CN103861477B - A kind of Kynoar/Pd nano particle hydridization hollow-fibre membrane and preparation method thereof - Google Patents
A kind of Kynoar/Pd nano particle hydridization hollow-fibre membrane and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to a kind of Kynoar/Pd nano particle hydridization hollow-fibre membrane and preparation method thereof.The present invention is by the hydrophily of polymer gel, and the high catalytic activity of Pd nano particle combines with the corrosion resistance of Kynoar and good film forming, has prepared and has had good contamination resistance, the hydridization hollow-fibre membrane of high catalytic activity and good separation.Use this hollow-fibre membrane can catalytic amino nitrobenzene, nitrophenol, nitrobenzene, methyl nitrobenzene, dimethyl nitrobenzene, cyanonitrobenzene, chloronitrobenzene, vinyl nitrobenzene, the reduction reaction of the nitro in nitrocyclohexane equimolecular, is converted into amino by nitro.Meanwhile, this film can also be used for the separation of different size material in liquid mixture.
Description
Technical field
The present invention relates to a kind of Kynoar/Pd nano particle hybridized film and preparation method thereof, be specially a kind of polymer gel/Pd nano particle hybrid and Kynoar (PVDF) is blended obtains Kynoar hydridization hollow-fibre membrane and preparation method thereof, belong to polymer science and technical field.
Background technology
Kynoar (PVDF) is ageing-resistant and anti-ultraviolet property excellent, and chemical stability is good, under room temperature, the strong oxidizer such as acid and alkali, alkali and halogen corrosion, also have excellent heat endurance and mechanical strength simultaneously, is the good separation membrane material of a kind of combination property.PVDF makes hollow-fibre membrane, has high film specific area and loading density, is widely used in chemical industry, biochemical, electronics, food, the industrial circles such as weaving.However, the application of pure PVDF hollow-fibre membrane mainly also concentrates on separation aspect, and the application of other side also needs further expansion.
Pd nano particle has the stability of the uniqueness relevant with size, small-size effect, quantum effect, skin effect and bioaffinity etc.It is study hotspot (DanielMC, AstrucD, the Chem.Rev. of the aspects such as optics, electronics, catalysis and biological medicine as a kind of good classical nano material; 2004,104,293).Pd nano particle has a large amount of surface atoms, has very high catalytic activity.But above the supporter that the Pd nano particle of high catalytic activity must be dispersed in, cause the decline of catalytic activity to prevent the accumulation of these nano particles.
Hollow-fibre membrane has high specific area, and high specific surface area can reach 30,000m
2/ m
3, there is very high palladium and belong to nanometer particle load ability.Therefore, Pd nano particle is loaded on PVDF hollow-fibre membrane, PVDF hollow-fibre membrane both can have been made to retain stalling characteristic, its high catalysis characteristics can have been given again, make it further be applied at catalytic field.
Summary of the invention
The object of this invention is to provide a kind of hybridized film integrating separation function and catalysis, another object of the present invention is to provide the preparation method of described film.The present invention relates to a kind of PVDF/ Pd nano particle hydridization doughnut hybridized film, it is characterized in that this film is made up of according to mass ratio 99: 1-60: 40 Kynoar and polymer gel/Pd nano particle hybrid; This film internal diameter is 0.1-2.5mm, wall thickness 0.1-0.5mm, average pore size 30-300nm, and under 0.05MPa20 DEG C of condition, pure water flux is 50-1000L/m
2h.
In this film, because hydrophilic polymer gel is positioned at fenestra surface, hydrophily and the antifouling property of pvdf membrane improve a lot.In addition, Pd nano particle load on the gel of fenestra, the catalytic performance that film has had.Therefore, outstanding advantages of the present invention is fixed in fenestra by close Shui polymer gel/Pd nano particle hybrid, thus make the catalysis of Pd nano particle, and the filtering function of separation membrane ideally combines, and is a kind of novel functional membrane.Another advantage of the present invention is that film-forming method is simple, is convenient to large-scale production.
Technical scheme
The technical scheme that the present invention solves described product technology problem is: design a kind of PVDF doughnut hybridized film, this film is by Kynoar (PVDF) and high molecular polymer gel/Pd nano particle hybrid physical blending gained, comprises the steps:
A) preparation of PVDF solution: PVDF is dissolved obtained 15-25Wt% Kynoar solution in a solvent;
The preparation of b) polymer gel/Pd nano particle hybrid dispersion liquid: by polymer gel/Pd nano particle hybrid dispersion in a solvent, obtained 15-25Wt% polymer gel/Pd nano particle hybrid dispersion liquid;
C) preparation of perforating agent solution: perforating agent is dissolved in solvent, obtained 15-25Wt% perforating agent solution;
D) spinning solution is prepared: Kynoar solution step (a) obtained, the perforating agent solution that the polymer gel that step (b) obtains/Pd nano particle hybrid dispersion liquid and step (c) obtain is 99 ~ 60: 1 ~ 40: 0 ~ 20 mixing in mass ratio, dissolve, degassed, obtain spinning solution;
E) core liquid preparation: use non-solvent or non-solvent and solvent mixture to prepare core liquid, wherein non-solvent and solvent mass ratio be 100: 0 to 90: 10;
F) coagulating bath preparation: use non-solvent or non-solvent and solvent mixture to prepare coagulating bath, wherein non-solvent and solvent mass ratio be 100: 0 to 90: 10;
G) hybridized film preparation: adopt dry-wet spinning process, at dry-spinning path 0.5-25cm, the temperature 50-70 DEG C of described spinning solution, under described core liquid and coagulation bath temperature 10-30 DEG C condition, coagulating bath prepared by the core liquid using above-mentioned steps (e) to prepare and above-mentioned steps (f), spinning solution above-mentioned steps (d) obtained spinning obtains described doughnut hybridized film.
Described polymer gel/Pd nano particle hybrid is adopted and is prepared with the following method:
A) preparation of polymer gel: by polymer monomer (methyl) acrylic acid or 4-vinylpridine 50g, crosslinking agent MBAA0.5g and initator KPS0.5g is dissolved in 1000mL water, 75 DEG C, carry out radical polymerization under nitrogen protection condition, gathered (methyl) acrylic acid or poly 4 vinyl pyridine gel;
B) polymer gel/Pd nano particle hybrid preparation: at 25 DEG C, poly-(methyl) acrylic acid step (a) obtained or poly 4 vinyl pyridine gel dispersion are in deionized water, add palladium bichloride 1g, use 1g sodium borohydride reduction, gathered (methyl) acrylic gel/Pd nano particle hybrid or poly-4-vinylpyridine gel/Pd nano particle hybrid;
The technical scheme that the present invention solves described product technology problem is: design a kind of PVDF doughnut hybridized film, and this film is by Kynoar (PVDF) and high molecular polymer gel/Pd nano particle hybrid physical blending gained.Physical blending method is by preparation method's defined of the present invention.
In the sense of the present invention, it is to dissolve PVDF polymer and dispersed polymeres gel/Pd nano particle hybrid that described solvent is construed as, and obtains the solvent of uniform dispersion.
In preparation method of the present invention, described solvent is the one in DMF, DMA or 1-METHYLPYRROLIDONE.
In the sense of the present invention, described perforating agent is construed as the agent that spinning solution can be helped in gelation process to form hole.
In preparation method of the present invention, described perforating agent is polyvinylpyrrolidone or polyethylene glycol.
In the sense of the present invention, described core liquid is construed as the cavity shape that can help to maintain doughnut in spinning process, promotes the gel solidification of Polymer Solution simultaneously, and forms the solution in hole.
Described core liquid prepares with the mixture of non-solvent or non-solvent and solvent.
Wherein, described solvent as defined above.
In the sense of the present invention, described non-solvent is construed as the non-solvent that can not dissolve PVDF.
In preparation method of the present invention, described non-solvent is the mixture of the one in water or water and ethanol, methyl alcohol or glycerine according to mass ratio 90: 10.
In the sense of the present invention, described coagulating bath is construed as and can makes spinning solution gel solidification in spinning process, and forms the bath of hollow-fibre membrane.
Described coagulating bath is prepared by the mixture of non-solvent or solvent and non-solvent.Described solvent and non-solvent are as defined above.
Implement the hollow fiber spinning machine that described dry-wet spinning uses to be produced by the new three-dimensional films Technology Co., Ltd. in Tianjin, its spinning technique flow process as shown in Figure 1.Above-mentioned spinning solution is extruded by the spinning head of hollow fiber spinning machine and the core liquid in spinning head central tube simultaneously, then enters in coagulating bath.Spinning solution is contained in feed liquid still 2, and core liquid is contained in core flow container 3.Spinning solution enters spinning head 4 under the nitrogen pressure of steel cylinder 1, and meanwhile, core liquid enters in the central tube of spinning head.Described spinning solution and core liquid are extruded through spinning head 4 simultaneously, then enter in coagulating tank 5.Solvent in described spinning solution and perforating agent enter coagulating bath, and coagulating bath diffuses in spinning solution.Polymer P VDF in described spinning solution passes through phase transfer Precipitation because solubility reduces, thus is spun into PVDF/ Pd nano particle hydridization hollow-fibre membrane.Made hollow-fibre membrane is wrapped on wire wrapping wheel 8 through guide wheel 7.Wire wrapping wheel in rotation process, the further gel solidification of the pure water of hollow-fibre membrane in wrapping wire rinse bath 9.
In the present invention, described hollow-fibre membrane is made up of according to mass ratio 99: 1-60: 40 Kynoar and polymer gel/Pd nano particle hybrid; This film internal diameter is 0.1-2.5mm, wall thickness 0.1-0.5mm, average pore size 30-300nm, and under 0.05MPa20 DEG C of condition, pure water flux is 50-1000L/m
2h.
In the present invention, the surfaces externally and internally of described hollow-fibre membrane is compacted zone, and section structure is finger-like pore and sponge hole.Film surface and section structure can by changing spinning solution, and the composition of core liquid and coagulating bath regulates, when in spinning solution, gel content is higher, when the non-solvent content in core liquid and coagulating bath is higher, and the section that easy formation finger-like pore is more; On the contrary, when spinning solution gel content is lower, when the non-solvent content in core liquid and coagulating bath is lower, the surfaces externally and internally of film easily forms chondritic, and the section of film easily forms the more structure in sponge hole.
In the present invention, because prepared hollow-fibre membrane is in film forming procedure, hybrid gel and PVDF are separated pore-forming, and hybrid gel is positioned on hollow-fibre membrane hole wall.Like this, obtained hollow-fibre membrane hole wall contains hydrophilic gel and Pd nano particle, has hydrophily and catalytic reaction activity two aspect function.
Preparation method's technique of hybrid gel film of the present invention is simple, and reagent used is conventional reagent, and device therefor is simple, is easy to the features such as industrializing implementation.
Accompanying drawing explanation
Fig. 1 is the spinning technique flow process of hollow fiber spinning machine.Wherein: 1-nitrogen cylinder; 2.-feed liquid still; 3-core flow container; 4-spinning head; 5-coagulating tank; 6-hollow-fibre membrane guide wheel; 7-guide wheel; 8-wire wrapping wheel; 9-wrapping wire rinse bath.
Detailed description of the invention
The pure water flux of described hollow-fibre membrane measures under 25 DEG C of conditions according to Chinese name republic ocean professional standard " doughnut miillpore filter method of testing HY/T051-1999 ".
Average pore size is the model adopting Merck & Co., Inc of the U.S. to produce is that AutoporeIV9500 type micropore Structure Analysis instrument (mercury injection apparatus) carries out measuring.
Internal diameter and external diameter use the light microscope determining of band scale, and light microscope used is the XTT zoom Stereo microscope that tech electric light instrument plant of Beijing produces.
The present invention is described further below in conjunction with embodiment:
The present invention is a kind of Kynoar/Pd nano particle hybridized film and preparation method thereof.This film selects Kynoar (PVDF) as film forming main material, by high molecular polymer gel/Pd nano particle hybrid and its physical blending, adopts the method for solution inversion of phases film forming to obtain.Its design principle is that Kynoar (PVDF) and incompatible high molecular polymer gel/Pd nano particle hybrid are formed dense dispersion liquid, and high-molecular gel/Pd nano particle hybrid is fixed in Kynoar by the mutual entanglement that solid-liquid phase changes in membrane process between macromolecule; Meanwhile, incompatiblely between Kynoar and high molecular polymer gel/Pd nano particle hybrid cause them to be separated in film forming procedure, form the Kynoar hybridized film that high molecular polymer gel/Pd nano particle hybrid is positioned at fenestra surface.Preparation method of the present invention specifically selects high molecular polymer gel/Pd nano particle hybrid such as (methyl) acrylic acid or poly 4 vinyl pyridine etc. and Kynoar physical blending inversion of phases film forming respectively, prepares Kynoar (PVDF)/Pd nano particle hybridized film.Because the high molecular polymer gel/Pd nano particle hybrid being positioned at fenestra has close Shui characteristic and catalysis characteristics, prepared film has stain resistance simultaneously, separating property and catalysis.Therefore, product of the present invention can have separating property and catalytic performance simultaneously, is a kind of new Kynoar (PVDF) hybridized film parting material.
In Kynoar of the present invention (PVDF)/Pd nano particle hybridized film preparation process, the film pure water obtained cleans repeatedly, and object is the high molecular polymer gel/Pd nano particle hybrid removing adsorption.
Although the method that the present invention narrates preferentially selects Kynoar (PVDF) hollow-fibre membrane, but it is equally applicable to the film of other form, comprise tubular membrane, other form such as Flat Membrane, and prepare corresponding Kynoar (PVDF) hybridized film with this.
Introduce specific embodiments of the invention below:
Embodiment 1.
(1) preparation of PVDF solution: PVDF is dissolved in obtained 15Wt% Kynoar solution in DMF;
(2) preparation of high molecular polymer gel: by polymer monomer (methyl) acrylic acid or 4-vinylpridine 50g, crosslinking agent MBAA0.5g and initator KPS0.5g is dissolved in 1000mL water, 75 DEG C, carry out radical polymerization 8h under nitrogen protection condition, centrifugation, vacuum drying, is gathered (methyl) acrylic acid or poly 4 vinyl pyridine gel;
(3) polymer gel/Pd nano particle hybrid preparation: at 25 DEG C, the polymer gel 20g that step (2) obtains is dispersed in 100mL deionized water, add chlorine palladium acid 1g, use 1g sodium borohydride reduction, centrifugation, drying, obtains polymer gel/Pd nano particle hybrid;
(4) preparation of polymer gel/Pd nano particle hybrid dispersion liquid: polymer gel/Pd nano particle hybrid step (3) obtained is dispersed in DMF, obtained 15wt% dispersion liquid;
(5) preparation of perforating agent solution: perforating agent polyvinylpyrrolidone is dissolved in DMF, obtained 15Wt% perforating agent solution;
(6) spinning solution is prepared: Kynoar solution step (1) obtained, the perforating agent solution that the polymer gel that step (4) obtains/Pd nano particle hybrid dispersion liquid and step (5) obtain is 99: 1: 0 mixing in mass ratio, dissolve, degassed, obtain 15wt% spinning solution;
(7) core liquid preparation: use non-solvent and solvent mixture to prepare core liquid, wherein the mass ratio of non-solvent water and solvent DMF is 90: 10;
(8) coagulating bath preparation: use non-solvent and solvent mixture to prepare coagulating bath, wherein the mass ratio of non-solvent water and solvent DMF is 90: 10;
(9) hybridized film preparation: adopt dry-wet spinning process, coagulating bath prepared by the core liquid using hollow fiber spinning machine (Fig. 1) and above-mentioned steps (7) to prepare and above-mentioned steps (8), at dry-spinning path 0.5cm, the temperature 50 C of spinning solution, under core liquid and coagulation bath temperature 30 DEG C of conditions, spinning solution spinning above-mentioned steps (6) obtained obtains described doughnut hybridized film.
Embodiment 2.
(1) with embodiment 1;
(2) with embodiment 1;
(3) with embodiment 1;
(4) with embodiment 1;
(5) with embodiment 1
(6) spinning solution is prepared: Kynoar solution step (1) obtained, the perforating agent solution that the polymer gel that step (4) obtains/Pd nano particle hybrid dispersion liquid and step (5) obtain is 80: 20: 0 mixing in mass ratio, dissolve, degassed, obtain 15wt% spinning solution;
(7) with embodiment 1;
(8) with embodiment 1;
(9) hybridized film preparation: adopt dry-wet spinning process, coagulating bath prepared by the core liquid using hollow fiber spinning machine (Fig. 1) and above-mentioned steps (7) to prepare and above-mentioned steps (8), at dry-spinning path 10cm, the temperature 50 C of spinning solution, under core liquid and coagulation bath temperature 30 DEG C of conditions, spinning solution spinning above-mentioned steps (6) obtained obtains described doughnut hybridized film.
Embodiment 3.
(1) with embodiment 1;
(2) with embodiment 1;
(3) with embodiment 1;
(4) with embodiment 1;
(5) with embodiment 1;
(6) spinning solution is prepared: Kynoar solution step (1) obtained, the perforating agent solution that the polymer gel that step (4) obtains/Pd nano particle hybrid dispersion liquid and step (5) obtain is 60: 40: 0 mixing in mass ratio, dissolve, degassed, obtain 15wt% spinning solution;
(7) with embodiment 1;
(8) with embodiment 1;
(9) hybridized film preparation: adopt dry-wet spinning process, coagulating bath prepared by the core liquid using hollow fiber spinning machine (Fig. 1) and above-mentioned steps (7) to prepare and above-mentioned steps (8), at dry-spinning path 25cm, the temperature 50 C of spinning solution, under core liquid and coagulation bath temperature 30 DEG C of conditions, spinning solution spinning above-mentioned steps (6) obtained obtains described doughnut hybridized film.
Embodiment 4.
(1) with embodiment 1;
(2) with embodiment 1;
(3) with embodiment 1;
(4) with embodiment 1;
(5) with embodiment 1;
(6) spinning solution is prepared: Kynoar solution step (1) obtained, the perforating agent solution that the polymer gel that step (4) obtains/Pd nano particle hybrid dispersion liquid and step (5) obtain is 80: 20: 10 mixing in mass ratio, dissolve, degassed, obtain 15wt% spinning solution;
(7) with embodiment 1;
(8) with embodiment 1;
(9) with embodiment 1.
Embodiment 5.
(1) with embodiment 1;
(2) with embodiment 1;
(3) with embodiment 1;
(4) with embodiment 1;
(5) with embodiment 1;
(6) spinning solution is prepared: Kynoar solution step (1) obtained, the perforating agent solution that the polymer gel that step (4) obtains/Pd nano particle hybrid dispersion liquid and step (5) obtain is 80: 20: 20 mixing in mass ratio, dissolve, degassed, obtain 15wt% spinning solution;
(7) with embodiment 1;
(8) with embodiment 1;
(9) with embodiment 1.
Embodiment 6.
(1) preparation of PVDF solution: PVDF is dissolved in obtained 25Wt% Kynoar solution in DMA;
(2) with embodiment 1;
(3) with embodiment 1;
(4) preparation of polymer gel/Pd nano particle hybrid dispersion liquid: polymer gel/Pd nano particle hybrid step (3) obtained is dispersed in DMA, obtained 25wt% dispersion liquid;
(5) preparation of perforating agent solution: perforating agent polyethylene glycol is dissolved in DMA, obtained 25Wt% perforating agent solution;
(6) spinning solution is prepared: Kynoar solution step (1) obtained, the perforating agent solution that the polymer gel that step (4) obtains/Pd nano particle hybrid dispersion liquid and step (5) obtain is 80: 20: 10 mixing in mass ratio, dissolve, degassed, obtain 25Wt% spinning solution;
(7) core liquid preparation: use non-solvent and solvent mixture to prepare core liquid, wherein the mass ratio of non-solvent water and solvent DMA is 90: 10;
(8) coagulating bath preparation: use non-solvent and solvent mixture to prepare coagulating bath, wherein the mass ratio of non-solvent water and solvent DMA is 90: 10;
(9) hybridized film preparation: adopt dry-wet spinning process, coagulating bath prepared by the core liquid using hollow fiber spinning machine (Fig. 1) and above-mentioned steps (7) to prepare and above-mentioned steps (8), at dry-spinning path 15cm, the temperature 70 C of spinning solution, under core liquid and coagulation bath temperature 30 DEG C of conditions, spinning solution spinning above-mentioned steps (6) obtained obtains described doughnut hybridized film.
Embodiment 7.
(1) with embodiment 6;
(2) with embodiment 1;
(3) with embodiment 1;
(4) with embodiment 6;
(5) with embodiment 6;
(6) spinning solution is prepared: Kynoar solution step (1) obtained, the perforating agent solution that the polymer gel that step (4) obtains/Pd nano particle hybrid dispersion liquid and step (5) obtain is 80: 20: 20 mixing in mass ratio, dissolve, degassed, obtain 25Wt% spinning solution;
(7) with embodiment 6;
(8) with embodiment 6;
(9) with embodiment 6.
Embodiment 8.
(1) with embodiment 6;
(2) with embodiment 1;
(3) with embodiment 1;
(4) with embodiment 6;
(5) with embodiment 6;
(6) with embodiment 6;
(7) with embodiment 6;
(8) with embodiment 6;
(9) hybridized film preparation: adopt dry-wet spinning process, coagulating bath prepared by the core liquid using hollow fiber spinning machine (Fig. 1) and above-mentioned steps (7) to prepare and above-mentioned steps (8), at dry-spinning path 10cm, the temperature 70 C of spinning solution, under core liquid and coagulation bath temperature 20 DEG C of conditions, spinning solution spinning above-mentioned steps (6) obtained obtains described doughnut hybridized film.
Embodiment 9.
(1) preparation of PVDF solution: PVDF is dissolved in obtained 20Wt% Kynoar solution in 1-METHYLPYRROLIDONE;
(2) with embodiment 1;
(3) with embodiment 1;
(4) preparation of polymer gel/Pd nano particle hybrid dispersion liquid: polymer gel/Pd nano particle hybrid step (3) obtained is dispersed in 1-METHYLPYRROLIDONE, obtained 20wt% dispersion liquid;
(5) preparation of perforating agent solution: perforating agent polyethylene glycol is dissolved in 1-METHYLPYRROLIDONE, obtained 20Wt% perforating agent solution;
(6) spinning solution is prepared: Kynoar solution step (1) obtained, the perforating agent solution that the polymer gel that step (4) obtains/Pd nano particle hybrid dispersion liquid and step (5) obtain is 70: 30: 10 mixing in mass ratio, dissolve, degassed, obtain 20Wt% spinning solution;
(7) core liquid preparation: use non-solvent to prepare core liquid, wherein the mass ratio of non-solvent water and ethanol is 90: 10;
(8) coagulating bath preparation: use non-solvent to prepare coagulating bath, wherein the mass ratio of non-solvent water and ethanol is 90: 10;
(9) hybridized film preparation: adopt dry-wet spinning process, coagulating bath prepared by the core liquid using hollow fiber spinning machine (Fig. 1) and above-mentioned steps (7) to prepare and above-mentioned steps (8), at dry-spinning path 25cm, the temperature 60 C of spinning solution, under core liquid and coagulation bath temperature 25 DEG C of conditions, spinning solution spinning above-mentioned steps (6) obtained obtains described doughnut hybridized film.
Embodiment 10.
(1) with embodiment 9;
(2) with embodiment 1;
(3) with embodiment 1;
(4) with embodiment 9;
(5) with embodiment 9;
(6) with embodiment 9;
(7) core liquid preparation: use non-solvent to prepare core liquid, wherein the mass ratio of non-solvent water and methyl alcohol is 90: 10;
(8) coagulating bath preparation: use non-solvent to prepare coagulating bath, wherein the mass ratio of non-solvent water and methyl alcohol is 90: 10;
(9) hybridized film preparation: adopt dry-wet spinning process, coagulating bath prepared by the core liquid using hollow fiber spinning machine (Fig. 1) and above-mentioned steps (7) to prepare and above-mentioned steps (8), at dry-spinning path 5cm, the temperature 60 C of spinning solution, under core liquid and coagulation bath temperature 10 DEG C of conditions, spinning solution spinning above-mentioned steps (6) obtained obtains described doughnut hybridized film.
Embodiment 11.
(1) with embodiment 6;
(2) with embodiment 1;
(3) with embodiment 1;
(4) with embodiment 6;
(5) with embodiment 6;
(6) spinning solution is prepared: Kynoar solution step (1) obtained, the perforating agent solution that the polymer gel that step (4) obtains/Pd nano particle hybrid dispersion liquid and step (5) obtain is 80: 20: 20 mixing in mass ratio, dissolve, degassed, obtain 25Wt% spinning solution;
(7) core liquid preparation: use non-solvent to prepare core liquid, wherein the mass ratio of non-solvent water and glycerine is 90: 10;
(8) coagulating bath preparation: use non-solvent to prepare coagulating bath, wherein the mass ratio of non-solvent water and glycerine is 90: 10;
(9) with embodiment 6.
Embodiment 12.
(1) with embodiment 6;
(2) with embodiment 1;
(3) with embodiment 1;
(4) with embodiment 6;
(5) with embodiment 6;
(6) spinning solution is prepared: Kynoar solution step (1) obtained, the perforating agent solution that the polymer gel that step (4) obtains/Pd nano particle hybrid dispersion liquid and step (5) obtain is 80: 20: 20 mixing in mass ratio, dissolve, degassed, obtain 25Wt% spinning solution;
(7) core liquid preparation: use non-solvent water to prepare core liquid;
(8) coagulating bath preparation: use non-solvent water to prepare coagulating bath;
(9) with embodiment 6.
After testing, prepared hollow-fibre membrane fenestra contains the high molecular polymer gel of 100-300nm, the Pd nano particle containing 5-25nm on gel, film internal diameter is 0.1-2.5mm, wall thickness 0.1-0.5mm, aperture 30-300nm, under 0.05MPa20 DEG C of condition, pure water flux is 50-1000L/m
2h.This film surfaces externally and internally is compacted zone or chondritic, and film section is the structure that finger-like pore combines with spongy hole.Filter with the polystyrene microsphere suspension of this film to 300nm, found that microballoon is all retained.The hollow-fibre membrane of pbz polymer polymer gel/Pd nano particle hybrid is fixed on flux measuring device, with the aqueous solution of cross-current flow circulation p-nitrophenol (concentration is for 0.05g/L) and sodium borohydride (saturated) under 0.1MPa pressure, found that p-nitrophenol is para-aminophenol by Restore All very soon, show that this doughnut hybridized film has very high catalytic activity.Through the aqueous solution of continuous circulation 1 month p-nitrophenol and sodium borohydride, after cleaning, again by the catalytic activity of the aqueous solution inspection film of p-nitrophenol and sodium borohydride, found that, membrane catalytic reaction activity does not obviously decline.Under identical experiment condition, use all right catalytic amino nitrobenzene of this hollow-fibre membrane, nitrobenzene, methyl nitrobenzene, dimethyl nitrobenzene, cyanonitrobenzene, chloronitrobenzene, vinyl nitrobenzene, the reduction reaction of the nitro in nitrocyclohexane equimolecular, is converted into amino by nitro.
Kynoar/Pd nano particle hybridized film that the present invention proposes and preparation method thereof, be described by embodiment, person skilled obviously can not depart from content of the present invention, spirit and scope content as herein described is changed or suitably change with combination realize the present invention.Special needs to be pointed out is, all similar replacements and change apparent to those skilled in the art, they are deemed to be included in spirit of the present invention, scope and content.
Claims (5)
1. Kynoar/Pd nano particle hydridization hollow-fibre membrane, it is characterized in that this film is made up of according to mass ratio 99: 1-60: 40 Kynoar and poly-(methyl) acrylic gel/Pd nano particle hybrid or poly 4 vinyl pyridine gel/Pd nano particle hybrid, poly-(methyl) acrylic gel/Pd nano particle hybrid or poly 4 vinyl pyridine gel/Pd nano particle hybrid are positioned at fenestra inwall; Film internal diameter is 0.1-2.5mm, wall thickness 0.1-0.5mm, average pore size 30-300nm, and under 0.05MPa and 20 DEG C condition, pure water flux is 50-1000L/m
2h.
2. a kind of Kynoar according to claim 1/Pd nano particle hydridization hollow-fibre membrane, is characterized in that the particle diameter of described poly-(methyl) acrylic gel or poly 4 vinyl pyridine gel is 100-300nm.
3. a kind of Kynoar according to claim 1/Pd nano particle hydridization hollow-fibre membrane, is characterized in that the particle diameter of described Pd nano particle is 5-25nm.
4. a kind of Kynoar according to claim 1/Pd nano particle hydridization hollow-fibre membrane, is characterized in that the preparation method of this film comprises the steps:
A) preparation of PVDF solution: PVDF is dissolved in obtained 15-25Wt% Kynoar solution in DMF or DMA or 1-METHYLPYRROLIDONE;
The preparation of b) polymer gel/Pd nano particle hybrid dispersion liquid: (methyl) acrylic gel/Pd nano particle hybrid will be gathered or poly 4 vinyl pyridine gel/Pd nano particle hybrid is dispersed in N, dinethylformamide or N, in N-dimethylacetylamide or 1-METHYLPYRROLIDONE, obtained 15-25Wt% polymer gel/Pd nano particle hybrid dispersion liquid;
C) preparation of perforating agent solution: polyvinylpyrrolidone or polyethylene glycol are dissolved in DMF or DMA or 1-METHYLPYRROLIDONE, obtained 15-25Wt% perforating agent solution;
D) spinning solution is prepared: Kynoar solution step (a) obtained, the perforating agent solution that the polymer gel that step (b) obtains/Pd nano particle hybrid dispersion liquid and step (c) obtain is 99 ~ 60: 1 ~ 40: 0 ~ 20 mixing in mass ratio, dissolve, degassed, obtain spinning solution;
E) core liquid preparation: use a kind of mixture in water or water and ethanol, methyl alcohol or glycerine and N, dinethylformamide or N, N-dimethylacetylamide or 1-METHYLPYRROLIDONE are mixed with core liquid, one wherein in water or water and ethanol, methyl alcohol or glycerine is according to the mixture of mass ratio 90: 10 and N, dinethylformamide or DMA or 1-METHYLPYRROLIDONE blended mass ratio be 100: 0 to 90: 10;
F) coagulating bath preparation: use the one in water or water and ethanol, methyl alcohol or glycerine according to the mixture of mass ratio 90: 10 and N, dinethylformamide or N, N-dimethylacetylamide or 1-METHYLPYRROLIDONE mixture prepare coagulating bath, one wherein in water or water and ethanol, methyl alcohol or glycerine is according to the mixture of mass ratio 90: 10 and N, the blended mass ratio of dinethylformamide, DMA or 1-METHYLPYRROLIDONE is 100: 0 to 90: 10;
G) hybridized film preparation: adopt dry-wet spinning process, at dry-spinning path 0.5-25cm, the temperature 50-70 DEG C of described spinning solution, under described core liquid and coagulation bath temperature 10-30 DEG C condition, coagulating bath prepared by the core liquid using above-mentioned steps (e) to prepare and above-mentioned steps (f), spinning solution above-mentioned steps (d) obtained spinning obtains described hydridization hollow-fibre membrane.
5. a kind of Kynoar according to claim 4/Pd nano particle hydridization hollow-fibre membrane, is characterized in that described polymer gel/Pd nano particle hybrid is adopted and prepares with the following method:
A) preparation of polymer gel: by polymer monomer (methyl) acrylic acid or 4-vinylpridine 50g, crosslinking agent MBAA0.5g and initator KPS0.5g is dissolved in 1000mL water, 75 DEG C, carry out radical polymerization under nitrogen protection condition, gathered (methyl) acrylic acid or poly 4 vinyl pyridine gel;
B) polymer gel/Pd nano particle hybrid preparation: at 25 DEG C, poly-(methyl) acrylic gel step (a) obtained or poly 4 vinyl pyridine gel dispersion are in deionized water, add palladium bichloride 1g, use 1g sodium borohydride reduction, gathered (methyl) acrylic gel/Pd nano particle hybrid or poly 4 vinyl pyridine gel/Pd nano particle hybrid.
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| CN112789106A (en) * | 2018-10-02 | 2021-05-11 | 巴斯夫欧洲公司 | Method for carrying out chemical reactions in a fluid phase in the presence of a membrane comprising catalyst particles |
| CN111467972B (en) * | 2020-04-02 | 2021-11-16 | 苏州立升净水科技有限公司 | Hollow fiber membrane production line and preparation method of hollow fiber membrane |
| 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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| CN102247770A (en) * | 2011-07-01 | 2011-11-23 | 南京理工大学 | In-situ preparation method of Al(Zr)-PVDF (polyvinylidene fluoride) hybrid film |
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