CN113201649A - Phenoxy carboxylic acid solid-phase extracting agent, and preparation method and application thereof - Google Patents
Phenoxy carboxylic acid solid-phase extracting agent, and preparation method and application thereof Download PDFInfo
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- CN113201649A CN113201649A CN202110494850.1A CN202110494850A CN113201649A CN 113201649 A CN113201649 A CN 113201649A CN 202110494850 A CN202110494850 A CN 202110494850A CN 113201649 A CN113201649 A CN 113201649A
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- QIIPQYDSKRYMFG-UHFFFAOYSA-N phenyl hydrogen carbonate Chemical compound OC(=O)OC1=CC=CC=C1 QIIPQYDSKRYMFG-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000007790 solid phase Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000003795 chemical substances by application Substances 0.000 title description 14
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 138
- -1 rare earth ions Chemical class 0.000 claims abstract description 104
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 34
- 125000004209 (C1-C8) alkyl group Chemical group 0.000 claims abstract description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 54
- 229920000642 polymer Polymers 0.000 claims description 50
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 41
- 238000006243 chemical reaction Methods 0.000 claims description 35
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- 238000002156 mixing Methods 0.000 claims description 27
- 150000007529 inorganic bases Chemical class 0.000 claims description 23
- 230000020477 pH reduction Effects 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 18
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 18
- 238000006959 Williamson synthesis reaction Methods 0.000 claims description 18
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 18
- 238000011049 filling Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 16
- 239000008098 formaldehyde solution Substances 0.000 claims description 14
- 150000007522 mineralic acids Chemical class 0.000 claims description 14
- 238000007127 saponification reaction Methods 0.000 claims description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 11
- 239000011734 sodium Substances 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 11
- HXDOZKJGKXYMEW-UHFFFAOYSA-N 4-ethylphenol Chemical compound CCC1=CC=C(O)C=C1 HXDOZKJGKXYMEW-UHFFFAOYSA-N 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- FDRCDNZGSXJAFP-UHFFFAOYSA-M sodium chloroacetate Chemical compound [Na+].[O-]C(=O)CCl FDRCDNZGSXJAFP-UHFFFAOYSA-M 0.000 claims description 9
- YQUQWHNMBPIWGK-UHFFFAOYSA-N 4-isopropylphenol Chemical compound CC(C)C1=CC=C(O)C=C1 YQUQWHNMBPIWGK-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 6
- ISAVYTVYFVQUDY-UHFFFAOYSA-N 4-tert-Octylphenol Chemical compound CC(C)(C)CC(C)(C)C1=CC=C(O)C=C1 ISAVYTVYFVQUDY-UHFFFAOYSA-N 0.000 claims description 4
- QHPQWRBYOIRBIT-UHFFFAOYSA-N 4-tert-butylphenol Chemical compound CC(C)(C)C1=CC=C(O)C=C1 QHPQWRBYOIRBIT-UHFFFAOYSA-N 0.000 claims description 4
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 claims description 4
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- IWDCLRJOBJJRNH-UHFFFAOYSA-N p-cresol Chemical compound CC1=CC=C(O)C=C1 IWDCLRJOBJJRNH-UHFFFAOYSA-N 0.000 claims description 4
- NRZWYNLTFLDQQX-UHFFFAOYSA-N p-tert-Amylphenol Chemical compound CCC(C)(C)C1=CC=C(O)C=C1 NRZWYNLTFLDQQX-UHFFFAOYSA-N 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- SESSOVUNEZQNBV-UHFFFAOYSA-M sodium;2-bromoacetate Chemical compound [Na+].[O-]C(=O)CBr SESSOVUNEZQNBV-UHFFFAOYSA-M 0.000 claims description 3
- AGDSCTQQXMDDCV-UHFFFAOYSA-M sodium;2-iodoacetate Chemical compound [Na+].[O-]C(=O)CI AGDSCTQQXMDDCV-UHFFFAOYSA-M 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 3
- 150000002910 rare earth metals Chemical class 0.000 abstract description 50
- 239000007788 liquid Substances 0.000 abstract description 13
- 239000007787 solid Substances 0.000 abstract description 10
- 238000000926 separation method Methods 0.000 abstract description 6
- 230000000694 effects Effects 0.000 abstract description 3
- 239000004005 microsphere Substances 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 58
- 239000002245 particle Substances 0.000 description 15
- 238000001035 drying Methods 0.000 description 9
- 239000012295 chemical reaction liquid Substances 0.000 description 7
- 238000012216 screening Methods 0.000 description 7
- 229910052684 Cerium Inorganic materials 0.000 description 6
- 229910052692 Dysprosium Inorganic materials 0.000 description 6
- 229910052691 Erbium Inorganic materials 0.000 description 6
- 229910052693 Europium Inorganic materials 0.000 description 6
- 229910052688 Gadolinium Inorganic materials 0.000 description 6
- 229910052689 Holmium Inorganic materials 0.000 description 6
- 229910052765 Lutetium Inorganic materials 0.000 description 6
- 229910052779 Neodymium Inorganic materials 0.000 description 6
- 229910052777 Praseodymium Inorganic materials 0.000 description 6
- 229910052772 Samarium Inorganic materials 0.000 description 6
- 229910052771 Terbium Inorganic materials 0.000 description 6
- 229910052775 Thulium Inorganic materials 0.000 description 6
- 229910052769 Ytterbium Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052746 lanthanum Inorganic materials 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 229910052727 yttrium Inorganic materials 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000001179 sorption measurement Methods 0.000 description 4
- KDVYCTOWXSLNNI-UHFFFAOYSA-N 4-t-Butylbenzoic acid Chemical compound CC(C)(C)C1=CC=C(C(O)=O)C=C1 KDVYCTOWXSLNNI-UHFFFAOYSA-N 0.000 description 3
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- FEIWNULTQYHCDN-UHFFFAOYSA-N mbba Chemical compound C1=CC(CCCC)=CC=C1N=CC1=CC=C(OC)C=C1 FEIWNULTQYHCDN-UHFFFAOYSA-N 0.000 description 3
- DBOAVDSSZWDGTH-UHFFFAOYSA-N n-(4-butylphenyl)-1-(4-ethoxyphenyl)methanimine Chemical compound C1=CC(CCCC)=CC=C1N=CC1=CC=C(OCC)C=C1 DBOAVDSSZWDGTH-UHFFFAOYSA-N 0.000 description 3
- 239000002699 waste material Substances 0.000 description 3
- LZDOYVMSNJBLIM-UHFFFAOYSA-N 4-tert-butylphenol;formaldehyde Chemical compound O=C.CC(C)(C)C1=CC=C(O)C=C1 LZDOYVMSNJBLIM-UHFFFAOYSA-N 0.000 description 2
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Natural products CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- USEUJPGSYMRJHM-UHFFFAOYSA-N formaldehyde;4-methylphenol Chemical compound O=C.CC1=CC=C(O)C=C1 USEUJPGSYMRJHM-UHFFFAOYSA-N 0.000 description 2
- CQPABIOWIMJISN-UHFFFAOYSA-N formaldehyde;4-propan-2-ylphenol Chemical compound O=C.CC(C)C1=CC=C(O)C=C1 CQPABIOWIMJISN-UHFFFAOYSA-N 0.000 description 2
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- UUKFYJQRHYQWSK-UHFFFAOYSA-N 4-ethylphenol;formaldehyde Chemical compound O=C.CCC1=CC=C(O)C=C1 UUKFYJQRHYQWSK-UHFFFAOYSA-N 0.000 description 1
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 1
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 235000012538 ammonium bicarbonate Nutrition 0.000 description 1
- 239000001099 ammonium carbonate Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- QWDJLDTYWNBUKE-UHFFFAOYSA-L magnesium bicarbonate Chemical compound [Mg+2].OC([O-])=O.OC([O-])=O QWDJLDTYWNBUKE-UHFFFAOYSA-L 0.000 description 1
- 239000002370 magnesium bicarbonate Substances 0.000 description 1
- 229910000022 magnesium bicarbonate Inorganic materials 0.000 description 1
- 235000014824 magnesium bicarbonate Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 125000001973 tert-pentyl group Chemical group [H]C([H])([H])C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
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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
-
- 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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- Engineering & Computer Science (AREA)
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Abstract
The invention relates to the technical field of rare earth enrichment and separation, in particular to a phenoxy carboxylic acid solid-phase extractant, and a preparation method and application thereof. The phenoxy carboxylic acid solid-phase extractant has a structure shown in a formula (I); in the formula (I), n is the polymerization degree of linear polymeric phenoxy carboxylic acid, n is a natural number of 2-100, and R is C1-C8 alkyl. The phenoxy carboxylic acid solid-phase extractant provided by the invention is solid at normal temperature and can selectively extract rare earth ions. The phenoxy carboxylic acid solid-phase extractant is granulated into microspheres to be filled in the column, and low-concentration rare earth ions are selectively adsorbed on a solid-liquid interface when passing through the column, so that enrichment is obtained, and the enrichment rate of the rare earth ions is high. Experimental results show that rare earth elements can be enriched and recovered from a low-concentration rare earth solution by adopting the phenoxy carboxylic acid solid-phase extractant, and the enrichment effect of rare earth ions is excellent.
Description
The priority of the Chinese patent application with the title of 'a phenoxy carboxylic acid solid phase extractant, preparation method and application thereof' filed by the Chinese patent office at 18/09/2020, application number of 202010989241.9 is required, and the entire content of the priority is incorporated in the application by reference.
Technical Field
The invention relates to the technical field of rare earth enrichment and separation, in particular to a phenoxy carboxylic acid solid-phase extractant, and a preparation method and application thereof.
Background
The south ionic rare earth ore is a special rare earth ore in China and is rich in medium and heavy rare earth elements. However, with the continuous development of rare earth ore resources, the rare earth grade is gradually reduced, the concentration of rare earth leachate is very low, and the concentration of rare earth needs to be increased by an enrichment technology so as to facilitate downstream extraction and separation. On the other hand, rare earth ions with extremely low concentration are contained in the rare earth mine leaching tail liquid and the waste water discharged in the rare earth separation process, the waste of the rare earth with low concentration wastes resources and easily causes environmental pollution, and an enrichment technology is urgently needed to recover the waste rare earth resources, particularly medium and heavy rare earth elements.
The traditional enrichment technology mainly comprises oxalic acid, ammonium bicarbonate and magnesium bicarbonate precipitation technology, the precipitation operation by using a reagent is simple and convenient, but the reagent consumption is very large, and the secondary pollution to the environment is easily caused. In addition, the rare earth can be enriched by liquid-liquid solvent extraction, but the extraction agent residue in the raffinate is large, and the extraction process is complex.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a phenoxy carboxylic acid solid-phase extractant, a preparation method and an application thereof, the phenoxy carboxylic acid solid-phase extractant of the present invention can enrich and recover rare earth elements from a low-concentration rare earth solution, and the enrichment rate of rare earth ions is high.
The invention provides a phenoxy carboxylic acid solid-phase extractant, which has a structure shown in a formula (I):
in the formula (I), n is the polymerization degree of linear polymeric phenoxy carboxylic acid, n is a natural number of 2-100, and R is C1-C8 alkyl.
Preferably, R is methyl, ethyl, isopropyl, tert-butyl, tert-pentyl or tert-octyl.
The invention also provides a preparation method of the phenoxy carboxylic acid solid-phase extractant, which comprises the following steps:
A) mixing alkylphenol, formaldehyde solution and inorganic base, and then carrying out polymerization reaction to obtain alkylphenol linear polymer;
B) carrying out Williamson reaction on the alkylphenol linear polymer, the sodium halocarboxylate and the inorganic base in a solvent to obtain a reaction solution;
C) and mixing the reaction solution with an inorganic acid solution, and then carrying out an acidification reaction to obtain the phenoxy carboxylic acid solid-phase extractant.
Preferably, in step a), the alkylphenol is selected from one of p-methylphenol, p-ethylphenol, p-isopropylphenol, p-tert-butylphenol, p-tert-amylphenol and p-tert-octylphenol;
the purity of the alkylphenol is more than 90%;
the mass concentration of the formaldehyde solution is 37%;
the inorganic base is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and ammonia water.
Preferably, in the step a), the mass ratio of the alkylphenol to the formaldehyde solution to the inorganic base is 1.0-3.5: 0.8-2.0: 0.1 to 0.3;
the temperature of the polymerization reaction is 80-120 ℃, and the time of the polymerization reaction is 0.5-3 h.
Preferably, in step B), the sodium halocarboxylate is selected from one of sodium chloroacetate, sodium bromoacetate and sodium iodoacetate;
the inorganic base is selected from one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and ammonia water;
the solvent comprises water and/or ethanol.
Preferably, the mass ratio of the sodium halocarboxylate in the step B), the inorganic base in the step B) and the alkylphenol in the step a) is 2.0 to 4.0: 0.5-1.2: 1.0 to 3.5;
the temperature of the Williamson reaction is 80-120 ℃, and the time of the Williamson reaction is 2-4 h.
Preferably, in step C), the inorganic acid solution is one or more selected from a hydrochloric acid solution, a nitric acid solution and a sulfuric acid solution;
the concentration of the inorganic acid solution is 0.5-12 mol/L;
the using amount ratio of the inorganic acid solution in the step C) to the alkylphenol in the step A) is 5-10 mL: 1.0-3.5 g;
the temperature of the acidification reaction is 0-50 ℃, and the time of the acidification reaction is 5-30 min.
The invention also provides a method for enriching the low-concentration rare earth ions, which comprises the following steps:
a) saponifying the extractant to obtain a saponified extractant; the extractant is the phenoxy carboxylic acid solid-phase extractant of claim 1;
b) filling the saponified extractant in a column body to prepare an enrichment column;
c) and (3) enabling a low-concentration rare earth ion solution to flow through the enrichment column, and obtaining enriched rare earth ions in the enrichment column.
Preferably, the reagent used for saponification is ammonia water with the mass fraction of 25%;
the concentration of rare earth ions in the low-concentration rare earth ion solution is 0.01-10 g/L.
The invention provides a phenoxy carboxylic acid solid-phase extractant which has a structure shown in a formula (I); in the formula (I), n is the polymerization degree of linear polymeric phenoxy carboxylic acid, n is a natural number of 2-100, and R is C1-C8 alkyl. The phenoxy carboxylic acid solid-phase extractant provided by the invention is solid at normal temperature and can selectively extract rare earth ions. The phenoxy carboxylic acid solid-phase extractant is granulated into microspheres to be filled in a column body, and selective adsorption is carried out on a solid-liquid interface when low-concentration rare earth ions pass through the column body, so that enrichment is obtained. The phenoxy carboxylic acid solid phase extractant provided by the invention has the advantages of large adsorption capacity, high liquid treatment capacity, obvious enrichment and separation effects, low cost and recycling.
Experimental results show that rare earth elements can be enriched and recovered from a low-concentration rare earth solution by adopting the phenoxy carboxylic acid solid-phase extractant, and the enrichment rate of rare earth ions is not lower than 75%.
Drawings
FIG. 1 shows the NMR spectrum of t-octylphenoxyacetic acid formaldehyde linear polymer (TOBBA) in example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood 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 phenoxy carboxylic acid solid-phase extractant, which has a structure shown in a formula (I):
in the formula (I), n is the polymerization degree of linear polymeric phenoxy carboxylic acid, n is a natural number of 2-100, and R is C1-C8 alkyl.
In certain embodiments of the present invention, R is methyl, ethyl, isopropyl, tert-butyl, tert-amyl, or tert-octyl.
In some embodiments of the present invention, the phenoxy carboxylic acid solid-phase extractant with the structure shown in formula (i) has an average polymerization degree (i.e. an average value of polymerization degrees n) of 4 to 80. In some embodiments of the present invention, the phenoxy carboxylic acid solid-phase extractant with the structure shown in formula (i) has an average polymerization degree (i.e. an average value of polymerization degrees n) of 16, 80, 50, 24, 8 or 4.
The phenoxy carboxylic acid solid-phase extractant provided by the invention is solid at normal temperature and can selectively extract rare earth ions. The phenoxy carboxylic acid solid-phase extractant is granulated into microspheres to be filled in a column body, and selective adsorption is carried out on a solid-liquid interface when low-concentration rare earth ions pass through the column body, so that enrichment is obtained. The phenoxy carboxylic acid solid phase extractant provided by the invention has the advantages of large adsorption capacity, high liquid treatment capacity, obvious enrichment and separation effects, low cost and recycling.
The invention also provides a preparation method of the phenoxy carboxylic acid solid-phase extractant, which comprises the following steps:
A) mixing alkylphenol, formaldehyde solution and inorganic base, and then carrying out polymerization reaction to obtain alkylphenol linear polymer;
B) carrying out Williamson reaction on the alkylphenol linear polymer, the sodium halocarboxylate and the inorganic base in a solvent to obtain a reaction solution;
C) and mixing the reaction solution with an inorganic acid solution, and then carrying out an acidification reaction to obtain the phenoxy carboxylic acid solid-phase extractant.
The invention firstly mixes the alkylphenol, formaldehyde solution and inorganic base and then carries out polymerization reaction to obtain the alkylphenol linear polymer.
In certain embodiments of the present invention, the alkylphenol is selected from one of p-methylphenol, p-ethylphenol, p-isopropylphenol, p-tert-butylphenol, p-tert-amylphenol, and p-tert-octylphenol. In certain embodiments of the present invention, the alkylphenol has a purity of greater than 90%. In certain embodiments, the alkylphenol is 99%, 95%, 97%, or 98% pure.
In some embodiments of the invention, the mass concentration of the formaldehyde solution is 36-38%. In certain embodiments, the formaldehyde solution has a mass concentration of 37%. In certain embodiments of the present invention, the solvent of the formaldehyde solution is water.
In certain embodiments of the invention, the inorganic base is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and aqueous ammonia.
In certain embodiments of the present invention, the mass ratio of the alkylphenol, the formaldehyde solution and the inorganic base is 1.0 to 3.5: 0.8-2.0: 0.1 to 0.4. In certain embodiments, the mass ratio of the alkylphenol, the formaldehyde solution and the inorganic base is 1.0-3.5: 0.8-2.0: 0.1 to 0.3. In certain embodiments, the mass ratio of the alkylphenol, the formaldehyde solution, and the inorganic base is 2.5: 1.2: 0.2, 1.8: 0.86: 0.2, 2.0: 0.98: 0.24, 2.3: 1.08: 0.25, 2.7: 1.3: 0.30 or 3.4: 1.64: 0.38.
in some embodiments of the present invention, the temperature of the polymerization reaction is 80 to 120 ℃, and the time of the polymerization reaction is 0.5 to 3 hours. In certain embodiments, the temperature of the polymerization reaction is 100 ℃, 90 ℃, 95 ℃, 110 ℃, or 120 ℃. In certain embodiments, the polymerization reaction time is 2 hours, 1.5 hours, or 3 hours.
After an alkylphenol linear polymer is obtained, the alkylphenol linear polymer, sodium halocarboxylate and inorganic base are subjected to Williamson reaction in a solvent to obtain a reaction solution.
In certain embodiments of the invention, the sodium halocarboxylate is selected from one of sodium chloroacetate, sodium bromoacetate, and sodium iodoacetate.
In certain embodiments of the present invention, the inorganic base is selected from one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, and aqueous ammonia.
In certain embodiments of the invention, the solvent comprises water and/or ethanol. In certain embodiments, the solvent comprises water and ethanol, the volume ratio of ethanol to water being 1: 1.
in certain embodiments of the present invention, the mass ratio of the sodium halocarboxylate in step B), the inorganic base in step B), and the alkylphenol in step a) is 2.0 to 4.0: 0.5-1.2: 1.0 to 3.5. In certain embodiments, the mass ratio of sodium halocarboxylate in step B), inorganic base in step B), and alkylphenol in step a) is 2.8: 0.8: 2.5, 2.0: 0.58: 1.8, 2.3: 0.65: 2.0, 2.5: 0.73: 2.3, 3.0: 0.88: 2.7 or 3.8: 1.10: 3.4.
in some embodiments of the present invention, the Williamson reaction temperature is 80-120 deg.C and the Williamson reaction time is 2-4 h. In certain embodiments, the temperature of the williamson reaction is 95 ℃. In certain embodiments, the williamson reaction time is 2 hours.
And (3) mixing the reaction solution with an inorganic acid solution to carry out acidification reaction after obtaining the reaction solution, thereby obtaining the phenoxy carboxylic acid solid-phase extractant.
In certain embodiments of the present invention, the inorganic acid solution is selected from one or more of a hydrochloric acid solution, a nitric acid solution, and a sulfuric acid solution. In certain embodiments of the present invention, the solvent of the mineral acid solution is water.
In some embodiments of the present invention, the concentration of the inorganic acid solution is 0.5 to 12 mol/L. In certain embodiments, the concentration of the inorganic acid solution is 6mol/L, 3mol/L, or 5 mol/L.
In certain embodiments of the present invention, the ratio of the amount of the inorganic acid solution in step C) to the amount of the alkylphenol in step a) is 5 to 10 mL: 1.0 to 3.5 g. In certain embodiments, the ratio of the amount of mineral acid solution in step C) to the amount of alkylphenol in step a) is 5 mL: 2.5g, 5 mL: 1.8g, 8 mL: 2.0g, 5 mL: 2.3g, 10 mL: 2.7g or 10 mL: 3.4 g.
In some embodiments of the present invention, the temperature of the acidification reaction is 0 to 50 ℃, and the time of the acidification reaction is 5 to 30 min. In certain embodiments, the temperature of the acidification reaction is 25 ℃. In certain embodiments, the time for the acidification reaction is 10min, 30min, or 20 min.
After the acidification reaction, the product obtained is a colloidal solid. In certain embodiments of the present invention, after the acidification reaction, the method further comprises: and drying, granulating and screening the product after the acidification reaction to obtain polymer particles, namely the alkyl phenoxy carboxylic acid formaldehyde linear polymer.
The method of drying and granulating is not particularly limited in the present invention, and a method of drying and granulating well known to those skilled in the art may be used. In certain embodiments of the present invention, the resulting polymer particles have a particle size of 75 to 150 μm.
The invention also provides a method for enriching the low-concentration rare earth ions, which comprises the following steps:
a) saponifying the extractant to obtain a saponified extractant; the extractant is the phenoxy carboxylic acid solid-phase extractant;
b) filling the saponified extractant in a column body to prepare an enrichment column;
c) and (3) enabling a low-concentration rare earth ion solution to flow through the enrichment column, and obtaining enriched rare earth ions in the enrichment column.
Firstly saponifying an extracting agent to obtain a saponified extracting agent; the extractant is the phenoxy carboxylic acid solid-phase extractant.
In certain embodiments of the present invention, the saponification agent is 25% by weight aqueous ammonia.
In certain embodiments of the invention, saponifying the extractant comprises:
and mixing the extracting agent with ammonia water, and performing saponification reaction to obtain a saponified extracting agent.
In some embodiments of the invention, the dosage ratio of the extracting agent to the ammonia water is 3.0-4.65 g: 2 mL. In certain embodiments, the amount ratio of extractant to aqueous ammonia is 3.68 g: 2mL, 3.0 g: 2mL, 3.24 g: 2mL, 3.47 g: 2mL, 3.94 g: 2mL or 4.65 g: 2 mL.
In some embodiments of the present invention, the temperature of the saponification reaction is 20 to 70 ℃, and the time of the saponification reaction is 5 to 30 min. In certain embodiments, the saponification reaction is at a temperature of 50 ℃ or 70 ℃. In certain embodiments, the saponification reaction time is 30min, 10min, or 20 min.
And filling the saponified extractant in a column body to prepare the enrichment column after the saponified extractant is obtained.
In certain embodiments of the invention, the diameter of the packed column is 16 mm. In certain embodiments of the invention, the height of the extractant fill is 100 mm.
After the enrichment column is obtained, the low-concentration rare earth ion solution flows through the enrichment column, and the enriched rare earth ions are obtained in the enrichment column.
In certain embodiments of the invention, the low concentration rare earth ion solution is an ionic rare earth leachate. In some embodiments of the invention, the concentration of the rare earth ions in the low-concentration rare earth ion solution is 0.01-10 g/L. In certain embodiments, the concentration of rare earth ions in the low-concentration rare earth ion solution is 0.67 g/L.
In certain embodiments of the present invention, the ratio of the amount of the low-concentration rare earth ion solution to the amount of the extractant is 20 mL: 3.0 to 4.65 g. In certain embodiments, the ratio of the amount of the low concentration rare earth ion solution to the amount of the extractant is 20 mL: 3.68g, 20 mL: 3.0g or 20 mL: 3.24 g.
In certain embodiments of the present invention, before flowing the low concentration rare earth ion solution through the enrichment column, the method further comprises: and adjusting the pH value of the low-concentration rare earth ion solution to 5-7. In certain embodiments of the present invention, the pH of the low concentration rare earth ion solution is adjusted to 6. In certain embodiments of the present invention, the adjusting agent that adjusts the pH of the low concentration rare earth ion solution is hydrochloric acid.
In certain embodiments of the invention, the flow rate of the low concentration rare earth ion solution through the enrichment column is 1.0 mL/min. The low-concentration rare earth ion solution flows through the enrichment column, and the rare earth ions are selectively adsorbed on a solid-liquid interface to be enriched.
According to the method for analyzing the rare earth metal and the compound thereof-the determination of the total amount of rare earth GB/T14635-2008, the calculation method of the enrichment ratio (represented by E) of the rare earth ions is shown as the following formula:
wherein C0 is the concentration of rare earth ions in the low-concentration rare earth ion solution before enrichment;
c1 is the concentration of rare earth ions in the low-concentration rare earth ion solution after enrichment.
The source of the above-mentioned raw materials is not particularly limited in the present invention, and may be generally commercially available.
In order to further illustrate the present invention, the following examples are provided to describe the phenoxy carboxylic acid solid-phase extractant, the preparation method and the application thereof in detail, but the invention should not be construed as limiting the scope of the present invention.
Example 1
The phenoxy carboxylic acid solid phase extractant has a structure shown in a formula (1):
in the formula (1), R is tert-octyl, n is a natural number of 2-100, the average polymerization degree is 4 through gel chromatography test, and the extractant is named as p-tert-octyl phenoxyacetic acid formaldehyde linear polymer (code number TOBBA). The preparation method of the TOBBA extractant comprises the following steps:
1) mixing 3.4g of p-tert-octylphenol (with the purity of 98%), 1.64g of formaldehyde aqueous solution with the mass fraction of 37% and 0.38g of sodium hydroxide, heating to 120 ℃, and carrying out polymerization reaction for 3 hours to obtain a p-tert-pentylphenoxyacetic acid formaldehyde linear polymer;
2) mixing the p-tert-octylphenoxyacetic acid formaldehyde linear polymer obtained in the step 1), 3.8g of sodium chloroacetate and 1.10g of sodium hydroxide in an ethanol/water mixed solution at 95 ℃ (volume ratio of ethanol to water is 1: 1) carrying out Williamson reaction for 2h to obtain reaction liquid;
3) and mixing the reaction solution with 10mL of hydrochloric acid solution of 5mol/L, carrying out acidification reaction at 25 ℃ for 20min to obtain colloidal solid of the p-tert-octylphenoxyacetic acid formaldehyde linear polymer (TOBBA), and drying, granulating and screening to obtain polymer particles with the particle size range of 75-150 mu m, namely the p-tert-octylphenoxyacetic acid formaldehyde linear polymer.
The nuclear magnetic resonance analysis of the prepared product TOBBA is carried out, and the result is shown in figure 1. FIG. 1 shows the NMR spectrum of t-octylphenoxyacetic acid formaldehyde linear polymer (TOBBA) in example 1 of the present invention. Hydrogen nuclear magnetic resonance spectroscopy:1H NMR(500MHz，CDCl3) The peak clusters of 0.44-1.79 are attributed to alkyl side chains, the peak of 3.27 is attributed to bridged methylene, the peak of 4.76 is attributed to methylene in oxyacetic acid substituent, and the peak clusters of 6.62-7.25 are attributed to benzene ring hydrogen.
The enrichment method of the low-concentration rare earth ions comprises the following steps:
1) mixing 4.65g of the extractant with 2mL of ammonia water with the mass fraction of 25%, and carrying out saponification reaction at 70 ℃ for 10min to obtain a saponified extractant;
2) filling the saponified extractant in a column (the diameter is 16mm, and the filling height is 100mm) to prepare an enrichment column;
3) the ionic rare earth leachate is derived from ionic rare earth in Longyan city of Fujian province. The concentration C0 of rare earth ions in the ionic rare earth leachate is 0.67g/L, wherein the mass content of each rare earth element is as follows: 27.5 percent of La, 2.5 percent of Ce, 5.86 percent of Pr, 21.7 percent of Nd, 5.12 percent of Sm, 0.35 percent of Eu, 4.76 percent of Gd, 0.7 percent of Tb, 3.77 percent of Dy, 0.63 percent of Ho, 1.98 percent of Er, 0.29 percent of Tm, 1.79 percent of Yb, 0.26 percent of Lu and 22.9 percent of Y. Adjusting the pH value of the ionic rare earth leachate to 6 by adopting hydrochloric acid, and allowing 20mL of the ionic rare earth leachate with the pH value adjusted to flow through the enrichment column (with the flow rate of 1.0mL/min), so as to obtain enriched rare earth ions in the enrichment column.
Through detection, the concentration (C1) of rare earth ions in the tail liquid is 0.167g/L, and the enrichment rate of the rare earth ions is 75%.
Example 2
The phenoxy carboxylic acid solid phase extractant has a structure shown in a formula (2):
in the formula (2), R is methyl, n is a natural number of 2-100, the average polymerization degree is 80 through gel chromatography test, and the extractant is named as a p-methyl phenoxy acetic acid formaldehyde linear polymer (code MBBA). The preparation method of the MBBA extractant comprises the following steps:
1) mixing 1.8g of p-methylphenol (with the purity of 95%), 0.86g of formaldehyde aqueous solution with the mass fraction of 37% and 0.2g of sodium hydroxide, heating to 90 ℃, and carrying out polymerization reaction for 1.5h to obtain a p-methylphenol formaldehyde linear polymer;
2) an ethanol/water mixed solution of the p-methylphenol formaldehyde linear polymer obtained in the step 1), 2.0g of sodium chloroacetate and 0.58g of sodium hydroxide at 95 ℃ (volume ratio of ethanol to water 1: 1) carrying out Williamson reaction for 2h to obtain reaction liquid;
3) and mixing the reaction solution with 5mL of 6mol/L hydrochloric acid solution, carrying out acidification reaction at 25 ℃ for 30min to obtain colloidal solid of the p-methylphenoxy acetic aldehyde linear polymer (MBBA), and drying, granulating and screening to obtain polymer particles with the particle size range of 75-150 mu m, namely the p-methylphenoxy acetic aldehyde linear polymer.
The enrichment method of the low-concentration rare earth ions comprises the following steps:
1) mixing 3.0g of the extractant with 2mL of ammonia water with the mass fraction of 25%, and performing saponification reaction at 50 ℃ for 10min to obtain a saponified extractant;
2) filling the saponified extractant in a column (the diameter is 16mm, and the filling height is 100mm) to prepare an enrichment column;
3) the ionic rare earth leachate is derived from ionic rare earth in Longyan city of Fujian province. The concentration C0 of rare earth ions in the ionic rare earth leachate is 0.67g/L, wherein the mass content of each rare earth element is as follows: 27.5 percent of La, 2.5 percent of Ce, 5.86 percent of Pr, 21.7 percent of Nd, 5.12 percent of Sm, 0.35 percent of Eu, 4.76 percent of Gd, 0.7 percent of Tb, 3.77 percent of Dy, 0.63 percent of Ho, 1.98 percent of Er, 0.29 percent of Tm, 1.79 percent of Yb, 0.26 percent of Lu and 22.9 percent of Y. Adjusting the pH value of the ionic rare earth leachate to 6 by adopting hydrochloric acid, and allowing 20mL of the ionic rare earth leachate with the pH value adjusted to flow through the enrichment column (with the flow rate of 1.0mL/min), so as to obtain enriched rare earth ions in the enrichment column.
Through detection, the concentration (C1) of the rare earth ions in the tail liquid is 0.147g/L, and the enrichment rate of the rare earth ions is 78%.
Example 3
The phenoxy carboxylic acid solid phase extractant has a structure shown in a formula (3):
in the formula (3), R is ethyl, n is a natural number of 2-100, the average polymerization degree is 50 through gel chromatography test, and the extractant is named as a p-ethylphenoxyacetic acid formaldehyde linear polymer (code EBBA). The preparation method of the EBBA extractant comprises the following steps:
1) mixing 2.0g of p-ethylphenol (the purity is 97%), 0.98g of formaldehyde aqueous solution with the mass fraction of 37% and 0.24g of sodium hydroxide, heating to 90 ℃, and carrying out polymerization reaction for 1.5h to obtain a p-ethylphenol formaldehyde linear polymer;
2) an ethanol/water mixed solution of the para-ethylphenol formaldehyde linear polymer obtained in step 1), 2.3g of sodium chloroacetate and 0.65g of sodium hydroxide at 95 ℃ (volume ratio of ethanol to water 1: 1) carrying out Williamson reaction for 2h to obtain reaction liquid;
3) and mixing the reaction solution with 8mL of hydrochloric acid solution of 3mol/L, carrying out acidification reaction at 25 ℃ for 30min to obtain colloidal solid of the linear polymer of p-ethyl phenoxy acetic acid formaldehyde (EBBA), and drying, granulating and screening to obtain polymer particles with the particle size range of 75-150 mu m, namely the linear polymer of p-ethyl phenoxy acetic acid formaldehyde.
The enrichment method of the low-concentration rare earth ions comprises the following steps:
1) mixing 3.24g of the extractant with 2mL of ammonia water with the mass fraction of 25%, and performing saponification reaction at 50 ℃ for 20min to obtain a saponified extractant;
2) filling the saponified extractant in a column (the diameter is 16mm, and the filling height is 100mm) to prepare an enrichment column;
3) the ionic rare earth leachate is derived from ionic rare earth in Longyan city of Fujian province. The concentration C0 of rare earth ions in the ionic rare earth leachate is 0.67g/L, wherein the mass content of each rare earth element is as follows: 27.5 percent of La, 2.5 percent of Ce, 5.86 percent of Pr, 21.7 percent of Nd, 5.12 percent of Sm, 0.35 percent of Eu, 4.76 percent of Gd, 0.7 percent of Tb, 3.77 percent of Dy, 0.63 percent of Ho, 1.98 percent of Er, 0.29 percent of Tm, 1.79 percent of Yb, 0.26 percent of Lu and 22.9 percent of Y. Adjusting the pH value of the ionic rare earth leachate to 6 by adopting hydrochloric acid, and allowing 20mL of the ionic rare earth leachate with the pH value adjusted to flow through the enrichment column (with the flow rate of 1.0mL/min), so as to obtain enriched rare earth ions in the enrichment column.
Through detection, the concentration (C1) of rare earth ions in the tail liquid is 0.134g/L, and the enrichment rate of the rare earth ions is 80%.
Example 4
The phenoxy carboxylic acid solid phase extractant has a structure shown in a formula (4):
in the formula (4), R is isopropyl, n is a natural number of 2-100, the average polymerization degree is 24 through gel chromatography test, and the extractant is named as a p-isopropyl phenoxyacetic acid formaldehyde linear polymer (code PBBA). The preparation method of the PBBA extractant comprises the following steps:
1) mixing 2.3g of p-isopropylphenol (with the purity of 98%), 1.08g of formaldehyde aqueous solution with the mass fraction of 37% and 0.25g of sodium hydroxide, heating to 95 ℃, and carrying out polymerization reaction for 2 hours to obtain a p-isopropylphenol formaldehyde linear polymer;
2) an ethanol/water mixed solution of the p-isopropylphenol formaldehyde linear polymer obtained in step 1), 2.5g of sodium chloroacetate and 0.73g of sodium hydroxide at 95 ℃ (volume ratio of ethanol to water 1: 1) carrying out Williamson reaction for 2h to obtain reaction liquid;
3) and mixing the reaction solution with 5mL of 6.0mol/L hydrochloric acid solution, carrying out acidification reaction at 25 ℃ for 10min to obtain colloidal solid of the p-isopropylphenoxyacetic formaldehyde linear Polymer (PBBA), and drying, granulating and screening to obtain polymer particles with the particle size range of 75-150 mu m, namely the p-isopropylphenoxyacetic formaldehyde linear polymer.
The enrichment method of the low-concentration rare earth ions comprises the following steps:
1) mixing 3.47g of the extracting agent with 2mL of ammonia water with the mass fraction of 25%, and carrying out saponification reaction at 50 ℃ for 30min to obtain a saponified extracting agent;
2) filling the saponified extractant in a column (the diameter is 16mm, and the filling height is 100mm) to prepare an enrichment column;
3) the ionic rare earth leachate is derived from ionic rare earth in Longyan city of Fujian province. The concentration C0 of rare earth ions in the ionic rare earth leachate is 0.67g/L, wherein the mass content of each rare earth element is as follows: 27.5 percent of La, 2.5 percent of Ce, 5.86 percent of Pr, 21.7 percent of Nd, 5.12 percent of Sm, 0.35 percent of Eu, 4.76 percent of Gd, 0.7 percent of Tb, 3.77 percent of Dy, 0.63 percent of Ho, 1.98 percent of Er, 0.29 percent of Tm, 1.79 percent of Yb, 0.26 percent of Lu and 22.9 percent of Y. Adjusting the pH value of the ionic rare earth leachate to 6 by adopting hydrochloric acid, and allowing 20mL of the ionic rare earth leachate with the pH value adjusted to flow through the enrichment column (with the flow rate of 1.0mL/min), so as to obtain enriched rare earth ions in the enrichment column.
Through detection, the concentration (C1) of rare earth ions in the tail liquid is 0.101g/L, and the enrichment rate of the rare earth ions is 85%.
Example 5
The phenoxy carboxylic acid solid phase extractant has a structure shown in a formula (5):
in the formula (5), R is tert-amyl, n is a natural number of 2-100, the average polymerization degree is 8 through gel chromatography test, and the extractant is named as p-tert-amyl phenoxy acetic acid formaldehyde linear polymer (code TPBBA). The preparation method of the TPBBA extractant comprises the following steps:
1) mixing 2.7g of p-tert-amylphenol (with the purity of 98 percent), 1.3g of formaldehyde aqueous solution with the mass fraction of 37 percent and 0.30g of sodium hydroxide, heating to 110 ℃, and carrying out polymerization reaction for 2 hours to obtain a p-tert-amylphenoxyacetic acid formaldehyde linear polymer;
2) subjecting the linear polymer of p-tert-pentylphenoxyacetic acid formaldehyde obtained in step 1), 3.0g of sodium chloroacetate and 0.88g of sodium hydroxide to 95 ℃ ethanol/water mixed solution (volume ratio of ethanol to water 1: 1) carrying out Williamson reaction for 2h to obtain reaction liquid;
3) and mixing the reaction solution with 10mL of 5mol/L hydrochloric acid solution, carrying out acidification reaction at 25 ℃ for 10min to obtain colloidal solid of the p-tert-pentylphenoxyacetic acid formaldehyde linear polymer (TPBBA), and drying, granulating and screening to obtain polymer particles with the particle size range of 75-150 mu m, namely the p-tert-pentylphenoxyacetic acid formaldehyde linear polymer.
The enrichment method of the low-concentration rare earth ions comprises the following steps:
1) mixing 3.94g of the extracting agent with 2mL of ammonia water with the mass fraction of 25%, and carrying out saponification reaction at 70 ℃ for 30min to obtain a saponified extracting agent;
2) filling the saponified extractant in a column (the diameter is 16mm, and the filling height is 100mm) to prepare an enrichment column;
3) the ionic rare earth leachate is derived from ionic rare earth in Longyan city of Fujian province. The concentration C0 of rare earth ions in the ionic rare earth leachate is 0.67g/L, wherein the mass content of each rare earth element is as follows: 27.5 percent of La, 2.5 percent of Ce, 5.86 percent of Pr, 21.7 percent of Nd, 5.12 percent of Sm, 0.35 percent of Eu, 4.76 percent of Gd, 0.7 percent of Tb, 3.77 percent of Dy, 0.63 percent of Ho, 1.98 percent of Er, 0.29 percent of Tm, 1.79 percent of Yb, 0.26 percent of Lu and 22.9 percent of Y. Adjusting the pH value of the ionic rare earth leachate to 6 by adopting hydrochloric acid, and allowing 20mL of the ionic rare earth leachate with the pH value adjusted to flow through the enrichment column (with the flow rate of 1.0mL/min), so as to obtain enriched rare earth ions in the enrichment column.
Through detection, the concentration (C1) of rare earth ions in the tail liquid is 0.120g/L, and the enrichment rate of the rare earth ions is 82%.
Example 6
The phenoxy carboxylic acid solid phase extractant has a structure shown in a formula (6):
in the formula (6), R is tert-butyl, n is a natural number of 2-100, the average polymerization degree (namely the average value of the polymerization degree n) is 16 through a gel chromatography test, and the extractant is named as p-tert-butylphenoxy acetic acid formaldehyde linear polymer (code TBBA). The preparation method of the TBBA extractant comprises the following steps:
1) mixing 2.5g of p-tert-butylphenol (with the purity of 99 percent), 1.2g of formaldehyde aqueous solution with the mass fraction of 37 percent and 0.2g of sodium hydroxide, heating to 100 ℃, and carrying out polymerization reaction for 2 hours to obtain a p-tert-butylphenol formaldehyde linear polymer;
2) subjecting the linear polymer of p-tert-butylphenol formaldehyde obtained in step 1), 2.8g of sodium chloroacetate and 0.8g of sodium hydroxide to a 95 ℃ ethanol/water mixed solution (volume ratio of ethanol to water 1: 1) carrying out Williamson reaction for 2h to obtain reaction liquid;
3) and mixing the reaction liquid with 5mL of 6mol/L hydrochloric acid solution, carrying out acidification reaction at 25 ℃ for 10min to obtain colloidal solid of the p-tert-butylphenoxyacetic aldehyde linear polymer (TBBA), and drying, granulating and screening to obtain polymer particles with the particle size range of 75-150 mu m, namely the p-tert-butylphenoxyacetic aldehyde linear polymer.
The enrichment method of the low-concentration rare earth ions comprises the following steps:
1) mixing 3.68g of the extractant with 2mL of ammonia water with the mass fraction of 25%, and carrying out saponification reaction at 50 ℃ for 30min to obtain a saponified extractant;
2) filling the saponified extractant in a column (the diameter is 16mm, and the filling height is 100mm) to prepare an enrichment column;
3) the ionic rare earth leachate is derived from ionic rare earth in Longyan city of Fujian province. The concentration C0 of rare earth ions in the ionic rare earth leachate is 0.67g/L, wherein the mass content of each rare earth element is as follows: 27.5 percent of La, 2.5 percent of Ce, 5.86 percent of Pr, 21.7 percent of Nd, 5.12 percent of Sm, 0.35 percent of Eu, 4.76 percent of Gd, 0.7 percent of Tb, 3.77 percent of Dy, 0.63 percent of Ho, 1.98 percent of Er, 0.29 percent of Tm, 1.79 percent of Yb, 0.26 percent of Lu and 22.9 percent of Y. Adjusting the pH value of the ionic rare earth leachate to 6 by adopting hydrochloric acid, and allowing 20mL of the ionic rare earth leachate with the pH value adjusted to flow through the enrichment column (with the flow rate of 1.0mL/min), so as to obtain enriched rare earth ions in the enrichment column.
Through detection, the concentration (C1) of the rare earth ions in the tail solution is 0.087g/L, and the enrichment rate of the rare earth ions is 87%.
Experimental results show that rare earth elements can be enriched and recovered from a low-concentration rare earth solution by adopting the phenoxy carboxylic acid solid-phase extractant, and the enrichment rate of rare earth ions is not lower than 75%.
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 phenoxy carboxylic acid solid phase extractant has a structure shown in formula (I):
in the formula (I), n is the polymerization degree of linear polymeric phenoxy carboxylic acid, n is a natural number of 2-100, and R is C1-C8 alkyl.
2. The phenoxy carboxylic acid solid phase extractant of claim 1, wherein R is methyl, ethyl, isopropyl, tert-butyl, tert-amyl, or tert-octyl.
3. A preparation method of a phenoxy carboxylic acid solid-phase extractant comprises the following steps:
A) mixing alkylphenol, formaldehyde solution and inorganic base, and then carrying out polymerization reaction to obtain alkylphenol linear polymer;
B) carrying out Williamson reaction on the alkylphenol linear polymer, the sodium halocarboxylate and the inorganic base in a solvent to obtain a reaction solution;
C) and mixing the reaction solution with an inorganic acid solution, and then carrying out an acidification reaction to obtain the phenoxy carboxylic acid solid-phase extractant.
4. The production method according to claim 3, wherein in step A), the alkylphenol is selected from one of p-methylphenol, p-ethylphenol, p-isopropylphenol, p-tert-butylphenol, p-tert-amylphenol and p-tert-octylphenol;
the purity of the alkylphenol is more than 90%;
the mass concentration of the formaldehyde solution is 37%;
the inorganic base is selected from one or more of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and ammonia water.
5. The preparation method according to claim 3, wherein in the step A), the mass ratio of the alkylphenol to the formaldehyde solution to the inorganic base is 1.0-3.5: 0.8-2.0: 0.1 to 0.3;
the temperature of the polymerization reaction is 80-120 ℃, and the time of the polymerization reaction is 0.5-3 h.
6. The production method according to claim 3, wherein in the step B), the sodium halogenocarboxylate is selected from one of sodium chloroacetate, sodium bromoacetate and sodium iodoacetate;
the inorganic base is selected from one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate and ammonia water;
the solvent comprises water and/or ethanol.
7. The production method according to claim 3, wherein the mass ratio of the sodium halocarboxylate in step B), the inorganic base in step B), and the alkylphenol in step A) is 2.0 to 4.0: 0.5-1.2: 1.0 to 3.5;
the temperature of the Williamson reaction is 80-120 ℃, and the time of the Williamson reaction is 2-4 h.
8. The preparation method according to claim 3, wherein in step C), the inorganic acid solution is selected from one or more of hydrochloric acid solution, nitric acid solution and sulfuric acid solution;
the concentration of the inorganic acid solution is 0.5-12 mol/L;
the using amount ratio of the inorganic acid solution in the step C) to the alkylphenol in the step A) is 5-10 mL: 1.0-3.5 g;
the temperature of the acidification reaction is 0-50 ℃, and the time of the acidification reaction is 5-30 min.
9. A method for enriching low-concentration rare earth ions comprises the following steps:
a) saponifying the extractant to obtain a saponified extractant; the extractant is the phenoxy carboxylic acid solid-phase extractant of claim 1;
b) filling the saponified extractant in a column body to prepare an enrichment column;
c) and (3) enabling a low-concentration rare earth ion solution to flow through the enrichment column, and obtaining enriched rare earth ions in the enrichment column.
10. The enrichment method according to claim 9, wherein the saponification is carried out by using 25% by weight of ammonia water as a reagent;
the concentration of rare earth ions in the low-concentration rare earth ion solution is 0.01-10 g/L.
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