CN101844041B - Hollow fiber nanofiltration membrane and preparation method thereof - Google Patents
Hollow fiber nanofiltration membrane and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a hollow fiber nanofiltration membrane. A polyacrylonitrile (PAN) ultrafiltration membrane is used as a basal membrane and the hollow fiber nanofiltration membrane is prepared by performing alkali wash, acid wash and amination sequentially by the chemical composite method, wherein the effective aperture of a membrane pore is 0.5 to 2 nanometers, the internal diameter of a membrane yarn is 0.5 to 1 mm and the external diameter of the membrane yarn is 1 to 1.6 mm. Without the processes of interface coating, or polymerization, and crosslinking, the hollow fiber nanofiltration membrane is prepared by utilizing low-price acid and alkali and through the simple acid washing and alkali washing processes, so that the use of high-cost polymeric materials is avoided, the production time is shortened; and the basal membrane is subjected to chemical combination to generate the nanofiltration membrane through simple process and in economical cost and short time.
Description
Technical field:
The invention belongs to the membrane separation technique field, relate to the method for preparing charged hollow fiber nanofiltration membrane through chemically composited method.
Background technology:
NF membrane is to develop new membrane isolation technics faster in recent years in the world.The traditional preparation process technology of NF membrane and the preparation of reverse osmosis membrane are similar, mainly contain phase inversion, blending method, surperficial lotus electrochemical process and composite algorithm.Composite algorithm is that using at most at present also is the method that the most effectively prepares NF membrane, and is the method that production commercialization NF membrane kind is maximum, output is maximum.
Composite algorithm comprises the preparation of preparation and ultra-thin cortex of basement membrane and compound.Usually the preparation of basement membrane adopts phase inversion to be formed by single high polymer, and basement membrane has suitable aperture, pore-size distribution, porosity, good resistance to pressure and chemical stability usually.Ultra-thin cortex commonly used adopts the interface coating process: it is basement membrane that Chinese patent 200510014733.1 discloses with polysulfones or polyvinylidene fluoride (PVDF) ultrafiltration membrane; The surface dip-coating polyacrylate and amino esters polymer aqueous solution is then through the crosslinked method for preparing composite nanometer filtering film of β x ray irradiation x; It is the film matrix that Chinese patent 02103752.3 discloses the employing milipore filter, through the method for synthesizing, make with extra care, filming and crosslinking process being made Nano filtering composite membrane.Also have interfacial polymerization: Chinese patent 200710172172.7 discloses the method for preparing crosslinked hyperbranched polyalcohol composite nano filter membrance through polyalcohol and polynary acyl chlorides interfacial polymerization aromatic polyester function cortex of utilizing on the porous support membrane; Chinese patent 200410098783.8 discloses a kind of technology that is prepared NF membrane by the big molecule of polyamide and polyacid, multicomponent isocyanate and the interfacial polymerization on porous supporting body of first acyl chlorides; One Chinese patent application numbers 200410068154.0 discloses a kind of method of on porous support membrane, carrying out polyamine and the ultra-thin aromatic polyamides functional membrane of modified aromatic polynary acyl chlorides interfacial polycondensation reaction formation; One Chinese patent application numbers 200710160239.5 discloses a kind of crosslinked hyperbranched polyalcohol composite nano filter membrance and preparation method thereof, and this NF membrane is to be basement membrane, to serve as to select layer, interfacial polymerization through dissaving polymer and polyacid, polynary acyl chlorides, polynary acid anhydride, polyamine to form with the crosslinked hyperbranched polyalcohol with a milipore filter.
The NF membrane of above-mentioned patent is prepared from interface coating process or interfacial polymerization in the composite algorithm respectively; Because the characteristic of these two kinds of methods; Make production technology comparatively complicated; The material cost that coating or polymerization relate to is high, needs the long time could accomplish chemically composited process, is unfavorable for the serialization large-scale industrial production.
Summary of the invention:
The technical problem that the present invention will solve provide a kind of low cost, technology simple, be easy to industrial hollow fiber nanofiltration membrane of serialization and preparation method thereof.
The present invention is a kind of hollow fiber nanofiltration membrane with regard to the technical solution that above-mentioned technical problem proposes; With polyacrylonitrile (PAN) milipore filter is basement membrane; Chemically composited method through alkali cleaning, pickling, amination is processed; It is characterized in that: the fenestra effective aperture is 0.5～2 nanometer, 0.5～1 millimeter of film silk internal diameter, 1～1.6 millimeter of external diameter.Its concrete preparation method may further comprise the steps:
A) configuration of casting solution:
Be mixed and made into by polyacrylonitrile (PAN) high polymer mass percent 18～26%, solvent orange 2 A mass percent 65～80% and aperture adjustment agent B mass percent 2～17%;
B) preparation of polyacrylonitrile (PAN) ultrafiltration basement membrane:
The casting solution that makes in water and the step a) is injected a spinning head through gear pump by core liquid passage and casting solution passage respectively, and be emitted into fiber tubulose liquid film through spinning head core liquid mouth and casting solution mouth simultaneously; Then, this liquid film gets into the coagulating bath pond after through 0.5～20cm centimetre the air gap and is wrapped on the wire wrapping wheel, and phase transformation is frozen into the Hollow Fiber Ultrafiltration basement membrane;
C) the Hollow Fiber Ultrafiltration basement membrane that step b) is made uses the alkali cleaning successively of chemically composited method, pickling, amination:
To be immersed in the alkali lye by the Hollow Fiber Ultrafiltration basement membrane that step b) makes and handle, used alkali lye is 0.5～6.25ML
-1NaOH (NaOH) or potassium hydroxide (KOH) or lithium hydroxide (LiOH) in, handled 5～15 minutes down at 20～60 ℃, take out and wash with running water; Immerse in the acid solution and handle, used acid solution is hydrochloric acid (HCl) or the sulfuric acid (H of 0.1～2M
2SO
4) or nitric acid (HNO
3), handled 5～10 minutes down at 20～40 ℃, take out and wash with running water; Immerse in the amine liquid and handle, used amine is polymine or the ethylenediamine or the p-phenylenediamine (PPD) aqueous solution of mass percent 1.0～10%, handles 5～30 minutes down at 20～60 ℃, takes out with the running water flushing, obtains hollow fiber nanofiltration membrane;
D) cleaning-drying: the hollow fiber nanofiltration membrane that step c) makes is put into 20: the glycerine of 80wt%～80: 20wt% and aqueous mixtures soaked 24～72 hours, in air, dried.
Preferably, in step a): polyacrylonitrile (PAN) molecular weight is 3～50,000;
Preferably; In step a): solvent orange 2 A is N; Dinethylformamide (DMF), N, one or more in N-dimethylacetylamide (DMAc), dimethyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO), the oxolane (THF) use together, and ratio can be regulated arbitrarily;
Preferably, in step a): aperture adjustment agent B is a kind of in ethylene glycol (EG), polyvinylpyrrolidone (PVP), the diethylene glycol (DEG) (DG).
Preferably, in step b): solidifying bathing pool is coagulation bath with water, and water temperature is 5～60 ℃;
Preferably, in step b): it is 1.2～2.5 millimeters with casting solution mouth diameter that core liquid mouth diameter is 0.7～1.6 millimeter;
Preferably, in step b): core liquid and casting solution temperature are 5～70 ℃;
Preferably, in step b): the casting solution flow velocity is 2～10ml/min, and the core flow velocity is 1～6ml/min;
Preferably, in step b): the drawing speed of wire wrapping wheel is 5～50m/min, and the spinning ambient humidity is 40%～85%;
The present invention adopts a kind of chemically composited legal system to be equipped with the high flux hollow fibre NF membrane; Compared with prior art; Hollow fiber nanofiltration membrane preparation method of the present invention need not interface coating or polymerization, crosslinking process; Utilize the more cheap soda acid of price to realize the preparation of hollow fiber nanofiltration membrane through simple pickling, alkali washing process; Avoided the use cost high polymerization material thus, and shortened the production time, made basement membrane through simple technology, economic cost, the very short chemically composited NF membrane that makes of interior completion of time.
The hollow fiber nanofiltration membrane lotus positive electricity that the present invention is prepared, water flux is 5.1～10.2L/ (m
2Hbar).Under 3 kilograms of operating pressures, the bivalent metal ion inorganic salts there is higher rejection, for example to 200ppm MgCl
2The rejection of solution is 88%～94%, to 200ppm MgSO
4The rejection of solution is 55%～75%; Rejection to the monovalent metallic ion inorganic salts is lower, for example to 200ppm NaSO
4The rejection of solution is 45%～65%,, to the rejection of 200ppm NaCl solution 18%～25%.
Description of drawings:
For content of the present invention is expressly understood more easily,, the present invention is done further detailed explanation below according to specific embodiment and combine accompanying drawing:
Fig. 1 is a kind of hollow fiber nanofiltration membrane preparation method's of the present invention device sketch map;
Fig. 2 is the structural representation of spinning head 6 among Fig. 1;
Wherein: casting solution passage 1, core liquid passage 4, gear pump 2, gear pump 3, spinning head 6 solidifies bathing pool 8, wire wrapping wheel 9, casting solution passage 7, core liquid passage 5, core liquid mouth 12, casting solution mouth 11.
The specific embodiment:
Specific embodiment (one):
The device that a kind of hollow fiber nanofiltration membrane preparation method of the present invention adopts is as shown in Figure 1, comprises casting solution passage 1, core liquid passage 4, and gear pump 2, gear pump 3, spinning head 6 solidifies bathing pool 8, wire wrapping wheel 9.The structural representation of spinning head 6 is seen Fig. 2 among Fig. 1, comprises casting solution passage 7, core liquid passage 5, core liquid mouth 12, casting solution mouth 11.
Casting solution is through the casting solution passage 7 of gear pump 2 by casting solution passage 1 injection spinning head 6, and core liquid is injected the core liquid passage 5 of spinning heads 6 by core liquid passage 4 through gear pump 3; Then, the core liquid mouth in spinning head 6 12 is emitted into fiber tubulose liquid film with casting solution mouth 11 simultaneously; Then, this liquid film gets into coagulating bath pond 8 after through the air gap and is wrapped on the wire wrapping wheel 9, and phase transformation is frozen into hollow fiber nanofiltration membrane.
The preparation process of the hollow fiber nanofiltration membrane of present embodiment is:
A) configuration of casting solution:
To be 3～50,000 polyacrylonitrile (PAN) high polymer, dimethyl pyrrolidone (NMP) and pore regulator ethylene glycol (EG) by molecular weight according to mass percent 22: 73: 5wt% mixed;
B) preparation of polyacrylonitrile (PAN) ultrafiltration basement membrane:
Water through the core liquid passage 5 of gear pump 3 by core liquid passage 4 injection spinning heads 6, will be injected the casting solution passage 7 of spinning head 6 by the casting solution that step a) makes by casting solution passage 1 through gear pump 2; Then, the casting solution mouth 11 of the core liquid mouth 12 of while diameter 0.7mm in spinning head 6 and diameter 1.5mm is emitted into fiber tubulose liquid film; Then, this liquid film is through getting into coagulating bath pond 8 and being wrapped on the wire wrapping wheel 9 behind the air gap of 3cm, and phase transformation is frozen into the Hollow Fiber Ultrafiltration basement membrane; Coagulation bath is a water, and water temperature is 25 ℃; Casting solution and core liquid temp are 25 ℃; The casting solution flow velocity is 10ml/min, and the core flow velocity is 5ml/min; The drawing speed of wire wrapping wheel is 12m/min, and the spinning ambient humidity is 70%.
C) the Hollow Fiber Ultrafiltration basement membrane of step b) being obtained uses the alkali cleaning successively of chemically composited method, pickling, amination:
To immerse 2.5ML by the Hollow Fiber Ultrafiltration basement membrane that step b) makes
-1NaOH (NaOH), handled 15 minutes down at 60 ℃, take out and wash with running water; Immerse 1ML then
-1Hydrochloric acid (HCl) in, handled 10 minutes down at 20 ℃, take out and wash with running water; Immerse in the polyethyleneimine: amine aqueous solution of mass percent 1wt%, handled 10 minutes down, take out, obtain hollow fiber nanofiltration membrane with the running water flushing at 40 ℃;
D) cleaning-drying: glycerine and aqueous mixtures that the hollow fiber nanofiltration membrane that step c) is made is put into mass percent 50: 50wt% soaked 24 hours, in air, dried.
The hollow fiber nanofiltration membrane water flux that this embodiment prepares reaches 10.2L/m
2Hbar, under 3 kilograms of operating pressures to 200ppm MgCl
2The rejection of solution is 88%, to 200ppm MgSO
4The rejection of solution is 55%, to 200ppm NaSO
4The rejection of solution is 45%, is 18% to the rejection of 200ppm NaCl solution.
Specific embodiment (two):
The same embodiment of device (one) that the present invention adopts, the preparation process of the hollow fiber nanofiltration membrane of present embodiment is:
A) configuration of casting solution:
By polyacrylonitrile (PAN) high polymer, the N of molecular weight 30,000～50,000, dinethylformamide (DMF) and aperture adjustment agent polyvinylpyrrolidone (PVP) were according to mass percent 18: 65: 17wt% is mixed and made into;
B) preparation of polyacrylonitrile (PAN) ultrafiltration basement membrane:
Water through the core liquid passage 5 of gear pump 3 by core liquid passage 4 injection spinning heads 6, will be injected the casting solution passage 7 of spinning head 6 by the casting solution that step a) makes by casting solution passage 1 through gear pump 2; Then, the casting solution mouth 11 of the core liquid mouth 12 of while diameter 0.7mm in spinning head 6 and diameter 1.5mm is emitted into fiber tubulose liquid film; Then, this liquid film is through getting into coagulating bath pond 8 and being wrapped on the wire wrapping wheel 9 behind the air gap of 0.5cm, and phase transformation is frozen into the Hollow Fiber Ultrafiltration basement membrane; Coagulation bath is a water, and water temperature is 5 ℃; Casting solution and core liquid temp are 5 ℃; The casting solution flow velocity is 2ml/min, and the core flow velocity is 1ml/min; The drawing speed of wire wrapping wheel is 5m/min, and the spinning ambient humidity is 40%.
C) the Hollow Fiber Ultrafiltration basement membrane of step b) being obtained uses the alkali cleaning successively of chemically composited method, pickling, amination:
To immerse 0.5ML by the Hollow Fiber Ultrafiltration basement membrane that step b) makes
-1Potassium hydroxide (NaOH), handled 5 minutes down at 60 ℃, take out and wash with running water; Immerse 2ML then
-1Sulfuric acid (H
2SO
4) in, handled 5 minutes down at 40 ℃, take out and wash with running water; Immerse in the ethylenediamine solution of mass percent 10wt%, handled 30 minutes down, take out, obtain hollow fiber nanofiltration membrane with the running water flushing at 60 ℃;
D) cleaning-drying: glycerine and aqueous mixtures that the hollow fiber nanofiltration membrane that step c) is made is put into mass percent 20: 80wt% soaked 72 hours, in air, dried.
Specific embodiment (three):
The same embodiment of device (one) that the present invention adopts, the preparation process of the hollow fiber nanofiltration membrane of present embodiment is:
A) configuration of casting solution:
Be 3～50,000 polyacrylonitrile (PAN) high polymer, dimethyl sulfoxide (DMSO) (DMSO) and oxolane (THF) by molecular weight with 1: 1 volume ratio mixed solvent orange 2 A and aperture adjustment agent diethylene glycol (DEG) (DG) according to mass percent 26: 72: the 2wt% mixing;
B) preparation of polyacrylonitrile (PAN) ultrafiltration basement membrane:
Water through the core liquid passage 5 of gear pump 3 by core liquid passage 4 injection spinning heads 6, will be injected the casting solution passage 7 of spinning head 6 by the casting solution that step a) makes by casting solution passage 1 through gear pump 2; Then, the casting solution mouth 11 of the core liquid mouth 12 of while diameter 1.6mm in spinning head 6 and diameter 2.5mm is emitted into fiber tubulose liquid film; Then, this liquid film is through getting into coagulating bath pond 8 and being wrapped on the wire wrapping wheel 9 behind the air gap of 8cm, and phase transformation is frozen into the Hollow Fiber Ultrafiltration basement membrane; Coagulation bath is a water, and water temperature is 60 ℃; Casting solution and core liquid temp are 70 ℃; The casting solution flow velocity is 10ml/min, and the core flow velocity is 6ml/min; The drawing speed of wire wrapping wheel is 50m/min, and the spinning ambient humidity is 85%.
C) the Hollow Fiber Ultrafiltration basement membrane of step b) being obtained uses the alkali cleaning successively of chemically composited method, pickling, amination:
To immerse 6.25ML by the Hollow Fiber Ultrafiltration basement membrane that step b) makes
-1Lithium hydroxide (LiOH), handled 8 minutes down at 20 ℃, take out and wash with running water; Immerse 0.8ML then
-1Nitric acid (HNO
3) in, handled 6 minutes down at 35 ℃, take out and wash with running water; Handle in the p-phenylenediamine (PPD) aqueous solution of immersion mass percent 4wt%, handled 5 minutes down, take out, obtain hollow fiber nanofiltration membrane with the running water flushing at 36 ℃;
D) cleaning-drying: glycerine and aqueous mixtures that the hollow fiber nanofiltration membrane that step c) is made is put into mass percent 80: 20wt% soaked 48 hours, in air, dried.
Specific embodiment (four):
The same embodiment of device (one) that the present invention adopts, the preparation process of the hollow fiber nanofiltration membrane of present embodiment is:
A) configuration of casting solution:
By molecular weight is 3～50,000 polyacrylonitrile (PAN) high polymer, N, and N-dimethylacetylamide (DMAc) and aperture adjustment agent ethylene glycol (EG) were according to mass percent 18: 80: 2wt% mixes;
B) preparation of polyacrylonitrile (PAN) ultrafiltration basement membrane:
Water through the core liquid passage 5 of gear pump 3 by core liquid passage 4 injection spinning heads 6, will be injected the casting film passage 7 of spinning head 6 by the casting solution that step a) makes by casting solution passage 1 through gear pump 2; Then, the casting solution mouth 11 of the core liquid mouth 12 of while diameter 0.7mm in spinning head 6 and diameter 1.2mm is emitted into fiber tubulose liquid film; Then, this liquid film is through getting into coagulating bath pond 8 and being wrapped on the wire wrapping wheel 9 behind the air gap of 20cm, and phase transformation is frozen into the Hollow Fiber Ultrafiltration basement membrane; Coagulation bath is a water, and water temperature is 5 ℃; Casting solution and core liquid temp are 5 ℃; The casting solution flow velocity is 8ml/min, and the core flow velocity is 4ml/min; The drawing speed of wire wrapping wheel is 30m/min, and the spinning ambient humidity is 62%.
C) the Hollow Fiber Ultrafiltration basement membrane of step b) being obtained uses the alkali cleaning successively of chemically composited method, pickling, amination:
To immerse 3ML by the Hollow Fiber Ultrafiltration basement membrane that step b) makes
-1Lithium hydroxide (LiOH), handled 10 minutes down at 30 ℃, take out and wash with running water; Immerse 0.1ML then
-1Nitric acid (HNO
3) in, handled 6 minutes down at 35 ℃, take out and wash with running water; Handle in the p-phenylenediamine (PPD) aqueous solution of immersion mass percent 7wt%, handled 18 minutes down, take out, obtain hollow fiber nanofiltration membrane with the running water flushing at 20 ℃;
D) cleaning-drying: glycerine and aqueous mixtures that the hollow fiber nanofiltration membrane that step c) is made is put into mass percent 45: 55wt% soaked 48 hours, in air, dried.
Above-described specific embodiment; Technical scheme of the present invention has been carried out further explain, and institute it should be understood that the above is merely specific embodiment of the present invention; Be not limited to the present invention; All within spirit of the present invention and principle, any modification of being made, be equal to replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (10)
1. a hollow fiber nanofiltration membrane is a basement membrane with polyacrylonitrile (PAN) milipore filter, processes through the chemically composited method of alkali cleaning, pickling, amination, and it is characterized in that: the fenestra effective aperture is 0.5～2 nanometer, 0.5～1 millimeter of film silk internal diameter, 1～1.6 millimeter of external diameter.
2. a kind of hollow fiber nanofiltration membrane according to claim 1 is characterized in that: polyacrylonitrile (PAN) molecular weight is 3～50,000.
3. according to claim 1 or the described a kind of hollow fiber nanofiltration membrane of claim 2, it is characterized in that: used alkali lye is 0.5～6.25ML in the said chemically composited method
-1NaOH (NaOH) or potassium hydroxide (KOH) or lithium hydroxide (LiOH).
4. according to claim 1 or the described a kind of hollow fiber nanofiltration membrane of claim 2, it is characterized in that: used acid solution is 0.1～2ML in the said chemically composited method
-1Hydrochloric acid (HCl) or sulfuric acid (H
2SO
4) or nitric acid (HNO
3).
5. according to claim 1 or the described a kind of hollow fiber nanofiltration membrane of claim 2, it is characterized in that: used amine is that mass percent is 1.0～10% polymine or the ethylenediamine or the p-phenylenediamine (PPD) aqueous solution in the said chemically composited method.
6. preparation method who prepares claim 1 or 2 described NF membrane is characterized in that: may further comprise the steps:
A) configuration of casting solution:
Be mixed and made into by polyacrylonitrile (PAN) high polymer mass percent 18～26%, solvent orange 2 A mass percent 65～80% and aperture adjustment agent B mass percent 2～17%;
B) preparation of polyacrylonitrile (PAN) ultrafiltration basement membrane:
The casting solution that makes in water and the step a) is injected a spinning head through gear pump by core liquid passage and casting solution passage respectively, and be emitted into fiber tubulose liquid film through said spinning head core liquid mouth and casting solution mouth simultaneously; Then, said liquid film gets into the coagulating bath pond after through 0.5～20cm centimetre the air gap and is wrapped on the wire wrapping wheel, and phase transformation is frozen into the Hollow Fiber Ultrafiltration basement membrane;
C) the Hollow Fiber Ultrafiltration basement membrane of step b) being obtained uses the alkali cleaning successively of chemically composited method, pickling, amination:
To be immersed in the alkali lye by the Hollow Fiber Ultrafiltration basement membrane that step b) makes and handle, used alkali lye is 0.5～6.25ML
-1NaOH (NaOH) or potassium hydroxide (KOH) or lithium hydroxide (LiOH) in, handled 5～15 minutes down at 20～60 ℃, take out and wash with running water; Immerse in the acid solution and handle, used acid solution is hydrochloric acid (HCl) or the sulfuric acid (H of 0.1～2M
2SO
4) or nitric acid (HNO
3), handled 5～10 minutes down at 20～40 ℃, take out and wash with running water; Immerse in the amine liquid and handle, used amine is polymine or the ethylenediamine or the p-phenylenediamine (PPD) aqueous solution of mass percent 1.0～10%, handles 5～30 minutes down at 20～60 ℃, takes out with the running water flushing, obtains hollow fiber nanofiltration membrane;
D) cleaning-drying:
The hollow fiber nanofiltration membrane that step c) makes is put into 20: the glycerine of 80wt%～80: 20wt% and aqueous mixtures soaked 24～72 hours, in air, dried.
7. the preparation method of NF membrane according to claim 6; It is characterized in that in the said step a): solvent orange 2 A is N; Dinethylformamide (DMF), N, one or more in N-dimethylacetylamide (DMAc), dimethyl pyrrolidone (NMP), dimethyl sulfoxide (DMSO) (DMSO), the oxolane (THF) use together.
8. the preparation method of NF membrane according to claim 6 is characterized in that in the said step a): aperture adjustment agent B is a kind of in ethylene glycol (EG), polyvinylpyrrolidone (PVP), the diethylene glycol (DEG) (DG).
9. the preparation method of NF membrane according to claim 6; It is characterized in that in the said step b): the said bathing pool that solidifies is coagulation bath with water; Water temperature is 5～60 ℃; Core liquid water and casting solution temperature are 5～70 ℃, and it is 1.2～2.5 millimeters with casting solution mouth diameter that said core liquid mouth diameter is 0.7～1.6 millimeter.
10. the preparation method of NF membrane according to claim 6; It is characterized in that in the said step b): the casting solution flow velocity is 2～10ml/min; The core flow velocity is 1～6ml/min, and the drawing speed of said wire wrapping wheel is 5～50m/min, and the spinning ambient humidity is 40%～85%.
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