CN115414791A - Surface quaternization modified nanofiltration membrane and application of surface quaternization modified nanofiltration membrane in preparation of surface quaternization modified nanofiltration membrane and separation of surface quaternization modified nanofiltration membrane from magnesium and lithium in salt lake - Google Patents
Surface quaternization modified nanofiltration membrane and application of surface quaternization modified nanofiltration membrane in preparation of surface quaternization modified nanofiltration membrane and separation of surface quaternization modified nanofiltration membrane from magnesium and lithium in salt lake Download PDFInfo
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- CN115414791A CN115414791A CN202210974449.2A CN202210974449A CN115414791A CN 115414791 A CN115414791 A CN 115414791A CN 202210974449 A CN202210974449 A CN 202210974449A CN 115414791 A CN115414791 A CN 115414791A
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- 239000012528 membrane Substances 0.000 title claims abstract description 155
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 85
- 238000005956 quaternization reaction Methods 0.000 title claims abstract description 40
- 238000000926 separation method Methods 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 229910052744 lithium Inorganic materials 0.000 title abstract description 44
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 title abstract description 42
- 239000011777 magnesium Substances 0.000 title abstract description 33
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title abstract description 28
- 229910052749 magnesium Inorganic materials 0.000 title abstract description 28
- 239000011248 coating agent Substances 0.000 claims abstract description 41
- 238000000576 coating method Methods 0.000 claims abstract description 41
- 238000000034 method Methods 0.000 claims abstract description 18
- 229920002873 Polyethylenimine Polymers 0.000 claims abstract description 17
- 239000000243 solution Substances 0.000 claims description 65
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 58
- GCICAPWZNUIIDV-UHFFFAOYSA-N lithium magnesium Chemical compound [Li].[Mg] GCICAPWZNUIIDV-UHFFFAOYSA-N 0.000 claims description 22
- 238000001035 drying Methods 0.000 claims description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000003795 chemical substances by application Substances 0.000 claims description 16
- 230000002140 halogenating effect Effects 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 14
- 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
- 229920002492 poly(sulfone) Polymers 0.000 claims description 11
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 claims description 9
- -1 sulfonyl imide ion Chemical class 0.000 claims description 8
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- 238000012695 Interfacial polymerization Methods 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
- 229920006393 polyether sulfone Polymers 0.000 claims description 6
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 6
- 150000001263 acyl chlorides Chemical class 0.000 claims description 5
- 150000002500 ions Chemical class 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 4
- XPDWGBQVDMORPB-UHFFFAOYSA-N Fluoroform Chemical compound FC(F)F XPDWGBQVDMORPB-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 239000003960 organic solvent Substances 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
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical group 0.000 claims description 3
- 125000003277 amino group 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
- 229910052740 iodine Inorganic materials 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
- YPJKMVATUPSWOH-UHFFFAOYSA-N nitrooxidanyl Chemical group [O][N+]([O-])=O YPJKMVATUPSWOH-UHFFFAOYSA-N 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 13
- 238000010438 heat treatment Methods 0.000 abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 8
- 230000004048 modification Effects 0.000 abstract description 8
- 238000012986 modification Methods 0.000 abstract description 8
- 239000000463 material Substances 0.000 abstract description 7
- 239000004952 Polyamide Substances 0.000 abstract description 6
- 229920002647 polyamide Polymers 0.000 abstract description 6
- 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
- 238000006116 polymerization reaction Methods 0.000 abstract 1
- 210000004379 membrane Anatomy 0.000 description 64
- 239000007788 liquid Substances 0.000 description 20
- 239000002585 base Substances 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 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 9
- 238000000605 extraction Methods 0.000 description 6
- 229910001629 magnesium chloride Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 239000012527 feed solution Substances 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 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
- 230000014759 maintenance of location 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
- 238000004364 calculation method Methods 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 229920001721 polyimide Polymers 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 150000003512 tertiary amines Chemical group 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- 238000007112 amidation reaction Methods 0.000 description 2
- 210000002469 basement membrane Anatomy 0.000 description 2
- 230000008901 benefit Effects 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
- 229940021013 electrolyte solution Drugs 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
- 239000000203 mixture Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 239000012466 permeate Substances 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
- 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
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 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
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 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
- 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
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
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- 229920000642 polymer Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 239000011148 porous 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
- 238000006467 substitution reaction Methods 0.000 description 1
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- 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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- 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
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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
- B01D2325/16—Membrane materials having positively charged functional groups
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Abstract
The invention relates to a surface quaternization modified nanofiltration membrane and application of the surface quaternization modified nanofiltration membrane in preparation of a nanofiltration membrane and separation of magnesium and lithium in a salt lake, 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 supporting base film by an interface polymerization method; (2) Coating a halogenated reagent on the primary layer, and performing 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 on the surface of the membrane is enhanced, the separation of magnesium and lithium ions with high flux (150 LMH) and high selectivity (20) is realized, a new preparation idea is provided for a nanofiltration membrane for separating magnesium and lithium in a salt lake, and the method has a good application prospect.
Description
Technical Field
The invention belongs to the technical field of membrane materials, and particularly relates to a nanofiltration membrane for surface quaternization modification of salt lake lithium extraction and an application of the nanofiltration membrane in preparation of a membrane for separating magnesium and lithium from salt lake.
Background
Lithium is a strategic resource in industries such as aerospace and new energy. China's lithium consumption is the first worldwide and the fourth worldwide, and is stored mainly in salt lakes. However, the magnesium/lithium ratio of most salt lakes in China is over hundreds or even thousands, the separation difficulty is high, and the high-efficiency lithium extraction by mature technologies such as a precipitation method is difficult, so that 80% of lithium is imported depending on the international market, and the safety development of key industries such as new energy sources is not guaranteed. In order to meet the national great demand for lithium, the development of new materials and technologies for extracting lithium from salt lakes is urgently needed.
The reduction of the magnesium/lithium ratio in the feed liquid is the key of the lithium extraction process in the salt lake in China, and an efficient and economic technology is lacked at present. The nanofiltration membrane separates the mono-valence/divalent ions through mechanisms such as electrostatic repulsion and the like, and has important potential of reducing magnesium and enriching lithium. However, the commercial nanofiltration membrane is electronegative, has weak charge repulsion on cations, has a magnesium rejection rate of only about 60 percent, and has low selectivity. The magnesium/lithium selectivity of the positive nanofiltration membrane is better, but the membrane selectivity and the permeability are restricted with each other, and the comprehensive performance has a larger distance from the process requirement, so that the positive nanofiltration membrane is one of the bottlenecks of the salt lake lithium extraction nanofiltration membrane.
CN114377551A discloses a positively charged polyimide nanofiltration membrane for magnesium-lithium separation and a preparation method and application thereof, and particularly discloses a positively charged polyimide nanofiltration membrane for magnesium-lithium separation, which is prepared by completely dissolving polyimide, amino polymers and a lithium molecular sieve adsorbent and by an immersion precipitation phase conversion technology. The rejection rate of the nanofiltration membrane prepared by the technology to magnesium chloride can reach more than 99%, but the lithium molecular sieve is physically blended into the membrane, the interaction with the substrate is weak, and the long-term stability is yet to be further investigated.
CN113332860A discloses preparation and application of a high-osmotic-selectivity magnesium-lithium separation nanofiltration membrane, and particularly discloses alternately coating polyelectrolytes with opposite charges, namely polycation and polyanion electrolyte solutions, on the surface of a porous support membrane; coating to the required number of layers and then carrying out crosslinking treatment; the porous support membrane, namely the base membrane, is made of the following high polymer materials, namely polyether sulfone, polysulfone and sulfonated polyether sulfone; coating polyelectrolyte, namely polycation and polyanion electrolyte solution for 1-10 periodic layers; after the polyelectrolyte solution is coated on the surface of the basement membrane, the pore diameter of the membrane is reduced in a cross-linking mode; however, the layer-by-layer self-assembly requires repeated coating of the polyelectrolyte solution, the process is tedious and time-consuming, and the flux of the prepared nanofiltration membrane is converted into 35.6LMH, which still needs to be improved.
CN110026091A discloses an ionic liquid modified positively charged composite nanofiltration membrane and a preparation method thereof, and particularly discloses a composite membrane prepared by performing interfacial polymerization on polyamine and polyacyl chloride on a supporting basement membrane to form a primary polyamide layer, and then performing amidation reaction on residual acyl chloride groups on the surface of the primary polyamide layer and amino functionalized ionic liquid. The functional layer is prepared by amidation reaction of amino functionalized ionic liquid and acyl chloride group on the surface of nascent polyamide layer; the nascent polyamide layer is prepared in the interfacial polymerization process of polyamine and polyacyl chloride. However, the nanofiltration membrane in the technical scheme takes piperazine-trimesoyl chloride as a primary layer, the primary layer is negatively charged, beneficial amplification (positive charge density) brought by ionic liquid is partially offset, and the selectivity of magnesium and lithium is only 6.7 after conversion.
In conclusion, the prior art still lacks a nanofiltration membrane for surface quaternization modification of salt lake lithium extraction and a preparation method thereof, so as to improve the efficiency of salt lake lithium extraction.
Disclosure of Invention
Aiming at the defects or improvement requirements of the prior art, the invention provides a preparation method of a high-flux and high-selectivity positively-charged nanofiltration membrane for separating magnesium from lithium in a salt lake, and solves the problems of insufficient positive charge density, low lithium flux, poor magnesium-lithium separation efficiency and the like when the conventional nanofiltration membrane is used for extracting lithium from the salt lake.
According to one aspect of the invention, a preparation method of a surface quaternization modified nanofiltration membrane is provided, which comprises the following steps:
(1) Dissolving polyethyleneimine in water, and dissolving trimesoyl chloride in an organic solvent, wherein the organic solvent is immiscible with water; sequentially coating the obtained aqueous solution and organic solution on a supporting base membrane, and preparing a polyethyleneimine-trimesoyl chloride primary layer through interfacial polymerization;
(2) Applying an aqueous solution of a halogenating agent containing a quaternary ammonium functionality when the amino and acid chloride have not reacted to completion; the halogenating agent and primary amine, secondary amine or tertiary amine groups on the polyethyleneimine are subjected to quaternization reaction;
(3) And (3) drying the membrane obtained in the step (2) to ensure that the amino and acyl chloride completely react to obtain the positively charged nanofiltration membrane.
Preferably, the halogenating agent has a formula as shown in formula 1:
wherein A is a halogen atom; x is a counter ion of a quaternary ammonium ion; r is at least one of alkane chain, imidazole, pyridine, bipyridine and azacyclo.
Preferably, wherein a is Cl, br or I; x is halogen, nitrate radical, tetrafluoroboric acid, hexafluorophosphoric acid or bis (trifluoromethane) sulfonyl imide ion.
Preferably, the structural formula of the halogenating agent 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 reagent in the aqueous solution of the halogenated reagent 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 supporting 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 drying time is 10-30 minutes.
According to another aspect of the invention, the surface-quaternized modified nanofiltration membrane prepared by any one of the methods is provided.
According to another aspect of the invention, the application of the surface quaternization modified nanofiltration membrane is provided, and the surface quaternization modified nanofiltration membrane is used for separating magnesium and lithium in a salt lake.
Generally, 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 (120-150LMH, 0.6 MPa), the retention rate of divalent 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 superior to that of the existing commercial nanofiltration membrane material.
(2) In the invention, 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) According to the positively charged nanofiltration membrane for separating magnesium and lithium in the salt lake, which is prepared by the invention, the amino group which traditionally provides positive charge is converted into quaternary ammonium ions to provide positive charge, so that the problem of charge density reduction caused by reversible protonation of amino in acid and alkali is solved, and the magnesium and lithium separation nanofiltration membrane material with high stability is obtained.
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 topographical view of the sections of example 3 (right) and comparative example (left);
FIG. 3 is a zeta potential plot of example 3 and a comparative example;
FIG. 4 shows the separation performance of the feed solution of example 3 for different Mg/Li ratios;
FIG. 5 is a long term stability test of example 3 with a separated feed solution Mg/Li ratio of 100.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and do not limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention relates to a surface quaternization modified nanofiltration membrane and application of the surface quaternization modified nanofiltration membrane in preparation of a salt lake magnesium-lithium separation membrane, which comprises the following steps:
(1) Sequentially coating a polyethyleneimine aqueous solution and an organic solution of trimesoyl chloride on a supporting base membrane, and preparing a polyethyleneimine-trimesoyl chloride primary layer by an interfacial polymerization method;
(2) After the n-hexane solution is coated, waiting for several 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 (3) placing the membrane in an oven for heat treatment to obtain the positively charged nanofiltration membrane.
In some embodiments, the mass concentration of the polyethyleneimine aqueous solution is 0.1 to 3wt%, the coating time is 1 to 10 minutes, the mass concentration of the n-hexane solution of trimesoyl chloride is 0.1 to 0.6wt%, and the coating time is 0.5 to 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:
in the formula, A is halogen atom (Cl, br, I); x is a counter ion of a quaternary ammonium ion, including a halogen, a nitrate, tetrafluoroboric acid, hexafluorophosphoric acid or bistrifluoromethanesulfonylimide ion; r is any one or more of alkane chain, imidazole, pyridine, bipyridine and azacycle.
As shown in the following structural formula:
in the formula 2, n is a positive integer of 2-6.
In some embodiments, after the n-hexane solution is applied, the time is allowed to wait for 1 to 30 minutes before applying the aqueous solution of the halogenating agent.
In some embodiments, the halogenating 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 supporting base membrane is a blend of one or more of polyvinylidene fluoride, polysulfone, polyethersulfone, and polyacrylonitrile membranes.
In some embodiments, the drying is at a temperature of 30-70 ℃ for a time of 10-30 minutes.
Example 1
A surface quaternization modified nanofiltration membrane and an application of the surface quaternization modified nanofiltration membrane in preparation of a salt lake magnesium-lithium separation membrane are prepared by the following steps:
(1) Coating a polyethyleneimine water solution with the mass concentration of 1wt% on a polysulfone supporting base film for 5 minutes, and splashing the water solution. After no liquid drop exists on the surface, a n-hexane solution of trimesoyl chloride with the mass concentration of 0.3wt% is coated for 1 minute, and the n-hexane solution is splashed.
(2) After the n-hexane solution is coated, waiting for 3 minutes, coating 3-bromopropyltrimethylammonium bromide with the mass concentration of 2wt%, wherein the pH value is 12, the coating time is 0.5 hour, splashing the surface solution, and drying at room temperature until no obvious liquid drops exist on the surface.
(3) And (3) placing the membrane in a 50 ℃ drying oven for heat treatment for 10 minutes to obtain the nanofiltration membrane for separating magnesium from lithium in the salt lake.
Example 2
A surface quaternization modified nanofiltration membrane and an application of the surface quaternization modified nanofiltration membrane in preparation of a salt lake magnesium-lithium separation membrane are prepared by the following steps:
(1) Coating a polyethyleneimine water solution with the mass concentration of 1wt% on the polysulfone supporting base membrane for 5 minutes, and splashing the water solution. After no liquid drop exists on the surface, a n-hexane solution of trimesoyl chloride with the mass concentration of 0.3wt% is coated for 1 minute, and the n-hexane solution is splashed.
(2) After the n-hexane solution is coated, waiting for 20 minutes, coating 3-bromopropyltrimethylammonium bromide with the mass concentration of 2wt%, with the pH of 12 and the coating time of 0.5 hour, splashing the surface solution, and drying at room temperature until no obvious liquid drops exist on the surface.
(3) And (3) placing the membrane in a 50 ℃ drying oven for heat treatment for 10 minutes to obtain the nanofiltration membrane for separating magnesium from lithium in the salt lake.
Example 3
A surface quaternization modified nanofiltration membrane and application of the surface quaternization modified nanofiltration membrane in preparation of a salt lake magnesium-lithium separation membrane are prepared by the following steps:
(1) Coating a polyethyleneimine water solution with the mass concentration of 1wt% on a polysulfone supporting base film for 5 minutes, and splashing the water solution. After no liquid drop exists on the surface, a n-hexane solution of trimesoyl chloride with the mass concentration of 0.3wt% is coated for 1 minute, and the n-hexane solution is splashed.
(2) After the n-hexane solution is coated, waiting for 3 minutes, coating 3-bromopropyltrimethylammonium bromide with the mass concentration of 2wt%, wherein the pH value is 12, the coating time is 4 hours, splashing the surface solution, and drying at room temperature until no obvious liquid drops exist on the surface.
(3) And (3) placing the membrane in a 50 ℃ oven for heat treatment for 10 minutes to prepare the nanofiltration membrane for separating magnesium and lithium in the salt lake.
Example 4
A surface quaternization modified nanofiltration membrane and an application of the surface quaternization modified nanofiltration membrane in preparation of a salt lake magnesium-lithium separation membrane are prepared by the following steps:
(1) Coating a polyethyleneimine water solution with the mass concentration of 1wt% on a polysulfone supporting base film for 5 minutes, and splashing the water solution. After no liquid drop exists on the surface, a n-hexane solution of trimesoyl chloride with the mass concentration of 0.3wt% is coated for 1 minute, and the n-hexane solution is splashed.
(2) After the n-hexane solution is coated, waiting for 3 minutes, coating 3-bromopropyltrimethylammonium bromide with the mass concentration of 0.5wt%, with the pH of 12 and the coating time of 0.5 hour, splashing the surface solution, and drying at room temperature until no obvious liquid drops exist on the surface.
(3) And (3) placing the membrane in a 50 ℃ oven for heat treatment for 10 minutes to prepare the nanofiltration membrane for separating magnesium and lithium in the salt lake.
Example 5
A surface quaternization modified nanofiltration membrane and an application of the surface quaternization modified nanofiltration membrane in preparation of a salt lake magnesium-lithium separation membrane are prepared by the following steps:
(1) Coating a polyethyleneimine water solution with the mass concentration of 1wt% on a polyether sulfone support base membrane for 5 minutes, and splashing a water solution. After no liquid drop exists on the surface, a n-hexane solution of trimesoyl chloride with the mass concentration of 0.3wt% is coated for 1 minute, and the n-hexane solution is splashed.
(2) After the n-hexane solution is coated, waiting for 3 minutes, coating 3-bromopropyltrimethylammonium bromide with the mass concentration of 2wt%, wherein the pH value is 12, the coating time is 0.5 hour, splashing the surface solution, and drying at room temperature until no obvious liquid drops exist on the surface.
(3) And (3) placing the membrane in a 50 ℃ drying oven for heat treatment for 10 minutes to obtain the nanofiltration membrane for separating magnesium from lithium in the salt lake.
Example 6
A surface quaternization modified nanofiltration membrane and application of the surface quaternization modified nanofiltration membrane in preparation of a salt lake magnesium-lithium separation membrane are prepared by the following steps:
(1) Coating a polyethyleneimine water solution with the mass concentration of 1wt% on a polysulfone supporting base film for 5 minutes, and splashing the water solution. After no liquid drop exists on the surface, a n-hexane solution of trimesoyl chloride with the mass concentration of 0.3wt% is coated for 1 minute, and the n-hexane solution is splashed.
(2) After the n-hexane solution is coated, waiting for 3 minutes, coating 1-methyl-4- (2-bromoethyl) pyridine iodine salt with the mass concentration of 2wt%, adjusting the pH to 12, coating for 4 hours, splashing the surface solution, and drying at room temperature until no obvious liquid drops exist on the surface.
(3) And (3) placing the membrane in a 50 ℃ drying oven for heat treatment for 10 minutes to obtain the nanofiltration membrane for separating magnesium from lithium in the salt lake.
Example 7
A surface quaternization modified nanofiltration membrane and an application of the surface quaternization modified nanofiltration membrane in preparation of a salt lake magnesium-lithium separation membrane are prepared by the following steps:
(1) Coating a polyethyleneimine water solution with the mass concentration of 1wt% on the polysulfone supporting base membrane for 5 minutes, and splashing the water solution. After no liquid drop exists on the surface, a n-hexane solution of trimesoyl chloride with the mass concentration of 0.3wt% is coated for 1 minute, and the n-hexane solution is splashed.
(2) After the n-hexane solution is coated, waiting for 3 minutes, coating 3-methyl-1- (2-bromoethyl) imidazole iodonium salt with the mass concentration of 2wt%, wherein the pH value is 12, the coating time is 4 hours, splashing the surface solution, and drying at room temperature until no obvious liquid drops exist on the surface.
(3) And (3) placing the membrane in a 50 ℃ oven for heat treatment for 10 minutes to prepare the nanofiltration membrane for separating magnesium and lithium in the salt lake.
Comparative example
(1) Coating a polyethyleneimine water solution with the mass concentration of 1wt% on the polysulfone supporting base membrane for 5 minutes, and splashing the water solution. After no liquid drop exists on the surface, a n-hexane solution of trimesoyl chloride with the mass concentration of 0.3wt% is coated for 1 minute, and the n-hexane solution is splashed.
(2) And (3) placing the membrane in a 50 ℃ drying oven for heat treatment for 10 minutes to obtain the positively charged nanofiltration membrane for separating magnesium from lithium in the salt lake.
Table 1 table of parameters of examples
Test examples and comparative examples
Nanofiltration membranes prepared in examples 1 to 7 and comparative examples were subjected to nanofiltration performance tests.
The nanofiltration performance test method is as follows. In the invention, the flux (J), the rejection 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 cross-flow nanofiltration instrument is used for testing, and the testing conditions are as follows: 1000ppm of magnesium chloride solution, a test pressure and temperature of 0.6MPa and 30 ℃ respectively. When testing the separation performance of magnesium and lithium, the total salt concentration of fixed magnesium chloride and lithium chloride is 2000ppm, the magnesium-lithium ratio of the feeding liquid is adjusted to be 1,5,10,20,50 and 100 respectively, and the testing pressure and temperature are 0.6MPa and 30 ℃ respectively.
The membrane flux calculation formula is as follows:
wherein J is membrane flux (LMH), and S is effective test area (m) 2 ) T is the operation time(s), and V is the volume (L) of the permeation solution during the time t.
The membrane rejection calculation formula is as follows:
wherein, C f And C p Feed solution and permeate solution solute concentrations, respectively. The magnesium chloride concentration is determined by a conductivity meter.
The magnesium-lithium selectivity calculation formula is as follows:
wherein, C f/Mg ,C f/Li And C p/Mg ,C p/Li The concentrations of magnesium ions and lithium ions in the feed solution and the permeate solution are respectively obtained by 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 by 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 topographical view of the cross-sections of example 3 (right) and comparative example (left). FIG. 3 is a zeta potential plot of example 3 and a comparative example. FIG. 4 shows the feed liquid separation performance of example 3 for different Mg/Li ratios. FIG. 5 is a long term stability test of example 3 with a separated feed solution Mg/Li ratio of 100.
As is clear from FIG. 1, a large number of unreacted primary, secondary and tertiary amine groups remained on the surface of the freshly prepared polyethyleneimine-trimesoyl chloride membrane. When a halogenating agent (taking 3-bromopropyltrimethylammonium bromide as an example) is coated, 3-bromopropyltrimethylammonium bromide can perform quaternization reaction with amino groups and be grafted on the surface of the membrane. When reacting with tertiary amines, quaternary ammonium ions can be further formed, increasing the positive charge density of the membrane surface and enhancing the rejection of divalent cations (such as magnesium ions).
In addition, interfacial polymerization is a dynamic reaction that proceeds continuously, and the amino and acyl chlorides have not reacted completely immediately after the polyethyleneimine-trimesoyl chloride nascent membrane is prepared. At this time, the application of the alkaline aqueous solution of the halogenating agent rapidly promotes the hydrolysis of the acid chloride groups, so that the reactive acid chloride groups are greatly reduced, the crosslinking degree of the whole membrane is reduced, the membrane is looser, and the permeation flux of the membrane is increased.
As can be seen from FIG. 2, the film thickness increased from 82nm to 112nm after modification with 3-bromopropyltrimethylammonium bromide. On the one hand, this is due to the grafting of 3-bromopropyltrimethylammonium bromide to the membrane surface, increasing the membrane thickness; on the other hand, the alkaline aqueous solution causes the polyamide to swell and loosen, further increasing the film thickness.
As can be seen from FIG. 3, the isoelectric point of the membrane was increased from 7.1 to 9.6 after modification with 3-bromopropyltrimethylammonium bromide, further indicating an increase in the positive charge on the surface of the membrane.
As can be seen from fig. 4, the flux of the positively charged nanofiltration membrane prepared in example 3 was 140 to 155LMH when it was separated from mixed solutions of different mg/li ratios. Along with the increase of the magnesium-lithium ratio of the feeding 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 selectivity of magnesium and lithium is the maximum when the magnesium-lithium ratio is 100 and reaches 20.8. By comprehensive flux and magnesium-lithium selectivity analysis, the performance of the positively charged nanofiltration membrane prepared in example 3 is far superior to that of a comparative example and the existing commercial nanofiltration membrane, and the method has an industrial prospect.
As can be seen from FIG. 5, the flux of the positively charged nanofiltration membrane prepared in example 3 is stabilized at 140LMH and the selectivity of Mg and Li is 20 in 80 hours of continuous operation. 3-bromopropyltrimethylammonium bromide is grafted on the surface of the membrane through quaternization, belongs to covalent bond connection, and therefore cannot fall off in a long-time test, and the membrane has good stability.
Further analyzing the test results in table 2, it can be seen that, compared with the comparative example, after the halogenated reagent is adopted for treatment, the membrane flux is significantly improved, and can reach 152LMH at most, meanwhile, the magnesium chloride rejection rate is greater than 95%, the magnesium-lithium selectivity is greater than 15, and the comprehensive performance is far better than that of the comparative example. With the increase of the concentration of the halogenated reagent and the coating time, the halogenated reagent grafted to the surface of the membrane is increased, the more obvious the modification effect is, and the flux of the membrane is increased. In addition, the preparation method is applicable to various substrate materials.
It will be understood by those skilled in the art that the foregoing is only an exemplary embodiment of the present invention, and is not intended to limit the invention to the particular forms disclosed, since various modifications, substitutions and improvements within the spirit and scope of the invention are possible and within the scope of the appended claims.
Claims (10)
1. A preparation method of a surface quaternization modified nanofiltration membrane is characterized by comprising the following steps:
(1) Dissolving polyethyleneimine in water, and dissolving trimesoyl chloride in an organic solvent, wherein the organic solvent is immiscible with water; sequentially coating the obtained aqueous solution and organic solution on a supporting base film, and preparing a polyethyleneimine-trimesoyl chloride primary layer through interfacial polymerization;
(2) Applying an aqueous solution of a halogenating agent, said halogenating agent containing a quaternary ammonium functionality, when the amino group and the acid chloride have not reacted to completion; the halogenating agent and primary amine, secondary amine or tertiary amine groups on the polyethyleneimine are subjected to quaternization reaction;
(3) And (3) drying the membrane obtained in the step (2) to ensure that the amino and acyl chloride completely react to obtain the positively charged nanofiltration membrane.
2. The method for preparing the surface-quaternized modified nanofiltration membrane of claim 1, wherein the structural formula of the halogenating agent is shown in formula 1:
wherein A is a halogen atom; x is a counter ion of a quaternary ammonium ion; r is at least one of alkane chain, imidazole, pyridine, bipyridine and azacyclo.
3. The method for preparing the surface-quaternized modified nanofiltration membrane of claim 2, wherein A is Cl, br or I; x is halogen, nitrate radical, tetrafluoroboric acid, hexafluorophosphoric acid or bis (trifluoromethane) sulfonyl imide ion.
4. The method for preparing the surface-quaternized modified nanofiltration membrane of claim 2, wherein the structural formula of the halogenating agent is specifically:
wherein n in formula 2 is a positive integer from 2 to 6.
5. The method for preparing the surface-quaternized modified nanofiltration membrane of claim 1, wherein in step (1), the mass concentration of polyethyleneimine in the aqueous solution is 0.1 to 3wt%, the coating time is 1 to 10 minutes, the mass concentration of trimesoyl chloride in the organic solution is 0.1 to 0.6wt%, and the coating time is 0.5 to 2 minutes;
in the step (2), the mass concentration of the halogenating agent in the aqueous solution of the halogenating agent is 0.5-5wt%, and the coating time is 0.5-6 hours.
6. The method for preparing the surface-quaternized modified nanofiltration membrane of claim 1, wherein the organic solution is n-hexane, cyclohexane, heptane, toluene or chloroform.
7. The method for preparing the surface-quaternized modified nanofiltration membrane of claim 1, wherein the support base membrane is a polyvinylidene fluoride membrane, a polysulfone membrane, a polyethersulfone membrane or a polyacrylonitrile membrane.
8. The method for preparing the surface-quaternized modified nanofiltration membrane of claim 1, wherein the drying temperature is 30-70 ℃ and the drying time is 10-30 minutes.
9. The surface quaternization modified nanofiltration membrane prepared by the method of any one of claims 1 to 8.
10. The application of the surface-quaternized modified nanofiltration membrane of claim 9, wherein the nanofiltration membrane is used for magnesium-lithium separation in salt lakes.
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