WO2016115908A1 - 原位成孔剂的聚偏氟乙烯中空纤维膜及其制备方法 - Google Patents
原位成孔剂的聚偏氟乙烯中空纤维膜及其制备方法 Download PDFInfo
- Publication number
- WO2016115908A1 WO2016115908A1 PCT/CN2015/089138 CN2015089138W WO2016115908A1 WO 2016115908 A1 WO2016115908 A1 WO 2016115908A1 CN 2015089138 W CN2015089138 W CN 2015089138W WO 2016115908 A1 WO2016115908 A1 WO 2016115908A1
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- WIPO (PCT)
- Prior art keywords
- hollow fiber
- pore former
- polyvinylidene fluoride
- situ pore
- solution
- Prior art date
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- 239000012528 membrane Substances 0.000 title claims abstract description 71
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 47
- 239000002033 PVDF binder Substances 0.000 title claims abstract description 40
- 229920002981 polyvinylidene fluoride Polymers 0.000 title claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title abstract description 13
- 239000000835 fiber Substances 0.000 title abstract description 5
- 239000003085 diluting agent Substances 0.000 claims abstract description 16
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 229920000642 polymer Polymers 0.000 claims abstract description 12
- 229920005989 resin Polymers 0.000 claims abstract description 12
- 239000011347 resin Substances 0.000 claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 11
- 239000002253 acid Substances 0.000 claims abstract description 8
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 150000003839 salts Chemical class 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000003513 alkali Substances 0.000 claims abstract description 4
- 239000011148 porous material Substances 0.000 claims description 58
- 239000012510 hollow fiber Substances 0.000 claims description 51
- 238000000034 method Methods 0.000 claims description 21
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical group NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 14
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 12
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 12
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000005642 Oleic acid Substances 0.000 claims description 12
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 12
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 12
- -1 silicon ion Chemical class 0.000 claims description 12
- 239000000126 substance Substances 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 9
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims description 9
- 239000004246 zinc acetate Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 7
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 6
- 125000005456 glyceride group Chemical group 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 6
- 229920000151 polyglycol Polymers 0.000 claims description 6
- 239000010695 polyglycol Substances 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 235000012424 soybean oil Nutrition 0.000 claims description 6
- 239000003549 soybean oil Substances 0.000 claims description 6
- 239000003381 stabilizer Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000011282 treatment Methods 0.000 claims description 5
- 239000011701 zinc Substances 0.000 claims description 5
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 4
- 229920001519 homopolymer Polymers 0.000 claims description 4
- 235000015112 vegetable and seed oil Nutrition 0.000 claims description 4
- 239000008158 vegetable oil Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- BQCIDUSAKPWEOX-UHFFFAOYSA-N 1,1-Difluoroethene Chemical compound FC(F)=C BQCIDUSAKPWEOX-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims description 3
- 229960000583 acetic acid Drugs 0.000 claims description 3
- 239000012752 auxiliary agent Substances 0.000 claims description 3
- 239000008139 complexing agent Substances 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 238000004804 winding Methods 0.000 claims description 3
- LVGKNOAMLMIIKO-UHFFFAOYSA-N Elaidinsaeure-aethylester Natural products CCCCCCCCC=CCCCCCCCC(=O)OCC LVGKNOAMLMIIKO-UHFFFAOYSA-N 0.000 claims description 2
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 2
- 230000009471 action Effects 0.000 claims description 2
- 239000003963 antioxidant agent Substances 0.000 claims description 2
- 230000003078 antioxidant effect Effects 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- LVGKNOAMLMIIKO-QXMHVHEDSA-N ethyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCC LVGKNOAMLMIIKO-QXMHVHEDSA-N 0.000 claims description 2
- 229940093471 ethyl oleate Drugs 0.000 claims description 2
- 238000001125 extrusion Methods 0.000 claims description 2
- 239000012760 heat stabilizer Substances 0.000 claims description 2
- 229910001410 inorganic ion Inorganic materials 0.000 claims description 2
- 239000000314 lubricant Substances 0.000 claims description 2
- 238000000465 moulding Methods 0.000 claims description 2
- 230000002093 peripheral effect Effects 0.000 claims description 2
- 229920000570 polyether Polymers 0.000 claims description 2
- 239000002952 polymeric resin Substances 0.000 claims description 2
- 229920005862 polyol Polymers 0.000 claims description 2
- 150000003077 polyols Chemical class 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 238000000638 solvent extraction Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229920003002 synthetic resin Polymers 0.000 claims description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims 3
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 claims 1
- LCKIEQZJEYYRIY-UHFFFAOYSA-N Titanium ion Chemical compound [Ti+4] LCKIEQZJEYYRIY-UHFFFAOYSA-N 0.000 claims 1
- 239000002250 absorbent Substances 0.000 claims 1
- 230000002745 absorbent Effects 0.000 claims 1
- 150000001298 alcohols Chemical class 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims 1
- 229920000131 polyvinylidene Polymers 0.000 abstract 1
- 238000007493 shaping process Methods 0.000 abstract 1
- 238000002145 thermally induced phase separation Methods 0.000 description 6
- 238000000614 phase inversion technique Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000654 additive Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 238000005187 foaming Methods 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 238000001471 micro-filtration Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000035699 permeability Effects 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 238000001223 reverse osmosis Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000002791 soaking Methods 0.000 description 2
- 238000011426 transformation method Methods 0.000 description 2
- 238000000108 ultra-filtration Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002351 wastewater Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 150000001242 acetic acid derivatives Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 150000002823 nitrates Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003361 porogen Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910000033 sodium borohydride Inorganic materials 0.000 description 1
- 239000012279 sodium borohydride Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Images
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
- B01D71/30—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
- 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
- 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
- B01D67/00111—Polymer pretreatment in the casting solutions
-
- 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
- B01D69/08—Hollow fibre membranes
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C19/00—Acyclic saturated compounds containing halogen atoms
- C07C19/01—Acyclic saturated compounds containing halogen atoms containing chlorine
- C07C19/03—Chloromethanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/18—Monomers containing fluorine
- C08F14/22—Vinylidene fluoride
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/09—Carboxylic acids; Metal salts thereof; Anhydrides thereof
- C08K5/098—Metal salts of carboxylic acids
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/18—Pore-control agents or pore formers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/218—Additive materials
- B01D2323/2181—Inorganic additives
- B01D2323/21817—Salts
Definitions
- the invention relates to a hollow fiber membrane, in particular to a polyvinylidene fluoride hollow fiber membrane which forms an in-situ pore former of an inorganic molecular solution by using an organosol and a preparation method thereof.
- the membrane bioreactor combines the traditional biological treatment wastewater method with modern membrane separation technology, and is a treatment method that can efficiently treat wastewater and improve water quality.
- membrane bioreactors the synthesis of high quality membrane materials with uniform pore size is a key issue.
- PVDF Polyvinylidene fluoride
- the field has broad application prospects.
- the preparation methods of the polyvinylidene fluoride hollow fiber membrane are mainly a solution phase transformation method and a thermal phase separation method.
- the hollow fiber membrane prepared by the solution phase inversion method has large water flux and high selectivity; the membrane induced by thermal induced phase separation has the advantages of pore structure and permeability control, and the two methods have wide application in the preparation of membrane materials. .
- the hollow fiber membrane yarn prepared by the solution phase inversion method has poor mechanical strength, and in the chemical cleaning, particularly in the alkaline washing solution cleaning, the filament becomes brittle and deteriorates.
- the thermally induced phase separation method has a mechanical degree of 4-5 times that of the membrane yarn prepared by the solution phase transformation method, and has high chemical resistance, and no mechanical strength of the membrane is generated in the chemical cleaning, especially in the alkaline washing solution cleaning. The change is therefore longer than the life of the hollow fiber membrane filament prepared by the solution phase inversion method.
- the membrane module in the membrane bioreactor especially in the treatment of industrial sewage, has high requirements on membrane pore size, water permeability, mechanical strength and chemical resistance, so the pyrolysis of hollow fiber membrane is prepared by thermally induced phase separation. It is more suitable for membrane modules of membrane bioreactors and plays an important role in membrane module preparation of membrane bioreactors. In the preparation process of the membrane module, how to prepare a controlled, uniform, and dispersible pore size is a key point and a difficulty.
- the Chinese patent with the publication number CN201664580U uses the centrifugal force generated by the rotation of the centrifugal cylinder to place the pore forming agent and the additive in the ultrafiltration membrane, the microfiltration membrane and the reverse osmosis membrane which are placed in the mesh centrifuge cylinder or wrapped around the centrifugal winding cylinder. Removal, the purpose of removing the pore former and additives in the ultrafiltration membrane, microfiltration membrane and reverse osmosis membrane and recycling.
- the Chinese patent publication number CN103706259A is prepared by introducing a foaming pore former sodium borohydride in a film formation system, and a foaming pore former generates a uniformly distributed microbubble by reaction, thereby forming a porous structure and increasing the porosity of the membrane. At the same time, the film does not form macropore defects.
- the Chinese patent with the publication number CN101108314A establishes a formula including parameters such as hydrophilicity. On the basis of comprehensive quantitative analysis, the control pore size is mainly used, and the single membrane material PES is synthesized in the formulation of the casting solution.
- the publication number is CN101590374B
- the Chinese patent describes a powder polymer, a nano-scale inorganic pore former, and an organic pore former.
- the high-strength hollow fiber membrane is prepared by a thermally induced phase separation method.
- the above patents have improved and innovated the preparation of the membrane module, the type of sewage is relatively complicated, and the requirements for the MBR membrane are relatively high.
- the Chinese patent of CN101590374B it is a nano-scale inorganic pore former, in fact, the nanoparticle itself In general, it is agglomerated, and the solid and solid are highly mixed. Compared with the high mixing of solid and solution, the former is difficult to mix uniformly, so it is urgent to develop a hydrophobicity that can achieve controllable, uniform and dispersible.
- the molecular fiber has good compatibility with the polymer, and the inorganic molecular solution pore former and the thermally induced phase separation method are used to prepare the vinylidene fluoride hollow fiber membrane.
- the object of the present invention is to provide an in-situ pore former for forming an inorganic molecular solution by using an organosol, in view of the above-mentioned problems of insufficient uniform pore size, insufficient dispersibility, and uncontrollable film preparation process.
- the polyvinylidene fluoride hollow fiber membrane of the in-situ pore former is composed of a mass percentage of raw materials:
- Polyvinylidene fluoride resin 30% to 50%
- the organosol forms an in-situ pore former of an inorganic molecular solution: 40% to 60%;
- Organic diluent 5% to 20%.
- the polyvinylidene fluoride resin may be a homopolymer of polyvinylidene fluoride or a copolymer of polyvinylidene fluoride, preferably a homopolymer of polyvinylidene fluoride.
- the organic sol forming inorganic molecular solution in-situ pore former may be at least one of soluble acetates and nitrates, wherein the inorganic ions are one of zinc ions, zirconium ions, titanium ions, silicon ions, and the like;
- the acetate may be zinc acetate or the like, the nitrate may be zinc nitrate or the like;
- the organosol may form an inorganic molecular solution.
- the in-situ pore-forming agent may be a stabilizer, and the stabilizer may be an alcohol amine-based network.
- the alcohol amine complexing agent is preferably ethanolamine
- the organic solvent used to form the inorganic molecular solution in situ pore former may be a polyptanol monoether, a polyol polyether or a monool.
- the organic diluent may be a vegetable oil or an oleic acid ester, and the vegetable oil may be an epoxidized soybean oil or the like; the oleic acid ester may be ethyl oleate, oleic acid glyceride or oleic acid polyglycol. At least one of glycerides and the like; the organic diluent is preferably epoxidized soybean oil or oleic acid polyglycol glyceride.
- an appropriate amount of an auxiliary agent such as an antioxidant, a lubricant, a heat stabilizer, a UV absorber or the like may be added as needed.
- the preparation method of the polyvinylidene fluoride hollow fiber membrane of the in-situ pore former comprises the following steps:
- the organosol is formed into an inorganic molecular solution in-situ pore former mixed with the polymer of the polymer and the organic diluent to obtain the material A;
- the hollow fiber is stretched 2 to 3 times in the line to obtain a hollow fiber yarn
- the specific method for preparing the organosol to form an in-situ pore former of the inorganic molecular solution may be: using a soluble inorganic salt of zinc such as zinc nitrate (Zn(NO 3 ) 2 ) or an organic salt such as zinc acetate ( Zn(CH 3 COO) 2 ) is dissolved in an organic solvent such as ethylene glycol methyl ether under the action of catalyst glacial acetic acid and stabilizer ethanolamine to form a solution, and zinc acetate is dissolved in ethylene glycol methyl ether, and then added.
- a soluble inorganic salt of zinc such as zinc nitrate (Zn(NO 3 ) 2 ) or an organic salt such as zinc acetate ( Zn(CH 3 COO) 2 ) is dissolved in an organic solvent such as ethylene glycol methyl ether under the action of catalyst glacial acetic acid and stabilizer ethanolamine to form a solution, and zinc acetate is dissolved in ethylene glycol methyl
- the specific method for mixing the organosol to form an inorganic molecular solution in-situ pore former and the polymer of the high molecular polymer and the organic diluent may be: polyvinylidene fluoride resin (30% to 50%).
- the organosol forms an inorganic molecular solution porogen (40% to 50%, based on the amount of the inorganic salt) and the organic diluent (10% to 20%) in a high-speed mixing mixer, and after mixing, forms a uniform material, that is, an organosol.
- the in-situ pore former and the organic diluent forming the inorganic molecular solution are uniformly mixed with the solid polymer resin.
- the extrusion may be performed by a molding machine.
- step 4 the hollow fiber is stretched in-line by uniaxial stretching of 50% to 100% in the longitudinal direction of the hollow fiber filament by using a roller having a different peripheral speed, and winding the hollow fiber filament On the wire wheel.
- the organic solvent extraction treatment may be an organic solvent extractant, which may be selected from a chlorinated hydrocarbon or a low molecular weight alcohol, preferably a chlorinated hydrocarbon, and a chlorinated hydrocarbon may be used. Use dichloromethane or the like.
- the acid may be hydrochloric acid or sulfuric acid or the like, and the base may be sodium hydroxide or potassium hydroxide.
- the strong acid or strong base removing agent of the organic substance is hydrochloric acid and sulfuric acid solution.
- the cleaning may be performed with water; the temperature of the heat treatment may be 120 to 140 °C.
- the organosol-forming solution of the present invention forms a solution of an inorganic molecule, that is, a solution of a stable complexing molecule, which has good compatibility with a polymer, dispersibility and uniformity, and the hollow fiber membrane prepared is kept in addition to the original one.
- a uniform network structure of three-dimensional space is provided to make the distribution of membrane pores more uniform.
- Fig. 1 is a cross-sectional scanning electron micrograph of a polyvinylidene fluoride hollow fiber membrane of an in-situ pore former which forms an inorganic molecular solution using an organosol prepared in the examples.
- FIG. 2 is a scanning electron micrograph of the outer surface of a polyvinylidene fluoride hollow fiber membrane of an in-situ pore former using an organosol to form an inorganic molecular solution prepared in the examples.
- Each of the raw materials is not limited to a mass percentage.
- the polyvinylidene fluoride resin PVDF 40%, 6.5% oleic acid polyglycol glyceride, 3.5% epoxidized soybean oil and the organosol prepared by the step 1) form a zinc molecular solution in situ pore former 50%
- the high-speed mixer is mixed at a high speed to uniformly disperse the polyvinylidene fluoride resin solid in a uniform organic phase, and then, after being kneaded by a screw extruder using 170, through a hollow fiber mold, the hollow fiber filament is extruded. After entering the cooling tank, the cooling water is solidified, and after being uniaxially stretched by 80%, the hollow fiber filament is wound around the collecting wheel.
- the process of preparing the hollow fiber membrane is the same as the step 2) of Example 1 except that the polyvinylidene fluoride resin PVDF 50%, 6.5% oleic acid polyglycol glyceride, 3.5% epoxy soybean oil and by step 1)
- the prepared organosol forms 40% of the in-situ pore former of the zinc molecular solution to obtain the final product.
- the performance test data of hollow fiber membrane samples are shown in Table 1.
- the organosol forming inorganic molecular solution that is, the stable complexing molecular solution, has good compatibility, dispersibility and uniformity with the high molecular polymer, and the prepared hollow fiber membrane retains the original thermally induced phase separation process.
- a uniform network structure having a three-dimensional space makes the distribution of the film pores more uniform.
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Artificial Filaments (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
Abstract
一种聚偏氟乙烯中空纤维膜及其制备方法，原料组成为：聚偏氟乙烯树脂30％～50％；以无机盐类的量计算，有机溶胶形成无机分子溶液原位成孔剂40％～60％；有机稀释剂5％～20％。制备时，先制备有机溶胶形成无机分子溶液原位成孔剂；将有机溶胶形成无机分子溶液原位成孔剂与高分子聚合物的树脂和有机稀释剂混合，得物料A，再挤压后经成型模具挤出中空纤维，然后在线拉伸2～3倍，得中空纤维丝；将中空纤维丝经有机溶剂萃取处理除去所有的有机物，再用酸或碱溶液除去分散在中空纤维丝中的无机物，形成多孔膜；将多孔膜清洗后，定型热处理，得到原位成孔剂的聚偏氟乙烯中空纤维膜。
Description
本发明涉及中空纤维膜，尤其是涉及一种利用有机溶胶形成无机分子溶液的原位成孔剂的聚偏氟乙烯中空纤维膜及其制备方法。
膜生物反应器(MBR)将传统的生物处理废水法和现代膜分离技术有机结合在一起，是一种能高效处理废水并提高水质的处理方法。在膜生物反应器中，合成孔径均匀的高质量膜材料是关键问题所在。聚偏氟乙烯(PVDF)是一种新兴的、综合性能优良的膜材料，机械强度高，耐酸碱等苛刻环境条件和化学稳定性好，具有高分离精度和高效率的特点，在膜分离领域具有广阔的应用前景。目前聚偏氟乙烯中空纤维膜的制备方法主要为溶液相转化法和热致相分离法。溶液相转化法制备的中空纤维膜水通量大、选择性高；热致相分离法制膜具有孔结构和通透性易控制的优点，两种方法在膜材料的制备中都有广泛的应用。然而溶液相转化法制备的中空纤维膜丝的机械强度差，在化学清洗中，特别是碱洗溶液清洗中，发生膜丝变脆而劣化。热致相分离法制膜丝具有机械度高是溶液相转化法制备的膜丝的4-5倍，抗化学性能高，在在化学清洗中，特别是碱洗溶液清洗中无发生膜丝机械强度的改变，因此比溶液相转化法制备的中空纤维膜丝的寿命。
在膜生物反应器中的膜组件特别在工业污水的处理中，对膜丝孔径，水通透性能，机械强度和抗化学性能要求较高，因此热致相分离法制备偏氟乙烯中空纤维膜更适用于膜生物反应器的膜组件，并在膜生物反应器的膜组件制备中起着重要作用。在膜组件的制备过程中，如何制备可控、均匀、分散性好的孔径是关键点和难点。
公开号为CN201664580U的中国专利采用通过离心筒转动产生的离心力作用，将置于网眼离心筒内或缠绕在离心缠绕筒外的超滤膜、微滤膜及反渗透膜中的成孔剂及添加剂脱除，实现脱除超滤膜、微滤膜及反渗透膜中成孔剂及添加剂及回收的目的。公开号为CN103706259A的中国专利在制备方法为在成膜体系中引入发泡成孔剂硼氢化钠，发泡成孔剂通过反应生成均匀分布的微量气泡，进而形成多孔结构，在提高膜孔隙率的同时并不会使膜形成大孔缺陷。公开号为CN101108314A的中国专利建立包括亲水性等参数在内的公式，在全面定量分析的基础上，以控制孔径为主，铸膜液配方中采用单一膜材料PES合成。公开号为CN101590374B的
中国专利中描述的是粉末高分子，纳米级无机成孔剂，以及有机成孔剂的配方用热致相分离法进行制备高强度的中空纤维膜。
尽管上述专利对膜组件的制备进行了改进和创新，但是污水类型较为复杂，对MBR膜的要求较高，如公开号为CN101590374B中国专利中，既是纳米级无机成孔剂，实际上纳米颗粒自身在一般情况下是团聚存在的，而且固体与固体的高混，相对于固体与溶液的高混，前者很难混合均匀，所以迫切开发一种能实现可控、均匀、分散性好的疏水性的分子状的能与高分子聚合物相容性好无机分子溶液成孔剂及热致相分离法制备偏氟乙烯中空纤维膜。
发明内容
本发明的目的是针对上述现有制备膜组件膜丝孔径不够均匀、分散性不够好以及膜制备过程中不可控等问题，提供一种利用有机溶胶形成无机分子溶液的原位成孔剂的聚偏氟乙烯中空纤维膜及其制备方法。
所述原位成孔剂的聚偏氟乙烯中空纤维膜按质量百分比的原料组成为：
聚偏氟乙烯树脂：30％～50％；
以无机盐类的量计算，有机溶胶形成无机分子溶液原位成孔剂：40％～60％；
有机稀释剂：5％～20％。
所述聚偏氟乙烯树脂可采用聚偏氟乙烯的均聚物或聚偏氟乙烯的共聚物，优先聚偏氟乙烯的均聚物。
所述有机溶胶形成无机分子溶液原位成孔剂可采用可溶性醋酸盐类和硝酸盐类中的至少一种，其中无机离子采用锌离子、锆离子、钛离子、硅离子等中的一种；所述醋酸盐类可采用醋酸锌等，所述硝酸盐类可采用硝酸锌等；所述有机溶胶形成无机分子溶液原位成孔剂可采用稳定剂，所述稳定剂可采用醇胺类络合剂，所述醇胺类络合剂优选乙醇胺；所述所述有机溶胶形成无机分子溶液原位成孔剂中采用的有机溶剂可采用多纯醇单醚、多醇类多醚或单醇类单醚，优选乙二醇甲醚。
所述有机稀释剂可采用植物油类或油酸酯类，所述植物油类可采用环氧大豆油等；所述油酸酯类可采用油酸乙酯、油酸甘油酯、油酸聚二醇甘油酯等中的至少一种；所述有机稀释剂优选环氧大豆油或油酸聚二醇甘油酯。
在上述配方中，根据需要可以添加适量助剂，如抗氧剂、润滑剂、热稳定剂、紫外线吸收剂等亲水性添加物。
所述原位成孔剂的聚偏氟乙烯中空纤维膜的制备方法，包括以下步骤：
1)制备有机溶胶形成无机分子溶液原位成孔剂；
2)将有机溶胶形成无机分子溶液原位成孔剂与高分子聚合物的树脂和有机稀释剂混合，得物料A；
3)将物料A挤压后经成型模具挤出中空纤维；
4)将中空纤维在线拉伸2～3倍，得中空纤维丝；
5)将拉伸后的中空纤维丝经有机溶剂萃取处理除去所有的有机物，再用酸或碱溶液除去分散在中空纤维丝中的无机物，形成多孔膜；
6)将多孔膜清洗后，定型热处理，得到原位成孔剂的聚偏氟乙烯中空纤维膜。
在步骤1)中，所述制备有机溶胶形成无机分子溶液原位成孔剂的具体方法可为：采用锌的可溶性无机盐如硝酸锌(Zn(NO3)2)或有机盐如醋酸锌(Zn(CH3COO)2)等在催化剂冰醋酸及稳定剂乙醇胺等作用下，溶解于乙二醇甲醚等有机溶剂中而形成溶液，将醋酸锌溶解于乙二醇甲醚中，再加入与醋酸锌等摩尔的乙醇胺，在40～80℃(优选50～70℃)经1～2h的充分搅拌后，形成透明的均质稳定的络合物溶液即有机溶胶形成无机分子溶液原位成孔剂；其反应方程式如下：
在步骤2)中，所述将有机溶胶形成无机分子溶液原位成孔剂与高分子聚合物的树脂和有机稀释剂混合的具体方法可为：聚偏氟乙烯树脂(30％～50％)、有机溶胶形成无机分子溶液成孔剂(40％～50％，以无机盐的量计)和有机稀释剂(10％～20％)在高速混合搅拌机，混合后，形成均匀的物料即有机溶胶形成无机分子溶液的原位成孔剂和有机稀释剂均匀地与固体的高分子聚合物树脂混合。
在步骤3)中，所述挤压可采用成型机械进行挤压。
在步骤4)中，所述将中空纤维在线拉伸可利用圆周速度不同的辊对等沿中空纤维丝的纵向按照50％～100％进行单轴向拉伸，并将中空纤维丝缠绕在收丝轮上。
在步骤5)中，所述有机溶剂萃取处理可采用有机溶剂萃取剂，所述有机溶剂萃取剂可选自氯代烃类或低分子量的醇类，优选氯代烃类，氯代烃类可采用二氯甲烷等。
所述酸可采用盐酸或硫酸等，所述碱可采用氢氧化钠或氢氧化钾等，优选所述机物的强酸或强碱的除去剂为盐酸和硫酸溶液。
在步骤6)中，所述清洗可采用水清洗；所述热处理的温度可为120～140℃。
与现有技术相比，本发明的有机溶胶形成无机分子溶液即稳定络合分子溶液具有与高分子聚合物很好相容性，分散性和均匀性，所制备的中空纤维膜除保持原有热致相分离法工艺所制备膜丝的应有特性外，还具有三维空间的均匀的网状结构使得膜孔的分布更均匀。适用于多种污水处理的膜生物反应器。
图1是在实施例制备的利用有机溶胶形成无机分子溶液的原位成孔剂的聚偏氟乙烯中空纤维膜的截面扫描电子显微镜照片。
图2是在实施例制备的利用有机溶胶形成无机分子溶液的原位成孔剂的聚偏氟乙烯中空纤维膜的外表面扫描电子显微镜照片。
以下实施例将结合附图对本发明作进一步说明。
其中的各原料配比如未限定均为质量百分比。
实施例1
1)在该原位成孔剂中，取一定量醋酸锌溶解于乙二醇甲醚中，再加入与醋酸锌等摩尔的乙醇胺溶液，少量的冰醋酸催化下，在65℃的搅拌下，变成最终配制的含有锌离子浓度为10％～30％的均质透明溶液。
2)将聚偏氟乙烯树脂PVDF 40％，6.5％油酸聚二醇甘油酯，3.5％环氧大豆油和由步骤1)制得的有机溶胶形成锌分子溶液原位成孔剂50％，在高速混合机高速混合，使聚偏氟乙烯树脂固体均匀地分散在在均匀的有机相中，然后使用螺杆挤出机经过170混炼后，经过中空纤维模具，挤出中空纤维丝状物，再进入冷却槽中冷却水凝固，再经单轴向拉伸80％后，将中空纤维丝缠绕在收丝轮上。中空纤维丝卸轮后，再经二氯甲烷在室温1h浸泡2次后除去所有的有机物，接着在10％硫酸溶液30min浸泡一次后除去所有的无机物，最后用纯水多次冲洗后，晾干并在140℃的烘箱中热定型3h，得到最终产品。中空纤维膜样品性能测试数据见表1，膜丝的截面和外表面如图1和图2。
实施例2
1)原位成孔剂制备方法与实施例1的步骤1)相同的配方。
2)制备中空纤维膜的过程与实施例1的步骤2)相同外区别在聚偏氟乙烯树脂PVDF 50％，6.5％油酸聚二醇甘油酯，3.5％环氧大豆油和由步骤1)制得的有机溶胶形成锌分子溶液原位成孔剂40％，得到最终产品。中空纤维膜样品性能测试数据见表1。
表1
本发明的有机溶胶形成无机分子溶液即稳定络合分子溶液具有与高分子聚合物很好相容性，分散性和均匀性，所制备的中空纤维膜除保持原有热致相分离法工艺所制备膜丝的应有特性外，还具有三维空间的均匀的网状结构使得膜孔的分布更均匀。适用于多种污水处理的膜生物反应器。
Claims (10)
- 原位成孔剂的聚偏氟乙烯中空纤维膜，其特征在于其按质量百分比的原料组成为：聚偏氟乙烯树脂：30％～50％；以无机盐类的量计算，有机溶胶形成无机分子溶液原位成孔剂：40％～60％；有机稀释剂：5％～20％。
- 如权利要求1所述原位成孔剂的聚偏氟乙烯中空纤维膜，其特征在于所述聚偏氟乙烯树脂采用聚偏氟乙烯的均聚物或聚偏氟乙烯的共聚物，优先聚偏氟乙烯的均聚物；所述有机溶胶形成无机分子溶液原位成孔剂采用可溶性醋酸盐类和硝酸盐类中的至少一种，其中无机离子采用锌离子、锆离子、钛离子、硅离子中的一种；所述醋酸盐类可采用醋酸锌，所述硝酸盐类可采用硝酸锌；所述有机溶胶形成无机分子溶液原位成孔剂可采用稳定剂，所述稳定剂可采用醇胺类络合剂，所述醇胺类络合剂优选乙醇胺；所述所述有机溶胶形成无机分子溶液原位成孔剂中采用的有机溶剂可采用多纯醇单醚、多醇类多醚或单醇类单醚，优选乙二醇甲醚。
- 如权利要求1所述原位成孔剂的聚偏氟乙烯中空纤维膜，其特征在于所述有机稀释剂采用植物油类或油酸酯类，所述植物油类可采用环氧大豆油；所述油酸酯类可采用油酸乙酯、油酸甘油酯、油酸聚二醇甘油酯中的至少一种；所述有机稀释剂优选环氧大豆油或油酸聚二醇甘油酯。
- 如权利要求1所述原位成孔剂的聚偏氟乙烯中空纤维膜，其特征在于所述原料组成中加入助剂，所述助剂选自抗氧剂、润滑剂、热稳定剂、紫外线吸收剂中的至少一种。
- 如权利要求1所述原位成孔剂的聚偏氟乙烯中空纤维膜的制备方法，其特征在于包括以下步骤：1)制备有机溶胶形成无机分子溶液原位成孔剂；2)将有机溶胶形成无机分子溶液原位成孔剂与高分子聚合物的树脂和有机稀释剂混合，得物料A；3)将物料A挤压后经成型模具挤出中空纤维；4)将中空纤维在线拉伸2～3倍，得中空纤维丝；5)将拉伸后的中空纤维丝经有机溶剂萃取处理除去所有的有机物，再用酸或碱溶液除去分散在中空纤维丝中的无机物，形成多孔膜；6)将多孔膜清洗后，定型热处理，得到原位成孔剂的聚偏氟乙烯中空纤维膜。
- 如权利要求5所述原位成孔剂的聚偏氟乙烯中空纤维膜的制备方法，其特征在于在步骤1)中，所述制备有机溶胶形成无机分子溶液原位成孔剂的具体方法 为：采用锌的可溶性无机盐如硝酸锌或有机盐如醋酸锌在催化剂冰醋酸及稳定剂乙醇胺作用下，溶解于乙二醇甲醚有机溶剂中而形成溶液，将醋酸锌溶解于乙二醇甲醚中，再加入与醋酸锌等摩尔的乙醇胺，在40～80℃经1～2h的搅拌后，形成透明的均质稳定的络合物溶液即有机溶胶形成无机分子溶液原位成孔剂。
- 如权利要求5所述原位成孔剂的聚偏氟乙烯中空纤维膜的制备方法，其特征在于在步骤2)中，所述将有机溶胶形成无机分子溶液原位成孔剂与高分子聚合物的树脂和有机稀释剂混合的具体方法为：聚偏氟乙烯树脂30％～50％、以无机盐的量计有机溶胶形成无机分子溶液成孔剂40％～50％和有机稀释剂10％～20％在混合搅拌机混合后，形成的物料即有机溶胶形成无机分子溶液的原位成孔剂和有机稀释剂与固体高分子聚合物树脂混合。
- 如权利要求5所述原位成孔剂的聚偏氟乙烯中空纤维膜的制备方法，其特征在于在步骤3)中，所述挤压采用成型机械进行挤压；在步骤4)中，所述将中空纤维在线拉伸可利用圆周速度不同的辊对等沿中空纤维丝的纵向按照50％～100％进行单轴向拉伸，并将中空纤维丝缠绕在收丝轮上。
- 如权利要求5所述原位成孔剂的聚偏氟乙烯中空纤维膜的制备方法，其特征在于在步骤5)中，所述有机溶剂萃取处理采用有机溶剂萃取剂，所述有机溶剂萃取剂可选自氯代烃类或低分子量的醇类，优选氯代烃类，氯代烃类可采用二氯甲烷；所述酸可采用盐酸或硫酸，所述碱可采用氢氧化钠或氢氧化钾，优选所述机物的强酸或强碱的除去剂为盐酸和硫酸溶液。
- 如权利要求5所述原位成孔剂的聚偏氟乙烯中空纤维膜的制备方法，其特征在于在步骤6)中，所述清洗采用水清洗；所述热处理的温度可为120～140℃。
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| CN104524988B (zh) | 2015-01-22 | 2017-09-22 | 联合环境技术（厦门）有限公司 | 原位成孔剂的聚偏氟乙烯中空纤维膜及其制备方法 |
| CN107447281B (zh) * | 2017-08-10 | 2020-04-07 | 武汉纺织大学 | 一种油相高分子中空纤维阵列材料的制备方法 |
| CN107475819A (zh) * | 2017-09-21 | 2017-12-15 | 成都新柯力化工科技有限公司 | 一种高仿棉纺织纤维及其制备方法 |
| CN108499361B (zh) * | 2018-04-10 | 2021-11-12 | 北京工业大学 | 一种孔径可调节的纳米多孔聚合物膜的制备方法 |
| US11738310B2 (en) | 2019-12-31 | 2023-08-29 | Industrial Technology Research Institute | Method for cleaning membrane |
| CN111569664A (zh) * | 2020-04-21 | 2020-08-25 | 李安武 | 一种可以调节膜孔径大小的有机无机杂化膜的制备方法 |
| CN114471190B (zh) * | 2020-10-28 | 2023-10-20 | 南京工大膜应用技术研究所有限公司 | 一种应用于农化废水的改性聚偏氟乙烯膜的制备方法 |
| CN112657342B (zh) * | 2020-12-02 | 2022-12-06 | 清华大学 | 一种聚酰胺中空纤维复合分离膜及制备方法 |
| CN114682101B (zh) * | 2020-12-30 | 2023-05-30 | 中国石油化工股份有限公司 | 一种碳中空纤维膜及其制备方法 |
| CN114762834B (zh) * | 2021-01-11 | 2023-07-28 | 中国石油化工股份有限公司 | 一种用于处理废水催化剂及其制法与应用 |
| CN114288868A (zh) * | 2021-12-24 | 2022-04-08 | 上海工程技术大学 | 编织管增强型聚偏氟乙烯中空纤维膜及其制备方法 |
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