CN113680215B - Rare earth yttrium ion water phase imprinting membrane and application thereof to separation of adjacent heavy rare earth - Google Patents
Rare earth yttrium ion water phase imprinting membrane and application thereof to separation of adjacent heavy rare earth Download PDFInfo
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- CN113680215B CN113680215B CN202110896874.XA CN202110896874A CN113680215B CN 113680215 B CN113680215 B CN 113680215B CN 202110896874 A CN202110896874 A CN 202110896874A CN 113680215 B CN113680215 B CN 113680215B
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- 239000012528 membrane Substances 0.000 title claims abstract description 103
- 229910052727 yttrium Inorganic materials 0.000 title claims abstract description 76
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000000926 separation method Methods 0.000 title claims abstract description 41
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 36
- 150000002910 rare earth metals Chemical class 0.000 title claims abstract description 17
- -1 rare earth yttrium ion Chemical class 0.000 claims abstract description 70
- 229920000642 polymer Polymers 0.000 claims abstract description 33
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium peroxydisulfate Substances [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 150000002500 ions Chemical class 0.000 claims abstract description 20
- 238000002360 preparation method Methods 0.000 claims abstract description 20
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 18
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 17
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 claims abstract description 14
- 239000002033 PVDF binder Substances 0.000 claims abstract description 13
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims abstract description 13
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims abstract description 13
- 238000002156 mixing Methods 0.000 claims abstract description 8
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims abstract description 4
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000001179 sorption measurement Methods 0.000 claims description 27
- 239000000243 solution Substances 0.000 claims description 21
- 238000000034 method Methods 0.000 claims description 16
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 239000004715 ethylene vinyl alcohol Substances 0.000 claims description 10
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 9
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 9
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 9
- QUXFOKCUIZCKGS-UHFFFAOYSA-N bis(2,4,4-trimethylpentyl)phosphinic acid Chemical compound CC(C)(C)CC(C)CP(O)(=O)CC(C)CC(C)(C)C QUXFOKCUIZCKGS-UHFFFAOYSA-N 0.000 claims description 8
- 239000011521 glass Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical group OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 5
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 4
- 238000009396 hybridization Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 238000000605 extraction Methods 0.000 claims description 3
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 2
- 239000011837 N,N-methylenebisacrylamide Substances 0.000 claims description 2
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 2
- 239000003480 eluent Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 13
- 239000000463 material Substances 0.000 abstract description 9
- 239000000178 monomer Substances 0.000 abstract description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 abstract description 5
- 239000003431 cross linking reagent Substances 0.000 abstract description 3
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 abstract description 2
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 abstract description 2
- 239000012966 redox initiator Substances 0.000 abstract description 2
- WBHQBSYUUJJSRZ-UHFFFAOYSA-M sodium bisulfate Chemical compound [Na+].OS([O-])(=O)=O WBHQBSYUUJJSRZ-UHFFFAOYSA-M 0.000 abstract description 2
- 229910000342 sodium bisulfate Inorganic materials 0.000 abstract description 2
- VAZSKTXWXKYQJF-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)OOS([O-])=O VAZSKTXWXKYQJF-UHFFFAOYSA-N 0.000 abstract 1
- 210000004379 membrane Anatomy 0.000 description 90
- 239000011148 porous material Substances 0.000 description 9
- 230000003068 static effect Effects 0.000 description 9
- 230000004907 flux Effects 0.000 description 6
- 239000000203 mixture Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000012086 standard solution Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 101100297651 Mus musculus Pim2 gene Proteins 0.000 description 2
- 101001001642 Xenopus laevis Serine/threonine-protein kinase pim-3 Proteins 0.000 description 2
- 210000002469 basement membrane Anatomy 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 239000013316 polymer of intrinsic microporosity Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- 241000533950 Leucojum Species 0.000 description 1
- 239000012736 aqueous medium Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000002887 superconductor Substances 0.000 description 1
- PYOOBRULIYNHJR-UHFFFAOYSA-K trichloroholmium Chemical compound Cl[Ho](Cl)Cl PYOOBRULIYNHJR-UHFFFAOYSA-K 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0023—Organic membrane manufacture by inducing porosity into non porous precursor membranes
- B01D67/0032—Organic membrane manufacture by inducing porosity into non porous precursor membranes by elimination of segments of the precursor, e.g. nucleation-track membranes, lithography or laser methods
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/268—Polymers created by use of a template, e.g. molecularly imprinted polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28033—Membrane, sheet, cloth, pad, lamellar or mat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/305—Addition of material, later completely removed, e.g. as result of heat treatment, leaching or washing, e.g. for forming pores
- B01J20/3057—Use of a templating or imprinting material ; filling pores of a substrate or matrix followed by the removal of the substrate or matrix
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
- C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
- C22B3/22—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition
- C22B3/24—Treatment or purification of solutions, e.g. obtained by leaching by physical processes, e.g. by filtration, by magnetic means, or by thermal decomposition by adsorption on solid substances, e.g. by extraction with solid resins
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- C—CHEMISTRY; METALLURGY
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- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B59/00—Obtaining rare earth metals
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
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- 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
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- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a rare earth yttrium ion water-phase imprinting membrane and application thereof to separation of adjacent heavy rare earth, and belongs to the technical field of material preparation and separation. A polymer hybrid film is prepared by blending polyvinylidene fluoride, an ethylene-vinyl alcohol copolymer and di (2, 4-trimethylpentyl) hypophosphorous acid as a base film. Y ions are used as imprinting template ions, itaconic acid IA is used as imprinting functional monomer, N-methylene bisacrylamide MBA is used as cross-linking agent, sodium bisulfate SBS ammonium persulfate APS is used as redox initiator in pure water phase medium, and yttrium ion water phase imprinting membrane is constructed by imprinting polymerization on the surface of the base membrane. The invention improves the hydrophilicity of the rare earth separation membrane and improves the separation coefficient among heavy rare earth holmium, yttrium and erbium. The preparation process is carried out in a pure water phase medium, so that the water contact angle of the film material is greatly reduced. Meanwhile, yttrium ions of the imprinting template are preferentially adsorbed and permeated, and the imprinting template has great advantages in similar rare earth separation membrane materials.
Description
Technical Field
The invention belongs to the technical field of material preparation and separation, and relates to a water phase imprinting method of rare earth yttrium ions and yttrium ion imprinting separation membrane materials prepared by the water phase imprinting method. Compared with other rare earth ion separation membranes at present, the rare earth ion separation membrane has excellent separation capability and hydrophilicity.
Background
Yttrium Y, which is the heavy rare earth element with the highest content in the ionic rare earth ore in south China, is widely applied to products such as fluorescent powder, laser generator, superconductor, etc. Yttrium has these fields of application and, due not only to its own electronic properties, but also to its purity grade, its price increases markedly with increasing purity. Therefore, the technical method for efficiently and environmentally separating and purifying yttrium has higher social and economic values.
The membrane separation method is a green separation method due to the characteristics of simple operation, low energy consumption, high-efficiency separation and the like. For yttrium separation, liquid membrane methods have been widely used in the past. Although the liquid film has a large mass transfer interface area, the problem of liquid film stability and experimental magnification are difficult to improve. Non-liquid membranes, such as polymer hybrid membranes, have better stability by entanglement of polymer chains to immobilize the rare earth extractant support. However, these studies in the past have not been high in the separation coefficient of the specific rare earth under study, and have not achieved a high adsorption separation performance of the target rare earth.
The ion imprinting technology is applied to a membrane separation method, and the prepared ion imprinting membrane has a certain research progress in the aspect of rare earth separation by virtue of the specific recognition capability of template ions. However, by using a polymer hybrid membrane as a matrix membrane material, a hydrophilic yttrium ion imprinting layer is constructed on the surface of the polymer hybrid membrane, so that the separation work of rare earth holmium Ho ions and erbium Er ions which coexist adjacent to yttrium ions is reported.
Disclosure of Invention
Aiming at the high-efficiency separation of adjacent heavy rare earth ions Ho, Y and Er, a polymer hybrid film is prepared by blending polyvinylidene fluoride PVDF, ethylene-vinyl alcohol copolymer EVOH and di (2, 4-trimethyl amyl) hypophosphorous acid Cyanex272 as a base film. Y ions are used as imprinting template ions, itaconic acid IA is used as imprinting functional monomer, N-methylene bisacrylamide MBA is used as cross-linking agent, sodium bisulfate SBS ammonium persulfate APS is used as redox initiator in pure water phase medium, and yttrium ion water phase imprinting membrane is constructed by imprinting polymerization on the surface of the base membrane.
A rare earth yttrium ion water phase imprinting separation membrane is provided, a snowflake imprinting polymer layer is generated on an inner pore canal, and compared with a base membrane, the average pore diameter is reduced from 1.70 mu m to 0.85 mu m; the formation of the water phase imprinting layer improves the surface hydrophilicity of the imprinting film, and compared with the base film, the water contact angle is reduced from 63.7 degrees to 20.3 degrees; under optimized static adsorption and dynamic permeation conditions, the yttrium ion water-phase blotting membrane has a Y equilibrium adsorption capacity (9.19 mg g -1 ) Higher than Ho (3.32 mg g) -1 ) And Er (4).24mg g -1 ) And the separation coefficient among Ho, Y and Er is improved by preferential penetration to Y, compared with the base film beta (Y/Ho) which is improved from 1.27 to 1.66, the beta (Y/Er) is improved from 0.88 to 1.36; beta (Y/Er) was increased from 0.94 to 1.36 compared to non-imprinted membrane beta (Y/Ho) from 1.26 to 1.66.
The preparation method of the rare earth yttrium ion water phase imprinting separation membrane provided by the invention comprises the following steps:
(1) Preparation of a polymer hybrid base film:
taking N, N' -dimethylacetamide (DMAc) as a solvent, adding polyvinylidene fluoride (PVDF), ethylene-vinyl alcohol copolymer (EVOH) and bis (2, 4-trimethylpentyl) hypophosphorous acid (Cyanex 272), mixing, heating and stirring, and carrying out vacuum defoaming for 30min after each component is completely dissolved into a uniform mixed solution to obtain a casting solution; slowly dripping the casting film liquid onto a smooth glass plate, immersing the glass plate in water bath for soaking after natural volatilization, taking out the film, and drying at room temperature to obtain the polymer hybridization base film.
Wherein the mass fraction ratio of PVDF to Cyanex272 is in the range of (0.75-0.6): (0.25-0.4); the addition mass fraction of EVOH is 10%; solid-to-liquid ratio of film component to DMAc 1g:10mL; the reaction condition of heating and stirring is magnetic stirring at 85 ℃ for 24 hours. The film laying height is 400 mu m, the natural volatilization time is 30s, the water bath condition is that the glass plate is immersed in secondary distilled water for 24 hours at room temperature, and the secondary distilled water is replaced for a plurality of times.
(2) Preparation of yttrium ion water phase blotting membrane:
mixing the base film of step (1) with yttrium chloride (YCl 3 ) Mixing with Itaconic Acid (IA) mixed water solution, stirring at 60deg.C for 1 hr (continuously introducing nitrogen), adding N, N-Methylene Bisacrylamide (MBA) solution dissolved in proper amount of secondary distilled water, ammonium Persulfate (APS) and Sodium Bisulphite (SBS) mixed solution, heating under nitrogen protection, stirring, taking out blotting membrane after reaction, eluting membrane plate ion, and drying at room temperature for use.
Wherein, the mass of the basal membrane is 50mg, YCl 3 Molar ratio to IA is 1:3-1:8, a base film and the yttrium chloride YCl 3 Solid-liquid of mixed aqueous solution of IA, MBA, APS and SBSRatio is kept at 1:600g mL -1 The method comprises the steps of carrying out a first treatment on the surface of the MBA mass is 0.45g, total mass of APS and SBS is 0.09g, mass ratio is 1:2; the reaction condition of heating and stirring is that magnetic stirring is carried out for 3-5 hours at 60 ℃, and nitrogen atmosphere is continuously introduced. The eluent is disodium ethylenediamine tetraacetate EDTA solution with the concentration of 0.2mol L -1 。
(3) Preparation of non-blotting membrane:
the same preparation step as step (2) except that YCl is not added 3 In addition to the aqueous solution, a non-blotting membrane was prepared.
The invention also provides application of the rare earth yttrium ion water-phase imprinting separation membrane in adsorption separation of adjacent heavy rare earth Ho, Y and Er, and efficient extraction separation of Y from Ho and Er is realized.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the surface imprinting of the polymer hybrid basement membrane and the imprinting polymerization system in the pure water medium changes the morphology of the basement membrane surface and the internal pore canal, and improves the surface hydrophilicity of the separation membrane. The water phase imprinting film has small surface hole diameter and a thumb-shaped macroporous structure on the lower surface. After blotting and non-blotting treatment, the membrane surface was covered with a blotting polymer layer. The membrane surface imprinted polymer particles after imprinting treatment are denser, the average pore diameter is reduced from 1.70 μm (base membrane) to 0.85 μm (imprinted membrane), and the average pore diameter of the non-imprinted membrane is 2.66 μm. Meanwhile, the water contact angle was reduced from 63.7 ° to 20.3 ° compared to the base film.
(2) In the invention, the affinity of the imprinting film to the water phase template ion Y is obviously improved by a water phase imprinting polymerization mode, so that the Y ion water phase imprinting film is subjected to preferential adsorption separation to the Y ion. Under optimized static adsorption and dynamic permeation conditions, the yttrium ion water-phase blotting membrane has a Y equilibrium adsorption capacity (9.19 mg g -1 ) Higher than Ho (3.32 mg g) -1 ) Er (4.24 mg g) -1 ) And preferentially penetrate Y; beta (Y/Er) was increased from 0.88 to 1.36 compared to the base film beta (Y/Ho) from 1.27 to 1.66; beta (Y/Er) was increased from 0.94 to 1.36 compared to non-imprinted membrane beta (Y/Ho) from 1.26 to 1.66.
Drawings
FIG. 1 is a scanning electron microscope photograph of a polymer hybridization base film (a 1: x2000; a2: x 6500), a non-imprinting film (b 1: x2000; b2: x 6500) and a yttrium ion water imprinting film (c 1: x2000; c2: x 6500) under different magnifications.
FIG. 2 is a sectional scanning electron micrograph of a polymer hybrid membrane (e 1) and a yttrium ion water-blotted membrane (e 2).
FIG. 3 is a graph of the water contact angle change of a polymer hybrid base film and yttrium ion water blotter film of different compositions (PIM-1:25 wt.% Cyanex272-75wt.% PVDF; PIM-2:40wt.% Cyanex272-60wt.% PVDF; PIMs:40wt.% Cyanex272-50wt.% PVDF-10wt.% EVOH).
FIG. 4 is a graph showing the change in static equilibrium adsorption capacity of yttrium ion water-phase blotting membranes prepared at different IA to Y molar ratios.
FIG. 5 is a graph showing the variation of static equilibrium adsorption capacity of yttrium ion water-phase blotting membranes prepared at different polymerization reaction times.
FIG. 6 is a graph showing the dynamic osmotic concentration of Y in the yttrium ion water-imprinted membrane and the non-imprinted membrane.
Detailed Description
The invention will be further described with reference to the drawings and the specific embodiments, but the scope of the invention is not limited thereto.
In the embodiment of the invention, the related adsorption separation performance of the yttrium ion water-phase blotting membrane is inspected by adopting the following method, and the specific method is as follows:
measurement of membrane static adsorption amount: accurately transferring standard solutions of yttrium chloride, holmium chloride and erbium chloride (purchased from national pharmaceutical systems and chemical reagents Co., ltd.) to prepare 20 mg.L -1 And (3) regulating the pH value of the standard solution to be 4, accurately weighing 5mg of the yttrium ion water-phase imprinting film, adding the standard solution into the solution, standing the solution in a constant-temperature water bath at 25 ℃ for 24 hours, and measuring the concentration of the residual rare earth in the solution by using an ultraviolet spectrophotometer. The volume of the solution was designated as V (unit L), the mass of the polymer hybrid microporous membrane was designated as m (unit g), and the initial concentration of the prepared solution was designated as c 0 (unit mg.L) -1 ) The method comprises the steps of carrying out a first treatment on the surface of the After the adsorption is completed, the concentration of the residual rare earth in the solution is c 1 (unit mg.L) -1 ) Equilibrium adsorption quantity Q of the film e (unit mg.g) -1 ) The method comprises the following steps: q (Q) e ＝(c 0 -c 1 )*V/m。
Determination of the permeation coefficient, initial membrane flux and separation coefficient of the membrane dynamic permeation process: a piece of membrane with the diameter of 1.5cm is placed in a dynamic permeation H-shaped pipe, and 100 mg.L is added to two sides of the pipe respectively -1 And carrying out dynamic transmission research on yttrium chloride rare earth solution and hydrochloric acid back extraction solution. Samples are taken from the material liquid tanks at two sides at regular intervals to analyze the rare earth solubility. Permeation rate constant k(s) -1 ) Permeability coefficient P (m.s) -1 ) Initial membrane flux J i (mol·m -2 ·s -1 ) The separation coefficient beta is calculated as follows:
k(s -1 )：ln(c/c i )＝-kt
wherein c i (mol·L -1 ) And c (mol.L) -1 ) The rare earth ion concentrations at the initial and different permeation times respectively; t(s) is the permeation time.
P(m·s -1 )：P＝(V/A)k
Wherein V (m 3 ) Is the volume of the solution at the feed liquid side; a (m) 2 ) Is the effective contact area of the film, k (s -1 ) Is the permeation rate constant.
J i (mol·m -2 ·s -1 )：J i ＝Pc i
Wherein c i (mol·L -1 ) To the initial soil ion concentration, P (m.s) -1 ) Is the permeability coefficient.
β：β＝J i,RE1 /J i,RE2 . Wherein J is i,RE1 And J i,RE1 The initial membrane fluxes of two different rare earth ions, respectively.
Example 1:
(1) Preparation of a polymer hybrid base film:
0.5g of PVDF powder, 0.1g of EVOH pellets and 0.4g of Cyanex272 are weighed out and dissolved in 10ml of DMAc at 85℃for 24 hours under continuous stirring, giving a homogeneous mixed solution. The casting solution was vacuum defoamed for 30 minutes to remove visible bubbles. The casting solution was coated on a smooth glass plate by a wet film coater having a height of 400 μm to obtain a new liquid film. After 30s naturally volatilized, the glass plate was immersed in secondary distilled water for 12 hours, and the coagulation bath was replaced 3 times. Drying at room temperature for 24 hours, the polymer hybrid base film was obtained.
(2) Preparation of yttrium ion water phase blotting membrane
Weighing 50mg and 20mL YCl of the base film in the step (1) 3 The aqueous solution (amount of yttrium ion-containing material 1 mmol) and IA (6 mmol) were mixed and stirred at 60℃for 1 hour (continuous nitrogen introduction). Subsequently, 0.45g of MBA (solution prepared by mixing with 5ml of water) was added and nitrogen was purged for 10 minutes, and finally APS and SBS (total mass 0.09g, mass ratio 1:2,5ml of water were dissolved to prepare a mixed solution) were added and purged with nitrogen for 3 hours. The membrane after completion of the reaction was taken out, washed with water, and then washed with 0.2mol L -1 And eluting with EDTA solution for 24h to obtain the yttrium ion water-phase blotting membrane, and drying at room temperature for later use.
(3) Preparation of non-blotting membrane
The same preparation step as step (2) except that YCl is not added 3 In addition to the aqueous solution, a non-blotting membrane was prepared.
FIG. 1 shows scanning electron micrographs of polymer hybrid base films (a 1: x2000; a2: x 6500), non-imprinted films (b 1: x2000; b2: x 6500) and yttrium ion water imprinted films (c 1: x2000; c2: x 6500) at different magnifications. As can be seen from the graph, compared with the base film, the yttrium ion water-phase imprinting film prepared in the embodiment changes the surface hole morphology of the base film, the surface of the yttrium ion water-phase imprinting film is covered with a uniform imprinting polymer layer, the imprinting polymer particles are denser and snowflake-shaped, the average pore diameter is reduced from 1.70 mu m (base film) to 0.85 mu m (imprinting film), and the average pore diameter of the non-imprinting film is 2.66 mu m.
FIG. 2 shows a sectional scanning electron micrograph of a polymer hybrid membrane (e 1) and a yttrium ion water-imprinted membrane (e 2). As can be seen from the figure, the yttrium ion water-phase blotting membrane prepared in the embodiment has an asymmetric upper and lower surface structure compared with the base membrane. The diameter of the hole on the upper surface is small, and the lower surface is in a thumb-shaped macroporous structure. After blotting treatment, the membrane surface and the internal pore canal become obviously smaller, and obvious snowflake-shaped blotting polymer particles are also arranged on the internal pore canal.
TABLE 1 permeability coefficients P (μms) of Polymer hybrid basal membrane, yttrium ion Water-phase blotting membrane and non-blotting membrane for Ho, Y, er -1 ) Initial membrane flux J i (μmol m -2 s -1 ) And a list of separation coefficients.
Example 2:
in this example, when preparing the polymer hybrid base film, the mass fractions of PVDF, EVOH and Cyanex272 were adjusted to investigate the hydrophilic changes of different base films and determine the optimal composition of the base film of the yttrium ion water-phase blotting film. The preparation methods of the polymer hybrid base film and the yttrium ion water-phase blotting film in this example are basically the same as in example 1, and the addition amounts of the specific raw materials are shown in table 2.
TABLE 2 list of raw material mass fractions for Polymer hybrid membranes
FIG. 3 is a graph showing the change in water contact angle between polymer hybrid membranes of different compositions and yttrium ion water blotting membranes. As can be seen from the figure, the water contact angle of PIM-2 (73.3 ℃) was slightly lower than PIM-1 (79.4 ℃) as the Cyanex272 content increased; when the EVOH content was increased from 0 to 10wt.%, the water contact angle of PIMs was reduced to 63.7. The lower water contact angle means that the film has better hydrophilic performance, and when yttrium ion imprinting polymerization is carried out in a subsequent aqueous medium, the film has better affinity to template yttrium ions, aqueous functional monomers, cross-linking agents, initiators and the like, and can obtain better imprinting effect. Thus, a polymer hybrid film with 10wt.% EVOH and 272.40 wt.% Cyanex added was chosen as the base film optimum composition for the yttrium ion water-blotted film.
Example 3:
in this embodiment, the molar ratio of the functional monomer IA to yttrium ions in the water phase imprinting process is adjusted to study the influence of different molar ratios on the static equilibrium adsorption amount of the yttrium ion water phase imprinting film, so as to determine the optimal molar ratio in the imprinting process. The preparation method of the yttrium ion water-phase blotting membrane in the embodiment is basically the same as that in the embodiment 1, except that the amount of the substances added with IA is 3mmol, 4mmol, 5mmol, 7mmol and 8mmol respectively.
FIG. 4 shows the variation of static equilibrium adsorption amounts of Ho, Y and Er for yttrium ion water-phase blotting membranes prepared at different IA/RE molar ratios. It can be found from the graph that along with the continuous increase of the functional monomer IA, the adsorption quantity of the yttrium ion water-phase imprinting film on Y ions is gradually increased and then reduced, and the adsorption quantity of the yttrium ion water-phase imprinting film on Y reaches the highest in the molar ratio of 6-7, and the change rules of Ho and Er are not obvious, but the adsorption quantity is lower than Y. This demonstrates that the imprinting polymerization process with Y as the template ion does enhance the recognition capability of the yttrium ion water-imprinted membrane for Y. When the IA content is too high (molar ratio 8), the Y adsorption amount decreases, probably because the adsorption sites on the membrane have reached saturation.
Example 4:
in this example, the polymerization time of the water phase blotting procedure was adjusted to study the effect of polymerization time on the static equilibrium adsorption capacity of the yttrium ion water phase blotting membrane, so as to determine the optimal reaction time of the blotting procedure. The preparation method of the yttrium ion water-phase blotting membrane is basically the same as that of the example 1, and the blotting reaction time is respectively 3.5h, 4h, 4.5h and 5h.
FIG. 5 shows the variation of static equilibrium adsorption amounts of Ho, Y and Er by yttrium ion water-phase blotting membranes prepared under different blotting polymerization reaction times. It can be found from the graph that the adsorption amount of the yttrium ion water-phase blotting membrane to three rare earth ions gradually decreases along with the continuous increase of the polymerization time, and the adsorption amounts of Ho and Er are lower than Y. This suggests that too long a polymerization time is detrimental to the increase in adsorption capacity, probably due to the increase in polymerization time, leading to an increasing number of imprinted polymer particles on the membrane, resulting in entrapment of part of the adsorption sites.
Example 5:
the preparation method of the yttrium ion water-phase imprinting membrane in the embodiment is the same as that in the embodiment 1, and the change of the concentration of rare earth ions in a material liquid pool in the dynamic permeation process of the yttrium ion imprinting membrane and the non-imprinting membrane to Ho, Y and Er is studied.
FIG. 6 shows the dynamic transport concentration of Y versus time for the yttrium ion water-imprinted, non-imprinted membranes. During the first 3 hours of initial permeation, both membranes permeated Y, but the permeation rate of the blotting membrane was significantly faster than that of the non-blotting membrane, indicating that the blotting membrane had a faster recognition capacity for Y ions.
Dynamic permeation data of Ho, Y and Er are calculated to obtain permeation coefficients P (mu m s) of a polymer hybridization basal membrane, a yttrium ion water-phase imprinting membrane and a non-imprinting membrane on Ho, Y and Er -1 ) Initial membrane flux J i (μmol m -2 s -1 ) And the separation coefficients are listed in table 1. As shown in Table 1, only the permeability coefficient P of the yttrium ion water-phase blotting membrane to Y ions and the initial membrane flux J i Is larger than Ho and Er. The yttrium ion water-phase imprinting membrane has higher permeation selectivity to Y ions. The mutual separation coefficient among Ho, Y and Er is improved, compared with the base film beta (Y/Ho) which is improved from 1.27 to 1.66, beta (Y/Er) which is improved from 0.88 to 1.36; beta (Y/Er) was increased from 0.94 to 1.36 compared to non-imprinted membrane beta (Y/Ho) from 1.26 to 1.66.
Claims (3)
1. The preparation method of the rare earth yttrium ion water phase imprinting separation membrane is characterized by comprising the following steps of:
(1) Preparation of a polymer hybrid base film:
taking N, N' -dimethylacetamide (DMAc) as a solvent, adding polyvinylidene fluoride (PVDF), ethylene-vinyl alcohol copolymer (EVOH) and bis (2, 4-trimethylpentyl) hypophosphorous acid (Cyanex 272), mixing, heating and stirring, and carrying out vacuum defoaming for 30min after each component is completely dissolved into a uniform mixed solution to obtain a casting solution; slowly dripping the casting film liquid onto a smooth glass plate, immersing the glass plate in water bath for soaking after natural volatilization, taking out the film, and drying at room temperature to obtain the polymer hybridization base film;
(2) Preparation of yttrium ion water phase blotting membrane:
combining the base film of step (1) withYttrium chloride (YCl) 3 ) Mixing Itaconic Acid (IA) mixed water solution, stirring for 1h at 60 ℃, continuously introducing nitrogen while stirring, then adding N, N-Methylene Bisacrylamide (MBA) solution dissolved by proper amount of secondary distilled water, ammonium Persulfate (APS) and Sodium Bisulphite (SBS) mixed solution in advance, heating and stirring under the protection of nitrogen, taking out a blotting membrane after the reaction is completed, eluting template ions, and drying at room temperature for standby;
the added mass fraction of PVDF in the step (1) is 50%; the added mass fraction of Cyanex272 is 40%; the addition mass fraction of EVOH is 10%; solid-to-liquid ratio of film component to DMAc 1g:10mL; the reaction condition of heating and stirring is magnetic stirring at 85 ℃ for 24 hours; the film laying height is 400 mu m, the natural volatilization time is 30s, the water bath condition is that the glass plate is immersed in secondary distilled water for 24 hours at room temperature, and the secondary distilled water is replaced for a plurality of times.
2. The method for preparing a rare earth yttrium ion water phase imprinting separation membrane according to claim 1, wherein in the step (2), the mass of the base membrane is 50mg, YCl 3 Molar ratio to IA is 1:3-1:8, a base film and the yttrium chloride YCl 3 The solid-to-liquid ratio of IA, MBA, APS to SBS mixed aqueous solution was kept at 1:600 g/mL; MBA mass is 0.45g, total mass of APS and SBS is 0.09g, mass ratio is 1:2; the reaction condition of heating and stirring is that magnetic stirring is carried out for 3-5 hours at 60 ℃, and nitrogen atmosphere is continuously introduced; the eluent is disodium ethylenediamine tetraacetate EDTA solution with the concentration of 0.2 mol/L.
3. The application of the membrane obtained by the preparation method of the rare earth yttrium ion water-phase imprinting separation membrane in adsorption separation of adjacent heavy rare earth Ho, Y and Er, which is disclosed in claim 1 or 2, realizes high-efficiency extraction separation of Y from Ho and Er.
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