CN114159980A - Preparation method of pH-responsive anti-pollution composite nanofiltration membrane - Google Patents
Preparation method of pH-responsive anti-pollution composite nanofiltration membrane Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 99
- 238000001728 nano-filtration Methods 0.000 title claims abstract description 61
- 239000002131 composite material Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 51
- 239000004372 Polyvinyl alcohol Substances 0.000 claims abstract description 44
- 229920002451 polyvinyl alcohol Polymers 0.000 claims abstract description 44
- 238000000108 ultra-filtration Methods 0.000 claims abstract description 34
- 229920002492 poly(sulfone) Polymers 0.000 claims abstract description 27
- 239000004745 nonwoven fabric Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 20
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims abstract description 15
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims abstract description 15
- 239000001630 malic acid Substances 0.000 claims abstract description 15
- 235000011090 malic acid Nutrition 0.000 claims abstract description 15
- 239000011248 coating agent Substances 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000004695 Polyether sulfone Substances 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 230000004048 modification Effects 0.000 claims abstract description 10
- 238000012986 modification Methods 0.000 claims abstract description 10
- 229920006393 polyether sulfone Polymers 0.000 claims abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 9
- 230000004044 response Effects 0.000 claims abstract description 9
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000004327 boric acid Substances 0.000 claims abstract description 8
- 238000004140 cleaning Methods 0.000 claims abstract description 5
- 238000007790 scraping Methods 0.000 claims abstract description 5
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 4
- 238000000614 phase inversion technique Methods 0.000 claims abstract description 4
- 239000000243 solution Substances 0.000 claims description 55
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 claims description 40
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 36
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- 239000012071 phase Substances 0.000 claims description 35
- YFHICDDUDORKJB-UHFFFAOYSA-N trimethylene carbonate Chemical compound O=C1OCCCO1 YFHICDDUDORKJB-UHFFFAOYSA-N 0.000 claims description 34
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000011259 mixed solution Substances 0.000 claims description 20
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 18
- MIOPJNTWMNEORI-GMSGAONNSA-N (S)-camphorsulfonic acid Chemical compound C1C[C@@]2(CS(O)(=O)=O)C(=O)C[C@@H]1C2(C)C MIOPJNTWMNEORI-GMSGAONNSA-N 0.000 claims description 12
- 230000035484 reaction time Effects 0.000 claims description 12
- 239000008346 aqueous phase Substances 0.000 claims description 11
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 10
- 239000003431 cross linking reagent Substances 0.000 claims description 10
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 238000006136 alcoholysis reaction Methods 0.000 claims description 7
- UWCPYKQBIPYOLX-UHFFFAOYSA-N benzene-1,3,5-tricarbonyl chloride Chemical compound ClC(=O)C1=CC(C(Cl)=O)=CC(C(Cl)=O)=C1 UWCPYKQBIPYOLX-UHFFFAOYSA-N 0.000 claims description 6
- LEQAOMBKQFMDFZ-UHFFFAOYSA-N glyoxal Chemical compound O=CC=O LEQAOMBKQFMDFZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000009826 distribution Methods 0.000 claims description 4
- 229920000642 polymer Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000004952 Polyamide Substances 0.000 claims description 3
- 230000002378 acidificating effect Effects 0.000 claims description 3
- IIEWJVIFRVWJOD-UHFFFAOYSA-N ethyl cyclohexane Natural products CCC1CCCCC1 IIEWJVIFRVWJOD-UHFFFAOYSA-N 0.000 claims description 3
- 229940015043 glyoxal Drugs 0.000 claims description 3
- 229920002647 polyamide Polymers 0.000 claims description 3
- 239000004971 Cross linker Substances 0.000 claims description 2
- 238000000926 separation method Methods 0.000 abstract description 6
- 230000006872 improvement Effects 0.000 abstract description 4
- 230000000704 physical effect Effects 0.000 abstract description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 239000010865 sewage Substances 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000010612 desalination reaction Methods 0.000 description 5
- 239000013535 sea water Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- -1 aromatic acyl chloride Chemical class 0.000 description 4
- 229910001385 heavy metal Inorganic materials 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000004065 wastewater treatment Methods 0.000 description 4
- BKFFTWAVRUYWIQ-UHFFFAOYSA-N C=C.C=C.C=C.OP(O)(O)=O Chemical compound C=C.C=C.C=C.OP(O)(O)=O BKFFTWAVRUYWIQ-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 239000004698 Polyethylene Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 229910001415 sodium ion Inorganic materials 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 235000013361 beverage Nutrition 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L magnesium sulphate Substances [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000036314 physical performance Effects 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920001184 polypeptide Polymers 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 102000004196 processed proteins & peptides Human genes 0.000 description 1
- 108090000765 processed proteins & peptides Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
-
- 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
- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0088—Physical treatment with compounds, e.g. swelling, coating or impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0095—Drying
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
- B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
- B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
- B32B5/022—Non-woven fabric
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/442—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by nanofiltration
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/08—Seawater, e.g. for desalination
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Water Supply & Treatment (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Textile Engineering (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
The invention discloses a preparation method of a pH response anti-pollution composite nanofiltration membrane, which comprises the following steps of firstly obtaining nanofiltration membranes with different intercepted monovalent ions by adopting a method of adjusting the pH value of a water phase in interfacial polymerization, and then obtaining the anti-pollution nanofiltration membrane through hydrophilic modification: (1) scraping a polysulfone or polyether sulfone ultrafiltration membrane on a non-woven fabric by an L-S phase inversion method, and cleaning with pure water and hot water; (2) preparing a water phase solution and an oil phase solution, and adjusting different pH values of the water phase solution to obtain nanofiltration membranes with different monovalent ion rejection rates; (3) preparing a solution of polyvinyl alcohol (PVA), malic acid and boric acid, coating the nanofiltration membrane obtained in the step (2), and then heating and drying; (4) and (4) drying to obtain the pollution-resistant composite nanofiltration membrane through the operation of the step (3). The method has the advantages of simple operation, controllable reaction and great improvement on the physical property and selective separation of the nanofiltration membrane.
Description
Technical Field
The invention relates to the field of preparation of composite nanofiltration membranes, in particular to a preparation method of a pH-responsive anti-pollution composite nanofiltration membrane.
Background
The nanofiltration membrane is a pressure-driven separation membrane, is characterized by high separation efficiency, lower pressure than reverse osmosis membranes and specific molecular weight interception, and is widely applied to the fields of the concentration and separation of food and beverage drinking water and liquid, the softened water treatment of seawater desalination and the like.
The nanofiltration membrane is mainly applied to the field of drinking water at present, has the characteristic of specific molecular weight cut-off, can retain beneficial mineral substances and can achieve a good water purification effect, so that the nanofiltration membrane is widely applied to the field of water purification, but has the characteristics of large flow, easiness in pollution blockage, short service life and the like in the fields of concentration and recovery of protein polypeptide, concentration of polysaccharide alcohol, high COD (chemical oxygen demand) sewage treatment, concentration and recycling of oil-containing liquid, and the like, so that the requirements on COD (chemical oxygen demand) of inlet water at the front stage of seawater pretreatment are high, the requirement on salt production from seawater requires high permeability of monovalent sodium ions, the requirement on pollution resistance performance is high, and the selectivity on monovalent ions is high in the fields of heavy metal sewage treatment and concentration and recycling, so the requirements on pollution resistance performance and ion selection performance of the nanofiltration membrane are increasingly outstanding.
In order to solve the problems, the traditional preparation method of the nanofiltration membrane is improved, and a preparation method of the pH response anti-pollution composite nanofiltration membrane is provided.
Disclosure of Invention
Aiming at the defects in the prior art, the invention provides the preparation method of the pH response anti-pollution composite nanofiltration membrane, which has the characteristics of simple operation, controllable reaction, great improvement on the physical performance and selective separability of the nanofiltration membrane, application to oily wastewater treatment, chemical material concentration, Chinese and western medicine preparation concentration, material recycling, sewage treatment, seawater desalination pretreatment and the like, and is particularly suitable for the fields of heavy metal wastewater treatment and concentration recovery.
In order to achieve the aim of the invention, the invention adopts the specific scheme that:
a preparation method of a pH response anti-pollution composite nanofiltration membrane comprises the following steps of firstly obtaining nanofiltration membranes with different interception univalent ions by adopting a method of adjusting the pH value of a water phase in interfacial polymerization, and then obtaining the anti-pollution nanofiltration membrane through hydrophilic modification:
(1) scraping a polysulfone or polyether sulfone ultrafiltration membrane on a non-woven fabric by an L-S phase inversion method, and cleaning with pure water and hot water;
(2) preparing a water phase solution and an oil phase solution, and adjusting different pH values of the water phase solution to obtain nanofiltration membranes with different monovalent ion rejection rates;
(3) preparing a solution of polyvinyl alcohol (PVA), malic acid and boric acid, coating the nanofiltration membrane obtained in the step (2), and then heating and drying;
(4) and (4) drying to obtain the pollution-resistant composite nanofiltration membrane through the operation of the step (3).
Preferably, the ultrafiltration membrane used in step (1) has a molecular weight cut-off distribution of from 5 to 15 ten thousand;
the step (1) comprises the following specific steps: stirring and dissolving the ultrafiltration membrane in a solvent at the temperature of 50-70 ℃ to prepare a solution, then coating the solution on non-woven fabrics, and arranging the non-woven fabrics in cold water at the temperature of 8-15 ℃ to prepare a flat ultrafiltration membrane;
the concentration of the Polysulfone (PS) solution in the step (1) is 12-20%;
the polyether sulfone ultrafiltration membrane used in the step (1) is polysulfone polymer, the non-woven fabric is PET non-woven fabric, and the gram weight of the polyether sulfone ultrafiltration membrane is 70-100 g.
Preferably, the aqueous phase solution prepared in the step (2) is a mixed solution containing piperazine, camphorsulfonic acid, citric acid and pure water or a mixed solution containing piperazine, camphorsulfonic acid, citric acid and pure water;
the oil phase solution is a mixed solution containing trimethylene carbonate (TMC), dimethyl sulfoxide (DMSO) and cyclohexane or a mixed solution containing trimethylene carbonate (TMC), ethyl acetate and cyclohexane.
Preferably, the concentration of the piperazine is 1.5% -5%, the concentration of the camphorsulfonic acid is 1.5% -5%, the concentration of the citric acid is 0.1% -0.5%, the concentration of the trimesoyl chloride (TMC) is 0.15% -0.5%, the concentration of the dimethyl sulfoxide (DMSO) is 0.15% -0.5%, the concentration of the triethylamine is 1.5% -5%, the concentration of the ethyl acetate is 0.15% -0.5%, and the pH value of an aqueous phase reaction solution is alkaline.
Preferably, the concentration of the piperazine is 1.5% -5%, the concentration of the camphorsulfonic acid is 1.5% -5%, the concentration of trimesoyl chloride (TMC) is 0.15% -0.5%, the concentration of dimethyl sulfoxide (DMSO) is 0.15% -0.5%, the concentration of the citric acid is 2.5% -5%, the concentration of the ethyl acetate is 0.15% -0.5%, and the pH value of an aqueous phase reaction solution is acidic.
Preferably, the ultrafiltration membrane in the step (2) has a reaction time of 0.5 to 2 minutes in the water phase and a reaction time of 0.5 to 2 minutes in the oil phase.
Preferably, the solution used in the coating modification process in step (3) is a PVA cross-linking agent obtained by reacting polyvinyl alcohol (PVA) with a degree of alcoholysis of 70% with sulfuric acid and glyoxal or a PVA cross-linking agent obtained by reacting polyvinyl alcohol (PVA) with a degree of alcoholysis of 70% with sulfuric acid and malic acid, the solution is coated on a nanofiltration membrane, and the nanofiltration membrane is heated by infrared for 5 to 10 minutes, wherein the infrared heating temperature is between 55 and 70 ℃.
Preferably, in the step (3), the concentration of polyvinyl alcohol (PVA) is 0.1-0.5%, the concentration of sulfuric acid is 0.5-3%, the concentration of malic acid is 0.1-0.3%, the concentrations of malic acid and boric acid are 0.1-0.3%, and the reaction time of PVA crosslinker is 30-60 minutes.
Preferably, the composite nanofiltration membrane prepared in the step (4) comprises a four-layer structure from inside to outside, and the four-layer structure sequentially comprises a non-woven fabric, a polysulfone ultrafiltration membrane, a polyamide layer and a modified layer.
The invention has the beneficial effects that:
the method has the characteristics of simple operation, controllable reaction, great improvement on the physical property and selective separation property of the nanofiltration membrane, application to oily wastewater treatment, chemical material concentration, Chinese and western medicine preparation concentration, material recycling, sewage treatment, seawater desalination pretreatment and the like, and is particularly suitable for the fields of heavy metal wastewater treatment and concentration recovery. By further limiting a formula for preparing different monovalent ion interception composite nanofiltration membranes through pH response and a preparation method thereof, the nanofiltration membrane with the monovalent sodium ion desalination rate of 20-80%, the interception rate of adjustable water flux of 30-45gfd can be obtained, and the nanofiltration membrane can be used in sewage with COD less than 10000ppm for a long time through modification; so that the application of the method to heavy metal sewage treatment and material concentration becomes possible.
Detailed Description
The present invention is further described below by way of specific examples, but the present invention is not limited to only the following examples. Variations, combinations, or substitutions of the invention, which are within the scope of the invention or the spirit, scope of the invention, will be apparent to those of skill in the art and are within the scope of the invention.
A preparation method of a pH response anti-pollution composite nanofiltration membrane comprises the following steps of firstly obtaining nanofiltration membranes with different interception univalent ions by adopting a method of adjusting the pH value of a water phase in interfacial polymerization, and then obtaining the anti-pollution nanofiltration membrane through hydrophilic modification:
(1) scraping a polysulfone or polyether sulfone ultrafiltration membrane on a non-woven fabric by an L-S phase inversion method, and cleaning with pure water and hot water;
(2) preparing a water phase solution and an oil phase solution, and adjusting different pH values of the water phase solution to obtain nanofiltration membranes with different monovalent ion rejection rates;
(3) preparing a solution of polyvinyl alcohol (PVA), malic acid and boric acid, coating the nanofiltration membrane obtained in the step (2), and then heating and drying;
(4) and (4) drying to obtain the pollution-resistant composite nanofiltration membrane through the operation of the step (3).
The cutoff molecular weight distribution of the ultrafiltration membrane used in the step (1) is 5-15 ten thousand;
the step (1) comprises the following specific steps: stirring and dissolving the ultrafiltration membrane in a solvent at the temperature of 50-70 ℃ to prepare a solution, then coating the solution on non-woven fabrics, and arranging the non-woven fabrics in cold water at the temperature of 8-15 ℃ to prepare a flat ultrafiltration membrane;
the concentration of the Polysulfone (PS) solution in the step (1) is 12-20%;
the polyether sulfone ultrafiltration membrane used in the step (1) is polysulfone polymer, the non-woven fabric is PET non-woven fabric, and the gram weight of the polyether sulfone ultrafiltration membrane is 70-100 g.
The water phase solution prepared in the step (2) is a mixed solution containing piperazine, camphorsulfonic acid, citric acid and pure water or a mixed solution containing piperazine, camphorsulfonic acid, citric acid and pure water;
the oil phase solution is a mixed solution containing trimethylene carbonate (TMC), dimethyl sulfoxide (DMSO) and cyclohexane or a mixed solution containing trimethylene carbonate (TMC), ethyl acetate and cyclohexane.
The concentration of the piperazine is 1.5% -5%, the concentration of the camphorsulfonic acid is 1.5% -5%, the concentration of the citric acid is 0.1% -0.5%, the concentration of the trimesoyl chloride (TMC) is 0.15% -0.5%, the concentration of the dimethyl sulfoxide (DMSO) is 0.15% -0.5%, the concentration of the triethylamine is 1.5% -5%, the concentration of the ethyl acetate is 0.15% -0.5%, and the pH value of a water-phase reaction solution is alkaline.
The piperazine concentration is 1.5% -5%, the camphorsulfonic acid concentration is 1.5% -5%, the trimesoyl chloride (TMC) concentration is 0.15% -0.5%, the dimethyl sulfoxide (DMSO) concentration is 0.15% -0.5%, the citric acid concentration is 2.5% -5%, the ethyl acetate concentration is 0.15% -0.5%, and the pH value of the water phase reaction solution is acidic.
In the step (2), the reaction time of the ultrafiltration membrane in the water phase is 0.5-2 minutes, and the reaction time in the oil phase is 0.5-2 minutes.
And (3) coating a solution used in the coating modification process in the step (3) on a nanofiltration membrane by using a PVA cross-linking agent obtained by reacting polyvinyl alcohol (PVA) with a degree of alcoholysis of 70% with sulfuric acid and glyoxal or a PVA cross-linking agent obtained by reacting polyvinyl alcohol (PVA) with a degree of alcoholysis of 70% with sulfuric acid and malic acid, and heating for 5-10 minutes by infrared, wherein the infrared heating temperature is 55-70 ℃.
In the step (3), the concentration of polyvinyl alcohol (PVA) is 0.1-0.5%, the concentration of sulfuric acid is 0.5-3%, the concentration of malic acid is 0.1-0.3%, the concentrations of malic acid and boric acid are 0.1-0.3%, and the reaction time of PVA cross-linking agent is 30-60 minutes.
The composite nanofiltration membrane prepared in the step (4) comprises four layers of structures from inside to outside, namely a non-woven fabric, a polysulfone ultrafiltration membrane, a polyamide layer and a modified layer in sequence.
Example 1
1) Scraping the polysulfone ultrafiltration membrane on the non-woven fabric by a phase transition method, and cleaning with pure water and hot water;
2) preparing polyfunctional group aromatic polyamine, a water phase additive and pure water into a water phase solution in a stainless steel tank;
3) preparing polyfunctional group aromatic acyl chloride, an oil phase additive and a solvent into an oil phase solution in a stainless steel tank;
4) soaking the polyethylene base film prepared in the step S1 in the aqueous phase solution, taking out the polyethylene base film, and squeezing the residual aqueous phase on the surface of the polyethylene base film by using an air knife;
5) dip-coating the polysulfone ultrafiltration membrane obtained in the step S4 with the oil phase solution, taking out the polysulfone ultrafiltration membrane, and drying the polysulfone ultrafiltration membrane to obtain a composite nanofiltration membrane;
6) preparing a solution of polyvinyl alcohol (PVA), malic acid and boric acid, coating the nanofiltration membrane obtained in the step (3), and then heating and drying.
As a preferred embodiment of this embodiment, the ultrafiltration membrane used in step (1) has a molecular weight cut-off distribution of 5 to 8 ten thousand, and the specific steps of step (1) include: the ultrafiltration membrane was dissolved in a dimethylacetamide (DMAc) solution at a temperature of 70 ℃ with stirring to prepare a Polysulfone (PS) solution, and then the Polysulfone (PS) solution was coated on a nonwoven fabric, and the nonwoven fabric was placed in cold water at 8-12 ℃ to prepare a flat ultrafiltration membrane, wherein the Polysulfone (PS) solution had a concentration of 15% as a preferred embodiment of this example.
As a preferred embodiment of this example, the ultrafiltration membrane material used in step (1) is polysulfone polymer, and the nonwoven fabric is PET nonwoven fabric, and its gram weight is 70-90 g.
As a preferred embodiment of this embodiment, the aqueous solution prepared in step (2) is a mixed solution containing piperazine, DMF, sodium hydroxide, and pure water; the oil phase solution is a mixed solution containing trimethylene carbonate (TMC), methyl cellosolve and cyclohexane.
In a preferred embodiment of this embodiment, the concentration of piperazine is 1.5-3%, the concentration of DMF is 1-1.5%, sodium hydroxide is 0.01-0.005%, the pH is 9.5-11, the concentration of trimethylene carbonate (TMC) is 0.01-0.15%, and the concentration of methylcellosolve is 0.01-0.015%.
As a preferred embodiment of this example, the reaction time of the ultrafiltration membrane in the step (2) in the water phase is 0.05 to 0.1 minute, and the reaction time in the oil phase is 0.05 to 0.1 minute.
As a preferred embodiment of this embodiment, the solution used in the coating modification process in step (4) is a PVA crosslinking agent obtained by reacting polyvinyl alcohol (PVA) with 90% alcoholysis degree with hydrochloric acid and malic acid, and the PVA crosslinking agent is coated on a nanofiltration membrane and heated by infrared for 5 minutes, wherein the infrared heating temperature is between 55 ℃.
As a preferred embodiment of this example, the concentration of the polyvinyl alcohol (PVA) is 0.05-0.1%, the concentration of hydrochloric acid is 0.1-0.5%, the concentration of apple is 0.05-0.1%, and the reaction time of the PVA cross-linking agent is 10 minutes.
Example 2:
example 2 differs from example 1 in the following step 5) in example 1;
as a preferred embodiment of this embodiment, the aqueous solution prepared in step (2) is a mixed solution including piperazine, acetic acid, and pure water; the oil phase solution is a mixed solution containing trimethylene carbonate (TMC), methyl cellosolve, triethylene phosphate and cyclohexane. In a preferred embodiment of this example, the piperazine concentration is 1.5-3%, the acetic acid concentration is 0.01% -0.05%, the test aqueous solution has a pH of 3-6.5, the trimethylene carbonate (TMC) concentration is 0.01% -0.15%, the methylcellosolve concentration is 0.01% -0.015%, and the triethylene phosphate concentration is 0.01% -0.005%.
Example 3:
example 3 differs from example 1 in the following step 5) in example 1;
as a preferred embodiment of this embodiment, the aqueous solution prepared in step (2) is a mixed solution including piperazine, hydrochloric acid, and pure water; the oil phase solution is a mixed solution containing trimethylene carbonate (TMC), methyl cellosolve and cyclohexane. In a preferred embodiment of this embodiment, the piperazine concentration is 1.5-3%, the hydrochloric acid concentration is 0.1-0.15%, the pH is 1-2, the trimethylene carbonate (TMC) concentration is 0.01-0.15%, the methyl cellosolve concentration is 0.01-0.015%, and the triethylene phosphate concentration is 0.01-0.005%.
Comparative example 1:
comparative example 1 differs from example 1 in the following step 5) in example 1;
as a preferred embodiment of this embodiment, the aqueous solution prepared in step (2) is a mixed solution containing piperazine and pure water; the oil phase solution is a mixed solution containing trimethylene carbonate (TMC), methyl cellosolve and cyclohexane. In a preferred embodiment of this embodiment, the piperazine concentration is 1.5-3%, the pH of the aqueous phase is 7.5-8, the trimethylene carbonate (TMC) concentration is 0.01-0.15%, the methylcellosolve concentration is 0.01-0.015%, and the pH of the aqueous phase is adjusted to a neutral solution with hydrochloric acid;
performance test:
the nanofiltration membranes prepared in the experimental examples 1-4 and the comparative example 1 were taken and subjected to a desalination test on a membrane detection table. The operating pressure of the detection table is 1Mpa, and the configured concentration of NaCl and CaCl is 1000PPM2、MgSO4The raw water solutions were tested at 25 ℃ and pH 6.5-7.5, and the water flux and salt rejection of each solution after the membrane was operated for 30min were determined, with the results shown in Table 1:
TABLE 1 removal rate and flow rate of each test solution
As can be seen from the above experimental results, experimental examples 1 and 2 have significant monovalent and divalent ion selective separation performance, and the methods of experimental examples 1 and 2 are preferred as the results of the present invention.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the present invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (9)
1. A preparation method of a pH response anti-pollution composite nanofiltration membrane is characterized in that firstly, nanofiltration membranes with different monovalent ion interception functions are obtained by adjusting the pH value of a water phase in interfacial polymerization, and then the anti-pollution nanofiltration membrane is obtained by hydrophilic modification, and the preparation method specifically comprises the following steps:
(1) scraping a polysulfone or polyether sulfone ultrafiltration membrane on a non-woven fabric by an L-S phase inversion method, and cleaning with pure water and hot water;
(2) preparing a water phase solution and an oil phase solution, and adjusting different pH values of the water phase solution to obtain nanofiltration membranes with different monovalent ion rejection rates;
(3) preparing a solution of polyvinyl alcohol (PVA), malic acid and boric acid, coating the nanofiltration membrane obtained in the step (2), and then heating and drying;
(4) and (4) drying to obtain the pollution-resistant composite nanofiltration membrane through the operation of the step (3).
2. The method for preparing the pH-responsive anti-pollution composite nanofiltration membrane according to claim 1, wherein the ultrafiltration membrane used in the step (1) has a molecular weight cut-off distribution of 5-15 ten thousand;
the step (1) comprises the following specific steps: stirring and dissolving the ultrafiltration membrane in a solvent at the temperature of 50-70 ℃ to prepare a solution, then coating the solution on non-woven fabrics, and arranging the non-woven fabrics in cold water at the temperature of 8-15 ℃ to prepare a flat ultrafiltration membrane;
the concentration of the Polysulfone (PS) solution in the step (1) is 12-20%;
the polyether sulfone ultrafiltration membrane used in the step (1) is polysulfone polymer, the non-woven fabric is PET non-woven fabric, and the gram weight of the polyether sulfone ultrafiltration membrane is 70-100 g.
3. The method for preparing the pH-responsive anti-pollution composite nanofiltration membrane according to claim 1, wherein the aqueous phase solution prepared in the step (2) is a mixed solution comprising piperazine, camphorsulfonic acid, citric acid and pure water or a mixed solution comprising piperazine, camphorsulfonic acid, citric acid and pure water;
the oil phase solution is a mixed solution containing trimethylene carbonate (TMC), dimethyl sulfoxide (DMSO) and cyclohexane or a mixed solution containing trimethylene carbonate (TMC), ethyl acetate and cyclohexane.
4. The method for preparing a pH response anti-pollution composite nanofiltration membrane according to claim 3, wherein the piperazine concentration is 1.5-5%, the camphorsulfonic acid concentration is 1.5-5%, the citric acid concentration is 0.1-0.5%, the trimesoyl chloride (TMC) concentration is 0.15-0.5%, the dimethyl sulfoxide (DMSO) concentration is 0.15-0.5%, the triethylamine concentration is 1.5-5%, the ethyl acetate concentration is 0.15-0.5%, and the pH value of the aqueous phase reaction solution is alkaline.
5. The method for preparing a pH response anti-pollution composite nanofiltration membrane according to claim 3, wherein the piperazine concentration is 1.5-5%, the camphorsulfonic acid concentration is 1.5-5%, the trimesoyl chloride (TMC) concentration is 0.15-0.5%, the dimethyl sulfoxide (DMSO) concentration is 0.15-0.5%, the citric acid concentration is 2.5-5%, the ethyl acetate concentration is 0.15-0.5%, and the pH value of the aqueous phase reaction solution is acidic.
6. The method for preparing a pH-responsive anti-pollution composite nanofiltration membrane according to claim 1, wherein the ultrafiltration membrane in the step (2) has a reaction time of 0.5-2 minutes in an aqueous phase and a reaction time of 0.5-2 minutes in an oil phase.
7. The method for preparing a pH-responsive anti-pollution composite nanofiltration membrane according to claim 1, wherein the solution used in the coating modification process in the step (3) is a PVA cross-linking agent obtained by reacting 70% alcoholysis degree of polyvinyl alcohol (PVA) with sulfuric acid and glyoxal or a PVA cross-linking agent obtained by reacting 70% alcoholysis degree of polyvinyl alcohol (PVA) with sulfuric acid and malic acid, the solution is coated on the nanofiltration membrane, and the nanofiltration membrane is heated by infrared heating for 5-10 minutes, wherein the infrared heating temperature is 55-70 ℃.
8. The method for preparing a pH-responsive anti-pollution composite nanofiltration membrane according to claim 1, wherein in the step (3), the concentration of polyvinyl alcohol (PVA) is 0.1-0.5%, the concentration of sulfuric acid is 0.5-3%, the concentration of malic acid is 0.1-0.3%, the concentrations of malic acid and boric acid are 0.1-0.3%, and the reaction time of the PVA crosslinker is 30-60 minutes.
9. The method for preparing a pH-responsive anti-pollution composite nanofiltration membrane according to claim 1, wherein the composite nanofiltration membrane prepared in the step (4) comprises a four-layer structure from inside to outside, and the four-layer structure comprises a nonwoven fabric, a polysulfone ultrafiltration membrane, a polyamide layer and a modified layer in sequence.
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