.000 description 20
- 239000002994 raw material Substances 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 238000012360 testing method Methods 0.000 description 16
- 238000007127 saponification reaction Methods 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 239000012071 phase Substances 0.000 description 10
- 239000008346 aqueous phase Substances 0.000 description 9
- 238000004821 distillation Methods 0.000 description 9
- 239000003795 chemical substances by application Substances 0.000 description 8
- 239000013067 intermediate product Substances 0.000 description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 4
- 150000007529 inorganic bases Chemical class 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 150000007530 organic bases Chemical group 0.000 description 4
- 230000020477 pH reduction Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000004913 activation Effects 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 3
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- VNJMFJOZOGJHNM-UHFFFAOYSA-N 5-oxo-5-(n-phenylanilino)pentanoic acid Chemical compound C=1C=CC=CC=1N(C(=O)CCCC(=O)O)C1=CC=CC=C1 VNJMFJOZOGJHNM-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000012670 alkaline solution Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000003350 kerosene Substances 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000344 soap Substances 0.000 description 2
- 239000008096 xylene Substances 0.000 description 2
- FCQAFXHLHBGGSK-UHFFFAOYSA-N 4-nonyl-n-(4-nonylphenyl)aniline Chemical compound C1=CC(CCCCCCCCC)=CC=C1NC1=CC=C(CCCCCCCCC)C=C1 FCQAFXHLHBGGSK-UHFFFAOYSA-N 0.000 description 1
- RTVWBENOBCZIJQ-UHFFFAOYSA-N CCCCCCC1(CCCCCC)C=CC(CNC(CCCC(O)=O)=O)=CC1(CCCCCC)CCCCCC Chemical compound CCCCCCC1(CCCCCC)C=CC(CNC(CCCC(O)=O)=O)=CC1(CCCCCC)CCCCCC RTVWBENOBCZIJQ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- LOLKAJARZKDJTD-UHFFFAOYSA-N butanedioic acid monoethyl ester Natural products CCOC(=O)CCC(O)=O LOLKAJARZKDJTD-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000005608 naphthenic acid group Chemical group 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
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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
- C22B59/00—Obtaining rare earth metals
-
- 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
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- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Manufacture And Refinement Of Metals (AREA)
Abstract
The invention relates to a method for separating rare earth elements from a rare earth solution, which activates a compound with a structure of formula (I)Reacting with a rare earth solution; in the formula (I), R 1 And R 2 Independently selected from H or C1-C9 alkyl, n is a natural number of 1-20, x is a natural number of 1-5, and y is a natural number of 1-5. The method provided by the invention can effectively separate yttrium from lanthanide, and the invention uses the specified compound as the extractant, compared with the naphthenic acid extractant applied in industry, the compound has single component, stable chemical structure, no reduction of the concentration of the extracted organic phase and stable extraction performance; moreover, the separation coefficient of the compound to light rare earth elements and yttrium is obviously higher than that of naphthenic acid, and the separation coefficient of the compound to heavy rare earth elements and yttrium is also higher than that of naphthenic acid, so that the compound can completely replace naphthenic acid in separation energy efficiency and has very good application prospect.
Description
Technical Field
The invention relates to the technical field of rare earth recovery, in particular to a method for separating rare earth elements from a rare earth solution.
Background
In the field of rare earth element ion separation, naphthenic acid is mainly used as an extractant to extract and separate yttrium element from a rare earth element mixture industrially. Naphthenic acid is a byproduct in petrochemical industry, has limited source and complex components, can extract rare earth only under the condition of higher pH, and has easily changed components after long-term use, thereby reducing the concentration of an organic phase and influencing the stability of a separation process. Currently, researchers are eagerly looking for new carboxylic acid extractants to replace naphthenic acids, such as: chinese patent CN1084574A discloses a separation methodCarboxylic acid type extractant for rare earth elements with ROCH molecular formula 2 COOH, wherein R is C8-C20 straight chain or branched chain alkyl or substituted phenyl of C4-C16 straight chain or branched chain alkyl, and acetic acid is preferably substituted by sec-octylphenoxy, the new extractant can effectively separate yttrium from all lanthanides in the rare earth element extraction separation process, and can overcome the problem of reduced organic phase concentration when yttrium is separated by naphthenic acid extraction, and in addition, the new extractant is also suitable for separation of lanthanides.
Although the molecular formula is ROCH 2 The alkyl phenoxy carboxylic acid of COOH can separate yttrium from lanthanide, and has stable extraction performance, but the separation coefficient of heavy rare earth and yttrium in the extraction system is obviously lower than that of naphthenic acid, which causes the heavy rare earth element and yttrium to be difficult to separate, thus more stages of extraction tanks need to be designed to achieve the separation effect.
Therefore, the molecular structure of the carboxylic acid extractant needs to be regulated and controlled, and the extractant which can overcome the problem of concentration reduction of an extracted organic phase and has a high separation coefficient for heavy rare earth elements and yttrium is developed.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to overcome the decrease of the concentration of the extracted organic phase and to improve the separation coefficient of heavy rare earth elements and yttrium. The invention provides a method for separating rare earth elements from a rare earth solution, wherein a compound used as an extracting agent has a stable chemical structure and a high separation coefficient for heavy rare earth elements and yttrium.
A method for separating rare earth elements from rare earth solution is characterized in that a compound with a structure of a formula (I) is activated and then reacts with the rare earth solution;
the structure of formula (I):
in the formula (I), R 1 And R 2 Independently selected from H or C1-C9 alkyl, n is selected from natural numbers of 1-20, x is selected from natural numbers of 1-5, and y is selected from natural numbers of 1-5.
Preferably, the compound is activated by inorganic alkali soap, and then mixed with rare earth solution for reaction.
Preferably, R 1 And R 2 Are all H.
Preferably, n is selected from natural numbers ranging from 1 to 6.
Preferably, n is 1 or 2 or 3.
Preferably, R 1 And R 2 Independently selected from C1-C6 alkyl.
Preferably, R 1 And R 2 Independently selected from methyl or octyl.
Preferably, x is 1 or 2 and y is 1 or 2.
Preferably, the rare earth solution comprises one or more rare earth ions of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
Preferably, the total concentration of the rare earth ions in the rare earth solution is 0.05-1.5 mol/L.
Preferably, the pH value of the rare earth solution is 1-7.
The invention provides a method for separating rare earth elements from rare earth solution, the compound used as extractant in the method can effectively separate yttrium and lanthanide elements, compared with naphthenic acid extractant applied in industry, the extractant has single component, stable chemical structure, no reduction of concentration of extracted organic phase and stable extraction performance; moreover, the separation coefficient of the compound to light rare earth elements and yttrium is obviously higher than that of naphthenic acid, and the separation coefficient of the compound to heavy rare earth elements and yttrium is also higher than that of naphthenic acid, so that the compound can completely replace naphthenic acid in separation energy efficiency and has very good application prospect.
Drawings
FIG. 1 is a NMR spectrum of 4- (4, 4' -di-n-octyldiphenylamino) -4-oxobutanoic acid in example 3 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely below with reference to embodiments of the present invention, and it should be apparent that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The invention provides a method for separating rare earth elements from a rare earth solution, which comprises the steps of carrying out activation reaction on a compound with a structure shown in a formula (I) and the rare earth solution;
the structure of formula (I):
in the formula (I), R 1 And R 2 Independently selected from H or C1-C9 alkyl, n is a natural number of 1-20, x is a natural number of 1-5, and y is a natural number of 1-5. (R) 1 ) x Represents R 1 The substitution position on the benzene ring can be ortho-position, meta-position or para-position, the number of the substituent groups can be x, and the x ranges from 1 to 5 natural numbers.
In some embodiments of the present invention, the compound is activated by an inorganic base soap and then mixed with a rare earth solution for reaction.
In some embodiments of the present invention, the method for separating rare earth elements from a rare earth solution specifically comprises the following steps:
a) Mixing the compound with an organic solvent to obtain an extractant solution;
b) Mixing the extractant solution with an inorganic alkali solution, and saponifying to obtain a saponified extractant solution;
c) And mixing the saponified extractant solution with a rare earth solution for extraction, wherein yttrium is enriched in a water phase, and yttrium-poor rare earth is enriched in an organic phase.
In certain embodiments of the invention, R 1 And R 2 Are all H.
In certain embodiments of the present invention, n is selected from a natural number from 1 to 6.
In certain embodiments of the invention, n is 1 or 2 or 3.
In certain embodiments of the invention, R 1 And R 2 Independently selected from C1-C6 alkyl.
In certain embodiments of the invention, x is 1 or 2 and y is 1 or 2.
In certain embodiments of the present invention, the R 1 And R 2 Independently selected from methyl or n-octyl.
In certain embodiments of the present invention, the compound is selected from one of the structures represented by formulas (I-1) to (I-7);
in certain embodiments of the present invention, the organic solvent is selected from one or more of toluene, xylene, heptane, octane, methylene chloride, chloroform, and sulfonated kerosene.
In certain embodiments of the invention, the concentration of the extractant solution is from 0.5 to 1.0mol/L. In certain embodiments, the concentration of the extractant solution is 0.60mol/L.
Mixing a compound with an organic solvent to obtain an extractant solution, mixing the extractant solution with an inorganic alkali solution, and saponifying to obtain a saponified extractant solution.
In certain embodiments of the invention, the inorganic base solution is an aqueous solution of sodium hydroxide. In certain embodiments of the present invention, the concentration of the inorganic base solution is 8 to 12mol/L. In certain embodiments, the concentration of the inorganic base solution is 10.8mol/L.
In some embodiments of the invention, the saponification is carried out at a temperature of 25-65 ℃ for a time of 0.5-2 hours. In certain embodiments, the temperature of the saponification is 65 ℃, 45 ℃, or 25 ℃. In certain embodiments, the saponification time is 0.5h, 1h, or 2h.
In certain embodiments of the invention, the saponified extractant solution has a saponification degree of 80% to 85%. In certain embodiments, the saponified extractant solution has a saponification degree of 83.3%.
And after obtaining the saponified extractant solution, mixing the saponified extractant solution with the rare earth solution for extraction, wherein yttrium is enriched in the water phase, and yttrium-poor rare earth is enriched in the organic phase.
In certain embodiments of the invention, the rare earth solution comprises one or more rare earth ions of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium. In certain embodiments of the present invention, the total concentration of rare earth ions in the rare earth solution is 0.05 to 1.5mol/L. In certain embodiments, the total concentration of rare earth ions in the rare earth solution is 1.15mol/L. In certain embodiments of the invention, the rare earth solution has a pH of 1 to 7. In certain embodiments, the rare earth solution has a pH of 5.5.
In certain embodiments of the invention, the volume ratio of the saponified extractant solution to the rare earth solution is from 70 to 100:20 to 40. In certain embodiments, the volume ratio of saponified extractant solution to rare earth solution is 80:30.
in certain embodiments of the invention, the temperature at which the saponified extractant solution is mixed with the rare earth solution is room temperature.
In certain embodiments of the invention, the temperature of the extraction is room temperature. In certain embodiments of the invention, the extraction time is 0.5 to 3 hours. In certain embodiments, the time for the extraction is 2 hours.
The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.
The compound provided by the invention can be used as an extracting agent to effectively separate yttrium from lanthanide, and compared with an industrially applied naphthenic acid extracting agent, the extracting agent has the advantages of single component, stable chemical structure, no reduction of the concentration of an extracted organic phase and stable extraction performance; and the extractant has obviously higher separation coefficient on light rare earth elements and yttrium than naphthenic acid, has the same separation coefficient on heavy rare earth elements and yttrium as naphthenic acid, can completely replace naphthenic acid in separation energy efficiency, and has very good application prospect.
The method provided by the invention is used for separating yttrium from lanthanide, can be provided with fewer stages of extraction tanks to achieve the separation effect, and is simple and easy to implement and low in cost.
The invention also provides a preparation method of the compound with the formula (I), which comprises the following steps:
a) Mixing the raw material I, the raw material II, an organic solvent and a catalyst, and reacting to obtain a reaction solution;
b) Mixing the reaction solution with water to obtain an oil phase and a water phase;
c) Carrying out reduced pressure distillation on the oil phase to obtain an intermediate product;
d) And heating and refluxing the intermediate product in an alkaline solution, and performing post-treatment to obtain a final product, namely the compound.
Wherein the structural formula of the raw material I is as follows:
in the formula (II), R 1 And R 2 Independently selected from H or C1-C9 alkyl;
the structural formula of the raw material II is as follows:
in the formula (III), n is a natural number of 1-20;
the intermediate product has the following structural formula:
in the formula (IV), R 1 And R 2 Independently selected from alkyl of C1-C9, and n is a natural number of 1-20.
The step A) comprises the following steps:
a) Mixing the raw material I, a catalyst and an organic solvent to obtain a mixed solution;
b) And mixing the raw material II with the mixed solution, and reacting to obtain a reaction solution.
The raw material I is one or more selected from diphenylamine, 4' -dimethyldiphenylamine, 4' -diethyldiphenylamine, 4' -dibutyldiphenylamine, 4' -dioctyldiphenylamine and 4,4' -dinonyldiphenylamine.
The raw material II is selected from one of malonic acid monoethyl ester acyl chloride, succinic acid monoethyl ester acyl chloride, glutaric acid monoethyl ester acyl chloride, adipic acid monoethyl ester acyl chloride, pimelic acid monoethyl ester acyl chloride and suberic acid monoethyl ester acyl chloride.
The organic solvent is selected from one or more of toluene, xylene, heptane, octane, dichloromethane, chloroform and sulfonated kerosene.
The catalyst is organic base.
The organic base is triethylamine. The organic alkali is used for neutralizing byproduct hydrogen chloride generated in the reaction, so that the product is prevented from being acidified and hydrolyzed by the hydrogen chloride.
The mass ratio of the first raw material to the second raw material is 16-40: 15-18, preferably, the mass ratio of the first raw material to the second raw material is 16.9:17.9 or 19.7:15.0 or 39.3:16.0.
the mass ratio of the raw material I to the organic base is 16-40: 14-16, preferably, the mass ratio of the raw material I to the organic base is 16.9:15.2 or 19.7:15.2 or 39.3:15.2.
in the step A), the dosage ratio of the organic solvent to the first raw material is 30-50 mL: 16-40 g. Preferably, the dosage ratio of the organic solvent to the first raw material is 40mL:16.9g.
In the step a), the mixing is stirring and uniformly mixing.
In the step b), before mixing the raw material two with the mixed solution, the method further comprises: and cooling the mixed solution to 0 ℃ by using ice water bath.
In step b), the reaction is a stirring reaction.
The stirring method and parameters for the stirring reaction are not particularly limited in the present invention, and the stirring method and parameters known to those skilled in the art may be used.
The reaction temperature is 0-20 ℃ and the reaction time is 15-60 min. In certain embodiments, the temperature of the reaction is 0 ℃. In certain embodiments, the time of the reaction is 30min.
The temperature of the reaction was 0 ℃. In certain embodiments, the time of the reaction is 30min.
After obtaining the reaction solution, mixing the reaction solution with water to obtain an oil phase and a water phase. The water is deionized water. The water can extract hydrochloride formed by reaction byproducts of hydrogen chloride and triethylamine into a water phase, and an oil phase is reserved as a target product, so that the product and the byproducts are separated. The present invention is not particularly limited in the amount ratio of the reaction solution to water, and the above separation can be achieved.
And carrying out reduced pressure distillation on the oil phase to obtain an intermediate product.
The method and parameters of the reduced pressure distillation are not particularly limited in the present invention, and those known to those skilled in the art can be used.
After an intermediate product is obtained, the intermediate product is heated and refluxed in a sodium hydroxide solution, and the compound is obtained after acidification and reduced pressure distillation.
The alkaline solution is a sodium hydroxide solution, and a solvent in the sodium hydroxide solution comprises ethanol and water. The volume ratio of ethanol to water in the solvent is 0.5-1.5: 0.5 to 1.5. In certain embodiments, the volume ratio of ethanol to water in the solvent is 1:1. the concentration of the sodium hydroxide solution is 0.01-0.10 g/mL. Preferably, the concentration of the sodium hydroxide solution is 0.05g/mL.
The temperature of the heating reflux is 60-90 ℃, the time is 1-4 h, and the temperature of the heating reflux is preferably 70 ℃. In certain embodiments, the heating reflux time is 4 hours.
In the present invention, the process of heating and refluxing the intermediate product in the sodium hydroxide solution is also a process of hydrolysis.
The post-treatment comprises acidification and reduced pressure distillation.
The reagent used for acidification is hydrochloric acid solution, and preferably, the concentration of the hydrochloric acid solution is 1-8 mol/L. In certain embodiments, the concentration of the hydrochloric acid solution is 6mol/L.
The present invention is not limited to any particular method or parameter for distillation under reduced pressure after acidification, and any method or parameter for distillation under reduced pressure known to those skilled in the art may be used. The reduced pressure distillation was used to remove the solvent.
After the reduced pressure distillation, the method further comprises the following steps: and (5) washing with water. The method of washing with water is not particularly limited in the present invention, and a method of washing with water known to those skilled in the art may be used.
The preparation method of the compound provided by the invention is simple to operate, and the prepared compound has single component and better chemical stability.
In order to further illustrate the present invention, the following examples are given to describe the compounds provided by the present invention, their preparation and use in detail, but should not be construed as limiting the scope of the present invention.
In the following examples and comparative examples, the content of yttrium and other rare earths in the aqueous phase was measured using an inductively coupled plasma emission spectrometer (hereinafter referred to as ICP-OES). The instrument model is JY ULTIMA 2, produced by France. ICP excitation power is 1.3kW, atomizer flow is 0.75L/min, solution lifting amount is 1.50mL/min, and observation height is 1.4cm. The analytical method refers to the determination of the fifteen rare earth element oxide proportioning quantities of the eighth part of the chemical analytical method of the rare earth concentrate of GB/T18114.8-2010. The separation effect of yttrium and other rare earth ions is measured by a separation coefficient beta, and the calculation method is as follows: let the concentrations of metal ion M1 before and after extraction be Ci1 and Cr1, respectively, and the concentrations of metal ion M2 before and after extraction be Ci2 and Cr2, respectively. The extraction rate E of the metal ions M1 and M2 is then:
metal ionSeparation factor beta of subunits M1 and M2 M1/M2 Expressed as:
it should be noted that in the following examples and comparative examples, the components of the rare earth solution to be extracted are consistent, and the specific preparation requirements are as follows: the total concentration of rare earth ions is 1.15mol/L, the pH value is 5.5, and the concentrations of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium and yttrium are all 0.0767mol/L.
Example 1
(a) 13.6g of 5-diphenylamino-5-oxopentanoic acid was mixed with 66.4mL of toluene to prepare an extractant solution having a concentration of 0.60mol/L. The chemical structure of the compound 5-diphenylamino-5-oxopentanoic acid is shown as the formula (I-1):
(b) The extractant solution was mixed with 3.70mL of 10.8mo/L aqueous sodium hydroxide solution and saponified at 65 ℃ for 0.5h to give a saponified extractant solution having a saponification degree of 83.3%.
(c) Mixing 80mL of saponified extractant solution with 30mL of rare earth solution at room temperature, extracting for 2h, testing the concentration of rare earth ions in aqueous phase before and after extraction, and calculating the relative separation coefficient beta of each rare earth ion (Ln) relative to yttrium ion (Y) Ln/Y The test results are shown in table 1.
Example 2
(a) Taking 13.6g of the compound 3- (4, 4' -dimethyl diphenylamino) -3-oxo-propionic acid and mixing with 66.4mL of toluene to prepare an extractant solution with the concentration of 0.60mol/L. The chemical structure of the compound 3- (4, 4' -dimethyl diphenylamino) -3-oxo-propionic acid is shown as the formula (I-2):
(b) The extractant solution was mixed with 3.70mL of a 10.8mol/L aqueous solution of sodium hydroxide and saponified at 45 ℃ for 1h to give a saponified extractant solution having a saponification degree of 83.3%.
(c) Mixing 80mL of saponified extractant solution with 30mL of rare earth solution at room temperature, extracting for 2h, testing the concentration of rare earth ions in aqueous phase before and after extraction, and calculating the relative separation coefficient beta of each rare earth ion (Ln) relative to yttrium ion (Y) Ln/Y The test results are shown in table 1.
Example 3
(a) 23.0g of 4- (4, 4' -di-n-octyldiphenylamino) -4-oxobutyric acid is mixed with 57mL of toluene to prepare an extractant solution with the concentration of 0.60mol/L. The chemical structure of the compound 4- (4, 4' -di-n-octyldiphenylamino) -4-oxobutanoic acid is shown as the formula (I-3):
(b) The extractant solution was mixed with 3.70mL of a 10.8mo/L aqueous solution of sodium hydroxide and saponified at 25 ℃ for 2h to give a saponified extractant solution having a degree of saponification of 83.3%.
(c) Mixing 80mL of saponified extractant solution with 30mL of rare earth solution at room temperature, extracting for 2h, testing the concentration of rare earth ions in aqueous phase before and after extraction, and calculating the relative separation coefficient beta of each rare earth ion (Ln) relative to yttrium ion (Y) Ln/Y The test results are shown in table 1.
Example 4
(a) 24.1g of 5- (4, 4' -dinonyldiphenylamino) -5-oxopentanoic acid was mixed with 57mL of toluene to prepare an extractant solution having a concentration of 0.60mol/L. The chemical structure of the compound 5- (4, 4' -dinonyldiphenylamino) -5-oxopentanoic acid is shown as the formula (I-4):
(b) The extractant solution was mixed with 3.70mL of a 10.8mo/L aqueous solution of sodium hydroxide and saponified at 25 ℃ for 2h to give a saponified extractant solution having a degree of saponification of 83.3%.
(c) Mixing 80mL of saponified extractant solution with 30mL of rare earth solution at room temperature, extracting for 2h, testing the concentration of rare earth ions in aqueous phase before and after extraction, and calculating the relative separation coefficient beta of each rare earth ion (Ln) relative to yttrium ion (Y) Ln/Y The test results are shown in table 1.
Example 5
(a) 15.8g of 8- (4-butyl-4' -ethyl diphenylamino) -8-oxo octanoic acid is mixed with 57mL of toluene to prepare an extractant solution with the concentration of 0.60mol/L. The chemical structure of the compound 5- (4, 4' -dinonyldiphenylamino) -5-oxopentanoic acid is shown as the formula (I-5):
(b) The extractant solution was mixed with 3.70mL of 10.8mo/L aqueous sodium hydroxide solution and saponified at 25 ℃ for 2h to give a saponified extractant solution with a saponification degree of 83.3%.
(c) Mixing 80mL of saponified extractant solution with 30mL of rare earth solution at room temperature, extracting for 2h, testing the concentration of rare earth ions in aqueous phase before and after extraction, and calculating the relative separation coefficient beta of each rare earth ion (Ln) relative to yttrium ion (Y) Ln/Y The test results are shown in table 1.
Example 6
(a) 27.5g of 5- (3, 4,3',4' -tetrahexylbenzylamino) -5-oxopentanoic acid was mixed with 57mL of toluene to prepare an extractant solution having a concentration of 0.60mol/L. The chemical structure of the compound 5- (4, 4' -dinonyldiphenylamino) -5-oxopentanoic acid is shown as the formula (I-6):
(b) The extractant solution was mixed with 3.70mL of 10.8mo/L aqueous sodium hydroxide solution and saponified at 25 ℃ for 2h to give a saponified extractant solution with a saponification degree of 83.3%.
(c) At the room temperature, the reaction kettle is used for heating,mixing 80mL of saponified extractant solution with 30mL of rare earth solution, extracting for 2h, testing the concentration of rare earth ions in aqueous phase before and after extraction, and calculating the relative separation coefficient beta of each rare earth ion (Ln) relative to yttrium ion (Y) Ln/Y The test results are shown in table 1.
Example 7
(a) 27.5g of the structural compound shown in the formula (1-7) was mixed with 57mL of toluene to prepare an extractant solution having a concentration of 0.60mol/L.
(b) The extractant solution was mixed with 3.70mL of a 10.8mo/L aqueous solution of sodium hydroxide and saponified at 25 ℃ for 2h to give a saponified extractant solution having a degree of saponification of 83.3%.
(c) Mixing 80mL of saponified extractant solution with 30mL of rare earth solution at room temperature, extracting for 2h, testing the concentration of rare earth ions in aqueous phase before and after extraction, and calculating the relative separation coefficient beta of each rare earth ion (Ln) relative to yttrium ion (Y) Ln/Y The test results are shown in table 1.
Comparative example 1
12g of industrial naphthenic acid is mixed with 68mL of toluene to prepare an extractant solution with the concentration of 0.60mol/L.
The extractant solution was mixed with 3.70mL of a 10.8mo/L aqueous solution of sodium hydroxide and saponified to give a saponified extractant solution having a degree of saponification of 83.3%.
Mixing 80mL of saponified extractant solution with 30mL of rare earth solution at room temperature, extracting for 2h, testing the concentration of rare earth ions in aqueous phase before and after extraction, and calculating the relative separation coefficient beta of each rare earth ion (Ln) relative to yttrium ion (Y) Ln/Y The test results are shown in table 1.
TABLE 1 relative separation coefficient β of each rare earth ion (Ln) with respect to yttrium ion (Y) Ln/Y
As can be seen from table 1, neither naphthenic acid nor the extractant provided by the present invention is capable of extracting rare earth ions without saponification activation. After saponification activation, the extraction agent prepared in the embodiment of the invention has the separation coefficient beta of heavy rare earth ions (Gd-Lu) and yttrium ions (Y) Ln/Y Both are more than 2.0, which shows that the separation effect is obvious, and compared with industrial naphthenic acid, the extraction agent prepared by the embodiment of the invention has obviously higher separation coefficient of light rare earth (La-Eu) and yttrium ion (Y), higher separation coefficient of heavy rare earth (Gd-Lu) and yttrium ion (Y), and better separation effect of heavy rare earth and yttrium ion, so the extraction agent prepared by the embodiment of the invention can completely replace naphthenic acid in separation energy efficiency, is a potential extraction agent capable of replacing naphthenic acid, and has good application prospect.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. A method for separating rare earth elements from a rare earth solution is characterized in that a compound with a structure shown in a formula (I) is mixed with an organic solvent to obtain an extractant solution, the extractant solution is mixed with an inorganic alkali solution and is saponified to obtain a saponified extractant solution, and the saponified extractant solution is reacted with the rare earth solution;
the structure of formula (I):
in the formula (I), R 1 And R 2 Independently selected from H or C1-C9 alkyl, n is a natural number from 1 to 6, x is 1, y is 1.
2. The method of claim 1, wherein R is 1 And R 2 Are all H.
3. The method according to any one of claims 1 or 2, wherein n is 1 or 2 or 3.
4. The method of claim 1, wherein R is 1 And R 2 Independently selected from methyl or octyl.
5. The method of claim 3, wherein R is 1 And R 2 Independently selected from methyl or octyl.
6. The method of claim 1 wherein the rare earth solution comprises one or more rare earth ions of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
7. The method of claim 4 or 5, wherein the rare earth solution comprises one or more rare earth ions of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, scandium, and yttrium.
8. The method according to claim 1, wherein the total concentration of rare earth ions in the rare earth solution is 0.05 to 1.5mol/L.
9. The method according to claim 7, wherein the total concentration of rare earth ions in the rare earth solution is 0.05 to 1.5mol/L.
10. The method according to claim 1, wherein the rare earth solution has a pH of 1 to 7.
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