CN105498553B - A kind of Kynoar-metal organic framework composite hyperfiltration membrane and preparation and application - Google Patents
A kind of Kynoar-metal organic framework composite hyperfiltration membrane and preparation and application Download PDFInfo
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- CN105498553B CN105498553B CN201510930541.9A CN201510930541A CN105498553B CN 105498553 B CN105498553 B CN 105498553B CN 201510930541 A CN201510930541 A CN 201510930541A CN 105498553 B CN105498553 B CN 105498553B
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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
- B01D71/30—Polyalkenyl halides
- B01D71/32—Polyalkenyl halides containing fluorine atoms
- B01D71/34—Polyvinylidene fluoride
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D61/00—Processes of separation using semi-permeable membranes, e.g. dialysis, osmosis or ultrafiltration; Apparatus, accessories or auxiliary operations specially adapted therefor
- B01D61/14—Ultrafiltration; Microfiltration
- B01D61/145—Ultrafiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D69/12—Composite membranes; Ultra-thin membranes
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/444—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by ultrafiltration or microfiltration
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The invention belongs to technical field of composite materials, disclose a kind of Kynoar metal organic framework composite hyperfiltration membrane and preparation and application.The preparation method is：MIL 100 (Fe) ultrasonic disperse prepared by hydro-thermal method successively adds in Kynoar, pore former in solvent, and stirring 12~dissolving blending for 24 hours is uniform, forms casting solution；It after casting solution deaeration, is placed on supporter and carries out film, after then stopping 30~60s in air, immerse in coagulating bath and carry out exchange of solvent, obtain Kynoar metal organic framework composite hyperfiltration membrane.The composite hyperfiltration membrane of the present invention is by adding in metal-organic framework materials MIL 100 (Fe), ultrafiltration membrane hydrophily is improved, improves the separating capacity of film, improves the contamination resistance of ultrafiltration membrane, the service life of film is extended, is had a good application prospect.
Description
Technical field
The invention belongs to technical field of composite materials, and in particular to a kind of Kynoar-metal organic framework is compound super
Filter membrane and preparation and application.
Background technology
Membrane technology has the features such as high treating effect, effluent quality are excellent, easy to operate, effect on environment is small, overcomes tradition
Water treatment technology shortcoming, become the optimization technique of 21 century water treatment field.But since service life etc. of fouling membrane, film asks
Topic, greatly limits membrane technology further in the application of water treatment field.
As extensive ultrafiltration membrane synthetic material is used at present, Kynoar is a kind of excellent macromolecule organic polymer
Object has good heat-resisting, radiation resistance, chemical stability and easy film forming.And with preferable impact strength and wear-resisting
Performance, oxidative resistance and the radiativity of resistance to ray, at room temperature not by characteristics such as the corrosion of the strong oxidizers such as acid, alkali gold and halogen.
But it is also suffered from certain drawbacks, and the strong-hydrophobicity of PVDF ultrafiltration membrane reduces pure water flux, and pvdf membrane is easily by albumen
The contaminants such as matter reduce the service life of ultrafiltration membrane.
Metal-organic framework materials MOFS (Metal Organic Frameworks) is by organic linker and metal sun
Ion is combined by being coordinated, and a kind of heterozygosis supra polymer material with regular network mechanism formed.MOFs shows excess of export
High specific surface area and Kong Rong, open pore structure, uniform pore-size distribution, the coordination of undersaturated metal, adjustable hole
Thousands of kinds of types of structure and surface property and a variety of fit systems composition.
At present, there are the sides such as blending and modifying, chemical modification and surface modification for the common method of ultrafiltration membrane modifying both at home and abroad
Method.But gained ultrafiltration membrane needs to be further improved to the processing capacity and contamination resistance of waste water at present.
Invention content
In order to solve the disadvantage that the more than prior art and shortcoming, primary and foremost purpose of the invention is to provide a kind of poly- inclined
The preparation method of vinyl fluoride-metal organic framework composite hyperfiltration membrane.
It is organic another object of the present invention is to provide a kind of Kynoar-metal being prepared by the above method
Skeleton composite hyperfiltration membrane.
It is still another object of the present invention to provide above-mentioned Kynoar-metal organic framework composite hyperfiltration membrane in protein
Application in the fields such as separation, wastewater treatment.
The object of the invention is achieved through the following technical solutions：
The preparation method of a kind of Kynoar-metal organic framework composite hyperfiltration membrane, including following preparation process：
(1) hydro-thermal method prepares metal-organic framework materials MIL-100 (Fe)；
(2) by MIL-100 (Fe) ultrasonic disperse in solvent, Kynoar (PVDF), pore former is added in successively, stirred
It is uniform to mix 12~dissolving blending for 24 hours, forms casting solution；
(3) it by after the casting solution deaeration being configured, is placed on supporter and carries out film；
(4) it after the supporter for being coated with casting solution being stopped 30~60s in air, immerses and solvent friendship is carried out in coagulating bath
It changes, obtains Kynoar-metal organic framework composite hyperfiltration membrane.
The process that the hydro-thermal method prepares metal-organic framework materials MIL-100 (Fe) is as follows：By iron powder, 1,3,5- benzene three
Formic acid, nitric acid, hydrofluoric acid and water are added in hydrothermal reaction kettle, are put into 150 DEG C of baking ovens and are reacted 12h, after product washing is dry
Obtain crocus solid product MIL-100 (Fe).
The iron powder be purity ＞ 99%, the reduced iron powder of 300 mesh；1,3,5- benzenetricarboxylic acid is 300 DEG C of fusing point ＞, pure
Spend the white powder of ＞ 98%；Nitric acid is the nitric acid of mass concentration ＞ 65%；Hydrofluoric acid is the hydrogen fluorine that mass concentration is ＞ 40%
Acid.
The washing refers to alternately be washed with absolute ethyl alcohol and deionized water；The drying refers in vacuum drying chamber
In 100 DEG C of dry 12h.
The mass percentage difference of MIL-100 (Fe), Kynoar, pore former and solvent described in step (2)
For MIL-100 (Fe) 0.05~2%, Kynoar 16%~20%, pore former 0.25%~1%, surplus is solvent.
Preferably, the solvent described in step (2) refers to N-Methyl pyrrolidone；The pore former refers to polyethylene pyrrole
Pyrrolidone (PVP).
Ultrasonic disperse described in step (2) refer to frequency for ultrasonic disperse 30 under conditions of 20~60kHz~
60min。
Preferably, the configuration process of casting solution described in step (2) carries out under the conditions of temperature 60 C.
Deaeration described in step (3) refers to stand 48h deaerations in 60 DEG C of baking ovens.
Preferably, the supporter described in step (3) refers to smooth polyester non-woven fabric, carbon fiber or glass plate；It is described
Coating thickness is 200~350 μm.
Preferably, it is 1 that the coagulating bath described in step (4), which is the volume ratio of deionized water and ethyl alcohol,:1 mixed solution.
A kind of Kynoar-metal organic framework composite hyperfiltration membrane, is prepared by above method.
Above-mentioned Kynoar-metal organic framework composite hyperfiltration membrane is in the fields such as Separation of Proteins, wastewater treatment
Using.
The present invention preparation method and obtained product has the following advantages that and advantageous effect：
(1) Kynoar-metal organic framework MIL-100 (Fe) composite hyperfiltration membranes prepared by the present invention are due to adding in
Large specific surface area, adsorption capacity are strong, aperture is big metal-organic framework materials MIL-100 (Fe) improves ultrafiltration membrane hydrophily,
The separating capacity of film is improved, improves the contamination resistance of ultrafiltration membrane, extends the service life of film；
(2) preparation method of the invention is by adjusting the addition of MIL-100 (Fe), casting solution concentration, the ratio of pore former
Example, can efficiently control pore structure, hydrophily, charge of film etc., and then optimize the separating property of film；
(3) preparation method of the invention is easy to operate, and production cost is low, is suitble to large-scale production.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but the implementation of the present invention is not limited to this.
Embodiment 1
(1) preparation of metal organic framework MIL-100 (Fe)：Weigh respectively iron powder 277.5mg (purity ＞ 99%, 300
Mesh), 1,3,5- benzenetricarboxylic acid 687.5mg (300 DEG C of fusing point ＞, the white powder of purity ＞ 98%) to polytetrafluoroethylliner liner
In, 20mL high purity waters are added in, then 200 μ L hydrofluoric acid (35wt%) and the mixing of 190 μ L nitric acid (65wt%) are added dropwise respectively
It is even, after capping moves to the stainless steel cauldron interior sealing that liner is polytetrafluoroethylene (PTFE), place 150 DEG C of electric heating air blast thermostatic drying chamber
React 12h.Product is after ethyl alcohol and high-purity water washing, high speed centrifugation drying.The crocus solid finally obtained is at 100 DEG C
Lower vacuum drying 12h obtains metal organic framework MIL-100 (Fe).
(2) casting solution is configured：The MIL-100 (Fe) of 2wt% is added in the N-Methyl pyrrolidone of 77wt%, in ultrasound
Frequency is ultrasonic disperse 30min under 50kHz, then is by the dried Kynoar of 20wt%, 1wt% average molecular weight
In solution after 5000 polyvinylpyrrolidone addition ultrasound, 12h is stirred under the conditions of 60 DEG C, obtains what dissolving was uniformly mixed
Casting solution；
(3) film：After standing and defoaming 48h, casting solution is coated on plate glass in 60 DEG C of drying boxes for casting solution, is applied
For the thickness control of overlay film at 250 μm, the speed of coating is 1.2m/min；
(4) it forms a film：After the supporter for being coated with casting solution is stopped 30s in air, ethyl alcohol and the body of deionized water are immersed
Product is than being 1:Exchange of solvent 12h is carried out in 1 coagulating bath, taking-up, which is placed in deionized water, impregnates 3 days, and a water is changed every 8h,
Taking-up is dried, and obtains 250 μm of Kynoar-metal organic framework MIL-100 (Fe) composite hyperfiltration membrane.
Embodiment 2
(1) preparation of metal organic framework MIL-100 (Fe)：Weigh respectively iron powder 277.5mg (purity ＞ 99%, 300
Mesh), 1,3,5- benzenetricarboxylic acid 687.5mg (300 DEG C of fusing point ＞, the white powder of purity ＞ 98%) to polytetrafluoroethylliner liner
In, 20mL high purity waters are added in, then 200 μ L hydrofluoric acid (35wt%) and the mixing of 190 μ L nitric acid (65wt%) are added dropwise respectively
It is even, after capping moves to stainless steel cauldron interior sealing, place 150 DEG C of reaction 12h of electric heating air blast thermostatic drying chamber.Product is through ethyl alcohol
After high-purity water washing, high speed centrifugation drying.The crocus solid finally obtained is dried in vacuo 12h at 100 DEG C, obtains
Metal organic framework MIL-100 (Fe).
(2) casting solution is configured：The MIL-100 (Fe) of 0.25wt% is added in the N-Methyl pyrrolidone of 83.5wt%,
It is ultrasonic disperse 30min under 50kHz, then dried Kynoar, the 0.25wt% of 16wt% is average in supersonic frequency
In solution after the polyvinylpyrrolidone addition ultrasound that molecular weight is 5000,12h is stirred under the conditions of 60 DEG C, it is mixed to obtain dissolving
Close uniform casting solution；
(3) film：After standing and defoaming 48h, casting solution is coated on plate glass in 60 DEG C of drying boxes for casting solution, is applied
For the thickness control of overlay film at 250 μm, the speed of coating is 1.2m/min；
(4) it forms a film：After the supporter for being coated with casting solution is stopped 30s in air, ethyl alcohol and the body of deionized water are immersed
Product is than being 1:Exchange of solvent 12h is carried out in 1 coagulating bath, taking-up, which is placed in deionized water, impregnates 3 days, and a water is changed every 8h,
Taking-up is dried, and obtains 250 μm of Kynoar-metal organic framework MIL-100 (Fe) composite hyperfiltration membrane.
Embodiment 3
(1) preparation of metal organic framework MIL-100 (Fe)：Weigh respectively iron powder 277.5mg (purity ＞ 99%, 300
Mesh), 1,3,5- benzenetricarboxylic acid 687.5mg (300 DEG C of fusing point ＞, the white powder of purity ＞ 98%) to polytetrafluoroethylliner liner
In, 20mL high purity waters are added in, then 200 μ L hydrofluoric acid (35wt%) and the mixing of 190 μ L nitric acid (65wt%) are added dropwise respectively
It is even, after capping moves to stainless steel cauldron interior sealing, place 150 DEG C of reaction 12h of electric heating air blast thermostatic drying chamber.Product is through ethyl alcohol
After high-purity water washing, high speed centrifugation drying.The crocus solid finally obtained is dried in vacuo 12h at 100 DEG C, obtains
Metal organic framework MIL-100 (Fe).
(2) casting solution is configured：The MIL-100 (Fe) of 1wt% is added in the N-Methyl pyrrolidone of 80.5wt%, super
Acoustic frequency is ultrasonic disperse 30min under 50kHz, then by the dried Kynoar of 18wt%, 0.5wt% average molecular weight
In the solution after 5000 polyvinylpyrrolidone addition ultrasound, to stir 12h under the conditions of 60 DEG C, obtaining dissolving and be uniformly mixed
Casting solution；
(3) film：After standing and defoaming 48h, casting solution is coated on plate glass in 60 DEG C of drying boxes for casting solution, is applied
For the thickness control of overlay film at 250 μm, the speed of coating is 1.2m/min；
(4) it forms a film：After the supporter for being coated with casting solution is stopped 30s in air, ethyl alcohol and the body of deionized water are immersed
Product is than being 1:Exchange of solvent 12h is carried out in 1 coagulating bath, taking-up, which is placed in deionized water, impregnates 3 days, and a water is changed every 8h,
Taking-up is dried, and obtains 250 μm of Kynoar-metal organic framework MIL-100 (Fe) composite hyperfiltration membrane.
Embodiment 4
(1) preparation of metal organic framework MIL-100 (Fe)：Weigh respectively iron powder 277.5mg (purity ＞ 99%, 300
Mesh), 1,3,5- benzenetricarboxylic acid 687.5mg (300 DEG C of fusing point ＞, the white powder of purity ＞ 98%) to polytetrafluoroethylliner liner
In, 20mL high purity waters are added in, then 200 μ L hydrofluoric acid (35wt%) and the mixing of 190 μ L nitric acid (65wt%) are added dropwise respectively
It is even, after capping moves to stainless steel cauldron interior sealing, place 150 DEG C of reaction 12h of electric heating air blast thermostatic drying chamber.Product is through ethyl alcohol
After high-purity water washing, high speed centrifugation drying.The crocus solid finally obtained is dried in vacuo 12h at 100 DEG C, obtains
Metal organic framework MIL-100 (Fe).
(2) casting solution is configured：The MIL-100 (Fe) of 0.75wt% is added in the N-Methyl pyrrolidone of 82wt%,
Supersonic frequency is ultrasonic disperse 30min under 50kHz, then by the dried Kynoar of 17wt%, 0.25wt% average marks
Son amount is in the solution after 5000 polyvinylpyrrolidone addition ultrasound, stirs 12h under the conditions of 60 DEG C, obtains dissolving mixing
Uniform casting solution；
(3) film：After standing and defoaming 48h, casting solution is coated on plate glass in 60 DEG C of drying boxes for casting solution, is applied
For the thickness control of overlay film at 250 μm, the speed of coating is 1.2m/min；
(4) it forms a film：After the supporter for being coated with casting solution is stopped 30s in air, ethyl alcohol and the body of deionized water are immersed
Product is than being 1:Exchange of solvent 12h is carried out in 1 coagulating bath, taking-up, which is placed in deionized water, impregnates 3 days, and a water is changed every 8h,
Taking-up is dried, and obtains 250 μm of Kynoar-metal organic framework MIL-100 (Fe) composite hyperfiltration membrane.
Embodiment 5
(1) preparation of metal organic framework MIL-100 (Fe)：Weigh respectively iron powder 277.5mg (purity ＞ 99%, 300
Mesh), 1,3,5- benzenetricarboxylic acid 687.5mg (300 DEG C of fusing point ＞, the white powder of purity ＞ 98%) to polytetrafluoroethylliner liner
In, 20mL high purity waters are added in, then 200 μ L hydrofluoric acid (35wt%) and the mixing of 190 μ L nitric acid (65wt%) are added dropwise respectively
It is even, after capping moves to stainless steel cauldron interior sealing, place 150 DEG C of reaction 12h of electric heating air blast thermostatic drying chamber.Product is through ethyl alcohol
After high-purity water washing, high speed centrifugation drying.The crocus solid finally obtained is dried in vacuo 12h at 100 DEG C, obtains
Metal organic framework MIL-100 (Fe).
(2) casting solution is configured：The MIL-100 (Fe) of 0.5wt% is added in the N-Methyl pyrrolidone of 82.25wt%,
It is ultrasonic disperse 30min under 50kHz, then dried Kynoar, the 0.25wt% of 17wt% is average in supersonic frequency
In solution after the polyvinylpyrrolidone addition ultrasound that molecular weight is 5000,12h is stirred under the conditions of 60 DEG C, it is mixed to obtain dissolving
Close uniform casting solution；
(3) film：After standing and defoaming 48h, casting solution is coated on plate glass in 60 DEG C of drying boxes for casting solution, is applied
For the thickness control of overlay film at 250 μm, the speed of coating is 1.2m/min；
(4) it forms a film：After the supporter for being coated with casting solution is stopped 30s in air, ethyl alcohol and the body of deionized water are immersed
Product is than being 1:Exchange of solvent 12h is carried out in 1 coagulating bath, taking-up, which is placed in deionized water, impregnates 3 days, and a water is changed every 8h,
Taking-up is dried, and obtains 250 μm of Kynoar-metal organic framework MIL-100 (Fe) composite hyperfiltration membrane.
To Kynoar made from above example-metal organic framework MIL-100 (Fe) composite hyperfiltration membrane progressive
It can test：
First, the measure of water flux
After the composite hyperfiltration membrane prepared is placed a period of time in deionized water, the circle of a diameter of 7.5cm of clip
Diaphragm is put into YL-300 ultrafiltration cups, after the precompressed 40min under 0.1MPa pressure is until water flux is basicly stable, Ran Hou
It is measured under 0.1MPa pressure.
2nd, the measure of antifouling property
(1) by manufactured film, precompressed 40min after water flux is basicly stable, measures pure water and leads under 0.1MPa pressure
Amount；
(2) bovine serum albumen solution of the 1g/L of 250mL is taken to import in ultrafiltration cup to be filtered；
(3) by the Modified Membrane turn-over after filtering, flushing is filtered with suitable deionized water；
(4) Modified Membrane turn-over is measured pure water flux and records data again.
3rd, the performance test results
(1) pure water of Kynoar-metal organic framework MIL-100 (Fe) composite hyperfiltration membrane obtained by above example is put down
Equal flux is 140L/m2H is substantially close with PVDF ultrafiltration membrane；
(2) Kynoar-metal organic framework MIL-100 (Fe) composite hyperfiltration membrane obtained by above example is to 1g/L's
The average rejection of bovine serum albumin reaches 96%, higher than the average rejection 85% of PVDF ultrafiltration membrane.
It can illustrate composite hyperfiltration membrane the adding by metal organic framework MIL-100 (Fe) of the present invention by result above
Add the contamination resistance for significantly improving PVDF ultrafiltration membrane and the interception capacity to pollutant.
Above-described embodiment is the preferable embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any Spirit Essences without departing from the present invention with made under principle change, modification, replacement, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (8)
1. the preparation method of a kind of Kynoar-metal organic framework composite hyperfiltration membrane, which is characterized in that including following preparation
Step：
(1) hydro-thermal method prepares metal-organic framework materials MIL-100 (Fe)；
(2) by MIL-100 (Fe) ultrasonic disperse in solvent, Kynoar, pore former are added in successively, stirring 12~for 24 hours
Dissolving blending is uniform, forms casting solution；The solvent refers to N-Methyl pyrrolidone；The pore former refers to polyethylene pyrrole
Pyrrolidone；The MIL-100 (Fe), Kynoar, pore former and solvent mass percentage be respectively MIL-100
(Fe) 0.05~2%, Kynoar 16%~20%, pore former 0.25%~1%, surplus is solvent；
(3) it by after the casting solution deaeration being configured, is placed on supporter and carries out film；
(4) it after the supporter for being coated with casting solution being stopped 30~60s in air, immerses in coagulating bath and carries out exchange of solvent, obtain
To Kynoar-metal organic framework composite hyperfiltration membrane.
2. a kind of preparation method of Kynoar-metal organic framework composite hyperfiltration membrane according to claim 1, special
Sign is：The process that the hydro-thermal method prepares metal-organic framework materials MIL-100 (Fe) is as follows：By iron powder, 1,3,5- benzene three
Formic acid, nitric acid, hydrofluoric acid and water are added in hydrothermal reaction kettle, are put into 150 DEG C of baking ovens and are reacted 12h, after product washing is dry
Obtain crocus solid product MIL-100 (Fe).
3. a kind of preparation method of Kynoar-metal organic framework composite hyperfiltration membrane according to claim 2, special
Sign is：The iron powder is purity ＞ 99%, and grain size is the reduced iron powder of 300 mesh；The 1,3,5- benzenetricarboxylic acids are fusing point
300 DEG C of ＞, the white powder of purity ＞ 98%；The nitric acid is the nitric acid of mass concentration ＞ 65%；The hydrofluoric acid is quality
The hydrofluoric acid of concentration ＞ 40%；The washing refers to alternately be washed with absolute ethyl alcohol and deionized water；The drying refers to
100 DEG C of dry 12h in vacuum drying chamber.
4. a kind of preparation method of Kynoar-metal organic framework composite hyperfiltration membrane according to claim 1, special
Sign is：Ultrasonic disperse described in step (2) refers to 30~60min of ultrasonic disperse under conditions of frequency is 20~60kHz；
The configuration process of the casting solution carries out under the conditions of temperature 60 C.
5. a kind of preparation method of Kynoar-metal organic framework composite hyperfiltration membrane according to claim 1, special
Sign is：Deaeration described in step (3) refers to stand 48h deaerations in 60 DEG C of baking ovens；The supporter refers to smooth
Polyester non-woven fabric, carbon fiber or glass plate；The coating thickness is 200~350 μm.
6. a kind of preparation method of Kynoar-metal organic framework composite hyperfiltration membrane according to claim 1, special
Sign is：Coagulating bath described in step (4) is that the volume ratio of deionized water and ethyl alcohol is 1:1 mixed solution.
7. a kind of Kynoar-metal organic framework composite hyperfiltration membrane passes through claim 1~6 any one of them method
It is prepared.
8. Kynoar-metal organic framework composite hyperfiltration membrane described in claim 7 is led in Separation of Proteins, wastewater treatment
Application in domain.
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