CN104841287B - A kind of preparation method of multi-functional graduation oil-water separation composite film material - Google Patents
A kind of preparation method of multi-functional graduation oil-water separation composite film material Download PDFInfo
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Abstract
The invention discloses the preparation method of a kind of multi-functional graduation oil-water separation composite film material, described method uses bubble hydrogen template to prepare holey Cu thin film;Chitosan (CS) and graphene oxide (GO) composite coating is prepared at above-mentioned porous C u film surface by infusion process.The area of Multifunctional oil moisture scrapping off film prepared by the present invention is 3*3cm2, holey film substrate aperture is 100 500 μm, and second hole footpath (that is: the aperture of the loose structure of plating in mesh substrate) is 10 120 μm.In chitosan coat nethike embrane air, water contact angle is 05 °, and oil contact angle is 160 ± 5 ° under water, and oil roll angle is less than 5 ° under water.Multi-function self-cleaning oil-water separation thin film prepared by the present invention can be used for manufacturing oil-water separation and heavy metal adsorption multifunctional material, and this material has the most superoleophobic character, good mechanical stability.
Description
Technical field
The present invention relates to the preparation method of a kind of oil-water separation material, be specifically related to the preparation method of a kind of multi-functional graduation oil-water separation composite film material.
Background technology
Oil spills and oil-containing industrial water discharge have been worldwide problems, this brings many noxious substances to ocean, be delivered to from rudimentary plant algae to higher mammal to include each species body of the mankind by marine food chain in, organism species and human health is made to be on the hazard.And except containing insoluble oil in industrial wastewater, often possibly together with a large amount of dispersion emulsions and heavy metal ion, due to its toxicity and carcinogenesis, heavy metal is considered as " killer " posed a health risk.Along with increase and the scarcity of freshwater resources of population, preparation stable circulation can use, have become as a urgent demand for removing the multi-functional separation film of different conditions oil and heavy metal ion in water.
Traditional weight-driven oil-water separation film can only separate emulsion or immiscible oil water mixture, it is impossible to enough metal ions separating dissolving in the solution.For existing oil-water separation mesh film and adsorbing material, separation process and adsorption process are carried out the most respectively, and after separation, water needs to carry out after-treatment and just can re-use.It is thus desirable to preparation can function match, carry out the separation film of oil-water separation and heavy metal adsorption simultaneously, and separate film and can realize " regeneration " afterwards using " poisoning ", continue cycling through use.
Summary of the invention
It is an object of the invention to provide the preparation method of a kind of multi-functional graduation oil-water separation composite film material, use bubble hydrogen template to combine infusion process and prepare multi-functional graduation porous and be combined nethike embrane.Graduation oil-water separation film prepared by the method can carry out oil-water separation and heavy metal adsorption simultaneously to the multi-component mixture containing emulsion, metal ion etc., and separation caudacoria is capable of automatically cleaning, it is possible to uses under the complex environments such as acid-alkali salt.This one body swimming purifies renewable membrane and has very important significance protection environment, maintenance ecosystem balance.
It is an object of the invention to be achieved through the following technical solutions:
The preparation method of a kind of multi-functional graduation oil-water separation composite film material, uses bubble hydrogen template to prepare holey Cu thin film;Chitosan (CS) and graphene oxide (GO) composite coating is prepared at above-mentioned porous C u film surface by infusion process.Specifically comprise the following steps that
One, the preparation of mesh structural porous Cu thin film
Using bubble hydrogen template to prepare mesh structural porous Cu thin film, it specifically comprises the following steps that after copper mesh substrate (20-400 mesh) is carried out pickling alkali cleaning oil removing and oxide, makees anode (2 × 2cm with platinized platinum2), copper mesh make to electrode cathode (3 × 3cm2) carrying out electro-deposition, plating solution composition includes 0.02-4mol L-1
CuSO4 With 0.1-5mol L-1 H2SO4, pH=4.0 ± 0.5, electric current density is 0.1-8.0 A cm-2, sedimentation time is 5-40s.
Two, the preparation of hydrophilic coating on mesh structural porous Cu thin film:
1, the preparation of CS/ GO/Cu nethike embrane
(1) the mesh structural porous Cu thin film of above-mentioned preparation is slowly immersed in the acetic acid mixed solution (0.1-10wt.%) of chitosan (CS)/glutaraldehyde (GA)/graphene oxide (GO), slowly extracting porous copper mesh after dipping 1-30min, copper mesh surface adhesion has mixing liquid.CS/GA/GO compound method is as follows: add the GA(0.1-10wt.% of 2-10mL in 100mL CS solution) solution, and add 0.05-5g graphene oxide suspension.
(2) being dried in atmosphere by the porous web after dipping, be then immersed in 0.5-20min in sodium hydroxide (4wt.%) solution, use deionized water rinsing 1-2min, the CS/ GO/Cu nethike embrane obtained is saved in deionized water or sodium chloride solution (2mol/L).
2, CS/PVA/GO/Cu is combined the preparation of nethike embrane
(1) compound concentration is 0.1-100wt.% polyvinyl acetate (PVA) and graphene oxide (GO) solution at 50-200 DEG C;
(2) being mixed with volume ratio 1:1-10 with 1-20 wt.%CS solution by 0.1-20wt.%PVA solution, add 0.05-5g graphene oxide suspension, ultrasonic 10-60min, stirring 0.5-10h becomes uniform mixed solution together;
(3) porous copper mesh is immersed in 1-60min in mixed solution, air drying, with sodium hydroxide (4 wt.%) and the dried copper mesh of deionized water rinsing, obtains CS/PVA/GO coating grid;
(4) during CS/PVA/GO coating grid is immersed in glutaraldehyde (GA) solution (0.5-2wt.%), full cross-linked 5-60min at 20-100 DEG C;
(5) at 20-100 DEG C, 0.1-10 wt.% NaBH it is immersed in4With 1-60min in 0.1-10wt.% NaOH mixed solution, with deionized water rinsing air drying, it is thus achieved that CS/PVA/GO/Cu is combined nethike embrane.
Present invention have the advantage that
1, chitosan is a kind of natural biomaterial, has good heavy metal ion adsorbed performance and good hydrophilic, and has good film-forming quality.Its surface of graphene oxide has a large amount of abundant functional group and has the adsorption that heavy metal ion is good, but GO is micro-nano lamellar structure is unfavorable for film forming, the present invention utilizes chitosan by graphene oxide-loaded on Porous Cu surface, GO and CS realizes oil-water separation and heavy metal adsorption jointly.
2, the present invention utilizes graduation porous copper mesh can prepare super hydrophilic oil-water separation and heavy metal adsorption multifunctional mesh as substrate, hydrophilic GO and CS as coating.
3, anti-oil pollution during the present invention utilizes the super hydrophilic character of chitosan coat can realize using.In order to preferably adapt to complicated applications environment, utilize CS/PVA can realize the oil-water separation under the complex environments such as soda acid and heavy metal adsorption through crosslinking further.
4, traditional oil-water separation material and the application of heavy metal ion adsorbing material are all single processes, can not separate the oil in sewage and the heavy metal ion in water, heavy metal ion adsorbed coating prepared by the present invention is capable of oil-water separation and heavy metal adsorption double process simultaneously.
5, the present invention utilizes bubble hydrogen template and infusion process to prepare chitosan coat is a kind of simple, method that convenience, low cost, parameter are controlled.
6, relative to other oil-water separation films, the multifunctional membrane of the present invention can be applied simultaneously in rapid heavy metal ion adsorption and oil-water separation, and separation process can anti-oil pollution and acid and alkali-resistance, automatically cleaning can be realized after separation, solve problems such as processing after-treatment during sewage, have a good application prospect.
The area of the Multifunctional oil moisture scrapping off film that 7, prepared by the present invention is 3*3cm2, holey film substrate aperture is 100-500 μm, and second hole footpath (that is: the aperture of the loose structure of plating in mesh substrate) is 10-120 μm.In chitosan coat nethike embrane air, water contact angle is 0-5 °, and oil contact angle is 160 ± 5 ° under water, and oil roll angle is less than 5 ° under water.
8, the Multi-function self-cleaning oil-water separation thin film that prepared by the present invention can be used for manufacturing oil-water separation and heavy metal adsorption multifunctional material, and this material has the most superoleophobic character, good mechanical stability.
Accompanying drawing explanation
Fig. 1 is that bubble hydrogen template prepares mesh structural porous Cu film apparatus schematic diagram;
Fig. 2 is preparation graduation Cu thin film and the preparation process schematic diagram of coating;
Fig. 3 is the porous C u microscopic appearance Electronic Speculum figure of preparation;
Fig. 4 is the application process schematic diagram of netted multifunctional oil-water separating net.
Detailed description of the invention
Below in conjunction with the accompanying drawings technical scheme is further described; but it is not limited thereto; every technical solution of the present invention is modified or equivalent, without deviating from the spirit and scope of technical solution of the present invention, all should contain in protection scope of the present invention.
Detailed description of the invention one: present embodiment prepares multi-functional graduation oil-water separation composite film material in accordance with the following steps:
One, the preparation (Fig. 1) of mesh structural porous Cu thin film:
Using bubble hydrogen template to prepare mesh structural porous Cu thin film (substrate 20-400 mesh), its microscopic appearance Electronic Speculum figure is as shown in Figure 3.Specifically comprise the following steps that after copper mesh substrate (20-400 mesh) is carried out pickling alkali cleaning oil removing and oxide, make anode (2 × 2cm with platinized platinum2), copper mesh make to electrode cathode (3 × 3cm2), plating solution composition includes 0.02-4mol L-1
CuSO4 With 0.1-5mol L-1 H2SO4, pH=4.0 ± 0.5, electric current density is 0.1-8.0 A cm-2, sedimentation time is 5-40s.
Two, the preparation (Fig. 2) of hydrophilic coating on mesh structural porous Cu thin film:
1, the preparation of CS/ GO/Cu nethike embrane:
(1) during the copper mesh of above-mentioned preparation is slowly immersed in the acetic acid mixed solution of chitosan (CS)/glutaraldehyde (GA)/graphene oxide (GO), CS/GA preparation is GA (0.1-10wt.%) solution of addition 3.70 milliliters in 100mL CS solution, and adds 0.05-5g graphene oxide suspension.Preparing copper mesh dipping 1-30min by above-mentioned, the most slowly extract porous copper mesh, copper mesh surface adhesion has mixing liquid.
(2) porous web after dipping is dried in atmosphere, then 1min in sodium hydroxide (4wt.%) solution it is immersed in, using deionized water rinsing 1-2min, the CS/ GO/Cu nethike embrane obtained is saved in deionized water or sodium chloride solution (2mol/L).
2, CS/PVA/GO/Cu is combined the preparation of nethike embrane
At (1) 90 DEG C, compound concentration is 0.1-100wt.% polyvinyl acetate (PVA) and graphene oxide (GO) solution.
(2) being mixed with volume ratio 1:1 with 1-20 wt.%CS solution by 0.1-20wt.%PVA solution, add 0.05-5g graphene oxide suspension, ultrasonic 30min, stirring 1 h together becomes uniform mixed solution.
(3) porous copper mesh is immersed in 5min in mixed solution, and air drying, with sodium hydroxide (4 wt %) and the dried copper mesh of deionized water rinsing.
(4) during CS/PVA/GO coating grid is immersed in glutaraldehyde (GA) solution (1 wt.%), full cross-linked 30min at 40 DEG C.
(5) at 40 DEG C, 0.1-10 wt.% NaBH it is immersed in4With 30min in 0.1-10wt.% NaOH mixed solution, with deionized water rinsing air drying, it is thus achieved that CS/PVA/GO/Cu is combined nethike embrane.
Three, CS/ GO/Cu nethike embrane and CS/PVA/ GO/Cu are combined nethike embrane oil-water separation and heavy metal adsorption process (Fig. 4)
Preparation heavy metal ion solution, as model pollutant, mixes with certain gauging.CS/ GO/Cu nethike embrane and CS/PVA/GO/Cu are combined nethike embrane and are placed on oily-water seperating equipment, carry out oil-water separation and heavy metal adsorption experiment simultaneously, separate and after absorption terminates, in transfer nethike embrane to aqueous solution, are carried out the oil stain of residual on compound nethike embrane.CS/PVA/GO/Cu is combined nethike embrane and carries out acid and alkali-resistance test, CS/PVA/GO/Cu is combined nethike embrane and is immersed in 1h in the solution that pH is 2 and 12 respectively, and test oil-water separation and the heavy metal adsorption performance of the nethike embrane after dipping.Utilizing oily-water seperating equipment to test nethike embrane for oil-water separation separation efficiency respectively, after separation, liquid is measured its oil content by Infrared Oil Determination Instrument and Atomic Absorption Spectrometer (AAS) and is recorded disengaging time.
The area of Multifunctional oil moisture scrapping off film prepared by present embodiment is 3*3cm2, holey film substrate aperture is 100-500 μm, and second hole footpath (that is: the aperture of the loose structure of plating in mesh substrate) is 10-120 μm.In chitosan coat nethike embrane air, water contact angle is 0-5 °, and oil contact angle is 160 ± 5 ° under water, and oil roll angle is less than 5 ° under water.
Control for micro array structure can be by regulation electric current density, electrodeposit reaction time, main salt concentration and electropolymerization pyrrole monomer concentration, pulse voltage, polymerization reaction time.Oil-water separation mixture includes non-oil water mixture and the emulsion of dissolving each other of dissolving each other.Adsorption of Heavy Metal Ions kind includes nickel ion, zinc ion, iron ion, cobalt ion, cadmium ion.
Detailed description of the invention two: present embodiment prepares multi-functional graduation oil-water separation composite film material in accordance with the following steps:
One, the preparation of mesh structural porous Cu thin film
Using bubble hydrogen template to prepare mesh structural porous Cu thin film (substrate 300 mesh), it specifically comprises the following steps that after copper mesh substrate is carried out pickling alkali cleaning oil removing and oxide, makees anode (2 × 2cm with platinized platinum2), copper mesh make to electrode cathode (3 × 3cm2), plating solution composition includes 0.1mol L-1
CuSO4 With 1mol L-1 H2SO4, pH=4.0 ± 0.5, electric current density is 7 A cm-2, sedimentation time is 20s.
Two, the preparation of functional coating on mesh structural porous Cu thin film
(1) during the copper mesh of above-mentioned preparation is slowly immersed in the acetic acid mixed solution of chitosan (CS)/glutaraldehyde (GA)/graphene oxide (GO), CS/GA/GO preparation is GA (1wt.%) solution of addition 3.70 milliliters in 100mL CS solution, and add 0.5g graphene oxide suspension, prepare copper mesh dipping 5min by above-mentioned.The most slowly extracting porous copper mesh, copper mesh surface adhesion has mixing liquid.
(2) porous web after dipping is dried in atmosphere, then 1min in sodium hydroxide (4wt.%) solution it is immersed in, using deionized water rinsing 1-2min, the CS/ GO/Cu nethike embrane obtained is saved in deionized water or sodium chloride solution (2mol/L).
Three, CS/ GO/Cu is combined nethike embrane oil-water separation and heavy metal adsorption process
Preparation heavy metal ion solution, as model pollutant, mixes with certain gauging.CS/ GO/Cu nethike embrane is placed on oily-water seperating equipment, carries out oil-water separation and heavy metal adsorption experiment simultaneously, separates and after absorption terminates, in transfer nethike embrane to aqueous solution, is carried out the oil stain of residual on compound nethike embrane.Utilizing oily-water seperating equipment to test nethike embrane for oil-water separation separation efficiency respectively, after separation, liquid is measured its oil content by Infrared Oil Determination Instrument and Atomic Absorption Spectrometer (AAS) and is recorded disengaging time.
The area of Multifunctional oil moisture scrapping off film prepared by present embodiment is 3*3cm2, holey membrane pore size is 40 μm, and second hole footpath (that is: the aperture of the loose structure of plating in mesh substrate) is 30 μm.In chitosan coat nethike embrane air, water contact angle is 0-2 °, and oil contact angle is 160 ± 2 ° under water, and oil roll angle is less than 3 ° under water.Multi-functional nethike embrane prepared by present embodiment is for the neutral and middle use of alkaline solution (pH=5-13).
Detailed description of the invention three: present embodiment prepares multi-functional graduation oil-water separation composite film material in accordance with the following steps:
One, the preparation of mesh structural porous Cu thin film
Using bubble hydrogen template to prepare mesh structural porous Cu thin film (substrate 300 mesh), it specifically comprises the following steps that after copper mesh substrate is carried out pickling alkali cleaning oil removing and oxide, makees anode (2 × 2cm with platinized platinum2), copper mesh make to electrode cathode (3 × 3cm2), plating solution composition includes 0.1mol L-1
CuSO4 With 1mol L-1 H2SO4, pH=4.0 ± 0.5, electric current density is 7 A cm-2, sedimentation time is 20s.
Two, the preparation of CS/PVA/GO coating on mesh structural porous Cu nethike embrane
At (1) 90 DEG C, compound concentration is 10wt% polyvinyl acetate (PVA) and graphene oxide (GO) solution.
(2) 2wt.%PVA solution and 10 wt.%CS solution being mixed with volume ratio 1:4, add 0.5g graphene oxide suspension, ultrasonic 30min, stirring 1 h together becomes uniform mixed solution.
(3) porous copper mesh is immersed in 5min in mixed solution, and air drying, with sodium hydroxide (4 wt.%) and the dried copper mesh of deionized water rinsing.
(4) during CS/PVA/GO coating grid is immersed in glutaraldehyde (GA) solution (1 wt %), full cross-linked 30min at 40 DEG C.
(5) at 40 DEG C, 1.5 wt.% NaBH it are immersed in4With 30min in 1wt.% NaOH mixed solution, with deionized water rinsing air drying, it is thus achieved that CS/PVA/GO/Cu is combined nethike embrane.
(3) CS/PVA/GO/Cu is combined nethike embrane oil-water separation and heavy metal adsorption process
Preparation heavy metal ion solution, as model pollutant, mixes with certain gauging.CS/PVA/GO/Cu is combined nethike embrane be placed on oily-water seperating equipment, carries out oil-water separation and heavy metal adsorption experiment simultaneously, separate and after absorption terminates, in transfer nethike embrane to aqueous solution, the oil stain of residual on compound nethike embrane is carried out.CS/PVA/GO/Cu is combined nethike embrane and carries out acid and alkali-resistance test, CS/PVA/GO/Cu is combined nethike embrane and is immersed in 1h in the solution that pH is 2 and 12 respectively, and test oil-water separation and the heavy metal adsorption performance of the nethike embrane after dipping.Utilizing oily-water seperating equipment to test nethike embrane for oil-water separation separation efficiency respectively, after separation, liquid is measured its oil content by Infrared Oil Determination Instrument and Atomic Absorption Spectrometer (AAS) and is recorded disengaging time.
The area of Multifunctional oil moisture scrapping off film prepared by present embodiment is 3*3cm2, holey film substrate aperture is 40 μm, and second hole footpath (that is: the aperture of the loose structure of plating in mesh substrate) is 30 μm (internal also more apertures).In CS/PVA/GO/Cu nethike embrane air, water contact angle is 0-2 °, and oil contact angle is 159 ± 2 ° under water, and oil roll angle is less than 3 ° under water.Multi-functional nethike embrane prepared by present embodiment uses under pH=2-12 environment.
Claims (4)
1. the preparation method of a multi-functional graduation oil-water separation composite film material, it is characterised in that described method step is as follows:
One, the preparation of mesh structural porous Cu thin film
Bubble hydrogen template is used to prepare mesh structural porous Cu thin film;
Two, the preparation of hydrophilic coating on mesh structural porous Cu thin film:
(1) being mixed with volume ratio 1:1-10 with 1-20 wt.% chitosan solution by 0.1-20wt.% polyvinyl acetate ester solution, add 0.05-5g graphene oxide suspension, ultrasonic 10-60min, stirring 0.5-10h becomes uniform mixed solution together;
(2) porous copper mesh is immersed in 1-60min in mixed solution, air drying, with the dried copper mesh of sodium hydroxide and deionized water rinsing, obtains chitosan/polyvinyl acetate/graphene oxide coating grid;
(3) chitosan/polyvinyl acetate/graphene oxide coating grid is immersed in glutaraldehyde solution, full cross-linked 5-60min at 20-100 DEG C;
(4) chitosan/polyvinyl acetate/graphene oxide coating grid after crosslinking is immersed in NaBH at 20-100 DEG C4With 1-60min in NaOH mixed solution, with deionized water rinsing air drying, it is thus achieved that chitosan/polyvinyl acetate/graphene oxide/Cu is combined nethike embrane.
The preparation method of multi-functional graduation oil-water separation composite film material the most according to claim 1, after it is characterized in that described employing bubble hydrogen template prepares the specifically comprising the following steps that copper mesh substrate is carried out pickling alkali cleaning oil removing and oxide of mesh structural porous Cu thin film, make anode with platinized platinum, copper mesh is made electrode cathode is carried out electro-deposition, and plating solution is by 0.02-4mol L-1 CuSO4 With 0.1-5mol L-1
H2SO4Composition, pH=4.0 ± 0.5, electric current density is 0.1-8.0 A cm-2, sedimentation time is 5-40s.
The preparation method of multi-functional graduation oil-water separation composite film material the most according to claim 1, it is characterised in that the concentration of described glutaraldehyde solution is 0.5-2wt.%.
The preparation method of multi-functional graduation oil-water separation composite film material the most according to claim 1, it is characterised in that described NaBH4With NaBH in NaOH mixed solution4Concentration is 0.1-10 wt.%, and NaOH concentration is 0.1-10wt.%.
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CN105797432A (en) * | 2016-03-25 | 2016-07-27 | 中山大学 | Preparation method of super-hydrophilic oil-water separating film |
CN106283161B (en) * | 2016-08-25 | 2018-08-03 | 山东清大银光金属海绵新材料有限责任公司 | The preparation method of sponge structure sections/SiC particulate base water-oil separating reinforcement material |
CN106745506B (en) * | 2016-12-30 | 2020-12-04 | 常州碳星科技有限公司 | Preparation method of anti-pollution super-hydrophilic oil-water separation net |
CN108671764A (en) * | 2018-06-13 | 2018-10-19 | 洛阳纳诺环保科技有限公司 | A kind of method that one-step method prepares super hydrophilic/underwater superoleophobic water-oil separationg film |
CN111715079B (en) * | 2020-05-20 | 2021-08-17 | 嘉兴市轩禾园艺技术有限公司 | Multifunctional film material and preparation method and application thereof |
CN112973470B (en) * | 2021-02-07 | 2022-10-25 | 杭州楠大环保科技有限公司 | Pressure-resistant oil-water separation membrane material, preparation method and application thereof in sewage treatment |
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US5102547A (en) * | 1991-06-21 | 1992-04-07 | Ionics, Incorporated | Anti-fouling semi-permeable membrane system |
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