CN107081075B - Preparation method and application of selective oil-water separation dynamic membrane - Google Patents
Preparation method and application of selective oil-water separation dynamic membrane Download PDFInfo
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- CN107081075B CN107081075B CN201710346237.9A CN201710346237A CN107081075B CN 107081075 B CN107081075 B CN 107081075B CN 201710346237 A CN201710346237 A CN 201710346237A CN 107081075 B CN107081075 B CN 107081075B
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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
- B01D71/02—Inorganic material
- B01D71/024—Oxides
- B01D71/027—Silicium oxide
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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
- B01D67/0039—Inorganic membrane manufacture
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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
- B01D69/14—Dynamic 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
- B01D71/02—Inorganic material
- B01D71/022—Metals
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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
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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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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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
Abstract
The invention belongs to the technical field of chemical separation materials, relates to an oil-water separation membrane, and particularly relates to a preparation method and application of a selective oil-water separation dynamic membrane. Firstly, adding zinc acetate into absolute ethyl alcohol, heating and refluxing to prepare zinc sol, then soaking a base membrane into the zinc sol, annealing at high temperature to obtain a porous base membrane coating zinc oxide seeds, then carrying out hydrothermal reaction on the porous base membrane and a zinc acetate pH regulator solution, and washing and drying to obtain a porous separation membrane precoated with zinc oxide; by utilizing the influence of the surface related defects of the precoated zinc oxide, the oxygen defects are removed in a hydrogen atmosphere or obtained in an oxygen atmosphere, and the super-hydrophobic and super-hydrophilic surfaces are respectively obtained, so that the problem of poor wetting selectivity of the oil-water separation membrane is solved. The wetting selectivity oil-water separation dynamic membrane prepared by the invention can be applied to oil-water separation and can be repeatedly regenerated and used. The invention has simple manufacturing process, no secondary pollution and toxic substance emission, energy saving and suitability for industrial production.
Description
Technical Field
The invention belongs to the technical field of chemical separation materials, relates to an oil-water separation membrane, and particularly relates to a preparation method and application of a selective oil-water separation dynamic membrane.
Background
As a high-pollution substance, oily wastewater, papermaking wastewater and printing and dyeing wastewater are called as three industrial wastewater, and the discharge amount is large, the source is wide, and the environmental pollution is serious. The sources of the oily wastewater mainly comprise: (1) oily wastewater generated in high-oil-consumption industries such as oil refining industry, textile industry, food industry and the like; (2) oil-containing wastewater generated in the processes of oil exploitation and transportation; (3) and a large amount of crude oil is leaked to the environment to form oily sewage due to frequent oil leakage events. At present, the treatment and resource utilization of oily sewage are classified as important work for developing recycling economy and building a conservation-oriented society in China. The effective separation and recovery of oil products in the oil-containing wastewater is a fundamental way for the future treatment of the oil-containing wastewater, and the research on oil-water separation and corresponding control methods is especially important.
The essence of selectively separating oil and water is the problem of interface design of an oil-water separation material, and the oil-water separation membrane with super-wettability is obtained by microstructural design and surface property optimization, which is undoubtedly the most effective means for improving the oil-water separation performance. The oil-water separation of the super-hydrophobic/super-oleophilic interface is based on the process of selectively separating oil products from water, the mechanism of the oil-water separation is 'oil removal', the oil products with the density higher than that of water have better separation effect, but the oil products floating on water and the oil-in-water emulsion are difficult to separate. The oil-water separation of the super-hydrophilic/super-oleophobic interface is based on a process of selectively separating water from oil, the mechanism of the oil-water separation is 'water removal', oil products floating on water can be effectively separated, but the separation is difficult for oil products with higher density and water-in-oil emulsion. Therefore, the core problem of membrane separation treatment of oily wastewater is the problem of improving oil-water separation selectivity and improving interfacial wettability.
In the actual oil-water separation process, the problems of serious membrane pollution, high price of a membrane component and the like limit the wide application of the membrane technology. The first problems of the oil-water separation membrane for treating the oily wastewater are as follows: the problems of low separation efficiency and poor reusability caused by membrane pollution are solved. The problems of membrane pollution and membrane regeneration performance are also considered while the bionic preparation of the oil-water separation membrane is researched. The current methods for preventing the pollution of the oil-water separation membrane comprise the surface treatment of a membrane material (comprising surface grafting, crosslinking, etching, surface spraying and the like) and the pretreatment of an oil-water mixed solution (comprising pre-filtration, heat treatment, addition of a compounding agent, addition of an adsorbent, a stabilizer and the like). The surface treatment of the membrane material can change the wettability, the charge property, the surface structure and the like of the membrane, thereby influencing the oil-water separation efficiency; the pretreatment process of the oily waste liquid is complex, and the problems of high cost, low efficiency, easy secondary pollution and the like are also caused.
As a special form of membrane technology, dynamic membranes are those that use a porous media to filter a solution containing organic or inorganic substances, and deposit or assemble a secondary membrane layer, i.e., a dynamic membrane layer, on the surface of the media. The dynamic membrane can reduce membrane pollution of the base membrane, reduce the price of the membrane component and has good permeability and interception effect. Once the surface of the oil-water separation membrane is polluted, the secondary membrane is easy to remove and can be formed into a membrane again. Compared with a fixed membrane, the dynamic oil-water separation membrane has the advantages of low cost, large flux, strong interception capability, simple preparation, convenient cleaning and the like. Therefore, the dynamic separation membrane is constructed, the problem of membrane pollution in the oil-water separation process can be solved, the price of a membrane group can be reduced, and the service life of the membrane can be prolonged.
Disclosure of Invention
In view of the above-mentioned shortcomings in the prior art, an object of the present invention is to disclose a method for preparing a dynamic membrane for selective oil-water separation.
The invention uses the porous net film as the basal film and the zinc oxide with the micro-nano structure as the secondary film to construct the dynamic oil-water separation film, and effectively solves the problem of film pollution in the oil-water separation process by utilizing the regeneration of the dynamic layer. According to the invention, by utilizing the influence of the surface related defects of the precoated zinc oxide, the oxygen defect is removed in a hydrogen atmosphere or obtained in an oxygen atmosphere, and the super-hydrophobic and super-hydrophilic surfaces are respectively obtained, so that the defect of poor wetting selectivity of the oil-water separation membrane material prepared in the prior art is solved, and the application range of the oil-water separation membrane material in oil-water separation is expanded.
A preparation method of a selective oil-water separation dynamic membrane comprises the following steps:
a) adding zinc acetate into absolute ethyl alcohol according to the proportion that 0.001-0.1 mol, preferably 0.1mol, of zinc acetate is added into each 100mL of absolute ethyl alcohol, stirring strongly until the zinc acetate is dissolved, and refluxing the obtained zinc acetate ethanol solution for 3 hours at 60-80 ℃, preferably 60 ℃ to obtain milky zinc sol;
b) soaking the base membrane in zinc sol for 10s according to the addition of 5-10 mL of zinc sol per square centimeter of the base membrane, drying at 60-120 ℃, preferably 60 ℃, for 10-40 min, preferably 20min, repeatedly soaking for 3-9 times, annealing at 200-350 ℃, preferably 250 ℃, for 15-45 min, preferably 15min, and obtaining the porous base membrane coated with zinc oxide seeds, wherein the base membrane is one or a combination of a copper net, a silicon dioxide fiber membrane, a stainless steel net, cotton cloth and nylon cloth, and preferably is a silicon dioxide fiber membrane;
c) uniformly mixing 0.01-0.1 mol/L, preferably 0.01mol/L, zinc acetate aqueous solution and 0.01-0.2 mol/L, preferably 0.01mol/L, pH regulator aqueous solution in equal volume to obtain zinc acetate pH regulator mixed solution; adding a porous base membrane coating zinc oxide seeds and a zinc acetate pH regulator solution into a polytetrafluoroethylene lining reaction kettle according to the proportion that 10mL of zinc acetate pH regulator mixed solution is added per square centimeter, reacting for 6-16 h at 60-120 ℃, taking out, washing for 2-5 times with deionized water, and drying for 4-8 h at normal temperature to obtain a zinc oxide precoated porous separation membrane, wherein the pH regulator is one or a combination of more of ammonium chloride, ammonium fluoride, ammonium nitrate, hexamethylenetetramine, ammonia water, urea and the like, preferably hexamethylenetetramine;
d) placing the porous separation membrane of the zinc oxide precoat in a tubular furnace according to a hydrogen meter with the flow of 9-20 sccm per square centimeter, and reacting at 200-400 ℃, preferably 300 ℃ for 1-6 h, preferably 3h to obtain the porous separation dynamic membrane of the zinc oxide precoat with super-hydrophobic property;
e) and (3) placing the porous separation membrane of the zinc oxide precoat in a tubular furnace according to an oxygen meter with the flow of 5-25 sccm per square centimeter, and reacting at 300-400 ℃, preferably 300 ℃ for 1-6 h, preferably 3h to obtain the super-hydrophilic porous separation dynamic membrane of the zinc oxide precoat.
The wetting selectivity oil-water separation dynamic membrane prepared by the method is formed by in-situ growth of a secondary membrane with wetting selectivity on the surface of a base membrane, wherein the base membrane is a porous fiber net membrane, the secondary membrane is zinc oxide with wetting selectivity, and the thickness of the secondary membrane is 200-2000 nm.
The invention also aims to provide the wetting selectivity oil-water separation dynamic membrane prepared by the method, which can be applied to oil-water separation.
The third purpose of the invention is to disclose a regeneration method of the selective oil-water separation dynamic membrane. The porous separation dynamic membrane with the zinc oxide precoat with the super-hydrophobic property and the porous separation dynamic membrane with the zinc oxide precoat with the super-hydrophilic property, which are prepared by the method, are polluted after being applied by oil-water separation for many times, and the regeneration method comprises the following steps:
soaking the polluted membrane in 0.01-0.1 mol/L dilute acid solution by using 10mL of dilute acid for a porous separation dynamic membrane of the polluted zinc oxide precoat per square centimeter, taking out the polluted membrane after 1-3 h, washing the polluted membrane for 3-6 times by using deionized water, and drying the polluted membrane for 1-5 h at 60 ℃; and repeating the preparation steps a-d or repeating the preparation steps a-c-e, and then regenerating.
According to the invention, by utilizing the influence of related defects on the surface of zinc oxide, oxygen defects are removed in a hydrogen atmosphere and oxygen defects are obtained in an oxygen atmosphere, and super-hydrophobic and super-hydrophilic surfaces are respectively obtained, so that the problem of poor wetting selectivity of the oil-water separation membrane is solved. The dynamic oil-water separation membrane is constructed by taking the porous fiber material as the base membrane and the zinc oxide with wetting selectivity as the secondary membrane, so that the problem of membrane pollution in the oil-water separation process can be effectively solved, and the dynamic oil-water separation membrane is simple in manufacturing process, low in cost and good in application prospect in the field of oil-water separation.
Advantageous effects
The invention discloses a preparation method of an oil-water separation dynamic membrane with wetting selectivity, which has the following advantages: (1) the wetting selective oil-water separation dynamic membrane completes the separation process only by the gravity action and the capillary effect in the oil-water separation process, does not need extra energy consumption except a small amount of energy consumed by material transfer, and has the advantage of energy conservation. (2) The wetting selective separation dynamic membrane does not need extra chemical modifier in the preparation process, has simple preparation process, avoids the use problem of chemical reagents in conventional modification, has no secondary pollution and has the characteristics of environmental protection. (3) The oil-water separation membrane has selective wettability, super-hydrophobic and super-hydrophilic surfaces can be respectively obtained by utilizing the wetting selectivity of zinc oxide, the defects of poor wetting selectivity and low separation efficiency of the traditional oil-water separation membrane are overcome, and the application range of oil-water separation is expanded. (4) The oil-water separation dynamic membrane can effectively solve the membrane pollution problem of the traditional oil-water separation membrane by utilizing the regeneration performance of the secondary membrane, prolongs the service life of the separation membrane and improves the separation efficiency of the oil-water separation membrane. (5) The raw materials required for preparing the oil-water separation membrane are cheap and easy to obtain, the preparation process is simple, secondary pollution and toxic substance emission cannot be caused, the method is easy to realize, and the method is suitable for large-scale and large-scale production.
Detailed Description
The present invention will be described in detail below with reference to examples to enable those skilled in the art to better understand the present invention, but the present invention is not limited to the following examples.
Example 1
A preparation method of a selective oil-water separation dynamic membrane comprises the following steps:
a) adding 0.1mol of zinc acetate into 100mL of absolute ethyl alcohol, stirring strongly until the zinc acetate is dissolved, and refluxing the obtained zinc acetate ethanol solution at 60 ℃ for 3h to obtain milky zinc sol;
b) soaking a 10-square-centimeter silica fiber membrane in 50mL of zinc sol for 10s, drying at 60 ℃ for 20min, repeatedly soaking for 5 times, and annealing at 350 ℃ for 15min to obtain the silica fiber membrane coated with zinc oxide seeds;
c) preparing 80mL of mixed solution of zinc acetate with the concentration of 0.01mol/L and hexamethylenetetramine with the concentration of 0.01mol/L, adding the silica fiber membrane coated with the zinc oxide seeds and 80mL of mixed solution into a reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at 60 ℃, taking out, washing for 3 times by using deionized water, and drying for 4 hours at normal temperature to obtain a silica fiber dynamic membrane;
d) placing the silicon dioxide fiber dynamic membrane in a tubular furnace, introducing hydrogen with the flow of 9sccm, and reacting for 6 hours at 200 ℃ to obtain the silicon dioxide fiber dynamic membrane with the super-hydrophobic property;
e) and (3) placing the silicon dioxide fiber dynamic membrane in a tubular furnace, introducing oxygen with the flow of 10sccm, and reacting for 3 hours at 300 ℃ to obtain the silicon dioxide fiber dynamic membrane with super-hydrophilic performance.
The regeneration method comprises the following steps: soaking the polluted super-hydrophilic and super-hydrophobic silica fiber dynamic membrane subjected to oil-water separation repeatedly for many times in 100mL of dilute hydrochloric acid solution with the concentration of 0.01mol/L, taking out after 1 hour, washing for 3 times by using deionized water, and drying for 1 hour at the temperature of 60 ℃; and (e) repeating the preparation steps a to e to obtain the regenerated wet selective dynamic membrane.
Example 2
A preparation method of a selective oil-water separation dynamic membrane comprises the following steps:
a) adding 0.1mol of zinc acetate into 100mL of absolute ethyl alcohol, stirring strongly until the zinc acetate is dissolved, and refluxing the obtained zinc acetate ethanol solution at 80 ℃ for 3h to obtain milky zinc sol;
b) soaking a 10-square-centimeter silica fiber membrane in 50mL of zinc sol for 10s, drying at 80 ℃ for 10min, repeatedly soaking for 5 times, and annealing at 200 ℃ for 15min to obtain the silica fiber membrane coated with zinc oxide seeds;
c) preparing 80mL of mixed solution of zinc acetate with the concentration of 0.01mol/L and ammonium chloride with the concentration of 0.01mol/L, adding the silicon dioxide fiber membrane coated with the zinc oxide seeds and the 80mL of mixed solution into a reaction kettle with a polytetrafluoroethylene lining, reacting for 6h at 60 ℃, taking out, washing for 3 times by using deionized water, and drying for 4h at normal temperature to obtain a silicon dioxide fiber dynamic membrane;
d) placing the silicon dioxide fiber dynamic membrane in a tubular furnace, introducing hydrogen with the flow of 9sccm, and reacting for 1h at 300 ℃ to obtain the silicon dioxide fiber dynamic membrane with the super-hydrophobic property;
e) and (3) placing the silicon dioxide fiber dynamic membrane in a tubular furnace, introducing oxygen with the flow of 5sccm, and reacting for 1h at 400 ℃ to obtain the silicon dioxide fiber dynamic membrane with super-hydrophilic performance.
The regeneration method comprises the following steps: soaking the polluted super-hydrophilic and super-hydrophobic silica fiber dynamic membrane subjected to oil-water separation repeatedly for many times in 100mL of dilute hydrochloric acid solution with the concentration of 0.01mol/L, taking out after 1 hour, washing for 3 times by using deionized water, and drying for 1 hour at the temperature of 60 ℃; and (e) repeating the preparation steps a to e to obtain the regenerated wet selective dynamic membrane.
Example 3
A preparation method of a selective oil-water separation dynamic membrane comprises the following steps:
a) adding 0.001mol of zinc acetate into 100mL of absolute ethyl alcohol, stirring strongly until the zinc acetate is dissolved, and refluxing the obtained zinc acetate ethanol solution at 70 ℃ for 3h to obtain milky zinc sol;
b) soaking a 10-square-centimeter copper net in 50mL of zinc sol for 10s, drying at 60 ℃ for 10min, repeatedly soaking for 5 times, and annealing at 200 ℃ for 45min to obtain the copper net coated with zinc oxide seeds;
c) preparing 80mL of mixed solution of zinc acetate with the concentration of 0.1mol/L and ammonium fluoride with the concentration of 0.1mol/L, adding the copper mesh material coated with the zinc oxide seeds and 80mL of mixed solution into a reaction kettle with a polytetrafluoroethylene lining, reacting for 6h at 60 ℃, taking out, washing for 3 times by using deionized water, and drying for 4h at normal temperature to obtain a copper mesh dynamic membrane;
d) placing the copper mesh dynamic membrane in a tubular furnace, introducing hydrogen with the flow of 20sccm, and reacting for 1h at 400 ℃ to obtain the copper mesh dynamic membrane with the super-hydrophobic property;
e) and (3) placing the copper mesh dynamic membrane in a tubular furnace, introducing oxygen with the flow of 25sccm, and reacting for 6 hours at 300 ℃ to obtain the copper mesh dynamic membrane with super-hydrophilic performance.
The regeneration method comprises the following steps: soaking the polluted super-hydrophilic and super-hydrophobic copper mesh dynamic membrane subjected to oil-water separation repeatedly for many times in 100mL of dilute hydrochloric acid solution with the concentration of 0.01mol/L, taking out after 1 hour, washing for 3 times by using deionized water, and drying for 1 hour at the temperature of 60 ℃; and (e) repeating the preparation steps a to e to obtain the regenerated wet selective dynamic membrane.
Example 4
A preparation method of a selective oil-water separation dynamic membrane comprises the following steps:
a) adding 0.05mol of zinc acetate into 100mL of absolute ethyl alcohol, stirring strongly until the zinc acetate is dissolved, and refluxing the obtained zinc acetate ethanol solution at 60 ℃ for 3h to obtain milky zinc sol;
b) soaking a nylon cloth membrane of 10 square centimeters in 50mL of zinc sol for 10s, drying at 120 ℃ for 40min, repeatedly soaking for 5 times, and annealing at 250 ℃ for 30min to obtain nylon cloth coated with zinc oxide seeds;
c) preparing 80mL of mixed solution of zinc acetate with the concentration of 0.1mol/L and ammonia water with the concentration of 0.02mol/L, adding the mixed solution of nylon cloth coated with zinc oxide seeds and 80mL into a reaction kettle with a polytetrafluoroethylene lining, reacting for 6h at 60 ℃, taking out, washing for 3 times by using deionized water, and drying for 4h at normal temperature to obtain a nylon cloth-based dynamic membrane;
d) placing the nylon cloth-based dynamic membrane in a tubular furnace, introducing hydrogen with the flow of 10sccm, and reacting for 3h at 300 ℃ to obtain the nylon cloth-based dynamic membrane with the super-hydrophobic property;
e) and (3) placing the nylon cloth-based dynamic membrane in a tubular furnace, introducing oxygen with the flow of 15sccm, and reacting for 3 hours at 300 ℃ to obtain the nylon cloth-based dynamic membrane with super-hydrophilic performance.
The regeneration method comprises the following steps: soaking the polluted super-hydrophilic and super-hydrophobic nylon cloth-based dynamic membrane subjected to oil-water separation repeatedly in 100mL of 0.01mol/L dilute hydrochloric acid solution for 1h, taking out, washing with deionized water for 3 times, and drying at 60 ℃ for 1 h; and (e) repeating the preparation steps a to e to obtain the regenerated wet selective dynamic membrane.
Example 5
A preparation method of a selective oil-water separation dynamic membrane comprises the following steps:
a) adding 0.1mol of zinc acetate into 100mL of absolute ethyl alcohol, stirring strongly until the zinc acetate is dissolved, and refluxing the obtained zinc acetate ethanol solution for 3h at 80 ℃ to obtain milky zinc sol.
b) Soaking a copper net film with the thickness of 10 square centimeters in 50mL of zinc sol for 10s, drying at 60 ℃ for 20min, repeatedly soaking for 5 times, and annealing at 250 ℃ for 15min to obtain a copper net coated with zinc oxide seeds;
c) preparing 80mL of mixed solution of zinc acetate with the concentration of 0.015mol/L and ammonium chloride with the concentration of 0.2mol/L, adding the copper mesh coated with the zinc oxide seeds and 80mL of mixed solution into a reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at 60 ℃, taking out, washing for 3 times by using deionized water, and drying for 4 hours at normal temperature to obtain a copper mesh-based dynamic membrane;
d) placing the copper mesh base dynamic membrane in a tubular furnace, introducing hydrogen with the flow of 15sccm, and reacting for 3h at 300 ℃ to obtain the copper mesh base dynamic membrane with the super-hydrophobic property;
e) and (3) placing the copper mesh-based dynamic membrane in a tubular furnace, introducing oxygen with the flow of 15sccm, and reacting for 6 hours at 350 ℃ to obtain the copper mesh-based dynamic membrane with super-hydrophilic performance.
The regeneration method comprises the following steps: soaking the polluted super-hydrophilic and super-hydrophobic copper mesh-based dynamic membrane subjected to oil-water separation repeatedly for many times in 100mL of 0.01mol/L dilute hydrochloric acid solution, taking out after 1 hour, washing with deionized water for 3 times, and drying at 60 ℃ for 1 hour; and (e) repeating the preparation steps a to e to obtain the regenerated wet selective dynamic membrane.
Example 6
A preparation method of a selective oil-water separation dynamic membrane comprises the following steps:
a) adding 0.05mol of zinc acetate into 100mL of absolute ethyl alcohol, stirring strongly until the zinc acetate is dissolved, and refluxing the obtained zinc acetate ethanol solution at 60 ℃ for 3h to obtain milky zinc sol;
b) soaking 10 square centimeter cotton cloth in 50mL zinc sol for 10s, drying at 80 deg.C for 10min, repeatedly soaking for 5 times, and annealing at 300 deg.C for 30min to obtain cotton cloth coated with zinc oxide seed;
c) preparing 80mL of mixed solution of zinc acetate with the concentration of 0.01mol/L and urea with the concentration of 0.015mol/L, adding the cotton cloth coated with the zinc oxide seeds and the 80mL of mixed solution into a reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at 80 ℃, taking out, washing for 3 times by using deionized water, and drying for 4 hours at normal temperature to obtain a cotton cloth-based dynamic membrane;
d) placing the cotton cloth-based dynamic membrane in a tubular furnace, introducing hydrogen with the flow of 20sccm, and reacting for 3h at 400 ℃ to obtain the cotton cloth-based dynamic membrane with the super-hydrophobic property;
e) and (3) placing the cotton cloth-based dynamic membrane in a tubular furnace, introducing oxygen with the flow of 25sccm, and reacting for 3 hours at 300 ℃ to obtain the super-hydrophilic cotton cloth-based dynamic membrane.
The regeneration method comprises the following steps: soaking the polluted super-hydrophilic and super-hydrophobic cotton cloth-based dynamic membrane subjected to repeated oil-water separation in 100mL of 0.01mol/L dilute hydrochloric acid solution for 1h, taking out, washing with deionized water for 3 times, and drying at 60 ℃ for 1 h; and (e) repeating the preparation steps a to e to obtain the regenerated wet selective dynamic membrane.
Example 7
A preparation method of a selective oil-water separation dynamic membrane comprises the following steps:
a) adding 0.01mol of zinc acetate into 100mL of absolute ethyl alcohol, stirring strongly until the zinc acetate is dissolved, and refluxing the obtained zinc acetate ethanol solution at 70 ℃ for 3h to obtain milky zinc sol;
b) soaking a 10-square-centimeter silica fiber membrane in 50mL of zinc sol for 10s, drying at 60 ℃ for 40min, repeatedly soaking for 5 times, and annealing at 350 ℃ for 15min to obtain the silica fiber membrane coated with zinc oxide seeds;
c) preparing 80mL of mixed solution of zinc acetate with the concentration of 0.01mol/L and ammonium nitrate with the concentration of 0.1mol/L, adding the silicon dioxide fiber membrane coated with the zinc oxide seeds and the 80mL of mixed solution into a reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at 60 ℃, taking out, washing for 3 times by using deionized water, and drying for 4 hours at normal temperature to obtain a silicon dioxide fiber dynamic membrane;
d) placing the silicon dioxide fiber dynamic membrane in a tubular furnace, introducing hydrogen with the flow of 20sccm, and reacting for 6 hours at 200 ℃ to obtain the silicon dioxide fiber dynamic membrane with the super-hydrophobic property;
e) and (3) placing the silicon dioxide fiber dynamic membrane in a tubular furnace, introducing oxygen with the flow of 5sccm, and reacting for 1h at 300 ℃ to obtain the silicon dioxide fiber dynamic membrane with super-hydrophilic performance.
The regeneration method comprises the following steps: soaking the polluted super-hydrophilic and super-hydrophobic silica fiber dynamic membrane subjected to oil-water separation repeatedly for many times in 100mL of dilute hydrochloric acid solution with the concentration of 0.01mol/L, taking out after 1 hour, washing for 3 times by using deionized water, and drying for 1 hour at the temperature of 60 ℃; and (e) repeating the preparation steps a to e to obtain the regenerated wet selective dynamic membrane.
Example 8
A preparation method of a selective oil-water separation dynamic membrane comprises the following steps:
a) adding 0.001mol of zinc acetate into 100mL of absolute ethyl alcohol, stirring strongly until the zinc acetate is dissolved, and refluxing the obtained zinc acetate ethanol solution at 70 ℃ for 3h to obtain milky zinc sol;
b) soaking a 10-square-centimeter copper net in 50mL of zinc sol for 10s, drying at 100 ℃ for 10min, repeatedly soaking for 5 times, and annealing at 200 ℃ for 45min to obtain the copper net coated with zinc oxide seeds;
c) preparing 80mL of mixed solution of zinc acetate with the concentration of 0.1mol/L and hexamethylenetetramine with the concentration of 0.02mol/L, adding the copper mesh material coated with the zinc oxide seeds and 80mL of mixed solution into a reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at 60 ℃, taking out, washing for 3 times by using deionized water, and drying for 4 hours at normal temperature to obtain a copper mesh-based dynamic membrane;
d) placing the copper mesh base dynamic membrane in a tubular furnace, introducing hydrogen with the flow of 9sccm, and reacting for 1h at 200 ℃ to obtain the copper mesh base dynamic membrane with the super-hydrophobic property;
e) and (3) placing the copper mesh-based dynamic membrane in a tubular furnace, introducing oxygen with the flow of 20sccm, and reacting for 6 hours at 300 ℃ to obtain the copper mesh-based dynamic membrane with super-hydrophilic performance.
The regeneration method comprises the following steps: soaking the polluted super-hydrophilic and super-hydrophobic copper mesh-based dynamic membrane subjected to oil-water separation repeatedly for many times in 100mL of 0.01mol/L dilute hydrochloric acid solution, taking out after 1 hour, washing with deionized water for 3 times, and drying at 60 ℃ for 1 hour; and (e) repeating the preparation steps a to e to obtain the regenerated wet selective dynamic membrane.
Example 9
A preparation method of a selective oil-water separation dynamic membrane comprises the following steps:
a) adding 0.01mol of zinc acetate into 100mL of absolute ethyl alcohol, stirring strongly until the zinc acetate is dissolved, and refluxing the obtained zinc acetate ethanol solution at 80 ℃ for 3h to obtain milky zinc sol;
b) soaking a stainless steel net with the thickness of 10 square centimeters in 50mL of zinc sol for 10s, drying at 120 ℃ for 10min, repeatedly soaking for 5 times, and annealing at 300 ℃ for 30min to obtain the stainless steel net coated with zinc oxide seeds;
c) preparing 80mL of mixed solution of zinc acetate with the concentration of 0.015mol/L and hexamethylenetetramine with the concentration of 0.05mol/L, adding the stainless steel mesh material coated with the zinc oxide seeds and 80mL of mixed solution into a reaction kettle with a polytetrafluoroethylene lining, reacting for 6h at 60 ℃, taking out, washing for 3 times by using deionized water, and drying for 4h at normal temperature to obtain a stainless steel base mesh dynamic membrane;
d) placing the stainless steel mesh-based dynamic membrane in a tubular furnace, introducing hydrogen with the flow of 10sccm, and reacting for 3h at 300 ℃ to obtain the stainless steel mesh-based dynamic membrane with the super-hydrophobic property;
e) and (3) placing the stainless steel mesh dynamic membrane in a tube furnace, introducing oxygen with the flow of 25sccm, and reacting for 1h at 300 ℃ to obtain the stainless steel mesh dynamic membrane with super-hydrophilic performance.
The regeneration method comprises the following steps: soaking the polluted super-hydrophilic and super-hydrophobic stainless steel mesh-based dynamic membrane subjected to oil-water separation repeatedly for many times in 100mL of 0.01mol/L dilute hydrochloric acid solution, taking out after 1 hour, washing with deionized water for 3 times, and drying at 60 ℃ for 1 hour; and (e) repeating the preparation steps a to e to obtain the regenerated wet selective dynamic membrane.
Example 10
A preparation method of a selective oil-water separation dynamic membrane comprises the following steps:
a) adding 0.001mol of zinc acetate into 100mL of absolute ethyl alcohol, stirring strongly until the zinc acetate is dissolved, and refluxing the obtained zinc acetate ethanol solution at 60 ℃ for 3h to obtain milky zinc sol;
b) soaking a 10-square-centimeter copper net in 50mL of zinc sol for 10s, drying at 120 ℃ for 20min, repeatedly soaking for 5 times, and annealing at 350 ℃ for 15min to obtain the copper net coated with zinc oxide seeds;
c) preparing 80mL of mixed solution of zinc acetate with the concentration of 0.01mol/L and ammonium chloride with the concentration of 0.2mol/L, adding the copper mesh material coated with the zinc oxide seeds and 80mL of mixed solution into a reaction kettle with a polytetrafluoroethylene lining, reacting for 5 hours at 60 ℃, taking out, washing for 3 times by using deionized water, and drying for 4 hours at normal temperature to obtain a copper mesh-based dynamic membrane;
d) placing the copper mesh base dynamic membrane in a tubular furnace, introducing hydrogen with the flow of 15sccm, and reacting for 1h at 400 ℃ to obtain the copper mesh base dynamic membrane with the super-hydrophobic property;
e) and (3) placing the copper mesh-based dynamic membrane in a tubular furnace, introducing oxygen with the flow of 15sccm, and reacting for 6 hours at 300 ℃ to obtain the copper mesh-based dynamic membrane with super-hydrophilic performance.
The regeneration method comprises the following steps: soaking the polluted super-hydrophilic and super-hydrophobic copper mesh-based dynamic membrane subjected to oil-water separation repeatedly for many times in 100mL of 0.01mol/L dilute hydrochloric acid solution, taking out after 1 hour, washing for 3 times by using deionized water, and drying for 3 hours at the temperature of 60 ℃; and (e) repeating the preparation steps a to e to obtain the regenerated wet selective dynamic membrane.
Example 11
A preparation method of a selective oil-water separation dynamic membrane comprises the following steps:
a) adding 0.005mol of zinc acetate into 100mL of absolute ethyl alcohol, stirring strongly until the zinc acetate is dissolved, and refluxing the obtained zinc acetate ethanol solution at 70 ℃ for 3h to obtain milky zinc sol;
b) soaking a 10-square-centimeter copper net in 50mL of zinc sol for 10s, drying at 60 ℃ for 10min, repeatedly soaking for 5 times, and annealing at 250 ℃ for 30min to obtain the copper net coated with zinc oxide seeds;
c) preparing 80mL of mixed solution of zinc acetate with the concentration of 0.05mol/L and ammonium nitrate with the concentration of 0.1mol/L, adding the copper mesh material coated with the zinc oxide seeds and 80mL of mixed solution into a reaction kettle with a polytetrafluoroethylene lining, reacting for 6h at 60 ℃, taking out, washing for 3 times by using deionized water, and drying for 4h at normal temperature to obtain a copper mesh-based dynamic membrane;
d) placing the copper mesh base dynamic membrane in a tubular furnace, introducing hydrogen with the flow of 20sccm, and reacting for 6h at 200 ℃ to obtain the copper mesh base dynamic membrane with the super-hydrophobic property;
e) and (3) placing the copper mesh-based dynamic membrane in a tubular furnace, introducing oxygen with the flow of 10sccm, and reacting for 6 hours at 300 ℃ to obtain the copper mesh-based dynamic membrane with super-hydrophilic performance.
The regeneration method comprises the following steps: soaking the polluted super-hydrophilic and super-hydrophobic copper mesh-based dynamic membrane subjected to oil-water separation repeatedly for many times in 100mL of 0.01mol/L dilute hydrochloric acid solution, taking out after 1 hour, washing with deionized water for 3 times, and drying at 60 ℃ for 1 hour; and (e) repeating the preparation steps a to e to obtain the regenerated wet selective dynamic membrane.
Example 12
A preparation method of a selective oil-water separation dynamic membrane comprises the following steps:
a) adding 0.1mol of zinc acetate into 100mL of absolute ethyl alcohol, stirring strongly until the zinc acetate is dissolved, and refluxing the obtained zinc acetate ethanol solution at 70 ℃ for 3h to obtain milky zinc sol;
b) soaking nylon cloth of 10 square centimeters in 50mL of zinc sol for 10s, drying at 60 ℃ for 10min, repeatedly soaking for 5 times, and annealing at 200 ℃ for 45min to obtain nylon cloth coated with zinc oxide seeds;
c) preparing 80mL of mixed solution of zinc acetate with the concentration of 0.01mol/L and hexamethylenetetramine with the concentration of 0.01mol/L, adding the nylon cloth material coated with the zinc oxide seeds and 80mL of mixed solution into a reaction kettle with a polytetrafluoroethylene lining, reacting for 6 hours at 60 ℃, taking out, washing for 3 times by using deionized water, and drying for 4 hours at normal temperature to obtain a nylon cloth-based dynamic membrane;
d) placing the nylon cloth-based dynamic membrane in a tubular furnace, introducing hydrogen with the flow of 90sccm, and reacting for 3 hours at 300 ℃ to obtain the nylon cloth-based dynamic membrane with the super-hydrophobic performance;
e) and (3) placing the nylon cloth-based dynamic membrane in a tubular furnace, introducing oxygen with the flow of 25sccm, and reacting for 4 hours at 300 ℃ to obtain the nylon cloth-based dynamic membrane with super-hydrophilic performance.
The regeneration method comprises the following steps: soaking the polluted super-hydrophilic and super-hydrophobic nylon cloth-based dynamic membrane subjected to oil-water separation repeatedly in 100mL of 0.01mol/L dilute hydrochloric acid solution for 1h, taking out, washing with deionized water for 3 times, and drying at 60 ℃ for 1 h; and (e) repeating the preparation steps a to e to obtain the regenerated wet selective dynamic membrane.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes performed by the present invention or directly or indirectly applied to other related technical fields are included in the scope of the present invention.
Claims (12)
1. The preparation method of the selective oil-water separation dynamic membrane is characterized by comprising the following steps:
a) adding zinc acetate into absolute ethyl alcohol according to the proportion that 0.001-0.1 mol of zinc acetate is added into each 100mL of absolute ethyl alcohol, stirring strongly until the zinc acetate is dissolved, and refluxing the obtained zinc acetate ethanol solution for 3 hours at the temperature of 60-80 ℃ to obtain milky zinc sol;
b) soaking the base membrane in zinc sol for 10s according to the addition of 5-10 mL of zinc sol per square centimeter of the base membrane, drying at 60-120 ℃ for 10-40 min, repeatedly soaking for 3-9 times, and annealing at 200-350 ℃ for 15-45 min to obtain a porous base membrane coated with zinc oxide seeds, wherein the base membrane is one or a combination of a copper net, a silicon dioxide fiber membrane, a stainless steel net, cotton cloth and nylon cloth;
c) uniformly mixing 0.01-0.1 mol/L zinc acetate aqueous solution and 0.01-0.2 mol/L pH regulator aqueous solution in equal volume to obtain zinc acetate pH regulator mixed solution; adding a porous base membrane coating zinc oxide seeds and a zinc acetate pH regulator solution into a polytetrafluoroethylene lining reaction kettle according to the proportion that 10mL of zinc acetate pH regulator mixed solution is added per square centimeter, reacting for 6-16 h at 60-120 ℃, taking out, washing for 2-5 times with deionized water, and drying for 4-8 h at normal temperature to obtain a zinc oxide precoated porous separation membrane, wherein the pH regulator is one or a combination of more of ammonium chloride, ammonium fluoride, ammonium nitrate, hexamethylenetetramine, ammonia water and urea;
d) putting the porous separation membrane of the zinc oxide precoat in a tubular furnace according to a hydrogen meter with the flow of 9-20 sccm per square centimeter, and reacting for 1-6 h at 200-400 ℃ to obtain the porous separation dynamic membrane of the zinc oxide precoat with super-hydrophobic property;
alternatively, the first and second electrodes may be,
and (3) placing the porous separation membrane of the zinc oxide precoat in a tubular furnace according to an oxygen meter with the flow of 5-25 sccm per square centimeter, and reacting for 1-6 h at the temperature of 300-400 ℃ to obtain the super-hydrophilic porous separation dynamic membrane of the zinc oxide precoat.
2. The method for producing a selective oil-water separation dynamic membrane according to claim 1, characterized in that: adding zinc acetate into absolute ethyl alcohol according to the proportion that 0.1mol of zinc acetate is added into each 100mL of absolute ethyl alcohol in the step a), stirring the mixture strongly until the zinc acetate is dissolved, and refluxing the obtained zinc acetate ethanol solution for 3h at the temperature of 60 ℃ to obtain milky zinc sol.
3. The method for producing a selective oil-water separation dynamic membrane according to claim 1, characterized in that: in step b), the base film was immersed in zinc sol for 10s and dried at 60 ℃ for 20 min.
4. The method for producing a selective oil-water separation dynamic membrane according to claim 1, characterized in that: annealing at 250 ℃ for 15min in the step b) to obtain the porous basement membrane coated with the zinc oxide seeds.
5. The method for producing a selective oil-water separation dynamic membrane according to claim 1, characterized in that: the base film in step b) is a silica fiber film.
6. The method for producing a selective oil-water separation dynamic membrane according to claim 1, characterized in that: in the step c), 0.01mol/L zinc acetate aqueous solution and 0.01mol/L pH regulator aqueous solution are mixed uniformly in equal volume to obtain zinc acetate pH regulator mixed solution.
7. The method for producing a selective oil-water separation dynamic membrane according to claim 1, characterized in that: in the step c), the pH regulator is hexamethylenetetramine.
8. The method for producing a selective oil-water separation dynamic membrane according to claim 1, characterized in that: and d), introducing hydrogen with the flow rate of 9-20 sccm per square centimeter, placing the porous separation membrane of the zinc oxide precoat in a tubular furnace, and reacting at 300 ℃ for 3 hours to obtain the super-hydrophobic porous separation dynamic membrane of the zinc oxide precoat.
9. The method for producing a selective oil-water separation dynamic membrane according to claim 1, characterized in that: and d), introducing an oxygen meter with the flow of 5-25 sccm per square centimeter, placing the porous separation membrane of the zinc oxide precoat in a tubular furnace, and reacting for 3 hours under 300 hours to obtain the super-hydrophilic porous separation dynamic membrane of the zinc oxide precoat.
10. The selective oil-water separation dynamic membrane prepared by the method according to any one of claims 1 to 9, which is characterized in that: the dynamic membrane is formed by in-situ growth of a secondary membrane with wetting selectivity on the surface of a base membrane.
11. The dynamic membrane for selective oil-water separation according to claim 10, wherein: the secondary film is zinc oxide with wetting selectivity, and the thickness of the secondary film is 200-2000 nm.
12. Use of the dynamic membrane for selective oil-water separation according to claim 10 or 11, wherein: it is applied to oil-water separation.
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