CN117654298A - Polyamine acid-base resistant composite filter membrane, preparation method and application thereof - Google Patents
Polyamine acid-base resistant composite filter membrane, preparation method and application thereof Download PDFInfo
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- CN117654298A CN117654298A CN202311662858.XA CN202311662858A CN117654298A CN 117654298 A CN117654298 A CN 117654298A CN 202311662858 A CN202311662858 A CN 202311662858A CN 117654298 A CN117654298 A CN 117654298A
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- polyamine
- composite filter
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- resistant composite
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- 239000012528 membrane Substances 0.000 title claims abstract description 152
- 229920000768 polyamine Polymers 0.000 title claims abstract description 115
- 239000002131 composite material Substances 0.000 title claims abstract description 85
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000000178 monomer Substances 0.000 claims abstract description 76
- 238000000926 separation method Methods 0.000 claims abstract description 70
- 239000002585 base Substances 0.000 claims abstract description 65
- 239000002253 acid Substances 0.000 claims abstract description 44
- 239000003513 alkali Substances 0.000 claims abstract description 43
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000004327 boric acid Substances 0.000 claims abstract description 28
- 230000004907 flux Effects 0.000 claims abstract description 28
- 230000014759 maintenance of location Effects 0.000 claims abstract description 27
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 24
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims abstract description 20
- 150000001335 aliphatic alkanes Chemical class 0.000 claims abstract description 7
- 150000001350 alkyl halides Chemical class 0.000 claims abstract 2
- 239000000243 solution Substances 0.000 claims description 32
- 239000007864 aqueous solution Substances 0.000 claims description 29
- 238000000108 ultra-filtration Methods 0.000 claims description 21
- 229910052744 lithium Inorganic materials 0.000 claims description 20
- 150000003839 salts Chemical class 0.000 claims description 18
- 238000004065 wastewater treatment Methods 0.000 claims description 16
- 150000002500 ions Chemical class 0.000 claims description 15
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 14
- 125000000217 alkyl group Polymers 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 10
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 8
- 238000000605 extraction Methods 0.000 claims description 7
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- 229910021645 metal ion Inorganic materials 0.000 claims description 7
- 239000004695 Polyether sulfone Substances 0.000 claims description 6
- 229920006393 polyether sulfone Polymers 0.000 claims description 6
- 238000000746 purification Methods 0.000 claims description 6
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 6
- 238000010612 desalination reaction Methods 0.000 claims description 5
- 239000003651 drinking water Substances 0.000 claims description 5
- 235000020188 drinking water Nutrition 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000000034 method Methods 0.000 claims description 5
- 239000013535 sea water Substances 0.000 claims description 5
- BHIFXIATEXVOQA-UHFFFAOYSA-N 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene Chemical compound CC1=C(CBr)C(C)=C(CBr)C(C)=C1CBr BHIFXIATEXVOQA-UHFFFAOYSA-N 0.000 claims description 4
- GHITVUOBZBZMND-UHFFFAOYSA-N 1,3,5-tris(bromomethyl)benzene Chemical compound BrCC1=CC(CBr)=CC(CBr)=C1 GHITVUOBZBZMND-UHFFFAOYSA-N 0.000 claims description 4
- ZQBFAOFFOQMSGJ-UHFFFAOYSA-N hexafluorobenzene Chemical compound FC1=C(F)C(F)=C(F)C(F)=C1F ZQBFAOFFOQMSGJ-UHFFFAOYSA-N 0.000 claims description 4
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 4
- JHBKHLUZVFWLAG-UHFFFAOYSA-N 1,2,4,5-tetrachlorobenzene Chemical compound ClC1=CC(Cl)=C(Cl)C=C1Cl JHBKHLUZVFWLAG-UHFFFAOYSA-N 0.000 claims description 3
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims description 3
- HPMGSGCDKVCZHC-UHFFFAOYSA-N 1,3-diiodo-2,2-bis(iodomethyl)propane Chemical compound ICC(CI)(CI)CI HPMGSGCDKVCZHC-UHFFFAOYSA-N 0.000 claims description 3
- 239000002033 PVDF binder Substances 0.000 claims description 3
- 150000001412 amines Chemical class 0.000 claims description 3
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 3
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 3
- -1 quaternium Chemical compound 0.000 claims description 3
- UGDSCHVVUPHIFM-UHFFFAOYSA-N 1,1,1-tris(aminomethyl)ethane Chemical compound NCC(C)(CN)CN UGDSCHVVUPHIFM-UHFFFAOYSA-N 0.000 claims description 2
- XJOUCILNLRXRTF-UHFFFAOYSA-N 1,2,3,4,5,6-hexakis(bromomethyl)benzene Chemical compound BrCC1=C(CBr)C(CBr)=C(CBr)C(CBr)=C1CBr XJOUCILNLRXRTF-UHFFFAOYSA-N 0.000 claims description 2
- QCKHVNQHBOGZER-UHFFFAOYSA-N 1,2,4,5-tetrabromobenzene Chemical compound BrC1=CC(Br)=C(Br)C=C1Br QCKHVNQHBOGZER-UHFFFAOYSA-N 0.000 claims description 2
- YWDUZLFWHVQCHY-UHFFFAOYSA-N 1,3,5-tribromobenzene Chemical compound BrC1=CC(Br)=CC(Br)=C1 YWDUZLFWHVQCHY-UHFFFAOYSA-N 0.000 claims description 2
- XKEFYDZQGKAQCN-UHFFFAOYSA-N 1,3,5-trichlorobenzene Chemical compound ClC1=CC(Cl)=CC(Cl)=C1 XKEFYDZQGKAQCN-UHFFFAOYSA-N 0.000 claims description 2
- WXLJJIHGDBUBJM-UHFFFAOYSA-N 1,3,5-triiodobenzene Chemical compound IC1=CC(I)=CC(I)=C1 WXLJJIHGDBUBJM-UHFFFAOYSA-N 0.000 claims description 2
- PJKMOHIGRNELRP-UHFFFAOYSA-N 1,3,5-tris(chloromethyl)benzene Chemical compound ClCC1=CC(CCl)=CC(CCl)=C1 PJKMOHIGRNELRP-UHFFFAOYSA-N 0.000 claims description 2
- MIVBPUGPPJIGKB-UHFFFAOYSA-N 1,3,5-tris(iodomethyl)benzene Chemical compound ICC1=CC(CI)=CC(CI)=C1 MIVBPUGPPJIGKB-UHFFFAOYSA-N 0.000 claims description 2
- OYSVBCSOQFXYHK-UHFFFAOYSA-N 1,3-dibromo-2,2-bis(bromomethyl)propane Chemical compound BrCC(CBr)(CBr)CBr OYSVBCSOQFXYHK-UHFFFAOYSA-N 0.000 claims description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- SEXZHJJUKFXNDY-UHFFFAOYSA-N 1-(bromomethyl)-2-phenylbenzene Chemical group BrCC1=CC=CC=C1C1=CC=CC=C1 SEXZHJJUKFXNDY-UHFFFAOYSA-N 0.000 claims description 2
- PVOAHINGSUIXLS-UHFFFAOYSA-N 1-Methylpiperazine Chemical compound CN1CCNCC1 PVOAHINGSUIXLS-UHFFFAOYSA-N 0.000 claims description 2
- YKSVXVKIYYQWBB-UHFFFAOYSA-N 1-butylpiperazine Chemical compound CCCCN1CCNCC1 YKSVXVKIYYQWBB-UHFFFAOYSA-N 0.000 claims description 2
- WGCYRFWNGRMRJA-UHFFFAOYSA-N 1-ethylpiperazine Chemical compound CCN1CCNCC1 WGCYRFWNGRMRJA-UHFFFAOYSA-N 0.000 claims description 2
- WHKWMTXTYKVFLK-UHFFFAOYSA-N 1-propan-2-ylpiperazine Chemical compound CC(C)N1CCNCC1 WHKWMTXTYKVFLK-UHFFFAOYSA-N 0.000 claims description 2
- NSMWYRLQHIXVAP-UHFFFAOYSA-N 2,5-dimethylpiperazine Chemical compound CC1CNC(C)CN1 NSMWYRLQHIXVAP-UHFFFAOYSA-N 0.000 claims description 2
- VARKIGWTYBUWNT-UHFFFAOYSA-N 2-[4-(2-hydroxyethyl)piperazin-1-yl]ethanol Chemical compound OCCN1CCN(CCO)CC1 VARKIGWTYBUWNT-UHFFFAOYSA-N 0.000 claims description 2
- JOMNTHCQHJPVAZ-UHFFFAOYSA-N 2-methylpiperazine Chemical compound CC1CNCCN1 JOMNTHCQHJPVAZ-UHFFFAOYSA-N 0.000 claims description 2
- RJWLLQWLBMJCFD-UHFFFAOYSA-N 4-methylpiperazin-1-amine Chemical compound CN1CCN(N)CC1 RJWLLQWLBMJCFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000004215 Carbon black (E152) Substances 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 239000012971 dimethylpiperazine Substances 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- CAYGQBVSOZLICD-UHFFFAOYSA-N hexabromobenzene Chemical compound BrC1=C(Br)C(Br)=C(Br)C(Br)=C1Br CAYGQBVSOZLICD-UHFFFAOYSA-N 0.000 claims description 2
- CKAPSXZOOQJIBF-UHFFFAOYSA-N hexachlorobenzene Chemical compound ClC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl CKAPSXZOOQJIBF-UHFFFAOYSA-N 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- KFIGICHILYTCJF-UHFFFAOYSA-N n'-methylethane-1,2-diamine Chemical compound CNCCN KFIGICHILYTCJF-UHFFFAOYSA-N 0.000 claims description 2
- BCIIMDOZSUCSEN-UHFFFAOYSA-N piperidin-4-amine Chemical compound NC1CCNCC1 BCIIMDOZSUCSEN-UHFFFAOYSA-N 0.000 claims description 2
- 229920002492 poly(sulfone) Polymers 0.000 claims description 2
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 2
- OHZZTXYKLXZFSZ-UHFFFAOYSA-I manganese(3+) 5,10,15-tris(1-methylpyridin-1-ium-4-yl)-20-(1-methylpyridin-4-ylidene)porphyrin-22-ide pentachloride Chemical compound [Cl-].[Cl-].[Cl-].[Cl-].[Cl-].[Mn+3].C1=CN(C)C=CC1=C1C(C=C2)=NC2=C(C=2C=C[N+](C)=CC=2)C([N-]2)=CC=C2C(C=2C=C[N+](C)=CC=2)=C(C=C2)N=C2C(C=2C=C[N+](C)=CC=2)=C2N=C1C=C2 OHZZTXYKLXZFSZ-UHFFFAOYSA-I 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 6
- 229910003002 lithium salt Inorganic materials 0.000 abstract description 4
- 159000000002 lithium salts Chemical class 0.000 abstract description 4
- 230000003321 amplification Effects 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000003199 nucleic acid amplification method Methods 0.000 abstract description 3
- 239000003054 catalyst Substances 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 24
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 description 24
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 19
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 19
- 229910052796 boron Inorganic materials 0.000 description 19
- 238000012360 testing method Methods 0.000 description 13
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 239000000706 filtrate Substances 0.000 description 6
- 239000004952 Polyamide Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000004993 emission spectroscopy Methods 0.000 description 5
- 238000009616 inductively coupled plasma Methods 0.000 description 5
- 229920002647 polyamide Polymers 0.000 description 5
- 238000001728 nano-filtration Methods 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000001223 reverse osmosis Methods 0.000 description 4
- 238000002791 soaking Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 3
- 230000035699 permeability Effects 0.000 description 3
- 208000029422 Hypernatremia Diseases 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000012527 feed solution Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000003436 Schotten-Baumann reaction Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 150000001263 acyl chlorides Chemical class 0.000 description 1
- VEGZHURRCWERMK-UHFFFAOYSA-N benzene-1,3-diamine;hydrochloride Chemical compound Cl.NC1=CC=CC(N)=C1 VEGZHURRCWERMK-UHFFFAOYSA-N 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- MSQACBWWAIBWIC-UHFFFAOYSA-N hydron;piperazine;chloride Chemical compound Cl.C1CNCCN1 MSQACBWWAIBWIC-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000005065 mining Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- RIUWBIIVUYSTCN-UHFFFAOYSA-N trilithium borate Chemical compound [Li+].[Li+].[Li+].[O-]B([O-])[O-] RIUWBIIVUYSTCN-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a polyamine acid-base resistant composite filter membrane, a preparation method and application thereof. The polyamine acid-base resistant composite filter membrane comprises a support base membrane and a separation layer which are combined in a laminated mode; the separation layer is formed by at least interfacial polymerization of a polyamine monomer and a polyhalogenated alkane monomer and/or a polyhalogenated aromatic hydrocarbon monomer. The polyamine acid-base resistant composite filter membrane provided by the invention is formed by forming a polyamine separation layer on the surface of a support bottom membrane through a water-oil interfacial polymerization reaction between a polyamine monomer and a polybasic alkyl halide and/or a polybasic aromatic hydrocarbon monomer, and has the advantages of high water flux and high ion retention rate; meanwhile, the catalyst has excellent acid and alkali resistance, and can directly separate inorganic alkali solution; and also has unique selective separation characteristics for lithium salts and boric acid; the corresponding preparation method is simple and easy to implement, and is beneficial to industrial amplification; has extremely high application value in various application fields related to water treatment.
Description
Technical Field
The invention relates to the technical field of membrane separation and purification materials, in particular to a polyamine acid-base resistant composite filter membrane, a preparation method and application thereof, and can realize separation of ions and molecules according to different application scene requirements.
Background
In industrial production and daily life, the application of the water treatment membrane separation technology is flexible and various, and the components of the separation object are complex and various, so that the separation membrane is often challenged by various factors. For example, ion separation membranes used in wastewater treatment and recovery in metallurgical, mining, printing and dyeing, paper-making and other industries, separation media of strong acids or strong bases place stringent demands on the acid-base stability of the chemical structure of the membrane material.
The traditional polyamide ion separation membrane is prepared based on Schotten-Baumann type water-oil interfacial polymerization reaction between a polybasic acyl chloride monomer and a polybasic amine monomer, and the generated amide bond is easy to hydrolyze and break in a strong acid or strong alkali medium, so that the membrane separation performance is seriously lost. In addition, since the ion separation membrane of the polyamide system was found, through the screening of monomers and the optimization of technology for decades by researchers, the most excellent separation performance is still the polyamide ion separation membrane system prepared based on the interfacial polymerization reaction between trimesoyl chloride-piperazine (TMC-PIP) or trimesoyl chloride-m-phenylenediamine (TMC-MPD).
Even so, other reaction forms and molecular structures that can polymerize into films at the two-phase interface are of little interest, so that the variety of ion separation membrane systems other than polyamide systems is very limited. Therefore, in view of the above, there is a strong need for a novel filter membrane that can withstand strong acid and strong base separation media with excellent ion separation performance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a polyamine acid-base resistant composite filter membrane, a preparation method and application thereof.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
in a first aspect, the invention provides a polyamine acid-base resistant composite filter membrane, which comprises a support base membrane and a separation layer which are combined in a laminated manner; the separation layer is formed by at least interfacial polymerization of polyamine monomer and polyhalogenated alkyl monomer and/or polyhalogenated aromatic hydrocarbon monomer.
In a second aspect, the invention also provides a preparation method of the polyamine acid-base resistant composite filter membrane, which comprises the following steps:
providing a support base film;
and enabling the polyamine monomer and the polyhalogenated alkyl monomer and/or the polyhalogenated aromatic hydrocarbon monomer to form a separation layer on the surface of the support bottom film through interfacial polymerization reaction, so as to form the polyamine acid-base resistant composite filter film.
Further, the preparation method specifically comprises the following steps:
fully infiltrating the support base film with an aqueous solution containing the polyamine monomer, and removing redundant liquid;
and (3) contacting the support base film soaked with the aqueous solution with the oily solution of the multi-halogenated alkyl monomer and/or the multi-halogenated aromatic hydrocarbon monomer, and performing the interfacial polymerization reaction to obtain the polyamine acid-base resistant composite filter film.
In a third aspect, the invention also provides application of the polyamine acid-base resistant composite filter membrane in any field of sea water desalination, drinking water purification, high-salt wastewater treatment, alkali wastewater treatment, acid wastewater treatment, salt lake lithium extraction and boron removal.
In a fourth aspect, as a specific application form, the present invention further provides a selective separation and extraction method of lithium salt-boric acid, including:
and selectively filtering the solution containing lithium salt and boric acid through the polyamine acid-base resistant composite filter membrane so as to enrich the lithium salt and the boric acid in the solution to two sides of the polyamine acid-base resistant composite filter membrane.
Based on the technical scheme, compared with the prior art, the invention has the beneficial effects that:
the polyamine acid-base resistant composite filter membrane provided by the invention is formed by forming a polyamine separation layer on the surface of a support base membrane through a water-oil interfacial polymerization reaction between a polyamine monomer and a multi-haloalkane/aromatic hydrocarbon monomer, and has the advantages of high water flux and high ion retention rate; meanwhile, the catalyst has excellent acid and alkali resistance, and can directly separate inorganic alkali solution; and also has unique permselective properties for lithium salts and boric acid; the corresponding preparation method is simple and easy to implement, and is beneficial to industrial amplification; has extremely high application value in various application fields related to water treatment.
The above description is only an overview of the technical solutions of the present invention, and in order to enable those skilled in the art to more clearly understand the technical means of the present application, the present invention may be implemented according to the content of the specification, the following description is given of the preferred embodiments of the present invention with reference to the accompanying drawings.
Drawings
FIG. 1 is a schematic diagram showing the principle of interfacial polymerization reaction and molecular structure of a separation layer according to an exemplary embodiment of the present invention;
FIG. 2a is a scanning electron micrograph of a surface of a polyamine acid and base resistant composite filter membrane according to an exemplary embodiment of the present invention;
FIG. 2b is a transmission electron micrograph of a cross section of a polyamine acid and base resistant composite filter membrane according to an exemplary embodiment of the present invention;
FIG. 3 is a graph showing the basic water flux, separation flux and salt rejection rate for separating 1000ppm of monovalent and divalent inorganic salt aqueous solutions for a polyamine acid and alkali resistant composite filter membrane according to an exemplary embodiment of the present invention;
FIG. 4 is a graph showing the basic water flux, the separation flux and the salt retention rate of 1000ppm of monovalent and divalent inorganic salt water solutions after soaking the polyamine acid-base resistant composite filter membrane in the concentrated alkaline water solution according to an exemplary embodiment of the present invention;
FIG. 5 is a graph showing the basic water flux, the separation flux and the salt retention rate of 1000ppm of monovalent and divalent inorganic salt water solutions after soaking a strong acid aqueous solution, for a polyamine acid-base resistant composite filter membrane according to an exemplary embodiment of the present invention;
FIG. 6 is a graph showing the separation flux and retention rate of a polyamine acid and alkali resistant composite filter membrane according to an exemplary embodiment of the present invention for 1000ppm aqueous sodium hydroxide or lithium hydroxide solution;
FIG. 7 is a graph showing the separation flux and retention rate of a polyamine acid and alkali resistant composite filter membrane according to an exemplary embodiment of the present invention for aqueous solutions of lithium chloride and boric acid at a total concentration of 1000ppm and different lithium/boron mass ratios.
Detailed Description
In view of the shortcomings in the prior art, the inventor of the present invention has long studied and practiced in a large number of ways to propose the technical scheme of the present invention. The technical scheme, the implementation process, the principle and the like are further explained as follows.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, however, the present invention may be practiced otherwise than as described herein, and therefore the scope of the present invention is not limited to the specific embodiments disclosed below.
The invention mainly aims to provide a novel polyamine acid-base resistant composite filter membrane and a preparation method thereof, so as to overcome the defects of the prior art. The invention also aims to provide application of the polyamine acid-base resistant composite filter membrane in any field of sea water desalination, drinking water purification, high-salt wastewater treatment, alkali wastewater treatment, acid wastewater treatment and salt lake lithium extraction and boron removal.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention comprises the following steps:
referring to fig. 1 and fig. 2a and 2b, an embodiment of the present invention provides a polyamine acid and alkali resistant composite filter membrane, which includes a support base membrane and a separation layer that are laminated and combined; the separation layer is formed by at least interfacial polymerization of polyamine monomer and polyhalogenated alkyl monomer and/or polyhalogenated aromatic hydrocarbon monomer.
Based on the above technical scheme, the embodiment of the invention essentially provides a polyamine acid and alkali-resistant film composite reverse osmosis/nanofiltration membrane (based on different structural characteristics such as pore diameter, which may be a reverse osmosis membrane or a nanofiltration membrane), the preparation process comprises: the ultrafiltration membrane is selected as a porous support bottom membrane, and a polyamine polymer separation layer is obtained on the surface of a substrate through the water-oil interfacial polymerization reaction between a polyamine monomer in an aqueous solution and a multi-halogenated alkyl monomer and/or a multi-halogenated aromatic hydrocarbon monomer in an organic solution, so that the expected acid and alkali resistant membrane composite reverse osmosis/nanofiltration membrane is prepared. Meanwhile, in the preparation process, the molecular weight cut-off of the membrane can be regulated and controlled through regulating and controlling the concentration and the proportion of the monomer, so that the membrane can be applied to different separation objects.
In some embodiments, the polyamine monomer comprises any one or a combination of two or more of piperazine, polyalkylamine, and polyaromatic amine monomers.
In some embodiments, the number of amine groups in the polyamine monomer is 2 to 4.
In some embodiments, the polyhalogenated alkane monomer and/or polyhalogenated aromatic hydrocarbon monomer has a halogen number of 3 to 6.
In some embodiments, the polyamine monomer comprises any one or a combination of two or more of piperazine, 1-methylpiperazine, N '-dimethylpiperazine, 2-methylpiperazine, 2, 5-dimethylpiperazine, 1-ethylpiperazine, 1-isopropylpiperazine, 1-butylpiperazine, 1-amino-4-methylpiperazine and 1, 4-bis (2-hydroxyethyl) piperazine, triethylenediamine, 4-aminopiperidine, ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, N-methylethylenediamine, N' -dimethylethylenediamine, 2- (aminomethyl) -2-methyl-1, 3-propylenediamine, quaternium, o-phenylenediamine, m-phenylenediamine.
In some embodiments, the polyhalogenated alkane monomer comprises any one or a combination of two or more of pentachloro-ene, tetrabromoneopentane, 1, 3-diiodo-2, 2-bis (iodomethyl) propane.
In some embodiments, the polyhaloaromatic hydrocarbon monomer includes any one or a combination of two or more of 1,3, 5-tris (chloromethyl) benzene, 1,3, 5-tris (bromomethyl) benzene, 1,3, 5-tris (iodomethyl) benzene, 1,3, 5-tris (bromomethyl) -2,4, 6-trimethylbenzene, hexa (bromomethyl) benzene, 4' -bis (bromomethyl) biphenyl, 1,3, 5-trichlorobenzene, 1,3, 5-tribromobenzene, 1,3, 5-triiodobenzene, 1,2,4, 5-tetrachlorobenzene, 1,2,4, 5-tetrabromobenzene, perfluorobenzene, hexachlorobenzene, hexabromobenzene.
In some embodiments, the support base membrane is selected from ultrafiltration membranes.
In some embodiments, the support base membrane comprises any one of polyethersulfone ultrafiltration membrane, polysulfone ultrafiltration membrane, polyvinylidene fluoride ultrafiltration membrane, polyacrylonitrile ultrafiltration membrane.
In some embodiments, the thickness of the separation layer is 10-1000nm.
In some embodiments, the polyamine acid and alkali resistant composite filter membrane has a molecular weight cut-off of 100-2000Da.
In some embodiments, the polyamine acid and alkali resistant composite filter membrane has a basal water flux of 1-20 L.m -2 ·h -1 ·bar -1 The retention rate of monovalent and/or divalent inorganic salt is 40-99%.
More specifically and preferably, the basic water flux of the polyamine acid and alkali resistant composite filter membrane provided by the embodiment of the invention under proper conditions is more than 2 L.m -2 ·h -1 ·bar -1 The retention rate of the 1000ppm of the multiple bivalent salts is 94-99%, and the retention rate of the 1000ppm of the multiple monovalent salts is 96-98%.
The polyamine acid-base resistant composite filter membrane provided by the invention has the further remarkable advantages of extremely strong acid-base resistance and high salt resistance, and is specifically expressed in:
further, the polyamine acid and alkali resistant composite filter membrane provided can maintain excellent ion separation performance after being soaked in a 20w/v% sulfuric acid solution or a 2mol/L sodium hydroxide solution for 7 days under proper conditions. Furthermore, the polyamine acid-base resistant composite filter membrane provided can directly separate inorganic alkali solution under proper conditions, and the retention rate of 1000ppm of sodium hydroxide or lithium hydroxide is not lower than 85%.
In addition, there is a significant advantage in terms of selective permeation of different ions, and in some embodiments, the polyamine acid and base resistant composite filter membrane has a boric acid rejection of 0-10%.
The advantages can be suitable for specific selective separation application of salt lake brine, such as lithium/boron separation, and can be represented by the fact that the provided polyamine acid-base resistant composite filter membrane can realize efficient selective separation of lithium and boron under proper conditions, and the total concentration of the lithium chloride and boric acid mixed solutions with different lithium/boron mass ratios can be separated to be higher than 94%, and meanwhile, the rejection rate of the lithium chloride to the boric acid can be lower than 8%.
Of course, not limited to this, it is obvious that selective separation can be achieved also for other mixed solutions of metal salts and boric acid with a higher rejection rate.
Corresponding to the composition and structure of the polyamine acid-base resistant composite filter membrane, the embodiment of the invention also provides a preparation method of the polyamine acid-base resistant composite filter membrane, which comprises the following steps:
a support base film is provided.
And enabling the polyamine monomer and the polyhalogenated alkyl monomer and/or the polyhalogenated aromatic hydrocarbon monomer to form a separation layer on the surface of the support bottom film through interfacial polymerization reaction, so as to form the polyamine acid-base resistant composite filter film.
In some embodiments, the preparation method specifically may include:
and (3) fully infiltrating the support base film with the aqueous solution containing the polyamine monomer, and removing redundant liquid.
And (3) contacting the support base film soaked with the aqueous solution with the oily solution of the multi-halogenated alkyl monomer and/or the multi-halogenated aromatic hydrocarbon monomer, and performing the interfacial polymerization reaction to obtain the polyamine acid-base resistant composite filter film.
In some embodiments, the concentration of the polyamine monomer in the aqueous solution is from 1 to 100g/L.
In some embodiments, the concentration of the polyhalogenated alkane monomer and/or polyhalogenated aromatic hydrocarbon monomer in the oily solution is from 1 to 10g/L.
In some embodiments, the interfacial polymerization reaction is at a temperature of from 10 to 50 ℃ for a time of from 1 to 48 hours.
As some typical application examples of the above technical solution, the preparation method in the implementation process may be implemented through the following specific processes:
(1) An ultrafiltration membrane is selected as a porous supporting substrate, and is fully soaked and rinsed by deionized water before use.
(2) Controlling the temperature of the film-forming environment between 10 ℃ and 50 ℃ and the relative humidity between 30% and 80%.
(3) After removing residual water on both sides of the ultrafiltration membrane, the membrane is fully soaked in aqueous solution containing 1-100g/L of polyamine monomer for 10-600 seconds.
(4) Removing residual aqueous solution on two sides of the ultrafiltration membrane until no obvious liquid drops exist, immersing the ultrafiltration membrane in oily solution containing 1-10g/L of multi-halogenated alkane monomer and/or multi-halogenated aromatic hydrocarbon monomer, and maintaining the temperature at 10-50 ℃ for interfacial polymerization for 1-48 hours.
(5) After the interface polymerization reaction is finished, the membrane is fully rinsed by using an organic solvent corresponding to the oily solution containing the multi-halogenated alkane monomer and/or the multi-halogenated aromatic hydrocarbon monomer to remove unreacted monomers, and then the membrane is subjected to aftertreatment and drying for 10-60 minutes at the temperature of 30-80 ℃ to prepare the polyamine acid-base resistant composite filter membrane.
As a third aspect of the embodiment of the present invention, there is also provided an application of the polyamine acid and alkali resistant composite filter membrane provided in any one of the above embodiments in any one of the fields of sea water desalination, drinking water purification, high salt wastewater treatment, alkali wastewater treatment, acid wastewater treatment, metal ion/boric acid separation. The application of the metal ion/boric acid separation field is specifically, for example, but not limited to, application of salt lake lithium extraction and boron removal.
As a specific expression of the above application, a fourth aspect of the embodiment of the present invention also provides a selective separation and extraction method of metal ion-boric acid, which includes the steps of:
the solution containing metal ions and boric acid is subjected to selective permeation filtration through the polyamine acid and alkali resistant composite filter membrane provided by the embodiment, so that the metal salts and boric acid in the solution are respectively enriched to the two sides of the polyamine acid and alkali resistant composite filter membrane.
In some embodiments, the metal salt comprises monovalent metal ions, and more preferably metallic lithium ions.
The technical scheme of the invention is further described in detail below through a plurality of embodiments and with reference to the accompanying drawings. However, the examples are chosen to illustrate the invention only and are not intended to limit the scope of the invention. The raw materials, reagents, reaction apparatus and test equipment used in the examples below are conventional and commercially available unless otherwise specified; and unless otherwise indicated, all partial processes involved are carried out at room temperature, for example at temperatures of from 15 to 35℃and at atmospheric pressure, as is usual.
Example 1
The preparation process of the polyamine acid-base resistant composite filter membrane is exemplified in the embodiment, and specifically comprises the following steps:
(1) The polyethersulfone ultrafiltration membrane is selected as a supporting base membrane, and is fully soaked and rinsed by deionized water before use.
(2) The temperature of the film-forming environment is controlled at 25 ℃ and the humidity is controlled at 60%.
(3) After removal of residual water on both sides of the polyethersulfone ultrafiltration membrane, the membrane was fully immersed for 120 seconds with an aqueous solution containing 68.9g/L piperazine.
(4) After wiping off the residual aqueous solution on both sides of the polyethersulfone ultrafiltration membrane until no obvious water drops exist, immersing the membrane in an n-hexane solution containing 2.1g/L of 1,3, 5-tris (bromomethyl) benzene, and maintaining the ambient temperature at 25 ℃ for interfacial polymerization for 24 hours.
(5) After the interfacial polymerization reaction is finished, the membrane is fully rinsed by n-hexane to remove unreacted 1,3, 5-tri (bromomethyl) benzene monomer, and then the membrane is subjected to aftertreatment at 60 ℃ and drying for 30 minutes to prepare the polyamine composite filter membrane taking the polyethersulfone ultrafiltration membrane as a support base membrane.
The surface and cross-sectional morphology of the prepared polyamine composite filter membrane are respectively shown in fig. 2a and 2b, and a continuous double-layer membrane structure can be formed.
The polyamine composite filter membrane prepared in this example was tested for basic water flux and separation flux and salt rejection rate for separating 1000ppm of various monovalent and divalent inorganic salt aqueous solutions, and the results are shown in fig. 3, which shows that the filter membrane provided in this example has a large flux and shows superior rejection performance for various ions.
Example 2
The polyamine composite filter membrane provided in example 1 of this example has strong alkali resistance, and is specifically shown as follows:
soaking the prepared polyamine composite filter membrane in 2mol/L sodium hydroxide aqueous solution at room temperature for 7 days, fully washing with deionized water, and maintaining the pressure at 6bar and flow rate at 50L h -1 The basic water flux of the test membrane and the separation flux and salt rejection rate of 1000ppm inorganic salt water solution under the cross-flow separation condition at 25 ℃, wherein the salt rejection rate is calculated by testing the conductivity of the filtrate and the feed solution.
The test results are shown in fig. 4, and it can be seen that the polyamine-based composite filter membrane exhibits excellent strong alkali resistance.
Example 3
The strong acid resistance of the polyamine composite filter membrane provided in example 1 is shown in the following specific examples:
the prepared polyamine composite filter membrane is placed in a 20w/v% sulfuric acid aqueous solution to be soaked for 7 days at room temperature, and after the membrane is fully rinsed by deionized water, the membrane is placed in a 2mol/L sodium hydroxide aqueous solution to be soaked for 1 day at room temperature. After thoroughly rinsing the membrane with deionized water, the membrane was rinsed under a pressure of 6bar at a flow rate of 50L h -1 The basic water flux of the test membrane and the separation flux and salt rejection rate of 1000ppm inorganic salt water solution under the cross-flow separation condition at 25 ℃, wherein the salt rejection rate is calculated by testing the conductivity of the filtrate and the feed solution.
As shown in FIG. 5, it is clear that the polyamine composite filter membrane provided in this example still maintains a good separation flux and ion retention rate after being treated with a strong acid aqueous solution.
Example 4
The performance of the polyamine composite filter membrane provided in the example 1 for directly filtering inorganic strong base is shown in the following specific examples:
at a pressure of 6bar, a flow rate of 50L h -1 And the separation flux and the retention rate of the prepared polyamine compound filter membrane to 1000ppm sodium hydroxide aqueous solution are tested under the cross-flow separation condition at the temperature of 25 ℃, and the retention rate is calculated through the sodium content in filtrate and feed liquid tested by an inductively coupled plasma emission spectrometry.
Example 5
The performance of the polyamine composite filter membrane provided in the example 1 for directly filtering inorganic strong base is shown in the following specific examples:
at a pressure of 6bar, a flow rate of 50L h -1 And testing the separation flux and the retention rate of the prepared polyamine composite filter membrane to 1000ppm of lithium hydroxide aqueous solution under the cross-flow separation condition at the temperature of 25 ℃, wherein the retention rate is calculated by the content of potassium in filtrate and feed liquid tested by an inductively coupled plasma emission spectrometry.
The test result is shown in fig. 6, and the polyamine composite filter membrane provided by the embodiment can directly filter inorganic strong alkali solution and has better interception effect.
Example 6
The lithium/boron selective permeability of the polyamine acid-base resistant composite filter membrane provided in the example 1 is shown in the following specific examples:
at a pressure of 6bar, a flow rate of 50L h -1 And the separation flux and the retention rate of the mixed aqueous solution of lithium chloride and boric acid, which are prepared by testing under the cross-flow separation condition with the temperature of 25 ℃, are 1000ppm, and the mass ratio of lithium to boron is 3/1, and the retention rates of the lithium chloride and the boric acid are calculated by respectively passing through the content of lithium and boron in the filtrate and the feed liquid tested by an inductively coupled plasma emission spectrometry.
Example 7
At a pressure of 6bar, a flow rate of 50L h -1 And the separation flux and the retention rate of the mixed aqueous solution of lithium chloride and boric acid, which are prepared by testing under the cross-flow separation condition of 25 ℃, are 1000ppm of total concentration and 1/1 of lithium/boron mass ratio, and the retention rates of the lithium chloride and the boric acid are calculated by respectively passing through the filtered liquid and the content of the lithium and the boron in the feed liquid tested by an inductively coupled plasma emission spectrometry.
Example 8
At a pressure of 6bar and a flow rate of 50Lh -1 The polyamine composite filter membrane prepared by testing under the cross-flow separation condition with the temperature of 25 ℃ has the separation flux and the retention rate of the mixed aqueous solution of lithium chloride and boric acid with the total concentration of 1000ppm and the lithium/boron mass ratio of 1/3The retention rates of lithium chloride and boric acid are calculated by the contents of lithium and boron in filtrate and feed liquid tested by inductively coupled plasma emission spectrometry respectively.
As shown in the test results of FIG. 7, it can be seen that the polyamine composite filter membrane provided by the embodiment of the invention maintains a better retention rate for lithium chloride and has a higher permeability for boric acid between the mass ratio of lithium/boron of 1/3-3/1, and can realize selective separation of lithium and boron.
In addition, the inventor also refers to the modes of the examples 1-8, tests are carried out on other raw materials, conditions and the like listed in the specification, and a series of polyamine acid and alkali resistant composite filter membranes with different ion interception performances are prepared in the same way, so that the excellent technical effects are achieved, including but not limited to the following implementation cases:
example 9
The preparation process of the polyamine acid and alkali resistant composite filter membrane is the same as that of the embodiment 1, and the main difference is that:
step (1) selecting a polyvinylidene fluoride ultrafiltration membrane as a support bottom membrane; in the step (2), the temperature of the film-forming environment is controlled at 10 ℃ and the humidity is controlled at 30%; fully infiltrating the film with an aqueous solution containing 100g/L piperazine for 10 seconds in the step (3); immersing in 1g/L of 1,3, 5-tri (bromomethyl) -2,4, 6-trimethylbenzene in n-hexane solution in the step (4), and maintaining the ambient temperature at 10 ℃ for interfacial polymerization reaction for 48 hours.
Example 10
The preparation process of the polyamine acid and alkali resistant composite filter membrane is the same as that of the embodiment 1, and the main difference is that:
step (1) selecting a polyacrylonitrile ultrafiltration membrane as a support bottom membrane; in the step (2), the temperature of the film-forming environment is controlled at 50 ℃ and the humidity is controlled at 80%; fully soaking the film in the water solution containing 1g/L piperazine for 600 seconds in the step (3); in the step (4), the reaction kettle is immersed in an n-hexane solution containing 10g/L of 1,3, 5-tris (bromomethyl) -2,4, 6-trimethylbenzene, and the interfacial polymerization reaction is carried out for 1 hour at the temperature of 50 ℃.
Example 11
The preparation process of the polyamine acid and alkali resistant composite filter membrane is the same as that of the embodiment 1, and the main difference is that:
a. the polyamine is selected from triethylene diamine, and the polyhalogenated monomer is selected from pentachloro-penem;
b. the polyamine is selected from ethylenediamine, and the polyhalogenated monomer is selected from 1, 3-diiodo-2, 2-bis (iodomethyl) propane;
c. the polyamine is selected from o-phenylenediamine, and the polyhalogenated monomer is selected from 1,2,4, 5-tetrachlorobenzene.
The flux, rejection, acid and alkali resistance and selective permeability of the composite filters prepared in examples 9-11 remain at the same level as in the previous examples, and are not described in detail herein.
Based on the above embodiments, it can be clarified that:
(1) The novel polyamine acid-base resistant composite filter membrane provided by the invention is formed by a polyamine separation layer formed on the surface of a support bottom membrane through a water-oil interfacial polymerization reaction between a polyamine monomer and a multi-halogenated alkyl monomer and/or a multi-halogenated aromatic hydrocarbon monomer. Under proper conditions, the basic water flux of the filter membrane is more than 2L m -2 h -1 bar -1 Meanwhile, the retention rate of the filter membrane on 1000ppm of various bivalent salts is 94-99%, and the retention rate of the filter membrane on 1000ppm of various monovalent salts is 96-98%.
(2) The novel polyamine composite filter membrane provided by the invention has excellent acid and alkali resistance, and can maintain excellent ion separation performance after being soaked in 2mol/L sodium hydroxide aqueous solution or 20w/v% sulfuric acid aqueous solution for 7 days under proper conditions.
(3) The novel polyamine composite filter membrane provided by the invention can directly separate inorganic strong alkali solution under specific conditions, and the retention rate of 1000ppm of sodium hydroxide or lithium hydroxide is not lower than 85%.
(4) The novel polyamine composite filter membrane provided by the invention can realize the efficient and selective separation of lithium and boron which cannot be completed by the traditional polyamide nanofiltration membrane and the reverse osmosis membrane, and under proper conditions, the mixed solution of lithium chloride and boric acid with the total concentration of 1000ppm and different lithium/boron mass ratios is separated, the retention rate of the lithium chloride can be higher than 94%, and the retention rate of the boric acid can be lower than 8%.
(5) The novel polyamine acid-base resistant composite filter membrane provided by the invention has the advantages of simple preparation method and easy industrial amplification, and has application value in the life and industrial fields such as sea water desalination, drinking water purification, high-salt wastewater treatment, alkali wastewater treatment, acid wastewater treatment, salt lake lithium extraction and boron removal.
It should be understood that the above embodiments are merely for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the present invention and implement the same according to the present invention without limiting the scope of the present invention. All equivalent changes or modifications made in accordance with the spirit of the present invention should be construed to be included in the scope of the present invention.
Claims (11)
1. The polyamine acid-base resistant composite filter membrane is characterized by comprising a support base membrane and a separation layer which are laminated and combined;
the separation layer is formed by at least interfacial polymerization of polyamine monomer and polyhalogenated alkyl monomer and/or polyhalogenated aromatic hydrocarbon monomer.
2. The polyamine acid-base resistant composite filter membrane according to claim 1, wherein the polyamine monomer comprises any one or a combination of more than two of piperazine, polyamine and polyaromatic amine monomers;
and/or the number of amine groups in the polyamine monomer is 2-4;
and/or the halogen number of the polyhalogenated alkyl monomer and/or the polyhalogenated aromatic hydrocarbon monomer is 3-6.
3. The polyamine acid and alkali resistant composite filter membrane according to claim 2, wherein the polyamine monomer comprises any one or a combination of more than two of piperazine, 1-methylpiperazine, N '-dimethylpiperazine, 2-methylpiperazine, 2, 5-dimethylpiperazine, 1-ethylpiperazine, 1-isopropylpiperazine, 1-butylpiperazine, 1-amino-4-methylpiperazine and 1, 4-bis (2-hydroxyethyl) piperazine, triethylenediamine, 4-aminopiperidine, ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, N-methylethylenediamine, N' -dimethylethylenediamine, 2- (aminomethyl) -2-methyl-1, 3-propylenediamine, quaternium, o-phenylenediamine, m-phenylenediamine;
and/or the polybasic alkyl halide monomer comprises any one or more than two of pentachloride, tetrabromoneopentane and 1, 3-diiodo-2, 2-bis (iodomethyl) propane;
and/or the polyhaloaromatic hydrocarbon monomer comprises any one or more than two of 1,3, 5-tri (chloromethyl) benzene, 1,3, 5-tri (bromomethyl) benzene, 1,3, 5-tri (iodomethyl) benzene, 1,3, 5-tri (bromomethyl) -2,4, 6-trimethylbenzene, hexa (bromomethyl) benzene, 4' -bis (bromomethyl) biphenyl, 1,3, 5-trichlorobenzene, 1,3, 5-tribromobenzene, 1,3, 5-triiodobenzene, 1,2,4, 5-tetrachlorobenzene, 1,2,4, 5-tetrabromobenzene, perfluorobenzene, hexachlorobenzene and hexabromobenzene.
4. The polyamine acid and alkali resistant composite filter membrane according to claim 1, wherein the support base membrane is selected from ultrafiltration membranes;
preferably, the support base membrane comprises any one of a polyethersulfone ultrafiltration membrane, a polysulfone ultrafiltration membrane, a polyvinylidene fluoride ultrafiltration membrane and a polyacrylonitrile ultrafiltration membrane.
5. The polyamine acid and alkali resistant composite filter membrane according to claim 1, wherein the thickness of the separation layer is 10-1000nm;
and/or the molecular weight cut-off of the polyamine acid-base resistant composite filter membrane is 100-2000Da.
6. The polyamine acid and alkali resistant composite filter membrane according to claim 1 or 5, wherein the basic water flux of the polyamine acid and alkali resistant composite filter membrane is 1-20 l.m -2 ·h -1 ·bar -1 The retention rate of monovalent and/or divalent inorganic salt is 40-99%;
preferably, the retention rate of the polyamine acid and alkali resistant composite filter membrane to boric acid is 0-10%.
7. The preparation method of the polyamine acid-base resistant composite filter membrane is characterized by comprising the following steps:
providing a support base film;
and enabling the polyamine monomer and the polyhalogenated alkyl monomer and/or the polyhalogenated aromatic hydrocarbon monomer to form a separation layer on the surface of the support bottom film through interfacial polymerization reaction, so as to form the polyamine acid-base resistant composite filter film.
8. The preparation method according to claim 7, characterized by comprising the following steps:
fully infiltrating the support base film with an aqueous solution containing the polyamine monomer, and removing redundant liquid;
and (3) contacting the support base film soaked with the aqueous solution with the oily solution of the multi-halogenated alkyl monomer and/or the multi-halogenated aromatic hydrocarbon monomer, and performing the interfacial polymerization reaction to obtain the polyamine acid-base resistant composite filter film.
9. The method of claim 8, wherein the concentration of the polyamine monomer in the aqueous solution is 1-100g/L;
and/or the concentration of the polyhalogenated alkane monomer and/or polyhalogenated aromatic hydrocarbon monomer in the oily solution is 1-10g/L;
and/or the interfacial polymerization reaction is carried out at a temperature of 10-50 ℃ for 1-48 hours.
10. Use of the polyamine acid and alkali resistant composite filter membrane according to any one of claims 1-6 in any one of the fields of sea water desalination, drinking water purification, high salt wastewater treatment, alkali wastewater treatment, acid wastewater treatment, metal ion/boric acid separation.
11. A selective separation and extraction method of metal ion-boric acid is characterized by comprising the following steps:
selectively filtering a solution containing metal ions and boric acid through the polyamine acid and alkali resistant composite filter membrane according to any one of claims 1-6, so that the metal salts and boric acid in the solution are respectively enriched to two sides of the polyamine acid and alkali resistant composite filter membrane;
preferably, the metal salt comprises monovalent metal ions, more preferably lithium metal ions.
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