CN108479433A - A kind of preparation method of hollow fiber compound nanofiltration membrane - Google Patents
A kind of preparation method of hollow fiber compound nanofiltration membrane Download PDFInfo
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- CN108479433A CN108479433A CN201810537922.4A CN201810537922A CN108479433A CN 108479433 A CN108479433 A CN 108479433A CN 201810537922 A CN201810537922 A CN 201810537922A CN 108479433 A CN108479433 A CN 108479433A
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- 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
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- 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
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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
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- 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
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- 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
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- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Water Supply & Treatment (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Separation Using Semi-Permeable Membranes (AREA)
- Artificial Filaments (AREA)
Abstract
The present invention relates to a kind of preparation methods of hollow fiber compound nanofiltration membrane, this method uses polysulfone hollow fibre basement membrane, with acrylic resin, carboxyl type vinyl chloride-vinyl acetate resin, methyl diphenylene diisocyanate is solute, butyl acetate and dimethyl carbonate are can making up organic hollow fiber composite nanometer filtering film at the hollow fiber compound nanofiltration membrane prepared after dense film on Best-Effort request in film liquid and being easily swollen for solvent composition, mechanical strength is low, the difficult deficiency of component sealing, ensuring compliance with NF membrane simultaneously has good salt rejection rate, higher water flux and chemical stability, it can realize serialization industrial production.
Description
Technical field
The present invention relates to technical field of water purification, more particularly to a kind of preparation method of hollow fiber compound nanofiltration membrane.
Background technology
In existing household water filter, mainly using reverse osmosis membrane filtration, the characteristics of due to household reverse osmosis film,
Desalination rate is very high, therefore water outlet salt content is substantially zeroed, while household reverse osmosis film needs high-voltage operation, its general operation pressure
Power needs 0.5MP~0.7MP.Existing household water filter is obtained water rate and is generally 50% left side due to the effect of household reverse osmosis film
The right side, therefore water resource waste is serious, and the daily water yield of every household water-purifying machine only has 50~100 gallons.In addition, household is anti-
Permeable membrane is generally rolled structure, and contamination resistance is not strong, and cleaning is complicated, can only periodically be replaced, be increased
Use cost.
The NF membrane being commercialized at present is mainly rolled film.Compared to rolled film, hollow-fibre membrane has packed density height, fortune
Annoying scrub water during row, the features such as fouling membrane is easily controllable, therefore as the important directions of current NF membrane area research
One of.The preparation method of existing hollow fiber compound nanofiltration membrane is broadly divided into two kinds：One is direct spinnings, that is, use acetic acid
Cellulose, sulfonated polyether sulfone etc. are used as filmogen, are directly configured to be spun to film system with solvent, additive etc., through solution
Phase inversion spinning technique obtains hollow fiber compound nanofiltration membrane.It the advantage is that whole process is easily achieved continuous production,
But disadvantage is to be limited by material, and the chemical stability and dimensional stability of gained NF membrane are poor, scale application by
Limitation；Another method is composite algorithm, i.e., is obtained by the direct coated polymer in surface and the method for crosslinking or interface direct polymerization
To hollow fiber compound nanofiltration membrane.It the advantage is that, the supportive and separating layer of basement membrane can be taken into account simultaneously using complex technique
Stalling characteristic, therefore, in nanofiltration field of membrane preparation, either rolled film or hollow-fibre membrane, composite algorithm all has become mainstream
Technology of preparing and praised highly by industrial circle.
The appearance of NF membrane compensates for the reverse osmosis blank between ultrafiltration, and NF membrane is also known as loose type reverse osmosis membrane.It is logical
The retention relative molecular mass boundary of reason condition, NF membrane is 200~1000, fenestra corresponding with retention relative molecular mass
Diameter is 1~3nm.Currently, existing NF membrane is all rolling NF membrane, rolling NF membrane is mainly used in feed separation industry,
Producing water ratio is also very low in its unit filled volume, meanwhile, because the production technology of rolling NF membrane is complicated, production cost and make
It is all very high with cost.
Invention content
In view of the technical drawbacks of the prior art, it is an object of the present invention to provide a kind of technical process is continuous, receive
It is uniform to filter functional layer, the preparation method of the few hollow fiber compound nanofiltration membrane of defect.
The technical solution adopted to achieve the purpose of the present invention is：
A kind of preparation method of hollow fiber compound nanofiltration membrane, includes following step：
(1) ceramic powder, high molecular polymer, organic solvent, dispersant are mixed in a certain ratio stirring, through vacuum suction
The bubble in film liquid is sloughed into, uniform and stable film forming raw material is formed；
(2) by film forming raw material through hollow spinning head and the spinning forming of double diffusion process, and primary solidification forms doughnut
Coagulating bath aqueous slkali during film gas, the aqueous film forming solvent of interior coagulating bath；
(3) aqueous solution that the hollow-fibre membrane of above-mentioned primary solidification is passed through to polyamine passes through excessively after wiping surface supernatant liquid away
The organic solution of first acyl chlorides, then through dry solidification, obtain hollow fiber compound nanofiltration membrane.
In step (1), the ceramic powder is one or both of aluminium oxide, zirconium oxide, titanium dioxide, and powder is put down
Equal grain size is 0.1~0.5 μm, and high molecular polymer is polyether sulfone, and organic solvent is N-Methyl pyrrolidone, and dispersant is poly- second
Alkene pyrrolidone.The mass ratio of ceramic powder is 50~60%, and the mass ratio of high molecular polymer is 6.5~7.5%, organic
The mass ratio of solvent is 35~45%, and the mass ratio of dispersant is 0.5~1.5%.
The time for being sucked by vacuum deaeration is 12~24 hours.
Aqueous slkali described in step (2) refer to polyelectrolyte, alkali mixing after be dissolved in the aqueous solution that water obtains.The poly- electrolysis
Matter is polymethylacrylic acid, polyvinyl or polyethyleneimine；The alkali is sodium hydroxide or potassium hydroxide.The poly- electrolysis
A concentration of 1-2g/L of matter, a concentration of 1-2g/L of the alkali.
The aqueous solution of polyamine described in step (2) is diethylenetriamine aqueous solution or triethylene tetramine aqueous solution；It is described
The mass concentration of diethylenetriamine aqueous solution or triethylene tetramine aqueous solution is 0.1-5%.
The organic solution of the polynary acyl chlorides is the hexamethylene or hexane solution of pyromellitic trimethylsilyl chloride.Pyromellitic trimethylsilyl chloride
Hexamethylene or hexane solution mass concentration be 0.05-3%.
Compared with prior art, the beneficial effects of the invention are as follows：
1, using polysulfone hollow fibre basement membrane, with acrylic resin, carboxyl type vinyl chloride-vinyl acetate resin, two isocyanide of diphenyl methane
Acid esters is solute, and butyl acetate and dimethyl carbonate are the standby at being blended after dense film on Best-Effort request in film liquid of solvent composition
Hollow fiber compound nanofiltration membrane can make up that organic hollow fiber composite nanometer filtering film is easily swollen, mechanical strength is low, component sealing is tired
Difficult deficiency, while NF membrane is ensured compliance with good salt rejection rate, higher water flux and chemical stability, it can realize
Serialization industrial production.
2, method of the invention uses medium of the polyelectrolyte aqueous slkali as outer coagulating bath, due to polyelectrolyte aqueous slkali
It is not direct in interfacial polymerization process to be contacted with polynary acyl chlorides, conventional protic absorbent can be substantially reduced, pair occurs with polynary acyl chlorides
The problem of reaction, improves the effective rate of utilization of monomer.
Specific implementation mode
The following is a clear and complete description of the technical scheme in the embodiments of the invention, it is clear that described embodiment
Only a part of the embodiment of the present invention, instead of all the embodiments.Based on the embodiments of the present invention, the common skill in this field
The every other embodiment that art personnel are obtained without making creative work belongs to the model that the present invention protects
It encloses.
【Embodiment 1】
(1) it is 0.3 μm of aluminium oxide ceramics powder, polyether sulfone, N-Methyl pyrrolidone, polyvinylpyrrolidine by average grain diameter
Ketone mass ratio 50%：7.2%：42%：0.8% ratio is mixed, and through vacuum suction 12 hours, sloughs into the gas in film liquid
Bubble, forms uniform and stable film forming raw material；
(2) based on mass concentration, polyvinyl 2g/L, potassium hydroxide are that the poly- electricity of 2g/L prepares solution matter aqueous slkali, with
Above-mentioned polyelectrolyte aqueous slkali is outer coagulating bath, and the dimethylformamide mass concentration formed with water and dimethylformamide is
70% mixed liquor is interior coagulating bath, and above-mentioned hollow fiber ultrafiltration membrane is spun to film system through hollow spinning head and double diffusion
Journey spinning forming.
(3) after above-mentioned Hollow Fiber Ultrafiltration membrane structure primary solidification, the divinyl three that mass concentration is 5% is passed it through
Amine aqueous solution is wiped away in the hexane solution for the pyromellitic trimethylsilyl chloride for being 3% by mass concentration after the supernatant liquid of surface, then through drying
Solidification process, obtains hollow fiber compound nanofiltration membrane, and the drying and curing process prepares NF membrane with conventional interface polymerization
Technique it is identical.
【Embodiment 2】
(1) it is 0.3 μm of zirconia ceramic powder, polyether sulfone, N-Methyl pyrrolidone, polyvinyl pyrrole by average grain diameter
Alkanone mass ratio 50%：7.2%：42%：0.8% ratio is mixed, and through vacuum suction 18 hours, sloughs into film liquid
Bubble forms uniform and stable film forming raw material；
(2) based on mass concentration, polyvinyl 1g/L, potassium hydroxide are that the poly- electricity of 1g/L prepares solution matter aqueous slkali, with
Above-mentioned polyelectrolyte aqueous slkali is outer coagulating bath, and the dimethylformamide mass concentration formed with water and dimethylformamide is
60% mixed liquor is interior coagulating bath, and above-mentioned hollow fiber ultrafiltration membrane is spun to film system through hollow spinning head and double diffusion
Journey spinning forming.
(3) after above-mentioned Hollow Fiber Ultrafiltration membrane structure primary solidification, the divinyl three that mass concentration is 5% is passed it through
Amine aqueous solution is wiped away in the hexane solution for the pyromellitic trimethylsilyl chloride for being 3% by mass concentration after the supernatant liquid of surface, then through drying
Solidification process, obtains hollow fiber compound nanofiltration membrane, and the drying and curing process prepares NF membrane with conventional interface polymerization
Technique it is identical.
【Embodiment 3】
(1) it is 0.5 μm of titanium dioxide ceramic powder, polyether sulfone, N-Methyl pyrrolidone, polyvinyl pyrrole by average grain diameter
Alkanone mass ratio 50%：7.2%：42%：0.8% ratio is mixed, and through vacuum suction 18 hours, sloughs into film liquid
Bubble forms uniform and stable film forming raw material；
(2) based on mass concentration, polyvinyl 2g/L, potassium hydroxide are that the poly- electricity of 2g/L prepares solution matter aqueous slkali, with
Above-mentioned polyelectrolyte aqueous slkali is outer coagulating bath, and the dimethylformamide mass concentration formed with water and dimethylformamide is
70% mixed liquor is interior coagulating bath, and above-mentioned hollow fiber ultrafiltration membrane is spun to film system through hollow spinning head and double diffusion
Journey spinning forming.
(3) after above-mentioned Hollow Fiber Ultrafiltration membrane structure primary solidification, the divinyl three that mass concentration is 3% is passed it through
Amine aqueous solution is wiped away in the hexane solution for the pyromellitic trimethylsilyl chloride for being 1% by mass concentration after the supernatant liquid of surface, then through drying
Solidification process, obtains hollow fiber compound nanofiltration membrane, and the drying and curing process prepares NF membrane with conventional interface polymerization
Technique it is identical.
【Embodiment 4】
(1) it is 0.3 μm of titanium dioxide ceramic powder, polyether sulfone, N-Methyl pyrrolidone, polyvinyl pyrrole by average grain diameter
Alkanone mass ratio 50%：7.2%：42%：0.8% ratio is mixed, and through vacuum suction 18 hours, sloughs into film liquid
Bubble forms uniform and stable film forming raw material；
(2) based on mass concentration, polyvinyl 1.5g/L, potassium hydroxide are that the poly- electricity of 1.0g/L prepares solution matter alkali soluble
Liquid is dense with the dimethylformamide quality that water and dimethylformamide form with above-mentioned polyelectrolyte aqueous slkali for outer coagulating bath
Degree is interior coagulating bath for 60% mixed liquor, and above-mentioned hollow fiber ultrafiltration membrane is spun to film system through hollow spinning head and double expansions
The process of dissipating spinning forming.
(3) after above-mentioned Hollow Fiber Ultrafiltration membrane structure primary solidification, the divinyl three that mass concentration is 4% is passed it through
Amine aqueous solution is wiped away in the hexane solution for the pyromellitic trimethylsilyl chloride for being 2% by mass concentration after the supernatant liquid of surface, then through drying
Solidification process, obtains hollow fiber compound nanofiltration membrane, and the drying and curing process prepares NF membrane with conventional interface polymerization
Technique it is identical.
【Embodiment 5】
Hollow fiber compound nanofiltration membrane cutoff performance is tested
The low pressure hollow composite nanometer filtering film of above-mentioned preparation and household reverse osmosis film, rolling NF membrane are compared,
The results are shown in Table 1.
Table 1
Above description has fully disclosed the specific implementation mode of the present invention.It should be pointed out that being familiar with the field
Technical staff is to any change for being done of specific implementation mode of the present invention all without departing from the range of claims of the present invention.
Correspondingly, the scope of the claims of the invention is also not limited only to previous embodiment.
Claims (8)
1. a kind of preparation method of hollow fiber compound nanofiltration membrane, which is characterized in that include the following steps：
(1) ceramic powder, high molecular polymer, organic solvent, dispersant are mixed in a certain ratio stirring, are sloughed through vacuum suction
At the bubble in film liquid, uniform and stable film forming raw material is formed；
(2) by film forming raw material through hollow spinning head and the spinning forming of double diffusion process, and primary solidification forms hollow-fibre membrane gas
Coagulating bath aqueous slkali in the process, the aqueous film forming solvent of interior coagulating bath；
(3) aqueous solution that the hollow-fibre membrane of above-mentioned primary solidification is passed through to polyamine, is wiped away after the supernatant liquid of surface by polynary acyl
The organic solution of chlorine, then through dry solidification, obtain hollow fiber compound nanofiltration membrane.
2. the preparation method of hollow fiber compound nanofiltration membrane according to claim 1, which is characterized in that in step (1), institute
It is one or both of aluminium oxide, zirconium oxide, titanium dioxide to state ceramic powder, and the average grain diameter of powder is 0.1~0.5 μm,
High molecular polymer is polyether sulfone, and organic solvent is N-Methyl pyrrolidone, and dispersant is polyvinylpyrrolidone.
3. the preparation method of hollow fiber compound nanofiltration membrane according to claim 1, which is characterized in that in step (1), pottery
The mass ratio of porcelain powder is 50~60%, and the mass ratio of high molecular polymer is 6.5~7.5%, the mass ratio of organic solvent
Example is 35~45%, and the mass ratio of dispersant is 0.5~1.5%.
4. the preparation method of hollow fiber compound nanofiltration membrane according to claim 1, which is characterized in that in step (1), very
The time of sky suction deaeration is 12~24 hours.
5. the preparation method of hollow fiber compound nanofiltration membrane according to claim 1, which is characterized in that institute in step (2)
State aqueous slkali refer to polyelectrolyte, alkali mixing after be dissolved in the aqueous solution that water obtains.
6. the preparation method of hollow fiber compound nanofiltration membrane according to claim 5, which is characterized in that the polyelectrolyte
For polymethylacrylic acid, polyvinyl or polyethyleneimine；The alkali is sodium hydroxide or potassium hydroxide；The polyelectrolyte
A concentration of 1~2g/L, a concentration of 1~2g/L of the alkali.
7. the preparation method of hollow fiber compound nanofiltration membrane according to claim 1, which is characterized in that institute in step (3)
The aqueous solution for stating polyamine is diethylenetriamine aqueous solution or triethylene tetramine aqueous solution；The diethylenetriamine aqueous solution or three
The mass concentration of four amine aqueous solution of ethylene is 0.1-5%.
8. the preparation method of hollow fiber compound nanofiltration membrane according to claim 1, which is characterized in that in step (3), institute
State polynary acyl chlorides organic solution be pyromellitic trimethylsilyl chloride hexamethylene or hexane solution, the hexamethylene of pyromellitic trimethylsilyl chloride or
The mass concentration of hexane solution is 0.05-3%.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111530286A (en) * | 2020-04-28 | 2020-08-14 | 南京工业大学 | Hollow fiber nanofiltration membrane and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103041713A (en) * | 2013-01-28 | 2013-04-17 | 天津膜天膜科技股份有限公司 | Preparation method of hollow fiber nanofiltration membrane |
| CN105289318A (en) * | 2015-11-18 | 2016-02-03 | 新疆德蓝股份有限公司 | Hollow fiber composite nanofiltration membrane and preparation method thereof |
| CN105396470A (en) * | 2015-12-10 | 2016-03-16 | 广州中国科学院先进技术研究所 | Hollow fiber composite nanofiltration membrane and preparation method thereof |
| CN106268378A (en) * | 2016-08-04 | 2017-01-04 | 李祥庆 | A kind of preparation method of hollow fiber compound nanofiltration membrane |
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103041713A (en) * | 2013-01-28 | 2013-04-17 | 天津膜天膜科技股份有限公司 | Preparation method of hollow fiber nanofiltration membrane |
| CN105289318A (en) * | 2015-11-18 | 2016-02-03 | 新疆德蓝股份有限公司 | Hollow fiber composite nanofiltration membrane and preparation method thereof |
| CN105396470A (en) * | 2015-12-10 | 2016-03-16 | 广州中国科学院先进技术研究所 | Hollow fiber composite nanofiltration membrane and preparation method thereof |
| CN106268378A (en) * | 2016-08-04 | 2017-01-04 | 李祥庆 | A kind of preparation method of hollow fiber compound nanofiltration membrane |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111530286A (en) * | 2020-04-28 | 2020-08-14 | 南京工业大学 | Hollow fiber nanofiltration membrane and preparation method thereof |
| CN111530286B (en) * | 2020-04-28 | 2022-02-11 | 南京工业大学 | Hollow fiber nanofiltration membrane and preparation method thereof |
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