CN115414791B - Surface quaternization modified nanofiltration membrane, preparation and application of surface quaternization modified nanofiltration membrane in separation of magnesium and lithium in salt lake - Google Patents
Surface quaternization modified nanofiltration membrane, preparation and application of surface quaternization modified nanofiltration membrane in separation of magnesium and lithium in salt lake Download PDFInfo
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- CN115414791B CN115414791B CN202210974449.2A CN202210974449A CN115414791B CN 115414791 B CN115414791 B CN 115414791B CN 202210974449 A CN202210974449 A CN 202210974449A CN 115414791 B CN115414791 B CN 115414791B
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- 239000012528 membrane Substances 0.000 title claims abstract description 130
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 75
- 238000000926 separation method Methods 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000005956 quaternization reaction Methods 0.000 title claims abstract description 11
- 229910052744 lithium Inorganic materials 0.000 title abstract description 51
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 50
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title abstract description 36
- 239000011777 magnesium Substances 0.000 title abstract description 36
- 229910052749 magnesium Inorganic materials 0.000 title abstract description 35
- 239000011248 coating agent Substances 0.000 claims abstract description 45
- 238000000576 coating method Methods 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 24
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 17
- 150000003839 salts Chemical class 0.000 claims abstract description 17
- 239000003153 chemical reaction reagent Substances 0.000 claims abstract description 13
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 7
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 49
- 239000000243 solution Substances 0.000 claims description 49
- 239000007864 aqueous solution Substances 0.000 claims description 30
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 claims description 19
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 14
- -1 bistrifluoromethane sulfonimide ion Chemical class 0.000 claims description 11
- 229920002492 poly(sulfone) Polymers 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- 150000001263 acyl chlorides Chemical class 0.000 claims description 8
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- 229920006393 polyether sulfone Polymers 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 5
- 230000002140 halogenating effect Effects 0.000 claims description 4
- 150000002500 ions Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical group [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 125000005843 halogen group Chemical group 0.000 claims description 3
- 150000002367 halogens Chemical group 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- PNGLEYLFMHGIQO-UHFFFAOYSA-M sodium;3-(n-ethyl-3-methoxyanilino)-2-hydroxypropane-1-sulfonate;dihydrate Chemical compound O.O.[Na+].[O-]S(=O)(=O)CC(O)CN(CC)C1=CC=CC(OC)=C1 PNGLEYLFMHGIQO-UHFFFAOYSA-M 0.000 claims description 3
- 239000002152 aqueous-organic solution Substances 0.000 claims description 2
- 150000001805 chlorine compounds Chemical class 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims 1
- 125000001302 tertiary amino group Chemical group 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 14
- 238000010438 heat treatment Methods 0.000 abstract description 10
- 239000000463 material Substances 0.000 abstract description 7
- 239000004952 Polyamide Substances 0.000 abstract description 6
- 229920002647 polyamide Polymers 0.000 abstract description 6
- 230000004048 modification Effects 0.000 abstract description 5
- 238000012986 modification Methods 0.000 abstract description 5
- 229910001425 magnesium ion Inorganic materials 0.000 abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 abstract description 3
- 239000007788 liquid Substances 0.000 description 24
- 239000002585 base Substances 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 238000012360 testing method Methods 0.000 description 14
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 12
- NNZGNZHUGJAKKT-UHFFFAOYSA-M 3-bromopropyl(trimethyl)azanium;bromide Chemical compound [Br-].C[N+](C)(C)CCCBr NNZGNZHUGJAKKT-UHFFFAOYSA-M 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 11
- 239000010410 layer Substances 0.000 description 11
- 230000001965 increasing effect Effects 0.000 description 8
- 229910001629 magnesium chloride Inorganic materials 0.000 description 6
- 230000014759 maintenance of location Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000002608 ionic liquid Substances 0.000 description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 4
- 230000007774 longterm Effects 0.000 description 4
- 229920000867 polyelectrolyte Polymers 0.000 description 4
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 3
- 239000004642 Polyimide Substances 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000012527 feed solution Substances 0.000 description 3
- 239000012466 permeate Substances 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 150000003512 tertiary amines Chemical group 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 239000008151 electrolyte solution Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920000768 polyamine Polymers 0.000 description 2
- 229920000447 polyanionic polymer Polymers 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 150000003335 secondary amines Chemical class 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- QAHSCHGHTZAEQW-UHFFFAOYSA-N C(C1=CC(C(=O)Cl)=CC(C(=O)Cl)=C1)(=O)Cl.N1CCNCC1 Chemical compound C(C1=CC(C(=O)Cl)=CC(C(=O)Cl)=C1)(=O)Cl.N1CCNCC1 QAHSCHGHTZAEQW-UHFFFAOYSA-N 0.000 description 1
- 229910019400 Mg—Li Inorganic materials 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 230000000051 modifying effect Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Classifications
-
- 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
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/027—Nanofiltration
-
- 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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
-
- 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
- B01D69/10—Supported membranes; Membrane supports
-
- 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
-
- 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
- C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
- C22B26/10—Obtaining alkali metals
- C22B26/12—Obtaining lithium
-
- 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
-
- 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
- C22B7/00—Working up raw materials other than ores, e.g. scrap, to produce non-ferrous metals and compounds thereof; Methods of a general interest or applied to the winning of more than two metals
- C22B7/006—Wet processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/16—Membrane materials having positively charged functional groups
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
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- Chemical Kinetics & Catalysis (AREA)
- Manufacturing & Machinery (AREA)
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- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Mechanical Engineering (AREA)
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- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
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- Geochemistry & Mineralogy (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention relates to a surface quaternized modified nanofiltration membrane and application thereof in preparation and separation of magnesium and lithium in salt lakes, and belongs to the technical field of membrane materials. The preparation method comprises the following steps: (1) Preparing a polyethyleneimine-trimesoyl chloride primary layer on a support base film by an interfacial polymerization method; (2) Coating a halogenated reagent on the primary layer, and carrying out quaternization reaction on the halogenated reagent and a polyethyleneimine chain segment in the polyamide primary layer to realize modification; (3) And carrying out heat treatment on the modified membrane to obtain the nanofiltration membrane for extracting lithium from the salt lake. According to the invention, through surface quaternization modification, the positive charge density of the surface of the membrane is enhanced, high flux (-150 LMH) and high selectivity (-20) separation of magnesium and lithium ions are realized, a new preparation thought is provided for nanofiltration membranes for magnesium and lithium separation of salt lakes, and the method has good application prospects.
Description
Technical Field
The invention belongs to the technical field of membrane materials, and particularly relates to a nanofiltration membrane for extracting lithium from a surface quaternized modified salt lake and application of the nanofiltration membrane in preparation and separation of magnesium and lithium from the salt lake.
Background
Lithium is a strategic resource in the aerospace and new energy industries. The lithium consumption in China is first worldwide, and the resource amount is fourth worldwide, and is mainly stored in salt lakes. However, most of salt lakes in China have a magnesium/lithium ratio of hundreds or thousands, are difficult to separate, are difficult to extract lithium efficiently by adopting mature technologies such as a precipitation method, and are limited by international markets due to 80% of lithium dependence import, so that the method is unfavorable for guaranteeing the safety development of key industries such as new energy. In view of the great national demand for lithium, development of new materials and technologies for extracting lithium from salt lakes is urgently needed.
Reducing the ratio of magnesium to lithium in the feed liquid is the key of the salt lake lithium extraction process in China, and the technology of high efficiency and economy is lacking at present. Nanofiltration membranes separate mono-and divalent ions through mechanisms such as electrostatic repulsion and the like, and have important potential of magnesium reduction and lithium enrichment. However, commercial nanofiltration membranes are electronegative, have weak charge rejection to cations, have a magnesium rejection rate of only about 60%, and have low selectivity. The magnesium/lithium selectivity of the positive nanofiltration membrane is better, but the membrane selectivity and the permeability are mutually restricted, the comprehensive performance has a larger distance from the process requirement, and the positive nanofiltration membrane is one of the bottlenecks of the lithium extraction nanofiltration membrane of the salt lake.
CN114377551a discloses a positively charged polyimide nanofiltration membrane for magnesium-lithium separation, a preparation method and application thereof, and in particular discloses a positively charged polyimide nanofiltration membrane for magnesium-lithium separation, which is prepared by completely dissolving polyimide, amino polymer and lithium molecular sieve adsorbent and performing immersion precipitation phase inversion technology. The retention rate of the nanofiltration membrane prepared by the technology on magnesium chloride can reach more than 99%, but the lithium molecular sieve is physically blended into the membrane, has weak interaction with a substrate, and has long-term stability to be further examined.
CN113332860a discloses a preparation and application of a magnesium-lithium separation nanofiltration membrane with high permeation selectivity, and in particular discloses alternately coating polyelectrolyte with opposite charges, namely polycation and polyanion electrolyte solution, on the surface of a porous support membrane; coating the coating to the required layer number, and then carrying out crosslinking treatment; the porous support membrane, namely the base membrane, is made of the following polymer materials, such as polyethersulfone, polysulfone and sulfonated polyethersulfone; coating polyelectrolyte, namely polycation and polyanion electrolyte solution, for 1-10 period layers; coating polyelectrolyte solution on the surface of a base film, and reducing the aperture of the film in a crosslinking mode; however, the layer-by-layer self-assembly requires repeated coating of polyelectrolyte solution, the process is tedious and time-consuming, and in addition, the flux of the prepared nanofiltration membrane is converted into 35.6LMH, which is still to be improved.
CN110026091a discloses an ionic liquid modified positively charged composite nanofiltration membrane and a preparation method thereof, in particular discloses a composite membrane which is prepared by firstly carrying out interfacial polymerization on polyamine and polybasic acyl chloride on a support base membrane to form a primary polyamide layer, and then carrying out amidation reaction on acyl chloride groups remained on the surface of the primary polyamide layer and amino functional ionic liquid. The functional layer is prepared by amidation reaction of amino functionalized ionic liquid and acyl chloride groups on the surface of the primary polyamide layer; the primary polyamide layer is prepared by interfacial polymerization of polyamine and polybasic acyl chloride. However, the nanofiltration membrane in the technical scheme takes piperazine-trimesoyl chloride as a primary layer, the primary layer is negatively charged, the beneficial amplification (positive charge density) brought by the ionic liquid is partially counteracted, and the magnesium-lithium selectivity is only 6.7 after conversion.
In summary, the prior art still lacks a nanofiltration membrane for extracting lithium from a surface quaternized modified salt lake and a preparation method thereof, so as to improve the lithium extraction efficiency of the salt lake.
Disclosure of Invention
Aiming at the defects or improvement demands of the prior art, the invention provides a preparation method of a positively charged nanofiltration membrane for separating magnesium and lithium in a salt lake with high flux and high selectivity, and solves the problems of insufficient positive charge density, low lithium flux, poor magnesium and lithium separation efficiency and the like when the conventional nanofiltration membrane is used for extracting lithium in the salt lake.
According to one aspect of the invention, there is provided a method for preparing a surface quaternized modified nanofiltration membrane, comprising the steps of:
(1) Dissolving polyethylenimine in water, and dissolving trimesoyl chloride in an organic solvent which is not mutually soluble with water; coating the obtained aqueous solution and organic solution on a supporting base film in sequence, and preparing a polyethyleneimine-trimesoyl chloride primary layer through interfacial polymerization reaction;
(2) Coating an aqueous solution of a halogenated reagent containing quaternary ammonium functionality when the amino groups and the acid chlorides are not fully reacted; the halogenating reagent is subjected to quaternization reaction with primary amine, secondary amine or tertiary amine groups on the polyethyleneimine;
(3) And (3) drying the membrane obtained in the step (2) to enable the amino and the acyl chloride to completely react, thus obtaining the positively charged nanofiltration membrane.
Preferably, the structural formula of the halogenated agent is shown in formula 1:
Wherein A is a halogen atom; x is the counter ion of the quaternary ammonium ion; r is at least one of an alkane chain, imidazole, pyridine, bipyridine and an nitrogen heterocycle.
Preferably, wherein a is Cl, br or I; x is halogen, nitrate, tetrafluoroboric acid, hexafluorophosphoric acid or bistrifluoromethane sulfonimide ion.
Preferably, the structural formula of the halogenated reagent is specifically:
Wherein n in formula 2 is a positive integer from 2 to 6.
Preferably, in the step (1), the mass concentration of the polyethyleneimine in the aqueous solution is 0.1-3 wt%, the coating time is 1-10 minutes, the mass concentration of the trimesoyl chloride in the organic solution is 0.1-0.6 wt%, and the coating time is 0.5-2 minutes;
In the step (2), the mass concentration of the halogenated agent in the aqueous solution of the halogenated agent is 0.5-5wt% and the coating time is 0.5-6 hours.
Preferably, the organic solution is n-hexane, cyclohexane, heptane, toluene or chloroform.
Preferably, the support base membrane is a polyvinylidene fluoride membrane, a polysulfone membrane, a polyethersulfone membrane or a polyacrylonitrile membrane.
Preferably, the drying temperature is 30-70 ℃ and the time is 10-30 minutes.
According to another aspect of the invention, there is provided a surface quaternized modified nanofiltration membrane prepared by any one of the methods.
According to another aspect of the invention, the application of the surface quaternized modified nanofiltration membrane is provided for magnesium-lithium separation of salt lakes.
In general, compared with the prior art, the above technical solution conceived by the present invention mainly has the following technical advantages:
(1) The membrane material prepared by the invention has excellent permeation flux (120-150 LMH,0.6 MPa), the retention rate of bivalent magnesium ions is more than 95%, the retention rate of monovalent lithium ions is less than 45%, the selectivity of magnesium and lithium is 20, and the comprehensive separation performance is far better than that of the prior commercial nanofiltration membrane material.
(2) The quaternary ammonium ions are introduced into the surface of the membrane in situ, so that the positive charge density of the surface of the membrane is greatly increased. The quaternary ammonium ions are grafted on the surface of the membrane through covalent bonds, so that the long-term separation stability can be maintained. The test result shows that the membrane can still maintain excellent stability after continuously separating the magnesium-lithium mixed solution for 80 hours.
(3) The positively charged nanofiltration membrane for separating magnesium from lithium in salt lakes, which is prepared by the invention, converts amino groups which are provided with positive charges in the prior art into quaternary ammonium ions to provide positive charges, and overcomes the problem of charge density reduction caused by reversible protonation of amino groups in acid and alkali, thereby obtaining the magnesium-lithium separation nanofiltration membrane material with high stability.
Drawings
FIG. 1 is a schematic diagram of a nanofiltration membrane for separating magnesium and lithium in a salt lake prepared by surface quaternization in example 3 of the present invention;
FIG. 2 is a cross-sectional profile of example 3 (right) and comparative example (left);
FIG. 3 is a zeta potential plot of example 3 and comparative example;
FIG. 4 is a graph of feed liquid separation performance for example 3 for different magnesium to lithium ratios;
FIG. 5 is a long-term stability test for the separation feed solution of example 3 at a magnesium to lithium ratio of 100.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The invention relates to a surface quaternized modified nanofiltration membrane and the preparation and the application of separating magnesium from lithium in salt lakes, which comprises the following steps:
(1) Sequentially coating an aqueous solution of polyethylenimine and an organic solution of trimesic acid chloride on a support base film, and preparing an initial layer of polyethylenimine-trimesic acid chloride by an interfacial polymerization method;
(2) After the normal hexane solution is coated, waiting for a plurality of minutes, coating the aqueous solution of the halogenated reagent, standing for a period of time, splashing the surface solution, and drying at room temperature until no obvious liquid drops exist on the surface;
(3) And (5) placing the membrane in an oven for heat treatment to obtain the positively charged nanofiltration membrane.
In some embodiments, the aqueous solution of polyethylenimine has a mass concentration of 0.1-3 wt%, a coating time of 1-10 minutes, and the trimesoyl chloride in-hexane has a mass concentration of 0.1-0.6 wt%, and a coating time of 0.5-2 minutes.
In some embodiments, the organic solution is a mixture of one or more of n-hexane, cyclohexane, heptane, toluene, or chloroform.
In some embodiments, the halogenating agent comprises a quaternary ammonium functionality having the formula:
Wherein A is a halogen atom (Cl, br, I); x is the counter ion of quaternary ammonium ions, including halogen, nitrate, tetrafluoroboric acid, hexafluorophosphoric acid or bistrifluoromethane sulfonimide ions; r is any one or more of alkane chain, imidazole, pyridine, bipyridine and nitrogen heterocycle.
The structural formula is as follows:
in formula 2, n is a positive integer of 2 to 6.
In some embodiments, the wait time is 1-30 minutes after the application of the n-hexane solution, before the application of the aqueous solution of the halogenated agent.
In some embodiments, the halogenated agent solution has a mass concentration of 0.5 to 5wt%, a pH of 8 to 12, and a coating time of 0.5 to 6 hours;
in some embodiments, the support base membrane is a blend of one or more of polyvinylidene fluoride, polysulfone, polyethersulfone, and polyacrylonitrile membrane.
In some embodiments, the drying is at a temperature of 30-70 ℃ for a time of 10-30 minutes.
Example 1
The surface quaternized modified nanofiltration membrane and the application of the surface quaternized modified nanofiltration membrane in separation from magnesium and lithium in salt lakes are prepared by the following method:
(1) An aqueous solution of polyethyleneimine with the mass concentration of 1wt% is coated on a polysulfone support base film, the coating time is 5 minutes, and the aqueous solution is sprayed. After the surface was free from liquid drops, an n-hexane solution of trimesic acid chloride with a mass concentration of 0.3wt% was applied for 1 minute, and the n-hexane solution was removed by pouring.
(2) After the normal hexane solution is coated, the mixture is waited for 3 minutes, the coating mass concentration is 2wt percent of 3-bromopropyl trimethyl ammonium bromide, the pH is 12, the coating time is 0.5 hour, the surface solution is removed, and the mixture is dried at room temperature until no obvious liquid drops are formed on the surface.
(3) And (3) placing the membrane in a 50 ℃ oven for heat treatment for 10 minutes to obtain the nanofiltration membrane for separating magnesium and lithium in the salt lake.
Example 2
The surface quaternized modified nanofiltration membrane and the application of the surface quaternized modified nanofiltration membrane in separation from magnesium and lithium in salt lakes are prepared by the following method:
(1) An aqueous solution of polyethyleneimine with the mass concentration of 1wt% is coated on a polysulfone support base film, the coating time is 5 minutes, and the aqueous solution is sprayed. After the surface was free from liquid drops, an n-hexane solution of trimesic acid chloride with a mass concentration of 0.3wt% was applied for 1 minute, and the n-hexane solution was removed by pouring.
(2) After the normal hexane solution is coated, the mixture is waited for 20 minutes, the 3-bromopropyl trimethyl ammonium bromide with the mass concentration of 2wt percent is coated, the pH value is 12, the coating time is 0.5 hour, the surface solution is removed, and the mixture is dried at room temperature until no obvious liquid drops are formed on the surface.
(3) And (3) placing the membrane in a 50 ℃ oven for heat treatment for 10 minutes to obtain the nanofiltration membrane for separating magnesium and lithium in the salt lake.
Example 3
The surface quaternized modified nanofiltration membrane and the application of the surface quaternized modified nanofiltration membrane in separation from magnesium and lithium in salt lakes are prepared by the following method:
(1) An aqueous solution of polyethyleneimine with the mass concentration of 1wt% is coated on a polysulfone support base film, the coating time is 5 minutes, and the aqueous solution is sprayed. After the surface was free from liquid drops, an n-hexane solution of trimesic acid chloride with a mass concentration of 0.3wt% was applied for 1 minute, and the n-hexane solution was removed by pouring.
(2) After the normal hexane solution is coated, the mixture is waited for 3 minutes, the coating mass concentration is 2wt percent of 3-bromopropyl trimethyl ammonium bromide, the pH is 12, the coating time is 4 hours, the surface solution is removed, and the mixture is dried at room temperature until no obvious liquid drops are formed on the surface.
(3) And (3) placing the membrane in a 50 ℃ oven for heat treatment for 10 minutes to obtain the nanofiltration membrane for separating magnesium and lithium in the salt lake.
Example 4
The surface quaternized modified nanofiltration membrane and the application of the surface quaternized modified nanofiltration membrane in separation from magnesium and lithium in salt lakes are prepared by the following method:
(1) An aqueous solution of polyethyleneimine with the mass concentration of 1wt% is coated on a polysulfone support base film, the coating time is 5 minutes, and the aqueous solution is sprayed. After the surface was free from liquid drops, an n-hexane solution of trimesic acid chloride with a mass concentration of 0.3wt% was applied for 1 minute, and the n-hexane solution was removed by pouring.
(2) After the normal hexane solution is coated, the mixture is waited for 3 minutes, the coating mass concentration is 0.5wt% of 3-bromopropyl trimethyl ammonium bromide, the pH is 12, the coating time is 0.5 hour, the surface solution is removed, and the mixture is dried at room temperature until no obvious liquid drops are formed on the surface.
(3) And (3) placing the membrane in a 50 ℃ oven for heat treatment for 10 minutes to obtain the nanofiltration membrane for separating magnesium and lithium in the salt lake.
Example 5
The surface quaternized modified nanofiltration membrane and the application of the surface quaternized modified nanofiltration membrane in separation from magnesium and lithium in salt lakes are prepared by the following method:
(1) And (3) coating an aqueous solution of polyethyleneimine with the mass concentration of 1wt% on the polyethersulfone support base film, wherein the coating time is 5 minutes, and pouring the aqueous solution. After the surface was free from liquid drops, an n-hexane solution of trimesic acid chloride with a mass concentration of 0.3wt% was applied for 1 minute, and the n-hexane solution was removed by pouring.
(2) After the normal hexane solution is coated, the mixture is waited for 3 minutes, the coating mass concentration is 2wt percent of 3-bromopropyl trimethyl ammonium bromide, the pH is 12, the coating time is 0.5 hour, the surface solution is removed, and the mixture is dried at room temperature until no obvious liquid drops are formed on the surface.
(3) And (3) placing the membrane in a 50 ℃ oven for heat treatment for 10 minutes to obtain the nanofiltration membrane for separating magnesium and lithium in the salt lake.
Example 6
The surface quaternized modified nanofiltration membrane and the application of the surface quaternized modified nanofiltration membrane in separation from magnesium and lithium in salt lakes are prepared by the following method:
(1) An aqueous solution of polyethyleneimine with the mass concentration of 1wt% is coated on a polysulfone support base film, the coating time is 5 minutes, and the aqueous solution is sprayed. After the surface was free from liquid drops, an n-hexane solution of trimesic acid chloride with a mass concentration of 0.3wt% was applied for 1 minute, and the n-hexane solution was removed by pouring.
(2) After the normal hexane solution is coated, the solution is waited for 3 minutes, the coating mass concentration is 2wt percent of 1-methyl-4- (2-bromoethyl) pyridine iodized salt, the pH is 12, the coating time is 4 hours, the surface solution is removed, and the solution is dried at room temperature until no obvious liquid drops are generated on the surface.
(3) And (3) placing the membrane in a 50 ℃ oven for heat treatment for 10 minutes to obtain the nanofiltration membrane for separating magnesium and lithium in the salt lake.
Example 7
The surface quaternized modified nanofiltration membrane and the application of the surface quaternized modified nanofiltration membrane in separation from magnesium and lithium in salt lakes are prepared by the following method:
(1) An aqueous solution of polyethyleneimine with the mass concentration of 1wt% is coated on a polysulfone support base film, the coating time is 5 minutes, and the aqueous solution is sprayed. After the surface was free from liquid drops, an n-hexane solution of trimesic acid chloride with a mass concentration of 0.3wt% was applied for 1 minute, and the n-hexane solution was removed by pouring.
(2) After the normal hexane solution is coated, the mixture is waited for 3 minutes, the coating mass concentration is 2wt percent of 3-methyl-1- (2-bromoethyl) imidazole iodized salt, the pH is 12, the coating time is 4 hours, the surface solution is removed, and the mixture is dried at room temperature until no obvious liquid drops are generated on the surface.
(3) And (3) placing the membrane in a 50 ℃ oven for heat treatment for 10 minutes to obtain the nanofiltration membrane for separating magnesium and lithium in the salt lake.
Comparative example
(1) An aqueous solution of polyethyleneimine with the mass concentration of 1wt% is coated on a polysulfone support base film, the coating time is 5 minutes, and the aqueous solution is sprayed. After the surface was free from liquid drops, an n-hexane solution of trimesic acid chloride with a mass concentration of 0.3wt% was applied for 1 minute, and the n-hexane solution was removed by pouring.
(2) And (3) placing the membrane in a 50 ℃ oven for heat treatment for 10 minutes to obtain the positively charged nanofiltration membrane for separating magnesium and lithium in the salt lake.
Table 1 example parameter table
Test examples and comparative examples
Nanofiltration performance tests were performed on nanofiltration membranes prepared in examples 1 to 7 and comparative examples.
The nanofiltration performance test method is as follows. In the invention, the flux (J), the retention rate (R) and the magnesium-lithium selectivity (S) are two important parameters for measuring the magnesium-lithium separation performance of the nanofiltration membrane. The result of the invention is that the test is carried out by a cross-flow nanofiltration instrument, and the test conditions are as follows: 1000ppm of magnesium chloride solution, the test pressure and the test temperature are respectively 0.6MPa and 30 ℃. When the magnesium-lithium separation performance is tested, the total salt concentration of magnesium chloride and lithium chloride is fixed to be 2000ppm, the magnesium-lithium ratio of the feed liquid is adjusted to be 1,5,10,20,50,100 respectively, and the test pressure and the test temperature are respectively 0.6MPa and 30 ℃.
The membrane flux calculation formula is as follows:
Wherein J is membrane flux (LMH), S is membrane effective test area (m 2), t is operation time (S), and V is volume (L) of permeate liquid in t time.
The membrane rejection rate was calculated as follows:
wherein, C f and C p are respectively the solute concentration of the feed solution and the permeate solution. The magnesium chloride concentration was determined by a conductivity meter.
The magnesium lithium selectivity calculation formula is as follows:
Wherein, C f/Mg,Cf/Li and C p/Mg,Cp/Li are the concentration of magnesium ions and lithium ions in the feed liquid and the permeate liquid respectively, and are obtained through an inductive coupling plasma test.
The test results are shown in table 2 below.
Table 2 test results table
The reaction mechanism of the present invention is exemplified in example 3 and comparative example. FIG. 1 is a schematic representation of the interfacial reaction and surface grafting of example 3 of the present invention. FIG. 2 is a cross-sectional profile of example 3 (right) and comparative example (left). FIG. 3 is a zeta potential plot of example 3 and comparative example. FIG. 4 is a graph of feed liquid separation performance for example 3 for different magnesium to lithium ratios. FIG. 5 is a long-term stability test for the separation feed solution of example 3 at a magnesium to lithium ratio of 100.
As can be seen from FIG. 1, a large amount of unreacted primary, secondary and tertiary amine groups remain on the surface of the as-prepared polyethyleneimine-trimesoyl chloride film. When coated with a halogenating agent (for example, 3-bromopropyl trimethylammonium bromide), the 3-bromopropyl trimethylammonium bromide reacts with amine groups in a quaternization reaction and grafts onto the membrane surface. When reacted with tertiary amines, quaternary ammonium ions may be further formed to increase the positive charge density of the membrane surface and enhance the rejection of divalent cations (e.g., magnesium ions).
In addition, interfacial polymerization is a dynamic reaction that proceeds continuously, and the amino groups and acid chlorides have not yet reacted completely just after the preparation of the polyethyleneimine-trimesoyl chloride primary membrane. At this time, the alkaline aqueous solution of halogenated reagent is coated to rapidly promote the hydrolysis of acyl chloride groups, so that the reactive acyl chloride groups are greatly reduced, the overall crosslinking degree of the membrane is reduced, and the membrane is more loose, thereby increasing the permeation flux of the membrane.
As can be seen from FIG. 2, the film thickness increased from 82nm to 112nm after modification with 3-bromopropyl trimethylammonium bromide. On the one hand, this is due to the grafting of 3-bromopropyl trimethylammonium bromide to the membrane surface, increasing the membrane thickness; on the other hand, aqueous alkaline solutions can loosen the polyamide swelling, further increasing the film thickness.
As can be seen from FIG. 3, the isoelectric point of the membrane increased from 7.1 to 9.6 after modification with 3-bromopropyl trimethylammonium bromide, further indicating an enhancement of the positive charge on the membrane surface.
As can be seen from FIG. 4, the flux of the positively charged nanofiltration membrane prepared in example 3 was 140-155 LMH when the positively charged nanofiltration membrane was separated from the mixed solution with different magnesium-lithium ratios. With the increase of the magnesium-lithium ratio of the feed liquid, the retention rate of magnesium chloride is maintained at 97 percent, the retention rate of lithium chloride is gradually reduced to 23.6 percent, and the magnesium-lithium selectivity is maximum when the magnesium-lithium ratio is 100 and reaches 20.8. The performance of the positively charged nanofiltration membrane prepared in the example 3 is far superior to that of the comparative example and the existing commercial nanofiltration membrane by combining flux and magnesium lithium selectivity analysis, and the method has an industrial prospect.
As can be seen from FIG. 5, the positively charged nanofiltration membrane prepared in example 3 was stable at-140 LMH flux and-20 Mg-Li selectivity in a continuous 80h operation. The 3-bromopropyl trimethyl ammonium bromide is grafted on the surface of the membrane through quaternization reaction, and belongs to covalent bond connection, so that the membrane can not fall off in long-time test, and has good stability.
Further analysis of the test results of Table 2 shows that when compared with the comparative example, the membrane flux is significantly improved, up to 152LMH, and the magnesium chloride rejection rate is >95%, the magnesium lithium selectivity is >15, and the overall performance is far better than that of the comparative example. With the increase of the concentration and the coating time of the halogenated reagent, the halogenated reagent grafted to the surface of the membrane is increased, and the more obvious the modifying effect is, the membrane flux is increased. In addition, the preparation method is applicable to various substrate materials.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (8)
1. The preparation method of the surface quaternized modified nanofiltration membrane is characterized by comprising the following steps of:
(1) Dissolving polyethylenimine in water, and dissolving trimesoyl chloride in an organic solvent which is not mutually soluble with water; coating the obtained aqueous solution and organic solution on a supporting base film in sequence, and preparing a polyethyleneimine-trimesoyl chloride primary layer through interfacial polymerization reaction;
(2) Coating an aqueous solution of a halogenated reagent containing quaternary ammonium functionality when the amino groups and the acid chlorides are not fully reacted; the halogenating reagent is subjected to quaternization reaction with primary amine, secondary amine or tertiary amine groups on the polyethyleneimine;
(3) Drying the membrane obtained in the step (2) to enable amino and acyl chloride to completely react, thus obtaining a positively charged nanofiltration membrane;
the structural formula of the halogenated reagent is shown in formula 1:
wherein A is a halogen atom; x is the counter ion of the quaternary ammonium ion; r is at least one of an alkane chain, imidazole, pyridine, bipyridine and an nitrogen heterocycle; wherein A is Cl, br or I; x is halogen, nitrate, tetrafluoroboric acid, hexafluorophosphoric acid or bistrifluoromethane sulfonimide ion;
the mass concentration of the polyethyleneimine in the aqueous solution is 0.1-3wt%;
The mass concentration of the trimesic acid chloride in the organic solution is 0.1-0.6wt%.
2. The method for preparing a surface quaternized modified nanofiltration membrane according to claim 1, wherein the halogenated reagent has a structural formula:
Wherein n in formula 2 is a positive integer from 2 to 6.
3. The method for preparing a surface quaternized modified nanofiltration membrane as defined in claim 1, wherein in the step (1), the coating time of the aqueous solution is 1 to 10 minutes, and the coating time of the organic solution is 0.5 to 2 minutes;
In the step (2), the mass concentration of the halogenated agent in the aqueous solution of the halogenated agent is 0.5-5wt% and the coating time is 0.5-6 hours.
4. The method for preparing a surface quaternized modified nanofiltration membrane according to claim 1, wherein the organic solution is n-hexane, cyclohexane, heptane, toluene or chloroform.
5. The method for preparing a surface quaternized modified nanofiltration membrane as defined in claim 1, wherein the support base membrane is a polyvinylidene fluoride membrane, a polysulfone membrane, a polyethersulfone membrane or a polyacrylonitrile membrane.
6. The method for preparing a surface quaternized modified nanofiltration membrane as defined in claim 1, wherein the drying temperature is 30-70 ℃ and the time is 10-30 minutes.
7. The surface quaternized modified nanofiltration membrane prepared by the method of any one of claims 1-6.
8. The use of a surface quaternized modified nanofiltration membrane as defined in claim 7 for magnesium-lithium separation in salt lakes.
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