CN116371221B - Polyamide nanofiltration membrane and preparation method and application thereof - Google Patents
Polyamide nanofiltration membrane and preparation method and application thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 93
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 69
- 239000004952 Polyamide Substances 0.000 title claims abstract description 63
- 229920002647 polyamide Polymers 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 46
- 229920005610 lignin Polymers 0.000 claims abstract description 43
- 239000000243 solution Substances 0.000 claims abstract description 37
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000008346 aqueous phase Substances 0.000 claims abstract description 20
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 19
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 239000012071 phase Substances 0.000 claims abstract description 15
- 229920000768 polyamine Polymers 0.000 claims abstract description 14
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- 230000008569 process Effects 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 13
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
- 229920002492 poly(sulfone) Polymers 0.000 claims description 6
- 238000010612 desalination reaction Methods 0.000 claims description 5
- 239000013535 sea water Substances 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- -1 polyethylene Polymers 0.000 claims description 4
- 238000011084 recovery Methods 0.000 claims description 4
- 239000002351 wastewater Substances 0.000 claims description 4
- 238000011038 discontinuous diafiltration by volume reduction Methods 0.000 claims description 3
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 claims description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002033 PVDF binder Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920002873 Polyethylenimine Polymers 0.000 claims description 2
- 229940018564 m-phenylenediamine Drugs 0.000 claims description 2
- 239000003208 petroleum Substances 0.000 claims description 2
- 229920002239 polyacrylonitrile Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 claims 2
- FDQSRULYDNDXQB-UHFFFAOYSA-N benzene-1,3-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC(C(Cl)=O)=C1 FDQSRULYDNDXQB-UHFFFAOYSA-N 0.000 claims 1
- LXEJRKJRKIFVNY-UHFFFAOYSA-N terephthaloyl chloride Chemical compound ClC(=O)C1=CC=C(C(Cl)=O)C=C1 LXEJRKJRKIFVNY-UHFFFAOYSA-N 0.000 claims 1
- 230000004907 flux Effects 0.000 abstract description 28
- 239000000178 monomer Substances 0.000 abstract description 25
- 230000014759 maintenance of location Effects 0.000 abstract description 13
- 238000012695 Interfacial polymerization Methods 0.000 abstract description 11
- 150000001412 amines Chemical class 0.000 abstract description 11
- 238000006243 chemical reaction Methods 0.000 abstract description 10
- 230000001105 regulatory effect Effects 0.000 abstract description 6
- 239000000654 additive Substances 0.000 abstract description 5
- 230000000996 additive effect Effects 0.000 abstract description 4
- 230000000052 comparative effect Effects 0.000 description 30
- 150000003839 salts Chemical class 0.000 description 14
- 239000002585 base Substances 0.000 description 12
- 239000007788 liquid Substances 0.000 description 9
- 238000000926 separation method Methods 0.000 description 9
- 239000011734 sodium Substances 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 8
- 238000012360 testing method Methods 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 239000002131 composite material Substances 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000002699 waste material Substances 0.000 description 5
- 238000004132 cross linking Methods 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
- 239000000975 dye Substances 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 229910017053 inorganic salt Inorganic materials 0.000 description 4
- 235000013824 polyphenols Nutrition 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011780 sodium chloride Substances 0.000 description 4
- 102000015863 Nuclear Factor 90 Proteins Human genes 0.000 description 3
- 108010010424 Nuclear Factor 90 Proteins Proteins 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 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 description 2
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000012466 permeate Substances 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- 150000008442 polyphenolic compounds Chemical class 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000001988 toxicity Effects 0.000 description 2
- 231100000419 toxicity Toxicity 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 206010015866 Extravasation Diseases 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- 208000029422 Hypernatremia Diseases 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FYXKZNLBZKRYSS-UHFFFAOYSA-N benzene-1,2-dicarbonyl chloride Chemical compound ClC(=O)C1=CC=CC=C1C(Cl)=O FYXKZNLBZKRYSS-UHFFFAOYSA-N 0.000 description 1
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical group ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000009295 crossflow filtration Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000036251 extravasation Effects 0.000 description 1
- 238000000445 field-emission scanning electron microscopy Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000001471 micro-filtration Methods 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 125000004193 piperazinyl group Chemical group 0.000 description 1
- 238000004537 pulping Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229920002994 synthetic fiber Polymers 0.000 description 1
- 229920002258 tannic acid Polymers 0.000 description 1
- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
- 229940033123 tannic acid Drugs 0.000 description 1
- 235000015523 tannic acid Nutrition 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/56—Polyamides, e.g. polyester-amides
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A20/00—Water conservation; Efficient water supply; Efficient water use
- Y02A20/124—Water desalination
- Y02A20/131—Reverse-osmosis
Abstract
The invention discloses a preparation method of a polyamide nanofiltration membrane. The method comprises the following steps: s1, mixing a base film with an aqueous phase solution, standing and removing the aqueous phase solution; s2, mixing the base film after the aqueous phase solution is removed with the oil phase solution, standing and drying to obtain the polyamide nanofiltration membrane; the aqueous phase solution is a mixed solution of alkaline lignin, polyamine and deionized water; the oil phase solution is a mixed solution of polybasic acyl chloride and an organic solvent; the structural formula of the alkaline lignin is shown as a formula (I). According to the preparation method, the additive alkaline lignin is added into the aqueous phase solution, and the reaction of the amine monomer and the acyl chloride monomer in the interfacial polymerization process is regulated and controlled, so that the prepared polyamide nanofiltration membrane has higher water flux and higher Na 2 SO 4 Retention rate and SO 4 2‑ /Cl ‑ Selectivity.
Description
Technical Field
The invention belongs to the technical field of separation membranes, and particularly relates to a polyamide nanofiltration membrane and a preparation method and application thereof.
Background
The membrane separation technology has the characteristics of small occupied area, low energy consumption, simple operation and the like, and is widely applied. Nanofiltration (NF), a typical pressure-driven membrane separation technique, can effectively separate divalent and multivalent ions and organic molecules having a molecular weight of 200-1000Da, and has gained a great deal of attention in the fields of sea water desalination, wastewater treatment, ion screening, and the like. Currently, commercial nanofiltration membranes mainly comprise thin layer composite (TFC) nanofiltration membranes, and the preparation method is generally as follows: the polyamide selective layer is formed by Interfacial Polymerization (IP) using an aqueous phase containing an amine monomer and an oil phase containing an acid chloride monomer on the surface of an ultrafiltration or microfiltration substrate. Although the process is simple, the 'trade-off' effect that the membrane flux and the rejection rate cannot be simultaneously improved always exists in the preparation process, so that the further popularization and the use of the membrane are limited. How to regulate the interfacial polymerization process and overcome the 'trade-off' effect is the key for popularizing the application of TFC nanofiltration membranes.
By adding additives (such as nano materials and polyphenols) into the water phase or the oil phase of interfacial polymerization, the diffusion speed of the amine monomer into the oil phase or the concentration of the reaction between the amine monomer and the acyl chloride monomer can be regulated and controlled, so that the polyamide selection layer (such as increasing the crosslinking degree, reducing the thickness, increasing the contact area between the polyamide and water, and the like) is regulated and controlled to optimize the TFC membrane performance. However, many nanomaterials are poorly stable in water or are at risk of extravasation toxicity (Liang, y.; zhu, y.; liu, c.; lee, k.; r.; hung, w.; s.; wang, z.; li, y.; elimelech, m.; jin, j.; lin, s.; polyamide nanofiltration membrane with highly uniform sub-nanometer pores for sub; i.precision separation. Nature communications 2020,11, (1), 1-9.); in addition, phenolic hydroxyl groups in the polyphenol compete with the amine monomer for acid chloride groups, such that the degree of crosslinking of the formed polyamide layer is low, resulting in a decrease in rejection rate (Li, q.; liao, z.; fang, x.; xie, j.; ni, l.; wang, d.; qi, j.; sun, x.; wang, l.; li, j.; tannic acid assisted interfacial polymerization based loose thin-filmcomposite NF membrane for dye/salt separation.
Chinese patent (a preparation method of a high-flux Gao Jieliu nanofiltration membrane based on sodium lignin sulfonate) discloses a method for preparing a nanofiltration membrane based on sodium lignin sulfonate as an aqueous phase reaction monomer. In order to improve the utilization rate of sodium lignin sulfonate, triethylamine is used as a catalyst to enable phenolic hydroxyl groups in sodium lignin sulfonate molecules to react with acyl chloride, so that the loose nanofiltration membrane is prepared. The retention rate of the prepared nanofiltration membrane on sunset yellow can reach 99.02 percent, and the permeation flux of the membrane reaches 14.03L m -2 h -1 bar -1 . However, in the presence of inorganic salts (solution Na 2 SO 4 Or NaCl solution) as a core component, the permeation flux of the raw material liquid still cannot meet the actual requirements, and the problems of long time consumption and high energy consumption exist; in addition, the comparison document is made of sunset yellowThe dye is the object of interception, and the dye is usually in the form of agglomerates in aqueous solution, and the size is larger. Inorganic salts are smaller in size, more difficult to entrap, and lower in entrapment than dyes.
At present, commercial polyamide nanofiltration membranes commonly used in the market are NF90 and NF270, and the pure water flux is 6.7L m respectively -2 h -1 bar -1 And 11.0. 11.0L m -2 h -1 bar -1 And for inorganic salt Na 2 SO 4 The retention rate of (2) is only 95.0-98.0%. Furthermore, in the case of inorganic Salts (SO) against a divalent anion 4 2- /Cl - ) In the aspect of selective separation of the commercial membrane, the selectivity coefficient of the commercial membrane can only reach 25 and 1.6, which means that more energy consumption is consumed in the practical application fields of selective recovery of inorganic salt, recycling of waste water, desalination of sea water and the like. Therefore, in the face of higher effluent quality, low energy consumption, selective separation of divalent anion inorganic salt and other scenes, the flux, the retention rate and the selectivity of the conventional commercial membrane still cannot meet the actual demands.
Therefore, a green regulator which is low in cost and does not compete with an amine monomer for acyl chloride groups is searched for regulating and controlling the interfacial polymerization process, the high-flux high-selectivity nanofiltration membrane is prepared, the blank of the application field of the commercial membrane is filled, and the method has important significance for the development of the TFC nanofiltration membrane.
Disclosure of Invention
Aiming at the prior art problems, the primary aim of the invention is to provide a preparation method of a polyamide nanofiltration membrane, which regulates and controls the reaction of an amine monomer and an acyl chloride monomer in the interfacial polymerization process by adding additive alkaline lignin into aqueous phase solution, so that the prepared polyamide nanofiltration membrane has higher water flux and higher Na 2 SO 4 Retention and excellent SO 4 2- Cl-selectivity.
The second aim of the invention is to provide a polyamide nanofiltration membrane prepared by the preparation method.
The third object of the invention is to provide the application of the polyamide nanofiltration membrane in the sea water desalination, wastewater volume reduction and/or water resource recovery processes.
In order to achieve the above object, the present invention is realized by the following technical scheme:
a method for preparing a polyamide nanofiltration membrane, comprising the following steps:
s1, mixing a base film with an aqueous phase solution, standing and removing the aqueous phase solution;
s2, mixing the base film after the aqueous phase solution is removed with the oil phase solution, standing and drying to obtain the polyamide nanofiltration membrane;
the aqueous phase solution is a mixed solution of alkaline lignin, polyamine and deionized water; the oil phase solution is a mixed solution of polybasic acyl chloride and an organic solvent;
the structural formula of the alkaline lignin is shown as the following formula (I):
the inventor discovers through long-term research that in the preparation process of the polyamide nanofiltration membrane, alkaline lignin is added into a reaction system, and the alkaline lignin can promote amine monomers in an aqueous phase to react with acyl chloride monomers in an oil phase, so that a polyamide selective layer with high crosslinking degree is formed. In the scheme, the alkaline lignin does not directly react with the polybasic acyl chloride monomer, and only plays roles in regulating and controlling the diffusion of the polybasic amine monomer and the concentration of the polybasic amine monomer at the interface of the oil phase and the water phase in the reaction process of the aqueous-phase polybasic amine monomer and the oil-phase polybasic acyl chloride monomer. The alkaline lignin can increase the diffusion rate of the polyamine monomer, promote the reaction between the polyamine monomer and the polyacyl chloride monomer, increase the crosslinking degree, reduce the pore diameter, and increase the interception of sodium sulfate and SO 4 2- Cl-selectivity. Meanwhile, as the molecular weight of the alkaline lignin is large, a steric hindrance effect can be generated, and therefore, the adsorption of the alkaline lignin on the surface of the base film can influence the uniformity degree of the diffusion of the polyamine monomer to the organic phase, so that the polyamide selective layer presents a fold-shaped morphology, the thickness of the polyamide selective layer is reduced, the filtering area is further remarkably increased, and the water flux is remarkably increased.
Compared with the traditional polyamide nanofiltration membrane, the polyamide nanofiltration membrane prepared by the invention has larger specific surface area under the condition that the inorganic salt retention rate is not reduced, can effectively enhance the water permeation flux of the nanofiltration membrane, and greatly reduces the operation pressure and energy consumption in use; in addition, the interception of sodium sulfate and SO are greatly improved 4 2- Cl-selectivity. The invention adopts the environment-friendly low-cost alkaline lignin additive, not only does not need to add a catalyst (such as triethylamine) in the reaction process, but also solves the problems of overflow toxicity, high cost and the like of the additive used in the conventional interfacial polymerization; the prepared polyamide nanofiltration membrane has higher water flux and higher Na 2 SO 4 Retention and excellent SO 4 2- /Cl - The water permeation flux of the catalyst can reach 26.0L m at the highest -2 h -1 bar -1 ，Na 2 SO 4 The retention rate is above 99.0%, SO 4 2- /Cl - The selectivity is up to 187 or more.
Specifically, the alkaline lignin in the invention can be replaced by not only the compound shown in the formula (I) but also papermaking waste liquid containing the alkaline lignin. Typically, such waste paper-making liquid is waste pulping liquid treated by an alkaline method such as a sulfate method or a caustic soda method.
Preferably, the mass-volume ratio of the alkaline lignin to the deionized water is 2.5-10:1 g/L; further preferably, the mass-to-volume ratio of the alkaline lignin to the deionized water is 5-10:1 g/L; more preferably, the mass-to-volume ratio of the alkaline lignin to the deionized water is 7.5-10:1 g/L; most preferably, the mass-to-volume ratio of the alkaline lignin to the deionized water is 7.5:1g/L. In the above preferred range, the polyamide nanofiltration membrane obtained has more excellent water flux, retention rate and SO 4 2- /Cl - Selectivity.
Preferably, the mass volume ratio of the polyamine to the deionized water is 2-7:1 g/L. Further preferably, the mass-to-volume ratio of the polyamine to the deionized water is 5-7:1 g/L; most preferably, the mass to volume ratio of the polyamine to the deionized water is 5:1g/L.
Preferably, the mass-volume ratio of the polybasic acyl chloride to the organic solvent is 0.75-2.25:1 g/L. Further preferably, the mass-volume ratio of the polybasic acyl chloride to the organic solvent is 0.75-1.5:1 g/L; more preferably, the mass-to-volume ratio of the polybasic acyl chloride to the organic solvent is 1.0-1.5:1 g/L; most preferably, the mass to volume ratio of the polyacyl chloride to the organic solvent is 1.5:1g/L.
Preferably, the polyamine is selected from one or more of piperazine, m-phenylenediamine and polyethyleneimine.
Further preferably, the polyamine is piperazine.
Further preferably, the polyacyl chloride is 1,3, 5-benzenetricarboxylic acid chloride.
Preferably, the base membrane is polysulfone, polyethersulfone, polyvinylidene fluoride, polyacrylonitrile, polyethylene, polyvinylchloride or polytetrafluoroethylene.
Further preferably, the base membrane is polysulfone.
Preferably, the organic solvent is selected from one or more of n-hexane, n-sunflower alkane, petroleum ether, n-heptane and cyclohexane.
Further preferably, the organic solvent is n-hexane.
Preferably, in the step S1, the standing time is 1 to 10 minutes.
Further preferably, in the step S1, the standing time is 3 to 5 minutes.
Preferably, in the step S2, the standing time is 0.5 to 3 minutes.
Further preferably, in the step S2, the standing time is 1 to 2 minutes.
Preferably, in the step S2, the drying temperature is 40 to 80 ℃.
Further preferably, in the step S2, the drying temperature is 60 to 80 ℃.
Furthermore, the invention also claims a polyamide nanofiltration membrane prepared by the preparation method.
Furthermore, the invention also claims the application of the polyamide nanofiltration membrane in the sea water desalination, wastewater volume reduction and/or water resource recovery processes.
Compared with the prior art, the invention has the following beneficial effects:
(1) According to the invention, the alkaline lignin is added in the preparation process of the polyamide nanofiltration membrane, so that the reaction of the polyamine monomer and the polyacyl chloride monomer in the interfacial polymerization process can be effectively regulated, and the polyamide nanofiltration membrane with the surface having the fold structure is prepared. Compared with the traditional polyamide nanofiltration membrane, the polyamide nanofiltration membrane has larger specific surface area, higher water flux and Na 2 SO 4 Is excellent in SO 4 2- /Cl - Selectivity.
(2) The modifier alkaline lignin used in the invention can be derived from papermaking waste liquid, belongs to waste recycling, and reduces the cost for preparing the polyamide nanofiltration membrane by using modifiers such as nano materials, other synthetic materials and the like.
(3) The preparation method of the polyamide nanofiltration membrane has simple formula, and only a certain amount of alkaline lignin is needed to be added into the traditional aqueous phase solution in the production process, so that the whole membrane preparation process is not changed, and the industrialization is convenient.
Drawings
FIG. 1 is a scanning electron microscope image of the surfaces of the polyamide nanofiltration membranes produced in examples 1 to 3 and comparative example 1.
Detailed Description
The invention is further illustrated in the following drawings and specific examples, which are not intended to limit the invention in any way. Unless specifically stated otherwise, the reagents, methods and apparatus employed in the present invention are those conventional in the art.
EXAMPLE 1 preparation of Polyamide nanofiltration membranes
(1) Adding 5.0g of piperazine and 5.0g of alkaline lignin (the alkaline lignin is purchased from sigma-aldrich, CAS:8068-05-1, the structural formula of which is shown in the formula (I) below) into 1L of deionized water solution, and stirring for 10min at a stirring speed of 100rpm to obtain piperazine-alkaline lignin mixed aqueous phase solution;
(2) Pouring piperazine-alkaline lignin mixed solution into the surface of the polysulfone base membrane, standing for 3min, and removing redundant liquid drops on the surface of the base membrane by using an air knife after the solution is poured out to obtain the piperazine-alkaline lignin adsorbed polysulfone base membrane;
(3) Adding 1.5g of 1,3, 5-benzene trimethyl chloride into 1L of normal hexane solution, obtaining oil phase solution after complete dissolution, pouring the solution on the surface of the treated polysulfone base membrane, standing for 1min, and carrying out interfacial polymerization; and (3) after the solution on the surface of the membrane is poured out, the unreacted 1,3, 5-benzene trimethyl chloride on the surface of the base membrane is removed by cleaning with normal hexane solution, and the base membrane is placed in a 60 ℃ oven for heat treatment for 10min, so that the polyamide nanofiltration membrane is obtained.
EXAMPLE 2 preparation of Polyamide nanofiltration membranes
This embodiment differs from embodiment 1 in that: in the step (1), the amount of the alkaline lignin added was 7.5g.
EXAMPLE 3 preparation of Polyamide nanofiltration membranes
This embodiment differs from embodiment 1 in that: in the step (1), the addition amount of the alkaline lignin was 10.0g.
EXAMPLE 4 preparation of Polyamide nanofiltration membranes
This embodiment differs from embodiment 1 in that: in the step (1), 7g of piperazine is added into 1L of deionized water solution; in the step (2), the mass-volume ratio of the 1,3, 5-benzene trimethyl acyl chloride to the normal hexane solution is 2.25:1g/L.
EXAMPLE 5 preparation of Polyamide nanofiltration membranes
This embodiment differs from embodiment 1 in that: in the step (1), 2g of piperazine and 2.5g of alkaline lignin are added into 1L of deionized water solution; in the step (2), the mass-volume ratio of the 1,3, 5-benzene trimethyl acyl chloride to the normal hexane solution is 0.75:1g/L.
Comparative example 1
The difference between this comparative example and example 1 is that: in step (1), no alkaline lignin is added.
Comparative example 2
The difference between this comparative example and example 1 is that: in the step (1), sodium lignin sulfonate is adopted to replace alkaline lignin.
Comparative example 3
The difference between this comparative example and example 4 is that: in step (1), no alkaline lignin is added.
Comparative example 4
The difference between this comparative example and example 5 is that: in step (1), no alkaline lignin is added.
Comparative example 5
The commercial polyamide nanofiltration membrane Dow-Filmect NF270 was used in this comparative example.
Comparative example 6
The commercial polyamide nanofiltration membrane Dow-Filmect NF90 was used in this comparative example.
Comparative example 7
This embodiment differs from embodiment 1 in that: in the step (3), phthaloyl chloride is adopted to replace 1,3, 5-benzene trimethyl acyl chloride.
Comparative example 8
The difference between this comparative example and comparative example 7 is that: in step (1), no alkaline lignin is added.
Test example 1 characterization of Polyamide nanofiltration membranes
The polyamide composite nanofiltration membranes synthesized in examples 1 to 3 and comparative example 1 were subjected to surface morphology observation using a field emission scanning electron microscope (FESEM, model Quanta 400). Drying the polyamide composite nanofiltration membrane in advance by a vacuum drying oven; before observation, adhering conductive adhesive on a sample copper table, and fixing the small membrane cut into square shape on the conductive adhesive; the surface of the sample was subjected to a metal spraying treatment and observed at an acceleration voltage of 5 kV.
FIG. 1 is a scanning electron microscope image of the surfaces of the polyamide nanofiltration membranes prepared in examples 1 to 3 and comparative example 1. As can be seen from fig. 1, the polyamide selective layer of comparative example 1 is a typical nodular morphology, which is generated by the reaction of piperazine and 1,3, 5-benzoyl chloride at the surface of the porous base film. Examples 1-3 are polyamide nanofiltration membranes prepared by adding alkaline lignin, and it can be seen that the polyamide selective layer on the membrane surface exhibits different degrees of fold-like morphology when the added alkaline lignin content is different. As the alkali lignin concentration increases from 5.0g/L to 7.5g/L, the folds on the film surface become more and more uniform. With further increase of the alkaline lignin content, the polyamide selective layer on the surface of the film has stacking phenomenon, but the appearance of wrinkles still exists, and the polyamide selective layer has complete structure and no defects.
Test example 2 Water permeation flux and salt rejection experiments with Polyamide nanofiltration membranes
Pure water permeation flux and Na-permeation to the polyamide nanofiltration membranes prepared in comparative and example 2 SO 4 The specific method is as follows:
(1) Pure water flux measurement:
the filtration experiment was performed using a cross-flow filtration device (CF 016D; sterlitech, USA) with experimental parameters: the effective area of the film was 16×10 -4 m 2 The temperature of the filtration experiment was 25.+ -. 2 ℃ and the test pressure was 5bar.
At the beginning of the test, after pure water is pre-pressed for 30min under the pressure of 5bar to reach stable flux, the volume of the pure water passing through the nanofiltration membrane is continuously measured in a certain time, and the permeation flux J of the composite nanofiltration membrane to be measured is calculated W (Lm -2 h -1 bar -1 ) The calculation formula is as follows:
wherein V is the penetration volume, m 3 The method comprises the steps of carrying out a first treatment on the surface of the A is the effective area of the film, m 2 The method comprises the steps of carrying out a first treatment on the surface of the t is sample filtering time, s; ΔP is the pressure at which the device is operating, bar.
(2) Salt rejection and selectivity determination:
filtering experiments are carried out by adopting a cross-flow filtering device, and the composite nanofiltration membrane pair Na prepared by the examples and the comparative examples is obtained 2 SO 4 Or the retention rate R of NaCl, and the selectivity of the composite nanofiltration membrane to salt is characterized by the retention rate R of NaCl.
Respectively preparing 1000mg L -1 Na of (2) 2 SO 4 Or NaCl solution is used as raw material liquid, when different raw material liquids are used for testing, the raw material liquid is pre-pressed for 30min at 5bar to reach stable flux, and concentrated solution is collectedAnd permeate, the conductivity of both were tested, and the salt rejection rate R (%) was calculated from formula (2). SO4 2- /Cl - The selectivity coefficient α of (2) is calculated by equation (3):
wherein C is P And C F Represents conductivity values of permeate and concentrate, respectively, in [ mu ] S/cm.
Pure water permeation flux, na of the polyamide nanofiltration membranes prepared in comparative examples and examples 2 SO 4 Is a ratio of the retention rate of (and) SO 4 2- /Cl - The results of the selectivity test are compared with the performance of the separation membrane reported in the prior art, and the specific comparison results are shown in table 1.
TABLE 1
As can be seen from Table 1, the polyamide nanofiltration membrane prepared by the present invention has excellent water permeability, high divalent salt rejection rate and SO 4 2- /Cl - Selectivity. A pure water permeation flux of 7.3L m compared to comparative example 1 -2 h -1 bar -1 Pure water permeation flux of comparative example 2 was 20.0. 20.0L m -2 h -1 bar -1 Pure water permeation flux of comparative example 3 5.9. 5.9L m -2 h -1 bar -1 Pure water permeation flux of comparative example 4 was 9.0. 9.0L m -2 h -1 bar -1 The pure water permeation flux of examples 1 to 3 is obviously improved, and the pure water permeation flux is more than or equal to 20.7 and 20.7L m -2 h -1 bar -1 The polyamide nanofiltration membrane with the surface provided with the fold structure has more excellent water permeability compared with the traditional polyamide nanofiltration membrane. Wherein example 2 has the maximum pure water permeation flux (26.0. 26.0L m -2 h -1 bar -1 ) Is 3.5 times or more than that of comparative example 1 due to the large and more uniform density of the surface wrinkle structure.
In addition, na relative to comparative example 1 2 SO 4 Rejection (98.0%), na of examples 1-3 2 SO 4 The retention rates are all improved and are respectively 99.0%,99.6%,99.3% and SO4 2- /Cl - The separation performance is also significantly improved, and the selectivity coefficients alpha are 79.1, 187.3 and 100.4, respectively, which are significantly higher than those of comparative example 1 (41.8) and commercial membranes NF270 (25.0) and NF90 (1.6). The results show that the polyamide nanofiltration membrane prepared by using the alkaline lignin has the advantages of improving the permeation flux and improving the divalent salt Na 2 SO 4 Retention, and divalent salt/monovalent salt selectivity.
The foregoing examples are illustrative only and serve to explain some features of the method of the invention. The claims that follow are intended to claim the broadest possible scope as conceivable and the embodiments presented herein are demonstrated for the applicant's true test results. It is, therefore, not the intention of the applicant that the appended claims be limited by the choice of examples illustrating the features of the invention. Some numerical ranges used in the claims also include sub-ranges within which variations in these ranges should also be construed as being covered by the appended claims where possible.
Claims (10)
1. The preparation method of the polyamide nanofiltration membrane is characterized by comprising the following steps of:
s1, mixing a base film with an aqueous phase solution, standing and removing the aqueous phase solution;
s2, mixing the base film after the aqueous phase solution is removed with the oil phase solution, standing and drying to obtain the polyamide nanofiltration membrane;
the aqueous phase solution is a mixed solution of alkaline lignin, polyamine and deionized water; the oil phase solution is a mixed solution of polybasic acyl chloride and an organic solvent;
the polybasic acyl chloride is selected from one or more of 1,3, 5-benzene trimethyl acyl chloride, terephthaloyl chloride or isophthaloyl chloride;
the alkaline lignin was purchased from sigma-aldrich, CAS:8068-05-1.
2. The preparation method according to claim 1, wherein the mass-to-volume ratio of the alkaline lignin to the deionized water is 2.5-10:1 g/L; the mass volume ratio of the polyamine to the deionized water is 2-7:1 g/L.
3. The preparation method according to claim 1, wherein the mass-to-volume ratio of the polyacyl chloride to the organic solvent is 0.75-2.25:1 g/L.
4. The preparation method according to claim 1, wherein the polyamine is one or more selected from piperazine, m-phenylenediamine, and polyethyleneimine.
5. The method of claim 1, wherein the base membrane is polysulfone, polyethersulfone, polyvinylidene fluoride, polyacrylonitrile, polyethylene, polyvinylchloride, or polytetrafluoroethylene.
6. The preparation method according to claim 1, wherein the organic solvent is one or more selected from the group consisting of n-hexane, n-decane, petroleum ether, n-heptane and cyclohexane.
7. The method according to claim 1, wherein the standing time in the step S1 is 1 to 10 minutes.
8. The method according to claim 1, wherein the standing time in the step S2 is 0.5 to 3 minutes.
9. The polyamide nanofiltration membrane prepared by the preparation method of any one of claims 1 to 8.
10. Use of the polyamide nanofiltration membrane of claim 9 in a process of sea water desalination, wastewater volume reduction and/or water resource recovery.
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