CN110252155A - A kind of pollution-resistant multi-walled carbon nano-tube composite membrane and preparation method thereof - Google Patents
A kind of pollution-resistant multi-walled carbon nano-tube composite membrane and preparation method thereof Download PDFInfo
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- CN110252155A CN110252155A CN201910537597.6A CN201910537597A CN110252155A CN 110252155 A CN110252155 A CN 110252155A CN 201910537597 A CN201910537597 A CN 201910537597A CN 110252155 A CN110252155 A CN 110252155A
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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
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
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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
- B01D67/0081—After-treatment of organic or inorganic membranes
- B01D67/0093—Chemical modification
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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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- 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
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/12—Specific ratios of components used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/32—Use of chain transfer agents or inhibitors
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/30—Chemical resistance
Abstract
The present invention provides a kind of pollution-resistant multi-walled carbon nano-tube composite membrane and preparation method thereof, belongs to material chemistry technical field.A kind of preparation method of pollution-resistant multi-walled carbon nano-tube composite membrane, the following steps are included: the preparation of MWCNTs-COOH, the preparation of MWCNTs-APTES, the preparation of MWCNTs-APTES-Br, the preparation of MWCNTs-g-SPMA, the preparation of multi-walled carbon nanotube composite membrane.Method is simple, and pollution-resistant multi-walled carbon nano-tube composite membrane obtained has preferable hydrophily, excellent antifouling property, higher flux and good separation performance.A kind of pollution-resistant multi-walled carbon nano-tube composite membrane has preferable water dispersible, excellent antifouling property, higher flux and good separation performance.
Description
Technical field
The invention belongs to technical field of material chemistry, specifically, it is compound to be related to a kind of pollution-resistant multi-walled carbon nano-tube
Film and preparation method thereof.
Background technique
Membrane separation technique is to be considered one of most effective technology in current water treatment technology, with the shortage of freshwater resources
And the aggravation of water pollution, better requirement is proposed to membrane separation technique.In recent years, a large number of studies show that, composite membrane is compared to biography
Membrane material (such as cellulose basement membrane, ceramic membrane basement membrane) table in terms of separative efficiency, antifouling property and chemical stability of system
Reveal bigger advantage.
Carbon nanomaterial (multi-walled carbon nanotube, graphene oxide etc.) be used to prepare the application study of composite film material by
Concern.Wherein carbon nanotube with its excellent thermal stability, good mechanical performance, chemical stability, high-specific surface area and
Its hollow tubular structure, therefore application of the carbon nanotube in membrane separation technique has huge prospect.
But it is current studies have shown that most of membrane material is easily contaminated the absorption of object such as dyestuff, albumen etc., seriously
A possibility that film is reused is reduced, fouling membrane is the maximum problem to be faced in membrane separation technique, the presence of fouling membrane
The serious cost for affecting membrane technology.
Summary of the invention
The purpose of the present invention is to provide a kind of preparation method of pollution-resistant multi-walled carbon nano-tube composite membrane, methods
Simply, pollution-resistant multi-walled carbon nano-tube composite membrane obtained has preferable hydrophily, excellent antifouling property, higher
Flux and good separation performance.
Another object of the present invention is to provide a kind of pollution-resistant multi-walled carbon nano-tube composite membranes, have preferable
Hydrophily, excellent antifouling property, higher flux and good separation performance.
In order to achieve the above object, the solution that the present invention uses is:
A kind of pollution-resistant multi-walled carbon nano-tube composite membrane, comprising the following steps:
The preparation of MWCNTs-COOH: then ultrasound, reflux after MWCNTs is mixed with acid solution are diluted, are filtered, washed
To pH=7, finally the MWCNTs-COOH, the MWCNTs and the acid is made in dry 22-26h under conditions of 55-65 DEG C
The ratio of solution is 1g:95-105mL；
The preparation of MWCNTs-APTES: by 0.8-1.2gMWCNTs-COOH in 100mL toluene ultrasonic disperse 25-
Then 35min reacts with 6-6.5gAPTES under the protection of nitrogen and generates MWCNTs-APTES；
The preparation of MWCNTs-APTES-Br: 600-1000mgMWCNTs-APTES is mixed into ultrasound with 100mL tetrahydrofuran
Then 8-12min is added 0.05mol triethylamine and mixed solution is made, after mixed solution is cooled to 0 DEG C using ice bath, is added dropwise
The reaction of 0.06-0.10mol2- bromine isobutyl acylbromide generates MWCNTs-APTES-Br；
The preparation of MWCNTs-g-SPMA: MWCNTs-APTES-Br is dispersed in a solvent, then in the feelings for being passed through nitrogen
0.06mol3- propyl sulfonic acid metering system acid potassium salt and 0.6mmol ligand are added under condition, causes under the effect of the catalyst poly-
It closes, 18-22h is reacted at 55-65 DEG C, the MWCNTs-g-SPMA is made；
The preparation of multi-walled carbon nanotube composite membrane: the MWCNTs-g-SPMA of 15-35mg is divided in 50mL deionized water
It dissipates, by the liquid after dispersion by Vacuum filtration device, mixes multi-walled carbon nanotube insertion CA-CN under the pressure of 0.09MPa
The multi-walled carbon nanotube composite membrane is made in sour fiber film surface.
A kind of pollution-resistant multi-walled carbon nano-tube composite membrane, it is compound by above-mentioned pollution-resistant multi-walled carbon nano-tube
The preparation method of film is made.
The beneficial effect of pollution-resistant multi-walled carbon nano-tube composite membrane provided by the invention and preparation method thereof is, more
Wall carbon nano tube causes atom transfer radical polymerization (SI-ATRP) method using surface and is modified to it, improves MWCNTs
Water dispersible, modified multi wall carbon mitron is being embedded in acetic acid/nitric acid (CA/CN) nitration mixture tunica fibrosa using vacuum filtration mode
The performance of film is improved on surface, specifically:
(1) pure water flux of the multi-walled carbon nanotube composite membrane prepared by is up to 82.62L (m at 0.09MPa2·h)-1,
The pure water flux with higher compared with other nanofiltration membranes.
(2) multi-walled carbon nanotube composite membrane can carry out effectively catching to methylene blue, rejection up to 98% or more,
And higher flux is still kept when retaining dyestuff.
(3) the multi-walled carbon nanotube composite membrane prepared by has excellent antifouling property, multi wall carbon prepared by embodiment 1
Nanometer tube composite film, first time RFR (fouling membrane rate) value of circulation is only 8.61%, the RFR (fouling membrane of second of circulation
Rate) it is only 24.4%, and in first time circulation and second of circulation, FRR (water flux) value of multi-walled carbon nanotube is distinguished
For 88.82% and 65.19%.
Detailed description of the invention
Fig. 1 is the grain size distribution that MWCNTs-g-SPMA prepared by the embodiment of the present invention 1 disperses in water；
Fig. 2 is the schematic diagram that the contact angle of MS-CA/CN-1 composite membrane prepared by the embodiment of the present invention 1 changes over time；
Fig. 3 is that MS-CA-CN-1 composite membrane, the MS-CA-CN-2 of the preparation of embodiment 2 prepared by the embodiment of the present invention 1 are compound
The SEM figure of MS-CA-CN-3 composite membrane prepared by film and embodiment 3；
Fig. 4 is that MS-CA-CN-1 composite membrane, the MS-CA-CN-2 of the preparation of embodiment 2 that the present invention prepares embodiment 1 are multiple
The MS-CA-CN-3 composite membrane of film and the preparation of embodiment 3 is closed respectively in the survey for carrying out pure water flux under 0.09MPa osmotic pressure
Test result figure；
Fig. 5 is that MS-CA-CN-1 composite membrane, the MS-CA-CN-2 of the preparation of embodiment 2 prepared by the embodiment of the present invention 1 are compound
The dyestuff rejection test result figure of MS-CA-CN-3 composite membrane prepared by film and embodiment 3；
Fig. 6 is rejection effect figure of the MS-CA-CN-1 composite membrane to dyestuff of the preparation of the embodiment of the present invention 1；
Fig. 7 is that MS-CA-CN-1 composite membrane, the MS-CA-CN-2 of the preparation of embodiment 2 prepared by the embodiment of the present invention 1 are compound
MS-CA-CN-3 composite membrane prepared by film and embodiment 3 has carried out the result figure that flux when dyestuff is cut is tested；
The antifouling property loop test figure of MS-CA/CN-1 composite membrane prepared by Fig. 8 embodiment of the present invention 1.
Specific embodiment
It in order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below will be in the embodiment of the present invention
Technical solution be clearly and completely described.The person that is not specified actual conditions in embodiment, according to normal conditions or manufacturer builds
The condition of view carries out.Reagents or instruments used without specified manufacturer is the conventional production that can be obtained by commercially available purchase
Product.
Below to a kind of pollution-resistant multi-walled carbon nano-tube composite membrane of the embodiment of the present invention and preparation method thereof into
Row illustrates.
A kind of preparation method of pollution-resistant multi-walled carbon nano-tube composite membrane provided in an embodiment of the present invention, including with
Lower step:
It is acidified the preparation of multi-walled carbon nanotube (MWCNTs-COOH): multi-walled carbon nanotube (MWCNTs) and acid solution is mixed
Then ultrasound, reflux after conjunction are diluted, are filtered, washed to pH=7, finally dry 22-26h is made under conditions of 55-65 DEG C
The ratio of MWCNTs-COOH, MWCNTs and acid solution is 1g:95-105mL.It is mixed with acid solution, multi-walled carbon nanotube is carried out
The purpose of acidification is the surface active point in order to increase multi-walled carbon nanotube, is changed conducive to subsequent to multi-walled carbon nanotube
Property, while acidification also can remove remaining catalyst in nanotube.
Further, acid solution is selected from least one of the concentrated sulfuric acid and concentrated nitric acid, that is to say that acid solution can be dense sulphur
Acid, or concentrated nitric acid can also be the mixing of the concentrated sulfuric acid and concentrated nitric acid, and acid solution uses the concentrated sulfuric acid in the embodiment of the present invention
With the mixing of concentrated nitric acid, the molar ratio of the concentrated sulfuric acid and concentrated nitric acid is 3:1.
In the preparation process of MWCNTs-COOH, the ultrasonic time is 60-80min, and the condition of reflux is at 100 DEG C
Back flow reaction 12 hours, dilute filtration the specific steps are being diluted using deionized water, and be 0.45 μm of filter membrane mistake with aperture
Filter.
The preparation of the multi-walled carbon nanotube (MWCNTs-APTES) of 3- aminopropyl triethoxysilane cladding: by 0.8-
1.2gMWCNTs-COOH ultrasonic disperse 25-35min in 100mL toluene, then under the protection of nitrogen with 6-6.5g 3- ammonia
Propyl-triethoxysilicane (APTES) reaction generates MWCNTs-APTES.The mesh that multi-walled carbon nanotube is modified with APTES
Be interface affinity in order to improve multi-walled carbon nanotube Yu subsequent CA-CN nitration mixture tunica fibrosa, while improving its water dispersion
Property.
In the preparation step of MWCNTs-APTES, the reaction condition reacted with APTES is to react 2.5- at 25-35 DEG C
Then 3.5h reacts 2.5-3.5h under conditions of 95-110 DEG C.
In the preparation step of MWCNTs-APTES, the MWCNTs-APTES of generation is cleaned 3-5 times with toluene, for going
Except unreacted APTES, 22-26h is then dried under conditions of 55-65 DEG C.
The preparation of MWCNTs-APTES-Br: 600-1000mgMWCNTs-APTES and 100mL tetrahydrofuran (THF) is mixed
Ultrasound 8-12min is closed, 0.05mol triethylamine (TEA) is then added, mixed solution is made, be cooled to mixed solution using ice bath
After 0 DEG C, 0.06-0.10mol 2- bromine isobutyl acylbromide (BBIB) reaction is added dropwise and generates MWCNTs-APTES-Br.
In the step of preparation of MWCNTs-APTES-Br, the MWCNTs-APTES-Br of generation is cleaned into 3- with methylene chloride
5 times, for removing by-product, 22-26h is then dried under conditions of 55-65 DEG C.
The preparation of MWCNTs-g-SPMA: MWCNTs-APTES-Br is dispersed in a solvent, then in the feelings for being passed through nitrogen
0.06mol 3- propyl sulfonic acid metering system acid potassium salt and 0.6mmol ligand are added under condition, causes under the effect of the catalyst poly-
It closes, 18-22h is reacted at 55-65 DEG C, the MWCNTs-g-SPMA. is made
In the preparation step of MWCNTs-g-SPMA, solvent is the mixed liquor of deionized water and dimethyl sulfoxide, wherein is gone
The volume ratio of ionized water and dimethyl sulfoxide is 3:2.
Further, the solution freezing after dispersion is vacuumized into logical nitrogen circulation three times before polymerization, with discharge
Air in solution.
Further, ligand is pentamethyl-diethylenetriamine, and catalyst is cuprous bromide, wherein ligand and catalyst
Molar ratio is 2:1.
The preparation of multi-walled carbon nanotube composite membrane: the MWCNTs-g-SPMA of 15-35mg is divided in 50mL deionized water
It dissipates, by the liquid after dispersion by Vacuum filtration device, mixes multi-walled carbon nanotube insertion CA-CN under the pressure of 0.09MPa
Multi-walled carbon nanotube composite membrane is made in sour fiber film surface.
During preparation, is cleaned with surface of the deionized water to insertion film, remove what surface was embedded in not successfully
Carbon nanotube filters the carbon nanotube being embedded in not successfully again until all carbon nanotubes are successfully embedded in film surface.
Embodiment 1
A kind of preparation method of pollution-resistant multi-walled carbon nano-tube composite membrane, comprising the following steps:
The preparation of MWCNTs-COOH: 1g grams of multi-walled carbon nanotube is dispersed in 100ml 3molL-1HNO3/H2SO4(1/
3, v/v) in mixed solution, ultrasonic 1h.By above-mentioned solution at 100 DEG C back flow reaction 12 hours, obtained product deionization
Water dilution, and the membrane filtration for being 0.45 μm with aperture, being washed repeatedly to solution is neutral (PH=7), is finally put it into true
It is 24 hours dry at 60 DEG C in empty drying box, obtain acidification multi-walled carbon nanotube (MWCNTs-COOH).
The preparation of MWCNTs-APTES: by 1g acidification multi-walled carbon nanotube MWCNTs-COOH ultrasound point in 100ml toluene
It dissipates 30 minutes, 6.2g 3- aminopropyl triethoxysilane (APTES) is added dropwise then in solution, after reacting 3 hours at 30 DEG C
The reaction was continued after being warming up to 100 DEG C 3 hours, whole nitrogen protection.Product is cleaned 3 times with toluene after reaction, is removed not
The APTES of reaction is placed 24 hours in 60 DEG C of vacuum ovens, obtains silane coupling agent 3- aminopropyl triethoxysilane packet
The multi-walled carbon nanotube (MWCNTs-APTES) covered.
The preparation of MWCNTs-APTES-Br: 800mg MWCNTs-APTES is taken to be dispersed in the dry tetra oxygen furyl of 100ml
(THF) in, ultrasound after ten minutes, is added triethylamine (TEA, 0.05mol).Above-mentioned solution is adopted and is cooled with an ice bath, is dropped to temperature
Down to after 0 DEG C, 2- bromine isobutyl acylbromide (BBIB) is slowly added dropwise into solution.It reacts at room temperature 12 hours, it after reaction, will
Product is cleaned with methylene chloride, removes by-product, and 24 hours dry in 60 DEG C of vacuum ovens, obtains initiator bromination 3-
Aminopropyl triethoxysilane multi-walled carbon nanotube (MWCNTs-APTES-Br).
The preparation of MWCNTs-g-SPMA: 200mg MWCNTs-APTES-Br is dispersed in 15mL deionized water and 10mL bis-
First sulfoxide in the mixed solvent, ultrasound vacuumize logical nitrogen circulation three times after ten minutes, by solution freezing, hold during final reaction
It is continuous to be passed through nitrogen.3- propyl sulfonic acid metering system acid potassium salt (SPMA, 0.06mol) and ligand pentamethyl-diethylenetriamine is added
(PMDETA, 0.6mmol), the catalyst cuprous bromide (Cu (I) Br, 0.3mmol) being eventually adding after purification causes polymerization, 60
It is reacted 20 hours at DEG C.After, product is centrifuged the copper ion and unreacted cuprous bromide in removal solution, obtains surface
It is grafted the modified multiwalled carbon nanotube (MWCNTs-g-SPMA) of anionic polymer pSPMA.
The preparation of multi-walled carbon nanotube composite membrane: first dispersing 15mg MWCNTs-g-SPMA in 50mL water respectively,
Obtain stable dispersion liquid.By Vacuum filtration device, multi-walled carbon nanotube is made to be embedded in pure CA- under the pressure of 0.09MPa
CN nitration mixture fiber film surface is cleaned with surface of the deionized water to insertion film, removes the carbon nanometer that surface is embedded in not successfully
Pipe, the carbon nanotube being embedded in not successfully is filtered again until all carbon nanotubes are successfully embedded in film surface.Prepared
Composite membrane is respectively labeled as MS-CA-CN-1.
Embodiment 2
A kind of preparation method of pollution-resistant multi-walled carbon nano-tube composite membrane, comprising the following steps:
The preparation of MWCNTs-COOH: 1g grams of multi-walled carbon nanotube is dispersed in 95ml 3molL-1HNO3/H2SO4(1/3,
V/v) in mixed solution, ultrasonic 1h.By above-mentioned solution at 100 DEG C back flow reaction 12 hours, obtained product deionized water
Dilution, and the membrane filtration for being 0.45 μm with aperture, being washed repeatedly to solution is neutral (PH=7), finally puts it into vacuum
It is 22 hours dry at 55 DEG C in drying box, obtain acidification multi-walled carbon nanotube (MWCNTs-COOH).
The preparation of MWCNTs-APTES: 0.8g acidification multi-walled carbon nanotube MWCNTs-COOH is ultrasonic in 100ml toluene
Dispersion 25 minutes is added dropwise 6g 3- aminopropyl triethoxysilane (APTES) then in solution, reacts 2.5 hours at 25 DEG C
After be warming up to 95 DEG C after the reaction was continued 2.5 hours, whole nitrogen protection.Product is cleaned 3 times with toluene after reaction, is removed
Unreacted APTES places 22 hours in 55 DEG C of vacuum ovens, obtains silane coupling agent 3- aminopropyl triethoxysilane
The multi-walled carbon nanotube (MWCNTs-APTES) of cladding.
The preparation of MWCNTs-APTES-Br: 600mg MWCNTs-APTES is taken to be dispersed in the dry tetra oxygen furyl of 100ml
(THF) in, ultrasound is added triethylamine (TEA, 0.05mol) after 8 minutes.Above-mentioned solution is adopted and is cooled with an ice bath, is reduced to temperature
To after 0 DEG C, 2- bromine isobutyl acylbromide (BBIB) is slowly added dropwise into solution.It reacts 12 hours, after reaction, will produce at room temperature
Object is cleaned with methylene chloride, removes by-product, and 22 hours dry in 55 DEG C of vacuum ovens, obtains initiator bromination 3- ammonia
Propyl-triethoxysilicane multi-walled carbon nanotube (MWCNTs-APTES-Br).
The preparation of MWCNTs-g-SPMA: 200mg MWCNTs-APTES-Br is dispersed in 15mL deionized water and 10mL bis-
First sulfoxide in the mixed solvent, ultrasound vacuumize logical nitrogen circulation three times after ten minutes, by solution freezing, hold during final reaction
It is continuous to be passed through nitrogen.3- propyl sulfonic acid metering system acid potassium salt (SPMA, 0.06mol) and ligand pentamethyl-diethylenetriamine is added
(PMDETA, 0.6mmol), the catalyst cuprous bromide (Cu (I) Br, 0.3mmol) being eventually adding after purification causes polymerization, 55
It is reacted 18 hours at DEG C.After, product is centrifuged the copper ion and unreacted cuprous bromide in removal solution, obtains surface
It is grafted the modified multiwalled carbon nanotube (MWCNTs-g-SPMA) of anionic polymer pSPMA.
The preparation of multi-walled carbon nanotube composite membrane: first dispersing 25mg MWCNTs-g-SPMA in 50mL water respectively,
Obtain stable dispersion liquid.By Vacuum filtration device, multi-walled carbon nanotube is made to be embedded in pure CA- under the pressure of 0.09MPa
CN nitration mixture fiber film surface is cleaned with surface of the deionized water to insertion film, removes the carbon nanometer that surface is embedded in not successfully
Pipe, the carbon nanotube being embedded in not successfully is filtered again until all carbon nanotubes are successfully embedded in film surface.Prepared
Composite membrane is respectively labeled as MS-CA-CN-2.
Embodiment 3
A kind of preparation method of pollution-resistant multi-walled carbon nano-tube composite membrane, comprising the following steps:
The preparation of MWCNTs-COOH: 1g grams of multi-walled carbon nanotube is dispersed in 105ml 3molL-1HNO3/H2SO4(1/
3, v/v) in mixed solution, ultrasonic 1h.By above-mentioned solution at 100 DEG C back flow reaction 12 hours, obtained product deionization
Water dilution, and the membrane filtration for being 0.45 μm with aperture, being washed repeatedly to solution is neutral (PH=7), is finally put it into true
It is 26 hours dry at 65 DEG C in empty drying box, obtain acidification multi-walled carbon nanotube (MWCNTs-COOH).
The preparation of MWCNTs-APTES: 1.2g acidification multi-walled carbon nanotube MWCNTs-COOH is ultrasonic in 100ml toluene
Dispersion 35 minutes, is added dropwise 6.5g 3- aminopropyl triethoxysilane (APTES) then in solution, and it is small that 3.5 are reacted at 35 DEG C
When after be warming up to 110 DEG C after the reaction was continued 3.5 hours, whole nitrogen protection.Product is cleaned 3 times with toluene after reaction,
Unreacted APTES is removed, is placed 26 hours in 65 DEG C of vacuum ovens, obtains silane coupling agent 3- aminopropyl-triethoxy
The multi-walled carbon nanotube (MWCNTs-APTES) of silane cladding.
The preparation of MWCNTs-APTES-Br: 1000mg MWCNTs-APTES is taken to be dispersed in the dry tetra oxygen furyl of 100ml
(THF) in, ultrasound is added triethylamine (TEA, 0.05mol) after 8 minutes.Above-mentioned solution is adopted and is cooled with an ice bath, is reduced to temperature
To after 0 DEG C, 2- bromine isobutyl acylbromide (BBIB) is slowly added dropwise into solution.It reacts 12 hours, after reaction, will produce at room temperature
Object is cleaned with methylene chloride, removes by-product, and 26 hours dry in 65 DEG C of vacuum ovens, obtains initiator bromination 3- ammonia
Propyl-triethoxysilicane multi-walled carbon nanotube (MWCNTs-APTES-Br).
The preparation of MWCNTs-g-SPMA: 200mg MWCNTs-APTES-Br is dispersed in 15mL deionized water and 10mL bis-
First sulfoxide in the mixed solvent, ultrasound vacuumize logical nitrogen circulation three times after ten minutes, by solution freezing, hold during final reaction
It is continuous to be passed through nitrogen.3- propyl sulfonic acid metering system acid potassium salt (SPMA, 0.06mol) and ligand pentamethyl-diethylenetriamine is added
(PMDETA, 0.6mmol), the catalyst cuprous bromide (Cu (I) Br, 0.3mmol) being eventually adding after purification causes polymerization, 65
It is reacted 22 hours at DEG C.After, product is centrifuged the copper ion and unreacted cuprous bromide in removal solution, obtains surface
It is grafted the modified multiwalled carbon nanotube (MWCNTs-g-SPMA) of anionic polymer pSPMA.
The preparation of multi-walled carbon nanotube composite membrane: first dispersing 35mg MWCNTs-g-SPMA in 50mL water respectively,
Obtain stable dispersion liquid.By Vacuum filtration device, multi-walled carbon nanotube is made to be embedded in pure CA- under the pressure of 0.09MPa
CN nitration mixture fiber film surface is cleaned with surface of the deionized water to insertion film, removes the carbon nanometer that surface is embedded in not successfully
Pipe, the carbon nanotube being embedded in not successfully is filtered again until all carbon nanotubes are successfully embedded in film surface.Prepared
Composite membrane is respectively labeled as MS-CA-CN-3.
Experimental example
1, the dispersibility test of MWCNTs-g-SPMA: the dispersibility of MWCNTs-g-SPMA prepared by embodiment 1 is carried out
Characterization, Fig. 1 are the grain size distribution of MWCNTs-g-SPMA in water, wherein the aqueous dispersions concentration of MWCNTs-g-SPMA is
1mg·mL-1, as shown in Figure 1, median particle size D (50)=447.5 ± 4.8nm of modified multi-walled carbon nanotube illustrates to be modified
Multi-walled carbon nanotube afterwards has good dispersibility in water.
2, the test of contact angle: MS-CA/CN-1 composite membrane prepared by embodiment 1 has carried out the test of contact angle, as a result
As shown in Fig. 2, the tendency chart that the contact angle size that Fig. 2 is MS-CA/CN-1 composite membrane changes over time.The observable from Fig. 2
It arrives, the contact angle of complex film M S-CA/CN-1 is 70.0 °, illustrates that composite film surface is hydrophilic, over time, contact angle is not
Disconnected decline, in 6s in water droplet in the complete drawout of film surface.This is because multi-walled carbon nanotube embedded in composite membrane
The surface of MWCNTs-g-SPMA have a large amount of sulfonic acid group, Yi Shuihua, so as to quickly with hydrone act on, therefore,
MS-CA/CN-1 composite film surface is soaked by water droplet rapidly.
3, SEM is characterized: MS-CA-CN-1 composite membrane, the MS-CA-CN-2 of the preparation of embodiment 2 prepared to embodiment 1 is compound
MS-CA-CN-3 composite membrane prepared by film and embodiment 3 carries out the characterization of SEM respectively, as a result (embodiment 1,2,3 as shown in Figure 3
Respectively correspond a, b in Fig. 3, c).It can be seen from the figure that being formed by composite film surface has a large amount of tubular structure, this is
It is embedded in and is formed in nitration mixture fiber film surface by modified multiwalled carbon nanotube (MWCNTs-g-SPMA), and multi-walled carbon nanotube
It is evenly distributed in film surface, illustrates multi-walled carbon nanotube after modified and realize stable dispersion in water.Therefore, it is formed by
Composite film surface is smooth and fine and close, and with the increase of MWCNTs-g-SPMA dosage, is formed by composite film surface and more causes
Close, the surface SEM that Fig. 3 c is MS-CA-CN-3 schemes, and the nanotube dosage of the composite membrane is maximum, therefore the membrane pores formed are minimum,
And show certain thickness.In order to verify the presence of modified multiwalled carbon nanotube, EDX energy spectrum analysis MS-CA- is used in text
The element on the surface of CN-2 forms, and as a result as shown in Figure 3b, show that there is composite film surface a large amount of Na element to deposit by test
Further illustrating composite film surface has largely modified multi-walled carbon nanotube deposition.
4, the test of pure water flux: the MS-CA- of MS-CA-CN-1 composite membrane, the preparation of embodiment 2 prepared by embodiment 1
MS-CA-CN-3 composite membrane prepared by CN-2 composite membrane and embodiment 3 is respectively to carry out pure water under 0.09MPa osmotic pressure logical
The test of amount, as a result as shown in Figure 4.It can be seen from the figure that under 0.09MPa osmotic pressure, MS-CA/CN-1, MS-CA/
The pure water flux of CN-2, MS-CA/CN-3 composite membrane is respectively 82.62L (m2·h)-1、54.25L·(m2·h)-1、
38.43L·(m2·h)-1.Document shows that the pure water flux of the modified obtained composite membrane of graphene oxide is only 21.8Lm-2·
h-1·bar-1.Illustrate the pure water flux with higher of composite membrane prepared by this paper.
It can obtain from Fig. 4, with the increase of modified multiwalled carbon nanotube MWCNTs-g-SPMA dosage, be formed by compound
The flux of film is gradually reduced.Illustrate that multi-walled carbon nanotube has good dispersion stabilization in water after modified, therefore
MWCNTs-g-SPMA can be embedded in nitration mixture fiber membrane pores and be formed by deposition of the nano material in hole finer and close
Film surface, with being continuously increased for nano material additional amount, the aperture for being formed by composite membrane is gradually reduced, and is directly translated into pure
The decline of water flux.
5, dyestuff rejection and rejection effect test: the MS-CA-CN-1 composite membrane of the preparation of embodiment 1, embodiment 2 are made
MS-CA-CN-3 composite membrane prepared by standby MS-CA-CN-2 composite membrane and embodiment 3 carries out the test of dyestuff rejection, with methylene
Base indigo plant (Mw=319.86gmol-1) is contamination model, as a result as shown in Figure 5.Pass through the survey to filtrate and mother liquor absorbance
It is fixed, MS-CA/CN-1, MS-CA/CN-2, MS-CA/CN-3 composite membrane are obtained to 50mgmL-1The rejection of methylene blue is distinguished
It is 99.93%, 98.59%, 99.86%, obtains MS-CA/CN-1, MS-CA/CN-2, MS-CA/CN-3 composite membrane to 100mg/L
The rejection of methylene blue is respectively 95.58%, 97.43%, 97.83%.
To embodiment 1 prepare MS-CA-CN-1 composite membrane carry out the test of dyestuff rejection effect, as a result as shown in fig. 6, from
Fig. 6 can be seen that MS-CA/CN-1 composite membrane to 50mgmL-1、100mg·mL-1Methylene blue solution retention after filtrate
Without apparent blue, observation show that it has good crown_interception to methylene blue.
Above data shows that three kinds of prepared composite membranes show excellent rejection effect to methylene blue.We
Know, nanofiltration membrane refers to relative molecular weight (Mw) in 200-1000gmol-1Between molecule have centrifugation film, from
Above-mentioned composite membrane schemes it is found that MS-CA/CN-1, MS-CA/CN- the effective rejection effect and film surface SEM of methylene blue
2, MS-CA/CN-3 composite membrane belongs to nanofiltration membrane scope.
6, MS-CA-CN-2 composite membrane prepared by the MS-CA-CN-1 composite membrane of experiment 5 embodiments 1 preparation, embodiment 2
And the flux that the MS-CA-CN-3 composite membrane of the preparation of embodiment 3 has carried out when dyestuff is cut is tested, test result such as Fig. 7 institute
Show.From figure 7 it can be seen that the methylene that MS-CA/CN-1, MS-CA/CN-2, MS-CA/CN-3 composite membrane are 50mg/L to concentration
Flux when blue solution retains is respectively 72.64L (m2·h)-1、40.47L·(m2·h)-1、32.27L·(m2·h)-1, multiple
Flux when closing film retention dyestuff is declined compared to pure water flux.But the amplitude of decline is minimum, this illustrates composite membrane hole stage property
There is good hydrophily, keeps higher flux while being able to achieve to the retention of methylene blue (MB) solution.When dye strength reaches
To 100mgL-1When, the flux of MS-CA/CN-1, MS-CA/CN-2, MS-CA/CN-3 are respectively 48.55L (m2·h)-1、
30.89L·(m2·h)-1、L·(m2·h)-1.Illustrate, with the increase of dye molecule concentration, it is on a declining curve to retain flux.
This is because the dense layer surface structure of the film of prepared composite membrane is related, a large amount of dye molecule causes envelope to membrane pores
It is stifled, thus flux when reducing retention.Meanwhile also further illustrating that prepared composite membrane mainly relies on Physical entrapment
Realization efficiently separates dyestuff.
7, resistance is polluted: the circulation that secondary pollution, cleaning are passed through to MS-CA-CN-1 composite membrane prepared by embodiment 1
After test, loop test result is as shown in Figure 8.It can be seen from the figure that MS-CA/CN-1 is when filtering pure water, flux is almost
Without too big change, numerical value is more steady.Penetrating fluid is 50mgL-1Methylene blue when, membrane flux present reduce become
Gesture.This is because being gathered in the surface of film by methylene blue (MB) molecule that fenestra retains, and accumulation over time
It being gradually increased, the osmotic resistance of film is caused to increase, membrane flux has the tendency that reduction, but after reducing and the phenomenon that increase,
But flux overall variation is little.After the soaking and washing of 20min, the retention of the water flux comparative dye of MS-CA/CN-1 film
When flux declined, this is likely due to dyestuff caused by the absorption in fenestra road.
It is learnt according to RFR and FRR calculated result, prepared MS-CA/CN-1 composite membrane has excellent resistance tocrocking
Can, from first time cyclic test, it can be concluded that, the value of RFR is only 8.61%, illustrates the addition of modified multiwalled carbon nanotube substantially
Degree improves the antifouling property of nitration mixture tunica fibrosa.Its reason mainly has following two points: (1) modified multiwalled carbon nanotube is due to table
Face has a large amount of hydrophilic radical, therefore improves the antifouling property of film.(2) composite film surface roughness prepared by compared with
It is low, therefore also illustrate that composite membrane has preferable antifouling property to a certain extent.And in first time circulation and for the second time
In circulation, the FRR value of MS-CA/CN-1 composite membrane is respectively 88.82%, 65.19%, illustrates that composite membrane is only impregnated by pure water
It can be achieved with preferable membrane flux recovery rate.In conclusion composite nanometer filtering film prepared by this paper can not only be to small molecule dyes
It is effectively retained, while also embodying preferable antifouling property.
In conclusion pollution-resistant multi-walled carbon nano-tube composite membrane produced by the present invention, has preferable water dispersion
Property, excellent antifouling property, higher flux and good separation performance.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (10)
1. a kind of preparation method of pollution-resistant multi-walled carbon nano-tube composite membrane, it is characterised in that: the following steps are included:
The preparation of MWCNTs-COOH: then ultrasound, reflux after MWCNTs is mixed with acid solution are diluted, are filtered, washed to pH
=7, finally the MWCNTs-COOH, the MWCNTs and the acid solution is made in dry 22-26h under conditions of 55-65 DEG C
Ratio be 1g:95-105mL；
The preparation of MWCNTs-APTES: by 0.8-1.2gMWCNTs-COOH in 100mL toluene ultrasonic disperse 25-35min, so
It is reacted under the protection of nitrogen with 6-6.5gAPTES afterwards and generates MWCNTs-APTES；
The preparation of MWCNTs-APTES-Br: 600-1000mgMWCNTs-APTES is mixed to ultrasound 8- with 100mL tetrahydrofuran
Then 12min is added 0.05mol triethylamine and mixed solution is made, after mixed solution is cooled to 0 DEG C using ice bath, is added dropwise
The reaction of 0.06-0.10mol2- bromine isobutyl acylbromide generates MWCNTs-APTES-Br；
The preparation of MWCNTs-g-SPMA: MWCNTs-APTES-Br is dispersed in a solvent, then in the case where being passed through nitrogen
0.06mol3- propyl sulfonic acid metering system acid potassium salt and 0.6mmol ligand is added, causes polymerization under the effect of the catalyst,
18-22h is reacted at 55-65 DEG C, and the MWCNTs-g-SPMA is made；
The preparation of multi-walled carbon nanotube composite membrane: the MWCNTs-g-SPMA of 15-35mg is dispersed in 50mL deionized water, will
Multi-walled carbon nanotube is embedded in CA-CN nitration mixture fiber under the pressure of 0.09MPa by Vacuum filtration device by the liquid after dispersion
The multi-walled carbon nanotube composite membrane is made in film surface.
2. the preparation method of pollution-resistant multi-walled carbon nano-tube composite membrane according to claim 1, it is characterised in that:
The acid solution is selected from least one of the concentrated sulfuric acid and concentrated nitric acid.
3. the preparation method of pollution-resistant multi-walled carbon nano-tube composite membrane according to claim 2, it is characterised in that:
The acid solution is the mixed liquor of the concentrated sulfuric acid and concentrated nitric acid, and the molar ratio of the concentrated sulfuric acid and the concentrated nitric acid is 3:1.
4. the preparation method of pollution-resistant multi-walled carbon nano-tube composite membrane according to claim 1, it is characterised in that:
In the preparation step of MWCNTs-APTES, the reaction condition reacted with APTES is that 2.5-3.5h is reacted at 25-35 DEG C, so
2.5-3.5h is reacted under conditions of 95-110 DEG C afterwards.
5. the preparation method of pollution-resistant multi-walled carbon nano-tube composite membrane according to claim 4, it is characterised in that:
The MWCNTs-APTES of generation is cleaned 3-5 times with toluene, then dry 22-26h under conditions of 55-65 DEG C.
6. the preparation method of pollution-resistant multi-walled carbon nano-tube composite membrane according to claim 1, it is characterised in that:
In the preparation of MWCNTs-APTES-Br the step of, the MWCNTs-APTES-Br of generation is cleaned into 3-5 with methylene chloride
It is secondary, 22-26h is then dried under conditions of 55-65 DEG C.
7. the preparation method of pollution-resistant multi-walled carbon nano-tube composite membrane according to claim 1, it is characterised in that:
In the preparation step of MWCNTs-g-SPMA, the solvent is the mixed liquor of deionized water and dimethyl sulfoxide, the deionized water
Volume ratio with the dimethyl sulfoxide is 3:2.
8. the preparation method of pollution-resistant multi-walled carbon nano-tube composite membrane according to claim 7, it is characterised in that:
The solution freezing after dispersion is vacuumized into logical nitrogen circulation three times before polymerization.
9. the preparation method of pollution-resistant multi-walled carbon nano-tube composite membrane according to claim 8, it is characterised in that:
The ligand is pentamethyl-diethylenetriamine, and the catalyst is cuprous bromide.
10. a kind of pollution-resistant multi-walled carbon nano-tube composite membrane, it is characterised in that: as described in claim any one of 1-9
Pollution-resistant multi-walled carbon nano-tube composite membrane preparation method be made.
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