CN110523302A - A kind of composite membrane and its preparation method and application of doping Cellulose nanocrystal palpus - Google Patents
A kind of composite membrane and its preparation method and application of doping Cellulose nanocrystal palpus Download PDFInfo
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- CN110523302A CN110523302A CN201910756287.3A CN201910756287A CN110523302A CN 110523302 A CN110523302 A CN 110523302A CN 201910756287 A CN201910756287 A CN 201910756287A CN 110523302 A CN110523302 A CN 110523302A
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- cellulose nanocrystal
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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
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/08—Polysaccharides
- B01D71/10—Cellulose; Modified cellulose
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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
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/42—Polymers of nitriles, e.g. polyacrylonitrile
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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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/46—Impregnation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
Abstract
The invention discloses a kind of composite membranes and its preparation method and application of doping Cellulose nanocrystal palpus.This method comprises the following steps: (1) must be added to the water Cellulose nanocrystal, being configured to Cellulose nanocrystal must suspension；Then NaHS is added, stirring and dissolving adds function additive, emulsified again after stirring and dissolving, obtain mixed liquor；(2) polyacrylonitrile is added in mixed liquor, stirring to polyacrylonitrile is completely dissolved, and then discontinuous degassing to bubble is eliminated completely under vacuum conditions, obtains blended liquid；(3) blended liquid is made to be put into coagulating bath at once after film and is impregnated, further taken out after immersion and rinse simultaneously naturally dry well, obtain the composite membrane of doping Cellulose nanocrystal palpus.Present invention process is simple, and cost is relatively low, and the composite membrane of acquisition has the characteristics that extremely strong hydrophily, good moisture holding capacity and preferable adsorption capacity, can be used for sewage treatment field.
Description
Technical field
The invention belongs to UF membrane field, in particular to the composite membrane of a kind of doping Cellulose nanocrystal palpus and its preparation side
Method and application.
Background technique
As social progress, industrial development and quality of life improve, water pollution problems is on the rise, and wherein trade effluent is
Mostly important pollution sources.It investigates and shows according to authoritative institution, the world, having 80% disease in developing country is by water pollution
It is caused, at least cause 00,000 people of global 200d dead every year；More areas once occurred different degrees of due to toxic chemical in the world
Extensive disease's spread phenomenon caused by article or the waste water of heavy metal ion, water pollution people be referred to as " world is No.1
Killer.With the propulsion that national sustainable development requires, the recycling of discharge of wastewater and water resource is increasingly by social each
The attention on boundary, waste water control have become a very intractable and unavoidable problem.Preferable water process knot in order to obtain
Fruit, people have used various methods, and wherein membrane processing method has proven to be a kind of efficient, convenient and low energy
The mode of consumption.
With deepening continuously for membrane separation technique research, more convenience, more effective membrane separation technique constantly emerges, must
More values will be created for sustainable development.Since polyacrylonitrile film has, chemical stability is good, thermal stability is strong and resistance to organic
The advantages that solvent, is widely used in UF membrane field.Application No. is a kind of 94116066.1, entitled " systems of polyacrylonitrile film
Make method " Chinese patent be using polyacrylonitrile matrix as material, by the water-immersed method preparative separation film of gel-like film, this
Kind method and process is simple, and condition relatively easily controls, and can be very good to reduce cost, but the water flux of the seperation film is smaller, real
It is not strong with property.Application No. is the China of 201110331954.7, entitled " a kind of preparation method of modified polyacrylonitrile film " specially
Benefit is to add the mode of fibroin protein using polyacrylonitrile as material preparation is blended, this method improves the water flux of seperation film
And hydrophily, extend polyacrylonitrile film uses the time.But the hydrophily of fibroin albumen itself is bad, does not add corresponding
Micropore auxiliary agent is controlled, the final effect that promoted is not obvious.
Currently, there are many researchers prepares composite membrane with polyacrylonitrile blended using different water wetted materials, though
Certain effect is so achieved, but the water flux of seperation film and porosity are not promoted significantly still, or even there are some hydrophilic materials
Inherently there are harmful components in material, therefore, it is necessary to research and develop the composite membrane of a kind of environmentally friendly, high water flux and high porosity
To meet the demand in market.
Summary of the invention
The primary purpose of the present invention is that the shortcomings that overcoming the prior art and deficiency, provide a kind of doping Cellulose nanocrystal
The preparation method of the composite membrane of palpus.
Another object of the present invention is to provide the composite membranes for the doping Cellulose nanocrystal palpus that the method is prepared.
A further object of the present invention is to provide the applications of the composite membrane of the doping Cellulose nanocrystal palpus.
The purpose of the invention is achieved by the following technical solution: a kind of preparation of the composite membrane of doping Cellulose nanocrystal palpus
Method includes the following steps:
(1) Cellulose nanocrystal must be added to the water, being configured to Cellulose nanocrystal must suspension；Then sulphur hydrogenation is added
Sodium, stirring and dissolving obtain mixed liquor A；Function additive is added in mixed liquor A again, is emulsified after stirring and dissolving, is mixed
Close liquid B；
(2) polyacrylonitrile is added in mixed liquid B obtained in step (1), stirring to polyacrylonitrile is completely dissolved, so
(vacuum heat-preserving) discontinuous degassing to bubble is eliminated completely under vacuum conditions afterwards, obtains blended liquid C；
(3) blended liquid C obtained in step (2) is made to be put into coagulating bath at once after film and is impregnated, taken out and use after immersion
Water is rinsed well, naturally dry, obtains the composite membrane of doping Cellulose nanocrystal palpus.
Water described in step (1) is preferably deionized water.
Cellulose nanocrystal described in step (1) must suspension concentration be preferably mass percent 0.5~
1.5%.
Cellulose nanocrystal described in step (1) must suspension configuration method it is as follows: must be by Cellulose nanocrystal
25 DEG C, stir evenly under 800rpm, obtaining Cellulose nanocrystal must suspension.
Cellulose nanocrystal described in step (1) must account for the 1~10% of the polyacrylonitrile quality.
The concentration of NaHS is preferably mass percent 40~60% in mixed liquor A described in step (1).
Function additive described in step (1) is at least one of polyvinylpyrrolidone and polyethylene glycol；Preferably
Polyvinylpyrrolidone and polyethylene glycol；The more preferably polyvinylpyrrolidone and molecular weight of molecular weight 45000~58000
2000~8000 polyethylene glycol；The most preferably poly- second two of the polyvinylpyrrolidone of molecular weight 58000 and molecular weight 2000
Alcohol.
The dosage of the polyvinylpyrrolidone is account for the blended liquid C mass 1~2%.
The dosage of the polyethylene glycol is account for the blended liquid C mass 1~2%.
Emulsification described in step (1) is to be emulsified using mulser.
The condition of emulsification described in step (1) is preferred are as follows: 10000rpm emulsifies 20min.
The molecular weight of polyacrylonitrile described in step (2) is 50000~150000；Preferably 50000.
The dosage of polyacrylonitrile described in step (2) is account for blended liquid C mass 10~20%.
The condition of stirring described in step (2) is preferred are as follows: under 60~80 DEG C of water bath conditions, 800rpm stir 2h.
The condition of discontinuous degassing described in step (2) is preferred are as follows: pressure 0.1MPa, 50~70 DEG C of temperature, time 36h.
Coagulating bath described in step (3) is one or more of ethyl alcohol, distilled water and n-hexane；Preferably distilled water.
Film is made in blended liquid C described in step (3) to realize preferably by following steps: with scraper by blended liquid C
In spreading to plate membrane on simple glass plate.
Doping Cellulose nanocrystal described in step (3) must composite membrane with a thickness of 0.10~0.15mm；Preferably
0.12mm。
The time of immersion described in step (3) is preferably one day or more.
Water described in step (3) is preferably distilled water.
A kind of composite membrane of doping Cellulose nanocrystal palpus, is prepared by method described in any of the above embodiments.
Application of the composite membrane of the doping Cellulose nanocrystal palpus in water treatment field.
The water process includes sewage treatment etc..
The present invention has the following advantages and effects with respect to the prior art:
1, polyacrylonitrile must sufficiently be blended the content of present invention with Cellulose nanocrystal, be obtained using coagulating bath film build method
Composite membrane, achieved the effect that simplified technique, processing cost it is lower, convenient for operation.
2, the Cellulose nanocrystal that the present invention is added must have specific surface area height, modulus big, and hydrophily is fabulous, and adsorption energy
The strong feature of power makes composite membrane have the characteristics that extremely strong hydrophily, good moisture holding capacity, preferable adsorption capacity, and its
Transparency is higher.Using the resulting composite membrane of this preparation method by with required high water flux and high porosity, show good
Good antifouling property, can apply in sewage treatment field.
3, the Cellulose nanocrystal palpus and auxiliary agent that the present invention uses will not generate environment all for biodegradable material
It influences, introduces new pollution sources when avoiding processing water.
Detailed description of the invention
Fig. 1 is the preparation method flow chart of the composite membrane of present invention doping Cellulose nanocrystal palpus.
Fig. 2 is the composite membrane pictorial diagram prepared in embodiment 6.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Unless stated otherwise, the method and apparatus that the present invention uses is the art conventional method and equipment.In the following example not
The test method for indicating specific experiment condition, usually according to conventional laboratory conditions.
Cellulose nanocrystal in the embodiment of the present invention and comparative example must be purchased from Shanghai Kai Xiang new material Science and Technology Ltd.
(nano cellulose crystal NCC)；Polyvinylpyrrolidone is purchased from Solution on Chemical Reagents in Shanghai company, Chinese Medicine group, and molecular weight is
45000~58000 (preferably 58000)；Polyethylene glycol is purchased from Tianjin Tian Li chemical reagent Co., Ltd, and molecular weight is
2000~8000 (preferably 2000)；NaHS is purchased from Tianjin good fortune morning chemical reagent factory；Polyacrylonitrile is purchased from Shanghai petroleum
Chemical inc, molecular weight are 50000~150000 (preferably 50000).
Embodiment 1
A kind of composite membrane of doping Cellulose nanocrystal palpus, preparation method are as follows:
(1) the Cellulose nanocrystal palpus lotion of purchase is diluted under the conditions of 25 DEG C, 800rpm and (deionized water is added) and matched
The suspension of mass fraction 1% is made, being then slowly added NaHS to its mass fraction thereto is 40%, to completely molten
Xie Houzai is slowly added polyvinylpyrrolidone (accounting for blended liquid C mass 1%) and polyethylene glycol (accounting for blended liquid C mass 1%), molten
Emulsification 20min is carried out at 10000rpm with mulser after solution is uniform, obtains the mixed liquor containing Cellulose nanocrystal palpus；
(2) polyacrylonitrile that molecular weight is 50000 is added obtained in (accounting for blended liquid C mass 10%) to step (1)
Containing Cellulose nanocrystal must mixed liquor in, 2h is stirred under conditions of bath temperature is 60 DEG C, revolving speed is 800rpm to poly-
Acrylonitrile is completely dissolved, and is vacuumized using vacuum pump, and discontinuous degassing 36h is to bubble at pressure 0.1MPa, 50~70 DEG C of temperature
It eliminates completely, obtains uniform blended liquid C；
(3) with scraper by the obtained blended liquid C of step (2) in spread on simple glass plate plate membrane (with a thickness of
After 0.12mm), immerses in distilled water impregnate one day at once, taking-up distilled water flushing is clean, at room temperature naturally dry, obtains
Adulterate the composite membrane of Cellulose nanocrystal palpus.
Embodiment 2
A kind of composite membrane of doping Cellulose nanocrystal palpus, preparation method are as follows:
(1) the Cellulose nanocrystal palpus lotion of purchase is diluted under the conditions of 25 DEG C, 800rpm and (deionized water is added) and matched
The suspension of mass fraction 1% is made, being then slowly added NaHS to mass fraction thereto is 45%, wait be completely dissolved
It is slowly added polyvinylpyrrolidone (accounting for blended liquid C mass 1%) and polyethylene glycol (accounting for blended liquid C mass 1%) again afterwards, dissolves
Emulsification 20min is carried out at 10000rpm with mulser after uniformly, obtains the mixed liquor containing Cellulose nanocrystal palpus；
(2) polyacrylonitrile (accounting for blended liquid C mass 12%) that molecular weight is 50000 is added to obtained in step (1)
Containing Cellulose nanocrystal must mixed liquor in, 2h is stirred under conditions of bath temperature is 80 DEG C, revolving speed is 800rpm to poly-
Acrylonitrile is completely dissolved, and is vacuumized using vacuum pump, under pressure 0.1MPa, temperature 50 C discontinuous degassing 36h to bubble eliminate
Completely, uniform blended liquid C is obtained；
(3) with scraper by the obtained blended liquid C of step (2) after spreading to plate membrane on simple glass plate (with a thickness of
0.12mm), it immerses in distilled water and impregnates one day at once, taking-up distilled water flushing is clean, at room temperature naturally dry, is mixed
The composite membrane of miscellaneous Cellulose nanocrystal palpus.
Embodiment 3
A kind of composite membrane of doping Cellulose nanocrystal palpus, preparation method are as follows:
(1) the Cellulose nanocrystal palpus lotion of purchase is diluted under the conditions of 25 DEG C, 800rpm and (deionized water is added) and matched
The suspension of mass fraction 1.5% is made, being then slowly added NaHS to mass fraction thereto is 50%.To completely molten
Xie Houzai is slowly added polyvinylpyrrolidone (accounting for blended liquid C mass 1.5%) and polyethylene glycol (accounts for blended liquid C mass
1.5%) emulsification 20min is carried out at 10000rpm with mulser after, being uniformly dissolved, and is obtained containing the mixed of Cellulose nanocrystal palpus
Close liquid；
(2) polyacrylonitrile (accounting for blended liquid C mass 20%) that molecular weight is 50000 is added to obtained in step (1)
Containing Cellulose nanocrystal must mixed liquor in, 2h is stirred under conditions of bath temperature is 70 DEG C, revolving speed is 800rpm to poly-
Acrylonitrile is completely dissolved, and is vacuumized using vacuum pump, under pressure 0.1MPa, temperature 70 C discontinuous degassing 36h to bubble eliminate
Completely, uniform blended liquid C is obtained；
(3) with scraper by the obtained blended liquid C of step (2) after spreading to plate membrane on simple glass plate (with a thickness of
0.12mm), it immerses in distilled water and impregnates one day at once, taking-up distilled water flushing is clean, at room temperature naturally dry, is mixed
The composite membrane of miscellaneous Cellulose nanocrystal palpus.
Embodiment 4
A kind of composite membrane of doping Cellulose nanocrystal palpus, preparation method are as follows:
(1) the Cellulose nanocrystal palpus lotion of purchase is diluted under the conditions of 25 DEG C, 800rpm and (deionized water is added) and matched
The suspension of mass fraction 1% is made, being then slowly added NaHS to mass fraction thereto is 60%.Wait be completely dissolved
It is slowly added polyvinylpyrrolidone (accounting for blended liquid C mass 1.5%) and polyethylene glycol (accounting for blended liquid C mass 1.5%) again afterwards,
Emulsification 20min is carried out at 10000rpm with mulser after being uniformly dissolved, and obtains the mixed liquor containing Cellulose nanocrystal palpus；
(2) polyacrylonitrile (accounting for blended liquid C mass 18%) that molecular weight is 50000 is added to obtained in step (1)
Containing Cellulose nanocrystal must mixed liquor in, 2h is stirred under conditions of bath temperature is 70 DEG C, revolving speed is 800rpm to poly-
Acrylonitrile is completely dissolved, and is vacuumized using vacuum pump, under pressure 0.1MPa, temperature 70 C discontinuous degassing 36h to bubble eliminate
Completely, uniform blended liquid C is obtained；
(3) with scraper by the obtained blended liquid C of step (2) after spreading to plate membrane on simple glass plate (with a thickness of
0.12mm), it immerses in distilled water and impregnates one day at once, taking-up distilled water flushing is clean, at room temperature naturally dry, is mixed
The composite membrane of miscellaneous Cellulose nanocrystal palpus.
Embodiment 5
A kind of composite membrane of doping Cellulose nanocrystal palpus, preparation method are as follows:
(1) the Cellulose nanocrystal palpus lotion of purchase is diluted under the conditions of 25 DEG C, 800rpm and (deionized water is added) and matched
The suspension of mass fraction 0.5% is made, being then slowly added NaHS to mass fraction thereto is 50%.To completely molten
Xie Houzai is slowly added polyvinylpyrrolidone (accounting for blended liquid C mass 2%) and polyethylene glycol (accounting for blended liquid C mass 2%), molten
Emulsification 20min is carried out at 10000rpm with mulser after solution is uniform, obtains the mixed liquor containing Cellulose nanocrystal palpus；
(2) polyacrylonitrile (accounting for blended liquid C mass 15%) that molecular weight is 50000 is added to obtained in step (1)
Containing Cellulose nanocrystal must mixed liquor in, 2h is stirred under conditions of bath temperature is 70 DEG C, revolving speed is 800rpm to poly-
Acrylonitrile is completely dissolved, and is vacuumized using vacuum pump, under pressure 0.1MPa, temperature 70 C discontinuous degassing 36h to bubble eliminate
Completely, uniform blended liquid C is obtained；
(3) with scraper by the obtained blended liquid C of step (2) after spreading to plate membrane on simple glass plate (with a thickness of
0.12mm), it immerses in distilled water and impregnates one day at once, taking-up distilled water flushing is clean, at room temperature naturally dry, is mixed
The composite membrane of miscellaneous Cellulose nanocrystal palpus.
Embodiment 6
A kind of composite membrane of doping Cellulose nanocrystal palpus, preparation method are as follows:
(1) the Cellulose nanocrystal palpus lotion of purchase is diluted under the conditions of 25 DEG C, 800rpm and (deionized water is added) and matched
The suspension of mass fraction 0.5% is made, being then slowly added NaHS to mass fraction thereto is 55%.To completely molten
Xie Houzai is slowly added polyvinylpyrrolidone (accounting for blended liquid C mass 2%) and polyethylene glycol (accounting for blended liquid C mass 2%), molten
Emulsification 20min is carried out at 10000rpm with mulser after solution is uniform, obtains the mixed liquor containing Cellulose nanocrystal palpus；
(2) polyacrylonitrile (accounting for blended liquid C mass 15%) that molecular weight is 50000 is added to obtained in step (1)
Containing Cellulose nanocrystal must mixed liquor in, 2h is stirred under conditions of bath temperature is 80 DEG C, revolving speed is 800rpm to poly-
Acrylonitrile is completely dissolved, and is vacuumized using vacuum pump, under pressure 0.1MPa, temperature 70 C discontinuous degassing 36h to bubble eliminate
Completely, uniform blended liquid C is obtained；
(3) with scraper by the obtained blended liquid C of step (2) after spreading to plate membrane on simple glass plate (with a thickness of
0.12mm), it immerses in distilled water and impregnates one day at once, taking-up distilled water flushing is clean, at room temperature naturally dry, is mixed
The composite membrane (Fig. 2) of miscellaneous Cellulose nanocrystal palpus.
Comparative example 1
A kind of polyacrylonitrile film for the Cellulose nanocrystal palpus that undopes, preparation method are as follows:
(1) NaHS is diluted to the sodium hydrosulfide for being configured to mass fraction 55% under the conditions of 25 DEG C, 800rpm,
Emulsification 20min is carried out at 10000rpm with mulser after being uniformly dissolved, and obtains the NaHS for being configured to mass fraction 55%
Solution；
(2) polyacrylonitrile (accounting for blended liquid C mass 15%) that molecular weight is 50000 is added to obtained in step (1)
In sodium hydrosulfide, 2h is stirred under conditions of bath temperature is 80 DEG C, revolving speed is 800rpm and is completely dissolved to polyacrylonitrile,
It is vacuumized using vacuum pump, discontinuous degassing 36h is eliminated completely to bubble under pressure 0.1MPa, temperature 70 C, is obtained uniform
Blended liquid C；
(3) with scraper by the obtained blended liquid C of step (2) after spreading to plate membrane on simple glass plate (with a thickness of
0.12mm), it immerses in distilled water and impregnates one day at once, taking-up distilled water flushing is clean, at room temperature naturally dry, is mixed
The composite membrane of miscellaneous Cellulose nanocrystal palpus.
Comparative example 2
A kind of composite membrane for the Cellulose nanocrystal palpus that undopes, preparation method are as follows:
(1) NaHS is diluted to the sodium hydrosulfide for being configured to mass fraction 55% under the conditions of 25 DEG C, 800rpm,
It is slowly added polyvinylpyrrolidone (accounting for blended liquid C mass 1%) again until completely dissolved and polyethylene glycol (accounts for blended liquid C matter
1%) amount, carries out emulsification 20min with mulser after being uniformly dissolved at 10000rpm, obtains mixed liquor；
(2) polyacrylonitrile (accounting for blended liquid C mass 15%) that molecular weight is 50000 is added to obtained in step (1)
In mixed liquor, 2h is stirred under conditions of bath temperature is 80 DEG C, revolving speed is 800rpm and is completely dissolved to polyacrylonitrile, using true
Empty pumping vacuum, discontinuous degassing 36h is eliminated completely to bubble at pressure 0.1MPa, 50~70 DEG C of temperature, is obtained uniformly altogether
Mixed liquid C；
(3) with scraper by the obtained blended liquid C of step (2) in spread on simple glass plate plate membrane (with a thickness of
After 0.12mm), immerses in distilled water impregnate one day at once, taking-up distilled water flushing is clean, at room temperature naturally dry, obtains
Adulterate the composite membrane of Cellulose nanocrystal palpus.
Comparative example 3
A kind of composite membrane of doping Cellulose nanocrystal palpus, preparation method are as follows:
(1) the Cellulose nanocrystal palpus lotion of purchase is diluted under the conditions of 25 DEG C, 800rpm and is configured to mass fraction 1%
Suspension, being then slowly added NaHS to mass fraction thereto is 55%, is existed after being uniformly dissolved with mulser
Emulsification 20min is carried out under 10000rpm, obtains the mixed liquor containing Cellulose nanocrystal palpus；
(2) polyacrylonitrile (accounting for blended liquid C mass 15%) that molecular weight is 50000 is added in step (1) and is contained
In the mixed liquor for having Cellulose nanocrystal palpus, 2h is stirred extremely under conditions of bath temperature is 60~80 DEG C, revolving speed is 800rpm
Polyacrylonitrile is completely dissolved, and is vacuumized using vacuum pump, and discontinuous degassing 36h is to gas at pressure 0.1MPa, 50~70 DEG C of temperature
Bubble is eliminated completely, and uniform blended liquid C is obtained；
(3) with scraper by the obtained blended liquid C of step (2) in spread on simple glass plate plate membrane (with a thickness of
After 0.12mm), immerses in distilled water impregnate one day at once, taking-up distilled water flushing is clean, at room temperature naturally dry, obtains
Adulterate the composite membrane of Cellulose nanocrystal palpus.
Effect example
(1) porosity () of film the porosity test of film: is calculated using volume weight method.The PAN film of the certain area of clip
(composite membrane prepared by Examples 1 to 6 and comparative example 1~3), measures thickness, and dry weighing calculates and determines its apparent density (ρ
1), wherein the density (ρ 2) of pure PAN is 1.17g/cm3.The porosimeter formula of film is shown in formula (1).
× 100% (1)=(1/ ρ 2 of 1- ρ)
(2) the water flux test of film: clip diameter is that the round PAN diaphragm of 3cm is placed in homemade ultrafiltration cup, In
Precompressed 30min under 0.2MPa pressure, then measures the water volume in certain time by film at 0.15MPa, and each sample is surveyed
Amount 3 times, is averaged.
The porosity and water flux of 1 film of table
Shown in upper table 1, when the embodiment of the present invention 1~6 and comparative example 1~3 are compared, cellulose nanometer is utilized
The characteristics of specific surface area, the hydrophily of whisker be fabulous and strong adsorption, it may be determined that must be answered with the Cellulose nanocrystal that undopes is used
Film is closed to compare, it is more superior in terms of water flux and porosity doped with the composite membrane of Cellulose nanocrystal palpus.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of preparation method of the composite membrane of doping Cellulose nanocrystal palpus, which comprises the steps of:
(1) Cellulose nanocrystal must be added to the water, being configured to Cellulose nanocrystal must suspension；Then NaHS is added,
Stirring and dissolving obtains mixed liquor A；Function additive is added in mixed liquor A again, is emulsified after stirring and dissolving, is mixed
Liquid B；
(2) polyacrylonitrile is added in mixed liquid B obtained in step (1), stirring is completely dissolved to polyacrylonitrile, is then existed
Discontinuous degassing to bubble is eliminated completely under vacuum condition, obtains blended liquid C；
(3) blended liquid C obtained in step (2) is made to be put into coagulating bath at once after film and is impregnated, taking-up is rushed with water after immersion
Wash clean, naturally dry obtain the composite membrane of doping Cellulose nanocrystal palpus.
2. the preparation method of the composite membrane of doping Cellulose nanocrystal palpus according to claim 1, it is characterised in that:
Function additive described in step (1) is at least one of polyvinylpyrrolidone and polyethylene glycol；
Coagulating bath described in step (3) is one or more of ethyl alcohol, distilled water and n-hexane.
3. the preparation method of the composite membrane of doping Cellulose nanocrystal palpus according to claim 2, it is characterised in that:
Function additive described in step (1) be molecular weight 45000~58000 polyvinylpyrrolidone and molecular weight 2000~
8000 polyethylene glycol；
The dosage of the polyvinylpyrrolidone is account for the blended liquid C mass 1~2%；
The dosage of the polyethylene glycol is account for the blended liquid C mass 1~2%.
4. the preparation method of the composite membrane of doping Cellulose nanocrystal palpus according to claim 1, it is characterised in that:
The concentration of the suspension of the palpus of Cellulose nanocrystal described in step (1) is mass percent 0.5~1.5%；
The concentration of NaHS is mass percent 40~60% in mixed liquor A described in step (1)；
The dosage of polyacrylonitrile described in step (2) is account for blended liquid C mass 10~20%.
5. the preparation method of the composite membrane of doping Cellulose nanocrystal palpus according to claim 1, it is characterised in that:
Cellulose nanocrystal described in step (1) must account for the 1~10% of the polyacrylonitrile quality.
6. the preparation method of the composite membrane of doping Cellulose nanocrystal palpus according to claim 1, which is characterized in that step
(3) film is made in blended liquid C is achieved by the steps of described in: blended liquid C is spread on simple glass plate with scraper
Plate membrane.
7. the preparation method of the composite membrane of doping Cellulose nanocrystal palpus according to claim 1, it is characterised in that:
The time of immersion described in step (3) is one day or more；
Doping Cellulose nanocrystal described in step (3) must composite membrane with a thickness of 0.10~0.15mm.
8. the preparation method of the composite membrane of doping Cellulose nanocrystal palpus according to claim 1, it is characterised in that:
The condition of emulsification described in step (1) are as follows: 10000rpm emulsifies 20min；
The molecular weight of polyacrylonitrile described in step (2) is 50000~150000；
The condition of stirring described in step (2) are as follows: under 60~80 DEG C of water bath conditions, 800rpm stir 2h；
The condition of discontinuous degassing described in step (2) are as follows: pressure 0.1MPa, 50~70 DEG C of temperature, time 36h.
9. a kind of composite membrane of doping Cellulose nanocrystal palpus, it is characterised in that: by according to any one of claims 1 to 8
Method is prepared.
10. application of the composite membrane of doping Cellulose nanocrystal palpus as claimed in claim 9 in water treatment field.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910756287.3A CN110523302A (en) | 2019-08-16 | 2019-08-16 | A kind of composite membrane and its preparation method and application of doping Cellulose nanocrystal palpus |
Applications Claiming Priority (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111926410A (en) * | 2020-08-24 | 2020-11-13 | 北京化工大学 | Cellulose nanocrystalline-polyacrylonitrile composite fiber and preparation method thereof |
| CN113457475A (en) * | 2021-07-09 | 2021-10-01 | 武汉纺织大学 | Polyacrylonitrile/nano whisker composite ultrafiltration membrane and preparation method thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108771978A (en) * | 2018-07-09 | 2018-11-09 | 海南立昇净水科技实业有限公司 | It is a kind of to utilize nano cellulose crystal blending and modifying ultrafiltration membrane preparation method |
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108771978A (en) * | 2018-07-09 | 2018-11-09 | 海南立昇净水科技实业有限公司 | It is a kind of to utilize nano cellulose crystal blending and modifying ultrafiltration membrane preparation method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111926410A (en) * | 2020-08-24 | 2020-11-13 | 北京化工大学 | Cellulose nanocrystalline-polyacrylonitrile composite fiber and preparation method thereof |
| CN111926410B (en) * | 2020-08-24 | 2021-12-14 | 北京化工大学 | Cellulose nanocrystalline-polyacrylonitrile composite fiber and preparation method thereof |
| CN113457475A (en) * | 2021-07-09 | 2021-10-01 | 武汉纺织大学 | Polyacrylonitrile/nano whisker composite ultrafiltration membrane and preparation method thereof |
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Application publication date: 20191203 |