CN114405276A - Preparation method of high-temperature-resistant separation membrane material - Google Patents
Preparation method of high-temperature-resistant separation membrane material Download PDFInfo
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- CN114405276A CN114405276A CN202111610040.4A CN202111610040A CN114405276A CN 114405276 A CN114405276 A CN 114405276A CN 202111610040 A CN202111610040 A CN 202111610040A CN 114405276 A CN114405276 A CN 114405276A
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- 239000012528 membrane Substances 0.000 title claims abstract description 103
- 239000000463 material Substances 0.000 title claims abstract description 79
- 238000000926 separation method Methods 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 238000005266 casting Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 26
- 239000002131 composite material Substances 0.000 claims abstract description 25
- 239000004642 Polyimide Substances 0.000 claims abstract description 20
- 229920001721 polyimide Polymers 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 18
- 239000002861 polymer material Substances 0.000 claims abstract description 12
- 239000011248 coating agent Substances 0.000 claims abstract description 10
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 239000012074 organic phase Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 6
- 239000012071 phase Substances 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 5
- 239000002904 solvent Substances 0.000 claims abstract description 5
- 238000012695 Interfacial polymerization Methods 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 239000010410 layer Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical group CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 239000011229 interlayer Substances 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 230000004048 modification Effects 0.000 claims description 7
- 238000012986 modification Methods 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- 238000003860 storage Methods 0.000 claims description 6
- 239000004695 Polyether sulfone Substances 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 239000003995 emulsifying agent Substances 0.000 claims description 5
- 229920006393 polyether sulfone Polymers 0.000 claims description 5
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 claims description 4
- KWOLFJPFCHCOCG-UHFFFAOYSA-N Acetophenone Chemical compound CC(=O)C1=CC=CC=C1 KWOLFJPFCHCOCG-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000002033 PVDF binder Substances 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 4
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims description 4
- 239000004745 nonwoven fabric Substances 0.000 claims description 4
- 229920002981 polyvinylidene fluoride Polymers 0.000 claims description 4
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 230000008595 infiltration Effects 0.000 claims description 3
- 238000001764 infiltration Methods 0.000 claims description 3
- 238000000614 phase inversion technique Methods 0.000 claims description 3
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 3
- 125000001174 sulfone group Chemical group 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N NMP Substances CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 229930188620 butyrolactone Natural products 0.000 claims description 2
- 238000007606 doctor blade method Methods 0.000 claims description 2
- 229960004756 ethanol Drugs 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 150000003949 imides Chemical class 0.000 claims description 2
- 239000012535 impurity Substances 0.000 claims description 2
- 229940073577 lithium chloride Drugs 0.000 claims description 2
- 229940057847 polyethylene glycol 600 Drugs 0.000 claims description 2
- 229920000136 polysorbate Polymers 0.000 claims description 2
- 230000004044 response Effects 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000004140 cleaning Methods 0.000 abstract description 4
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 22
- 238000001223 reverse osmosis Methods 0.000 description 15
- 238000001728 nano-filtration Methods 0.000 description 11
- 239000003921 oil Substances 0.000 description 10
- 238000004659 sterilization and disinfection Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000010612 desalination reaction Methods 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 230000004907 flux Effects 0.000 description 3
- 229910021389 graphene Inorganic materials 0.000 description 3
- 229920002492 poly(sulfone) Polymers 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000000108 ultra-filtration Methods 0.000 description 3
- GLUUGHFHXGJENI-UHFFFAOYSA-N Piperazine Chemical compound C1CNCCN1 GLUUGHFHXGJENI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-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
- 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 description 2
- 239000000919 ceramic Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 238000005374 membrane filtration Methods 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 description 2
- 235000011152 sodium sulphate Nutrition 0.000 description 2
- WZCQRUWWHSTZEM-UHFFFAOYSA-N 1,3-phenylenediamine Chemical compound NC1=CC=CC(N)=C1 WZCQRUWWHSTZEM-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- VDRSDNINOSAWIV-UHFFFAOYSA-N [F].[Si] Chemical compound [F].[Si] VDRSDNINOSAWIV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 229920006015 heat resistant resin Polymers 0.000 description 1
- 239000012510 hollow fiber Substances 0.000 description 1
- 229940018564 m-phenylenediamine Drugs 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011342 resin composition Substances 0.000 description 1
- 239000012465 retentate Substances 0.000 description 1
- 239000010865 sewage Substances 0.000 description 1
- 238000004904 shortening Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000002791 soaking Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 229910000406 trisodium phosphate Inorganic materials 0.000 description 1
- 235000019801 trisodium phosphate Nutrition 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- B01D61/02—Reverse osmosis; Hyperfiltration ; Nanofiltration
- B01D61/025—Reverse osmosis; Hyperfiltration
-
- 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
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- 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
- B01D67/0009—Organic membrane manufacture by phase separation, sol-gel transition, evaporation or solvent quenching
- B01D67/0011—Casting solutions therefor
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- 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
- 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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
-
- 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
- B01D71/66—Polymers having sulfur in the main chain, with or without nitrogen, oxygen or carbon only
- B01D71/68—Polysulfones; Polyethersulfones
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/22—Thermal or heat-resistance properties
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Water Supply & Treatment (AREA)
- Nanotechnology (AREA)
- Manufacturing & Machinery (AREA)
- Dispersion Chemistry (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
A preparation method of a high-temperature resistant separation membrane material belongs to the technical field of preparation of membrane separation materials. The method comprises the following steps: adding the modified polyimide into a film-forming polymer material to prepare a film casting solution, solidifying and rinsing the film casting solution to obtain a porous supporting layer material, fully infiltrating the porous supporting layer material through a water-phase solution tank, removing surface moisture, coating solvent oil containing an organic phase monomer on the surface of the porous supporting layer material, and performing oven heat treatment to complete the interfacial polymerization process of the composite film to obtain the high-heat-resistant separation film material. The preparation method of the high-heat-resistant separation membrane material improves the thermal-mechanical stability properties of the porous supporting layer material, such as thermal shrinkage resistance, thermal deformation resistance and the like; the prepared high-temperature resistant separation membrane material has continuous and stable operation in medium with high temperature and high temperature above 70 ℃ and cyclic intermittent cleaning for more than 30 minutes and more than or equal to 45 times in the medium with high temperature and high temperature above 90 ℃; has equal or more than equal separation performance, such as interception performance, water production efficiency and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of membrane separation materials, and particularly relates to a preparation method of a high-heat-resistant separation membrane material.
Background
The membrane material is one of the key points for realizing the high-performance membrane separation technology, and mainly comprises a reverse osmosis and nanofiltration composite organic membrane material represented by polysulfone and polyamide, a hollow fiber ultrafiltration membrane material represented by organic silicon fluorine materials such as polyvinylidene fluoride and polytetrafluoroethylene, and an inorganic membrane material represented by ceramics and the like. The organic membrane material is superior to the inorganic ceramic membrane in good toughness and high separation precision, is widely applied to the application fields of salt ion separation/regulation, drinking water purification and the like, and according to the difference of separation scales, the service life of the membrane is challenged, especially the influence of heat resistance on the membrane structure often causes the attenuation of membrane flux, the increase of operation cost and the shortening of the service life of the membrane, thereby becoming a main obstacle for the wide application of the membrane separation technology in the treatment of drinking water, sewage and waste water.
The high-heat-resistant separation membrane material is one of key components for preparing the sanitary-grade heat disinfection separation membrane element. The sanitary reverse osmosis membrane element is a membrane element product specially designed for the pharmaceutical industry, the food industry and the like with strict sanitary indexes such as bacteria or heat sources. The main difference with a conventional reverse osmosis membrane element is the complete fill (Full-Fit) design without a retentate zone. The sanitary reverse osmosis membrane element has two types of standard type and heat disinfection type, wherein the heat disinfection type product can be washed and disinfected by using hot water, and the standard type product does not support the hot water washing and disinfection treatment. The sanitary reverse osmosis membrane element is mainly used for production of pure water for pharmacy and application in food industry. The membrane material used as one of the key components of the sanitary reverse osmosis membrane element is composed of three-layer structures of a PET non-woven fabric, a support membrane and a composite membrane, the conventional reverse osmosis or nanofiltration composite membrane material can be directly applied to a standard sanitary membrane product, and the conventional reverse osmosis or nanofiltration composite membrane material is applied to the membrane material of a heat disinfection membrane product.
The heat-resistant technology is combined with the membrane modification technology to form the composite heat-resistant separation modified membrane, so that the stability and the interception characteristic of the membrane during the treatment of hot materials can be effectively improved, and the service life of the membrane is prolonged. At present, the technology of coupling heat resistance and membrane separation is gradually applied to membrane separation research, and chinese patent CN1066474C discloses a heat-resistant resin composition, a heat-resistant membrane adhesive and a manufacturing method thereof, which endow products with excellent high oxygen resistance and creep resistance, wherein the glass transition temperature of the product is 350 ℃ or lower, but the permeation flux of the membrane is low.
Chinese patent CN103408892A discloses a graphene-containing heat-resistant film, wherein the graphene-containing film material has good heat-resistant performance, but the separation precision of the film is not high, and the film cannot meet the requirement of high-precision separation of small molecular substances.
Chinese patent CN 105617887A discloses a preparation method of a high-temperature resistant nanofiltration membrane, which is prepared by a one-step phase inversion method of solvent evaporation of high polymer polypropylene, polyether sulfone, graphene, silicon dioxide fiber, an additive and a pore-forming agent. However, the continuous and stable separation precision of the method in a high-heat medium environment is still insufficient, and the method has no selective separation performance on salt ions.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to design and provide a technical scheme for a preparation method of a high-heat-resistant separation membrane material, which utilizes the high thermal stability of a polyimide material to further thermally stabilize porous base materials such as a poly-sulphone material and a polyether sulfone material for preparing the reverse osmosis membrane material in the traditional interfacial polymerization reaction process and strengthen the material interface, so that the membrane separation material capable of supporting the thermal sterilization and high-temperature membrane filtration process is prepared, and the defects of sudden reduction of water production flux, unstable performance and the like caused by poor thermal stability of membrane pores of the conventional membrane material in the high-temperature membrane filtration process are overcome. The heat-resistant separation membrane material prepared by the invention can be widely applied to the industry fields of pharmacy, petrifaction, food and the like which can not carry out traditional sterilization (need to carry out heat sterilization) or directly carry out separation operation in high-temperature environment.
The preparation method of the high-temperature resistant separation membrane material comprises the following steps: the method is characterized by comprising the following steps:
1) putting the modified polyimide, an organic solvent, a pore-forming agent and an emulsifier into a blending kettle, setting the temperature of interlayer heat conduction oil of the blending kettle to be 45-55 ℃, starting a stirrer to stir for 1-2 hours at the rotation speed of 200 plus 250rpm, adding a film-forming polymer material, raising the temperature of interlayer heat conduction oil of the blending kettle to 85-95 ℃, continuously keeping stirring, filtering the feed liquid by a filter after the whole casting liquid is transparent, removing impurities from the feed liquid, transferring the feed liquid to a storage tank, defoaming the casting liquid in the storage tank by using a vacuum pump, and keeping constant temperature when the temperature of the casting liquid is slowly reduced to 20-30 ℃ for later use;
2) coating a layer of casting solution with the thickness of 30-50 microns on a PET non-woven fabric by using the casting solution prepared in the step 1), and carrying out primary curing through a gel bath and fully rinsing through a rinsing tank to obtain a porous supporting layer material;
3) the porous support layer material prepared in the step 2) enters an aqueous phase solution tank for full infiltration, and then surface moisture is removed for later use;
4) and 3) coating solvent oil containing an organic phase monomer on the surface of the porous supporting layer material containing the water phase monomer formed in the step 3), and finishing the interfacial polymerization process of the composite membrane through oven heat treatment to obtain the high-heat-resistant separation membrane material.
The preparation method of the high-temperature resistant separation membrane material comprises the following steps: it is characterized in that in the step 1): the modified polyimide is soluble in organic solvent, and the solubility is more than or equal to 15 wt%; the molecular weight of the modified polyimide is between 1000 and 3500Da, preferably 1500 and 3500Da, and more preferably 2000 and 3000 Da; the organic solvent is dimethylformamide, dimethylacetamide, N-methylpyrrolidone-NMP, dichloromethane, tetrahydrofuran, chloroform, acetophenone, cyclohexanone or butyrolactone.
The preparation method of the high-temperature resistant separation membrane material comprises the following steps: it is characterized in that in the step 1): setting the temperature of heat conducting oil in the interlayer of the batching kettle at 48-53 ℃, preferably at 50-51 ℃; the stirring time is 1.5 to 1.7 hours, the rotating speed is 220-; keeping the constant temperature of the casting solution at 23-26 ℃.
The preparation method of the high-temperature resistant separation membrane material comprises the following steps: it is characterized in that in the step 1): the film-forming polymer material is at least one of sulphone, polyether sulfone and polyvinylidene fluoride.
The preparation method of the high-temperature resistant separation membrane material comprises the following steps: it is characterized in that in the step 1): 0.1-20wt% of modified polyimide, 10.0-20.0wt% of film-forming polymer material and 60.0-89.9wt% of organic solvent; preferably 1-18wt% of modified polyimide, 12-18wt% of film-forming polymer material and 65-80wt% of organic solvent; more preferably 5-10wt% of imide modified body, 15-16wt% of film-forming polymer material and 70-75wt% of organic solvent. (parameters are preferably used to modify the file in response to a physical examination, since modifications cannot go beyond what is described in the original application file.)
The preparation method of the high-temperature resistant separation membrane material comprises the following steps: it is characterized in that in the step 1): the viscosity of the casting film liquid is 300-600mpa.s, preferably 400-500mpa.s at 25 ℃.
The preparation method of the high-temperature resistant separation membrane material comprises the following steps: it is characterized in that in the step 1): the pore-forming agent is one of polyethylene glycol 400, polyethylene glycol 600, ethanol, lithium chloride and water, and the emulsifier is one of tween 20,40,60 and 80.
The preparation method of the high-temperature resistant separation membrane material comprises the following steps: it is characterized in that in the step 2): the thickness of the doctor-blade coating solution is 35-45 microns, preferably 40-42 microns.
The preparation method of the high-temperature resistant separation membrane material comprises the following steps: it is characterized in that in the step 2): the support layer is prepared by slit preset amount coating or doctor blade casting coating and a wet phase inversion method.
The preparation method of the high-temperature-resistant separation membrane material has the following technical effects:
1) the thermo-mechanical stability performances of the porous supporting layer material, such as thermal shrinkage resistance, thermal deformation resistance and the like, are improved by blending a heat-resistant and rigid modified polyimide material in a conventional non-heat-resistant porous supporting layer material, such as polysulfone, polyether sulfone and polyvinylidene fluoride;
2) the high-temperature resistant separation membrane materials such as a nanofiltration membrane, a reverse osmosis membrane, an ultrafiltration membrane material and the like prepared by using the support material have continuous and stable operation in a medium with high temperature and high temperature above 70 ℃ and cyclic intermittent cleaning in a medium with high temperature and high temperature above 90 ℃ for more than 30 minutes and more than or equal to 45 times;
3) compared with the conventional support body material which is not blended, the nanofiltration membrane, the reverse osmosis membrane and the ultrafiltration membrane material prepared by using the support body material have the same or more separation performances, such as interception performance, water production efficiency and the like.
Detailed Description
The present invention will be described more fully hereinafter with reference to the following specific examples and comparative examples, but it should be understood that the examples described are only a few, but not all, of the examples of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Examples 1 to 5 and comparative example 1
1) According to a configuration list in table 1, a modified polyimide with a molecular weight of 2200Da and a solubility of 55wt% in dimethylformamide, polyethylene glycol 400 and Tween 80 serving as an emulsifier are put into a blending kettle, the temperature of interlayer heat-conducting oil of the blending kettle is set to be 50 ℃, a stirrer is started to stir for 1-2 hours at a rotation speed of 200-250rpm, a certain amount of polysulfone P3500 is added, the temperature of interlayer heat-conducting oil of the blending kettle is raised to 90 ℃, stirring is continuously maintained, after the whole casting solution is transparent, the casting solution is filtered and impurity-removed through a filter and then transferred to a storage tank. And (3) defoaming the casting solution in the storage tank by using a vacuum pump, slowly cooling the casting solution to 20-30 ℃, and keeping the temperature constant for later use, wherein the viscosity of the casting solution is 438 mpa.s.
2) Coating a layer of casting solution with the thickness of 30 microns on a PET non-woven fabric by using the casting solution prepared in the step 1), soaking for 15 seconds in 20-wt% aqueous solution gel bath of dimethyl formamide at 20 ℃, primarily curing, and fully rinsing with warm water at 50 ℃ to obtain the porous supporting layer material. Comparative example 1: conventional porous support layer materials have a thickness of 30 microns.
3) And 2) after the porous support layer material prepared in the step 2) enters an aqueous phase solution tank for full infiltration, the film surface is blown off for 1min by an extrusion roller with the extrusion of 0.4mpa and a dry compressed air knife, and residual liquid drops on the film surface are fully removed for later use. Preparing a composite membrane water phase: 15g/L of m-phenylenediamine, 30g/L of triethylamine hydrochloride and 10ml/L of triethylamine, wherein the temperature is as follows: at 25 ℃.
4) And (3) organic phase configuration of the composite membrane: 1.0g/l of trimesoyl chloride, isodecaalkane solvent oil, the temperature is 25 ℃, the surface of the supporting layer containing the water phase monomer formed in the step 3) is coated with organic phase solution, the organic phase solution is subjected to heat treatment in a 90 ℃ oven for 5 minutes to obtain the high-heat-resistant reverse osmosis composite membrane, and the prepared composite membrane is stored in deionized water for later use.
Examples 6 to 10 and comparative example 2
Table 2 the configuration list and the thickness of the support membrane are the same as those in table 1, but the composite membrane is a composite nanofiltration membrane.
Preparing a composite membrane water phase: 1g/l of piperazine and 3g/l of trisodium phosphate at 25 ℃, and removing surface moisture after the support membrane is fully soaked for later use. And (3) organic phase configuration of the composite membrane: after the organic phase solution is coated on one side of trimesoyl chloride of 1.0g/l and isomeric decaalkane solvent oil at the temperature of 25 ℃, the composite membrane is thermally treated for 5 minutes by a baking oven at the temperature of 90 ℃ to obtain the high-heat-resistant nanofiltration composite membrane, and the prepared composite membrane is stored in deionized water for later use.
In the invention, the supporting layer is prepared by enhancing the film pore structure, heat resistance, interface and the like of the polyimide modified material to the bulk polymer material. The high-temperature resistant separation membrane material supports long-time continuous stable operation in a hot water medium at the temperature of less than 70 ℃. The high-temperature resistant separation membrane material supports the operation frequency of intermittent heat disinfection of 90 ℃ high-temperature water within 30 minutes to be more than or equal to 45.
In the invention, in step 1): setting the temperature of the interlayer heat conduction oil of the batching kettle at 45 ℃, 48 ℃, 52 ℃ or 55 ℃, starting a stirrer to stir for 1 or 2 hours at the rotating speed of 200 rpm, 220 rpm or 250rpm, raising the temperature of the interlayer heat conduction oil of the batching kettle to 85 ℃, 92 ℃ or 95 ℃, slowly reducing the temperature of the casting solution to 20 ℃, 23 ℃, 28 ℃ or 30 ℃ and keeping the constant temperature; the molecular weight of the modified polyimide is 1000Da, 1500Da, 2000Da, 2500Da, 3000Da or 3500 Da; the casting solution has a viscosity of 300 mPa.s, 400mPa.s, 500mPa.s or 600 mPa.s. In step 2): the dope solution was knife coated at a thickness of 35 microns, 40 microns, 45 microns, or 50 microns. The performance test of the high-temperature resistant separation membrane material prepared by the other steps of the examples 1 to 5 can also achieve the beneficial effects of the invention.
The advantageous effects of the present invention are further illustrated by the corresponding test data below.
The composite reverse osmosis membranes of examples 1-5 and comparative example 1 were tested for desalination and water permeability in 2000ppm sodium chloride solution at four operating temperatures of 25, 50, 70, 90 ℃ and an operating pressure of 1.55MPa, see Table 3.
The composite reverse osmosis membranes of examples 1 to 5 and comparative example 1 were soaked in hot water at 90 ℃ for 30 minutes as one washing cycle, and after each washing cycle, the desalination and water permeation performance were measured at 2000ppm of a saline solution at an operating temperature of 25 ℃ and an operating pressure of 1.55MPa, as shown in tables 4 and 5.
Tables 4 and 5 show that: the performance change trend of the high-heat-resistant reverse osmosis composite membrane prepared by different addition proportions of the polyimide modification body and zero addition in a hot water cleaning frequency period of 90 ℃ shows that more stable and excellent performance can be obtained when the polyimide modification body is added.
The composite nanofiltration membranes of examples 6-10 and comparative example 2 were tested for desalination and water permeation performance at 2000ppm sodium sulfate solution, four operating temperatures of 25, 50, 70, 90 ℃ and an operating pressure of 0.5MPa, see table 6.
The composite nanofiltration membranes of examples 6 to 10 and comparative example 2 were immersed in hot water at 90 ℃ for 30 minutes to form a washing cycle, and after each washing cycle, the desalination and water permeation performance were measured at an operating temperature of 25 ℃ and an operating pressure of 0.5MPa in 2000ppm sodium sulfate solution, as shown in tables 7 and 8.
Tables 7 and 8 show that: the performance change trend of the high-heat-resistant nanofiltration composite membrane prepared by different addition proportions of the polyimide modification body and zero addition in a hot water cleaning frequency period at 90 ℃ shows that more stable and excellent performance can be obtained when the polyimide modification body is added.
The embodiments described in this specification are merely illustrative of implementations of the inventive concepts, which are intended for purposes of illustration only. The scope of the present invention should not be construed as being limited to the particular forms set forth in the examples, but rather as being defined by the claims and the equivalents thereof which can occur to those skilled in the art upon consideration of the present inventive concept.
Claims (9)
1. A preparation method of a high-heat-resistant separation membrane material comprises the following steps: the method is characterized by comprising the following steps:
1) putting the modified polyimide, an organic solvent, a pore-forming agent and an emulsifier into a blending kettle, setting the temperature of interlayer heat conduction oil of the blending kettle to be 45-55 ℃, starting a stirrer to stir for 1-2 hours at the rotation speed of 200 plus 250rpm, adding a film-forming polymer material, raising the temperature of interlayer heat conduction oil of the blending kettle to 85-95 ℃, continuously keeping stirring, filtering the feed liquid by a filter after the whole casting liquid is transparent, removing impurities from the feed liquid, transferring the feed liquid to a storage tank, defoaming the casting liquid in the storage tank by using a vacuum pump, and keeping constant temperature when the temperature of the casting liquid is slowly reduced to 20-30 ℃ for later use;
2) coating a layer of casting solution with the thickness of 30-50 microns on a PET non-woven fabric by using the casting solution prepared in the step 1), and carrying out primary curing through a gel bath and fully rinsing through a rinsing tank to obtain a porous supporting layer material;
3) the porous support layer material prepared in the step 2) enters an aqueous phase solution tank for full infiltration, and then surface moisture is removed for later use;
4) and 3) coating solvent oil containing an organic phase monomer on the surface of the porous supporting layer material containing the water phase monomer formed in the step 3), and finishing the interfacial polymerization process of the composite membrane through oven heat treatment to obtain the high-heat-resistant separation membrane material.
2. A method of preparing a high heat resistant separation membrane material as claimed in claim 1: it is characterized in that in the step 1): the modified polyimide is soluble in organic solvent, and the solubility is more than or equal to 15 wt%; the molecular weight of the modified polyimide is between 1000 and 3500Da, preferably 1500 and 3500Da, and more preferably 2000 and 3000 Da; the organic solvent is dimethylformamide, dimethylacetamide, N-methylpyrrolidone-NMP, dichloromethane, tetrahydrofuran, chloroform, acetophenone, cyclohexanone or butyrolactone.
3. A method of preparing a high heat resistant separation membrane material as claimed in claim 1: it is characterized in that in the step 1): setting the temperature of heat conducting oil in the interlayer of the batching kettle at 48-53 ℃, preferably at 50-51 ℃; the stirring time is 1.5 to 1.7 hours, the rotating speed is 220-; keeping the constant temperature of the casting solution at 23-26 ℃.
4. A method of preparing a high heat resistant separation membrane material as claimed in claim 1: it is characterized in that in the step 1): the film-forming polymer material is at least one of sulphone, polyether sulfone and polyvinylidene fluoride.
5. A method of preparing a high heat resistant separation membrane material as claimed in claim 1: it is characterized in that in the step 1): 0.1-20wt% of modified polyimide, 10.0-20.0wt% of film-forming polymer material and 60.0-89.9wt% of organic solvent; preferably 1-18wt% of modified polyimide, 12-18wt% of film-forming polymer material and 65-80wt% of organic solvent; more preferably 5-10wt% of imide modified body, 15-16wt% of film-forming polymer material and 70-75wt% of organic solvent.
(parameters preferably for modifying the file in response to a physical examination, since the modification cannot go beyond what is described in the original application document.)
A method of preparing a high heat resistant separation membrane material as claimed in claim 1: it is characterized in that in the step 1): the viscosity of the casting film liquid is 300-600mpa.s, preferably 400-500mpa.s at 25 ℃.
7. A method of preparing a high heat resistant separation membrane material as claimed in claim 1: it is characterized in that in the step 1): the pore-forming agent is one of polyethylene glycol 400, polyethylene glycol 600, ethanol, lithium chloride and water, and the emulsifier is one of tween 20,40,60 and 80.
8. A method of preparing a high heat resistant separation membrane material as claimed in claim 1: it is characterized in that in the step 2): the thickness of the doctor-blade coating solution is 35-45 microns, preferably 40-42 microns.
9. A method of preparing a high heat resistant separation membrane material as claimed in claim 1: it is characterized in that in the step 2): the support layer is prepared by slit preset amount coating or doctor blade casting coating and a wet phase inversion method.
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Application publication date: 20220429 |