CN108273397B - Preparation method of oil-water separation membrane with underwater super-oleophobic property and antibacterial property - Google Patents
Preparation method of oil-water separation membrane with underwater super-oleophobic property and antibacterial property Download PDFInfo
- Publication number
- CN108273397B CN108273397B CN201810144838.6A CN201810144838A CN108273397B CN 108273397 B CN108273397 B CN 108273397B CN 201810144838 A CN201810144838 A CN 201810144838A CN 108273397 B CN108273397 B CN 108273397B
- Authority
- CN
- China
- Prior art keywords
- membrane
- oil
- water
- sodium alginate
- water separation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0079—Manufacture of membranes comprising organic and inorganic components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/12—Composite membranes; Ultra-thin membranes
- B01D69/125—In situ manufacturing by polymerisation, polycondensation, cross-linking or chemical reaction
-
- 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
-
- 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
-
- 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
- B01D2325/00—Details relating to properties of membranes
- B01D2325/36—Hydrophilic membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/48—Antimicrobial properties
Abstract
The invention relates to a preparation method of an oil-water separation membrane with underwater super oleophobic property and antibacterial property, which comprises the following steps: dissolving sodium alginate in water to obtain a sodium alginate solution; coating the obtained sodium alginate solution, and then sieving water-soluble salts with a certain particle size to obtain a mixed membrane; immediately carrying out ultrasonic oscillation on the mixed membrane in a cross-linking agent aqueous solution, and then soaking the mixed membrane in a cross-linking agent to obtain a sodium alginate porous membrane; and sequentially soaking the sodium alginate porous membrane in a silver nitrate solution and a reducing agent solution to obtain the oil-water separation membrane. The contact angle of the oil-water separation membrane obtained by the method to oil in water is 155-168 degrees, the roughness of the surface of the membrane is increased by the silver cluster particles with the micro-nano composite structure, the membrane has more excellent underwater super-oleophobic property, the membrane is not easily adhered by oil, and the oil-water separation membrane is suitable for separating the mixture of oil and water with higher viscosity.
Description
Technical Field
The invention relates to a preparation method of an oil-water separation membrane, in particular to a preparation method of an oil-water separation membrane with underwater super oleophobic property and antibacterial property.
Background
Along with the discharge of a large amount of oily sewage in production and life and the frequent occurrence of offshore crude oil leakage accidents, oil-water separation has become an important research subject related to people's life, economic development and environmental safety. Because the separation of oil and water is a problem of interface science, the realization of high-efficiency and high-selectivity separation by utilizing different actions of the special wettability of materials on oil and water is a research hotspot at the present stage.
Chinese patents CN1387932A, CN1721030A, CN101518695A and CN102698471B all disclose an oil-water separation net film or an oil-water separation net with super-hydrophobic and super-oleophilic functions. The oil-water separation net film is partially prepared from fluorine-containing compounds, has certain pollution to the environment, is partially complicated in preparation process, is easily adhered by oil due to the super-oleophylic property of the material, is not suitable for separating oil and water mixtures with high viscosity, and is not suitable for separating a mixture system containing a small amount of oil in a large amount of water.
The oil-water separation net film has opposite wetting property, namely, the material with super-hydrophilic and underwater super-oleophobic property can solve the problems, is more suitable for separating the mixture of high-viscosity oil such as crude oil and water, and is also more suitable for separating the mixture system containing a small amount of oil in a large amount of water. Chinese patents CN102029079B, CN103157299B, CN103331039B, CN103657156B and CN104492276B all disclose oil-water separation net membranes with super-hydrophilic and underwater super-oleophobic properties. The oil-water separation net film is a composite net film prepared by wrapping materials such as organic hydrogel, inorganic gel and polymer on porous substrates such as fabric, quartz fiber cloth and filter paper, and the materials are easy to have the problem of coating peeling in long-time use and complex oil-water environment, so that the oil-water separation capability is weakened or even lost. Moreover, the underwater super-hydrophobic oil separation net membranes have no antibacterial performance and have no antibacterial capability on oily sewage containing a large number of bacteria in production and life.
As for the oil-water separation net membrane having antibacterial properties, chinese patents CN103173998B, CN204506003U, CN105413496B and CN106381690A all disclose an oil-water separation net membrane having antibacterial properties. The net film part is used for spraying or dipping silver or copper nanoparticles and silver-loaded silicon dioxide nanoparticles onto the surface of the fabric, and the part is used for adhering the silver nanoparticles onto the surface of the composite metal net film by adopting a reduction method. The materials are complex to prepare, do not have super-hydrophilic/underwater super-oleophobic properties, and have low separation efficiency, low separation selectivity and poor oil adhesion resistance.
Disclosure of Invention
The invention provides a preparation method of an oil-water separation membrane with underwater super-oleophobic property and antibacterial property, aiming at the defects of the existing oil-water separation membrane with super-hydrophilic and underwater super-oleophobic properties in the application process.
The technical scheme for solving the technical problems is as follows:
a preparation method of an oil-water separation membrane with underwater super oleophobic property and antibacterial property comprises the following steps:
1) dissolving sodium alginate in water to prepare a sodium alginate aqueous solution, and then coating the sodium alginate aqueous solution to control the film thickness to be 20-200 mu m;
2) screening water-soluble inorganic salt with the particle size of 20-500 mu m on the surface of the sodium alginate film obtained in the step 1) by using a screen to obtain a mixed film, and controlling the mass ratio of the sodium alginate to the water-soluble inorganic salt to be 1: (0.1-2);
3) immediately placing the mixed membrane obtained in the step 2) in a cross-linking agent aqueous solution for ultrasonic oscillation for 30-180 s, then soaking in the cross-linking agent aqueous solution to fully cross-link the membrane, and then cleaning with deionized water to obtain the sodium alginate porous membrane, wherein the cross-linking agent is any one or a mixture of more of zinc chloride, barium chloride, ferric chloride, aluminum chloride, calcium dihydrogen phosphate, calcium nitrate and hydrochloric acid;
4) soaking the sodium alginate porous membrane obtained in the step 3) in a soluble silver salt aqueous solution, taking out and then washing with deionized water;
5) and (3) soaking the porous membrane obtained in the step 4) in a reducing agent water solution, taking out the porous membrane, and washing the porous membrane with deionized water to obtain the porous membrane.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, in the step 2), the water-soluble inorganic salt is any one or a mixture of two or more of a sodium salt, a potassium salt and an ammonium salt, and preferably, the water-soluble inorganic salt is any one or a mixture of two or more of sodium chloride, sodium sulfate, sodium carbonate, sodium nitrate, potassium chloride, potassium sulfate, potassium carbonate and potassium nitrate.
Further, the mass concentration of the cross-linking agent aqueous solution in the step 3) is 0.01-10 wt%, and preferably, the mass concentration of the cross-linking agent aqueous solution is 3-5 wt%.
Further, the soluble silver salt in the step 4) is silver nitrate, and the concentration of the soluble silver salt aqueous solution is 0.05-0.5 mol/L, preferably 0.1-0.2 mol/L.
Further, in the step 5), the reducing agent is any one or a mixture of two or more of tyrosine, ascorbic acid, sodium borohydride and sodium hypophosphite, and the concentration of the reducing agent aqueous solution is 0.05-0.5 mol/L, preferably 0.1-0.2 mol/L.
Further, the mass concentration of the sodium alginate aqueous solution in the step 1) is 0.5-10 wt%, preferably 3-5 wt%.
Further, the soaking time in the step 3), the step 4) and the step 5) is 1-12 hours.
The preparation method of the invention has the following action principle:
after the sodium alginate membrane is deposited with the soluble inorganic salt, the soluble inorganic salt penetrates through the sodium alginate membrane to form a hole under the action of ultrasound, the inorganic salt crystal is dissolved in the penetrating process, the membrane is crosslinked and cured in the soaking process in the crosslinking agent aqueous solution, then the soluble silver salt aqueous solution is used for loading silver cluster particles on the surface of the porous membrane, the silver is reduced under the action of a reducing agent, the roughness of the surface of the membrane is increased by the silver cluster particles with the micro-nano composite structure, and the membrane has more excellent underwater super-oleophobic property.
The oil-water separation membrane prepared by the method has the following structural characteristics:
1) the oil-water separation membrane has a micron porous structure and a micro-nano composite silver cluster structure, and the size of the silver cluster is 100-1000 nm;
2) the aperture of the front surface of the membrane is larger than that of the back surface of the membrane, the aperture of the front surface of the membrane is 20-400 mu m, and the aperture of the back surface of the membrane is 15-150 mu m.
The oil-water separation membrane obtained by the method can be widely applied to separation of oily sewage such as normal hexane, petroleum ether, animal oil, vegetable oil, diesel oil, gasoline, silicone oil, kerosene or crude oil and the like.
The invention has the beneficial effects that:
1) the contact angle of the oil-water separation membrane obtained by the method to oil in water is 155-168 degrees, the roughness of the surface of the membrane is increased by the silver cluster particles with the micro-nano composite structure, the membrane has more excellent underwater super-oleophobic property, the membrane is not easily adhered by oil, and the oil-water separation membrane is suitable for separating the mixture of oil and water with higher viscosity.
2) The oil-water separation mesh membrane prepared by the invention has the characteristics of high separation speed and high separation efficiency, the separated oil can be recycled, and the separation membrane has a porous structure, does not depend on a porous substrate, can be repeatedly used for many times, and does not influence the separation effect;
3) the separation membrane has excellent antibacterial performance on various bacteria such as escherichia coli, staphylococcus aureus and the like in sewage;
4) the oil-water separation membrane obtained by the method can be degraded in natural environment after being used and abandoned, and does not produce secondary pollution.
Drawings
FIG. 1 is an SEM photograph of the surface morphology of the front surface of the oil-water separation membrane prepared in example 1;
FIG. 2 is an SEM photograph of the surface morphology of the back surface of the oil-water separation membrane prepared in example 1;
fig. 3 is a photograph showing the shape of oil droplets (2 μ l) of 1, 2-dichloroethane measured underwater on the surface of the oil-water separation membrane prepared in example 1.
Detailed Description
The principles and features of this invention are described below in conjunction with examples, which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
Example 1:
a preparation method of an oil-water separation membrane with underwater super oleophobic property and antibacterial property comprises the following steps:
1) at normal temperature, adding 100ml of water and 3g of sodium alginate into a 250ml beaker, magnetically stirring and uniformly mixing to obtain a 3 wt% sodium alginate solution, and scraping the obtained sodium alginate solution on a glass plate to form a film with the thickness of about 70 microns;
2) grinding sodium chloride, screening by using a standard sieve, taking 3g of sodium chloride crystal particles with the particle size of about 300 mu m for later use, and screening the sodium chloride crystal particles on the surface of the sodium alginate membrane obtained in the step 1) by using a sieve to obtain a mixed membrane;
3) immediately putting the mixed membrane obtained in the step 2) into a 5 wt% calcium chloride solution, performing ultrasonic treatment for 60s, then soaking the obtained primarily cured membrane in the 5 wt% calcium chloride solution for 6h to fully crosslink the membrane, and washing the membrane with deionized water;
4) soaking the membrane obtained in the step 3) in 0.1mol/L silver nitrate solution for 3h, taking out and washing with deionized water;
5) soaking the membrane obtained in the step 4) in 0.1mol/L ascorbic acid solution for 3h, taking out and washing with deionized water to obtain the calcium alginate oil-water separation membrane.
The calcium alginate oil-water separation membrane obtained in the example 1 has a through micron pore structure, the pore diameter of the front surface is 200-350 microns (shown in figure 1), the pore diameter of the back surface is 70-100 microns (shown in figure 2), and silver cluster particles with the particle size of 400-500 nm are arranged on the surface and inside of the membrane (shown in figures 1 and 2).
The contact angle of the oil-water separation membrane obtained in the step 3) to 1, 2-dichloroethane is 150 degrees, after silver cluster particles are loaded by a reduction method, the roughness of the membrane surface is increased, the surface energy of silver is high, the hydrophilicity is stronger, the underwater oleophobic property of the material is improved, and the contact angle of the membrane obtained in the step 5) to 1, 2-dichloroethane is 158 degrees (see fig. 3). Meanwhile, different types of oils including n-hexane, petroleum ether, animal oil, vegetable oil, diesel oil, gasoline, silicone oil, kerosene and crude oil are tested, contact angles are all larger than 150 degrees, and the underwater super-oleophobic property of the net film has universality.
The oil-water separation net membrane obtained in example 1 is sandwiched between glass tubes, a mixture (volume ratio 1: 2) of crude oil and water is poured onto the oil-water separation membrane through an upper feeding glass tube, water flows out from the lower part after passing through the oil-water separation membrane, and the crude oil is blocked at the upper end of the oil-water separation membrane to obtain separated oil, so that the purpose of oil-water separation is achieved. And measuring the residual content of the crude oil in the separated water sample by using an infrared oil tester, wherein the residual content of the crude oil reaches a trace amount, and the separation efficiency is over 99 percent. Can be used normally after being separated twenty times.
An antibacterial experiment was performed on the oil-water separation membrane obtained in example 1, and the membrane which is not loaded with silver cluster particles and is obtained in step 3) and the membrane which is loaded with silver cluster particles and is obtained in step 5) were subjected to an antibacterial experiment by a bacteriostatic ring method and a film pasting method, and the antibacterial effect of the membrane was evaluated from two aspects of qualitative and quantitative. The bacteriostatic loop method comprises cutting the membranes obtained in steps 3) and 5) into 2cm × 2cm, placing in the center of a plate with bacteria culture medium, covering, and culturing at 37 deg.C for 48 h. The membrane obtained in the step 3) has no inhibition zone to escherichia coli and staphylococcus aureus. The inhibition zone of the membrane obtained in the step 5) on escherichia coli is 2.05 +/-0.2 mm, and the inhibition zone on staphylococcus aureus is 1.02 +/-0.1 mm. The film sticking method is to use a film with a concentration of 5.0X 105～10.0×105The cfu/mL bacterial liquid diluent contacts an oil-water separation membrane, and the membrane is cultured for 24h under the conditions of 37 ℃ and relative humidity of more than 90%. Adding eluent to wash the sample, inoculating the sample in nutrient agar culture medium, culturing at 37 deg.C for 24h, and counting viable bacteria according to GB/T4789.2-2003 "determination of total number of bacterial colonies for food hygiene microorganism test". The antibacterial rate is calculated by comparing the number of colonies of the prepared membrane with that of the blank membrane. Through three groups of parallel tests, the film antibacterial rate of the silver cluster particle-free film obtained in the step 3) is 0, the antibacterial rate of the silver cluster particle-loaded film obtained in the step 5) to escherichia coli is 100%, and the antibacterial rate to staphylococcus aureus is 99.2%.
Example 2:
a preparation method of an oil-water separation membrane with underwater super oleophobic property and antibacterial property comprises the following steps:
1) at normal temperature, adding 100ml of water and 0.5g of sodium alginate into a 250ml beaker, magnetically stirring and uniformly mixing to obtain a 0.5 wt% sodium alginate solution, and scraping the obtained sodium alginate solution on a glass plate to form a film with the thickness of about 20 microns;
2) grinding sodium chloride, screening by using a standard sieve, taking 0.05g of potassium sulfate crystal particles with the particle size of about 20 mu m for standby, and screening the sodium chloride crystal particles on the surface of the sodium alginate membrane obtained in the step 1) by using a sieve to obtain a mixed membrane;
3) immediately putting the mixed membrane obtained in the step 2) into 0.01 wt% ferric chloride solution for ultrasonic treatment for 30s, then soaking the obtained preliminarily cured membrane in 0.01 wt% ferric chloride solution for 12h to fully crosslink the membrane, and washing the membrane with deionized water;
4) soaking the membrane obtained in the step 3) in 0.05mol/L silver nitrate solution for 12h, taking out and washing with deionized water;
5) soaking the membrane obtained in the step 4) in 0.05mol/L sodium borohydride solution for 12h, taking out and washing with deionized water to obtain the iron alginate oil-water separation membrane.
The ferric alginate oil-water separation membrane obtained in the embodiment 2 has a through micron pore structure, the aperture of the front surface is 20-35 mu m, the aperture of the back surface is about 15 mu m, and silver cluster particles with the particle size of 100-200 nm are arranged on the surface and inside of the membrane.
The contact angle of the oil-water separation membrane obtained in the step 3) to 1, 2-dichloroethane is 148 degrees, after silver cluster particles are loaded by a reduction method, the roughness of the membrane surface is increased, the surface energy of silver is high, the hydrophilicity is stronger, the underwater oleophobic property of the material is improved, and the contact angle of the membrane obtained in the step 5) to 1, 2-dichloroethane is 157 degrees. Meanwhile, different types of oils including n-hexane, petroleum ether, animal oil, vegetable oil, diesel oil, gasoline, silicone oil, kerosene and crude oil are tested, contact angles are all larger than 150 degrees, and the underwater super-oleophobic property of the net film has universality.
The oil-water separation mesh membrane obtained in example 2 is sandwiched between glass tubes, a mixture (volume ratio 1: 2) of vegetable oil and water is poured onto the oil-water separation membrane through an upper feeding glass tube, water flows out from the lower part after passing through the oil-water separation membrane, and meanwhile vegetable oil is blocked at the upper end of the oil-water separation membrane, so that separated oil is obtained, and the purpose of oil-water separation is achieved. And (3) measuring the residual content of the vegetable oil in the separated water sample by using an infrared oil tester, wherein the residual content of the crude oil reaches a trace amount, and the separation efficiency is more than 98%. Can be used normally after being separated twenty times.
We proceed to the examples2, performing an antibacterial experiment on the oil-water separation membrane obtained in the step 3), performing an antibacterial experiment on the membrane which is not loaded with the silver cluster particles obtained in the step 5) and the membrane loaded with the silver cluster particles obtained in the step 5) by adopting a bacteriostatic ring method and a film pasting method, and evaluating the antibacterial effect of the membrane from two aspects of qualitative and quantitative aspects. The bacteriostatic loop method comprises cutting the membranes obtained in steps 3) and 5) into 2cm × 2cm, placing in the center of a plate with bacteria culture medium, covering, and culturing at 37 deg.C for 48 h. The membrane obtained in the step 3) has no inhibition zone to escherichia coli and staphylococcus aureus. The inhibition zone of the membrane obtained in the step 5) on escherichia coli is 2.25 +/-0.1 mm, and the inhibition zone on staphylococcus aureus is 2.00 +/-0.2 mm. The film sticking method is to use a film with a concentration of 5.0X 105～10.0×105The cfu/mL bacterial liquid diluent contacts an oil-water separation membrane, and the membrane is cultured for 24h under the conditions of 37 ℃ and relative humidity of more than 90%. Adding eluent to wash the sample, inoculating the sample in nutrient agar culture medium, culturing at 37 deg.C for 24h, and counting viable bacteria according to GB/T4789.2-2003 "determination of total number of bacterial colonies for food hygiene microorganism test". The antibacterial rate is calculated by comparing the number of colonies of the prepared membrane with that of the blank membrane. Through three groups of parallel tests, the film antibacterial rate of the silver cluster particle-free film obtained in the step 3) is 0, the antibacterial rate of the silver cluster particle-loaded film obtained in the step 5) to escherichia coli is 100%, and the antibacterial rate to staphylococcus aureus is 99.5%.
Example 3:
a preparation method of an oil-water separation membrane with underwater super oleophobic property and antibacterial property comprises the following steps:
1) at normal temperature, adding 100ml of water and 10g of sodium alginate into a 250ml beaker, magnetically stirring and uniformly mixing to obtain a 10 wt% sodium alginate solution, and scraping the obtained sodium alginate solution on a glass plate to form a film with the thickness of about 200 microns;
2) grinding sodium sulfate, screening by using a standard sieve, taking 20g of sodium sulfate crystal particles with the particle size of about 500 mu m for later use, and screening the sodium sulfate crystal particles on the surface of the sodium alginate membrane obtained in the step 1) by using a sieve to obtain a mixed membrane;
3) immediately putting the mixed membrane obtained in the step 2) into a 10 wt% hydrochloric acid solution for ultrasonic treatment for 180s, then soaking the obtained primarily cured membrane in the 10 wt% hydrochloric acid solution for 0.1h to fully crosslink the membrane, and washing the membrane with deionized water;
4) soaking the membrane obtained in the step 3) in 0.5mol/L silver nitrate solution for 1h, taking out and washing with deionized water;
5) soaking the membrane obtained in the step 4) in 0.5mol/L tyrosine solution for 1h, taking out and washing with deionized water to obtain the alginic acid oil-water separation membrane.
The alginic acid oil-water separation membrane obtained in the embodiment 3 has a through-micron pore structure, the pore diameter of the front surface is about 400 microns, the pore diameter of the back surface is about 150 microns, and the surface and the inside of the membrane have 800-1000 nm silver cluster particles.
The contact angle of the oil-water separation membrane obtained in the step 3) to 1, 2-dichloroethane is 152 degrees, after silver cluster particles are loaded by a reduction method, the roughness of the membrane surface is increased, the surface energy of silver is high, the hydrophilicity is stronger, the underwater oleophobic property of the material is improved, and the contact angle of the membrane obtained in the step 5) to 1, 2-dichloroethane is 168 degrees. Meanwhile, different types of oils including n-hexane, petroleum ether, animal oil, vegetable oil, diesel oil, gasoline, silicone oil, kerosene and crude oil are tested, contact angles are all larger than 150 degrees, and the underwater super-oleophobic property of the net film has universality.
The oil-water separation net membrane obtained in example 3 is sandwiched between glass tubes, a mixture (volume ratio 1: 2) of n-hexane and water is poured onto the oil-water separation membrane through an upper feeding glass tube, water flows out from the lower part after passing through the oil-water separation membrane, and meanwhile n-hexane is blocked at the upper end of the oil-water separation membrane, so that separated oil is obtained, and the purpose of oil-water separation is achieved. And (3) measuring the residual content of the n-hexane in the separated water sample by using an infrared oil tester, wherein the residual content of the n-hexane reaches a trace amount, and the separation efficiency is more than 99%. Can be used normally after being separated twenty times.
The oil-water separation membrane obtained in example 3 was subjected to an antibacterial experiment, the membrane not loaded with silver cluster particles obtained in step 3) and the membrane loaded with silver cluster particles obtained in step 5) were subjected to an antibacterial experiment using a bacteriostatic ring method and a film pasting method, and the antibacterial effect of the membrane was evaluated from both qualitative and quantitative aspectsAnd (5) fruit. The bacteriostatic loop method comprises cutting the membranes obtained in steps 3) and 5) into 2cm × 2cm, placing in the center of a plate with bacteria culture medium, covering, and culturing at 37 deg.C for 48 h. The membrane obtained in the step 3) has no inhibition zone to escherichia coli and staphylococcus aureus. The inhibition zone of the membrane obtained in the step 5) on escherichia coli is 1.98 +/-0.1 mm, and the inhibition zone on staphylococcus aureus is 1.89 +/-0.1 mm. The film sticking method is to use a film with a concentration of 5.0X 105～10.0×105The cfu/mL bacterial liquid diluent contacts an oil-water separation membrane, and the membrane is cultured for 24h under the conditions of 37 ℃ and relative humidity of more than 90%. Adding eluent to wash the sample, inoculating the sample in nutrient agar culture medium, culturing at 37 deg.C for 24h, and counting viable bacteria according to GB/T4789.2-2003 "determination of total number of bacterial colonies for food hygiene microorganism test". The antibacterial rate is calculated by comparing the number of colonies of the prepared membrane with that of the blank membrane. Through three groups of parallel tests, the film antibacterial rate of the silver cluster particle-free film obtained in the step 3) is 0, the antibacterial rate of the silver cluster particle-loaded film obtained in the step 5) to escherichia coli is 99.5%, and the antibacterial rate to staphylococcus aureus is 100%.
Example 4:
a preparation method of an oil-water separation membrane with underwater super oleophobic property and antibacterial property comprises the following steps:
1) at normal temperature, adding 100ml of water and 5g of sodium alginate into a 250ml beaker, magnetically stirring and uniformly mixing to obtain a 5 wt% sodium alginate solution, and scraping the obtained sodium alginate solution on a glass plate to form a film with the thickness of about 120 microns;
2) grinding ammonium chloride, screening by using a standard sieve, taking 5g of ammonium chloride crystal particles with the particle size of about 300 mu m for later use, and screening the ammonium chloride crystal particles on the surface of the sodium alginate membrane obtained in the step 1) by using a sieve to obtain a mixed membrane;
3) immediately putting the mixed membrane obtained in the step 2) into 3 wt% calcium dihydrogen phosphate solution, performing ultrasonic treatment for 60s, soaking the obtained primarily cured membrane in 3 wt% calcium dihydrogen phosphate solution for 6h to fully crosslink the membrane, and washing the membrane with deionized water;
4) soaking the membrane obtained in the step 3) in 0.2mol/L silver fluoride solution for 2h, taking out and washing with deionized water;
5) soaking the membrane obtained in the step 4) in 0.2mol/L sodium hypophosphite solution for 2h, taking out and washing with deionized water to obtain the calcium alginate oil-water separation membrane.
The calcium alginate oil-water separation membrane obtained in the embodiment 4 has a through micron pore structure, the aperture of the front surface is 200-350 microns, the aperture of the back surface is 70-100 microns, and silver cluster particles with the particle size of 300-400 nm are arranged on the surface and inside of the membrane.
The contact angle of the oil-water separation membrane obtained in the step 3) to 1, 2-dichloroethane is 150 degrees, after silver cluster particles are loaded by a reduction method, the roughness of the membrane surface is increased, the surface energy of silver is high, the hydrophilicity is stronger, the underwater oleophobic property of the material is improved, and the contact angle of the membrane obtained in the step 5) to 1, 2-dichloroethane is 158 degrees. Meanwhile, different types of oils including n-hexane, petroleum ether, animal oil, vegetable oil, diesel oil, gasoline, silicone oil, kerosene and crude oil are tested, contact angles are all larger than 150 degrees, and the underwater super-oleophobic property of the net film has universality.
The oil-water separation mesh membrane obtained in example 4 is sandwiched between glass tubes, a mixture (volume ratio 1: 2) of petroleum ether and water is poured onto the oil-water separation membrane through an upper feeding glass tube, water flows out from the lower part after passing through the oil-water separation membrane, and simultaneously the petroleum ether is blocked at the upper end of the oil-water separation membrane, so that separated petroleum ether is obtained, and the purpose of oil-water separation is achieved. And measuring the residual content of the crude oil in the separated water sample by using an infrared oil tester, wherein the residual content of the crude oil reaches a trace amount, and the separation efficiency is over 99 percent. Can be used normally after being separated twenty times.
An antibacterial experiment was performed on the oil-water separation membrane obtained in example 4, and the membrane which is not loaded with silver cluster particles and is obtained in step 3) and the membrane which is loaded with silver cluster particles and is obtained in step 5) were subjected to an antibacterial experiment by a bacteriostatic ring method and a film pasting method, and the antibacterial effect was evaluated from two aspects of qualitative and quantitative. The bacteriostatic loop method comprises cutting the membranes obtained in steps 3) and 5) into 2cm × 2cm, placing in the center of a plate with bacteria culture medium, covering, and culturing at 37 deg.C for 48 h. The membrane obtained in the step 3) has no inhibition zone to escherichia coli and staphylococcus aureus. The inhibition zone of the membrane obtained in the step 5) on escherichia coli is 2.05 +/-0.1 mm, and the inhibition zone on staphylococcus aureus is 1.76 +/-0.2 mm. The film sticking method is to use a film with a concentration of 5.0X 105～10.0×105The cfu/mL bacterial liquid diluent contacts an oil-water separation membrane, and the membrane is cultured for 24h under the conditions of 37 ℃ and relative humidity of more than 90%. Adding eluent to wash the sample, inoculating the sample in nutrient agar culture medium, culturing at 37 deg.C for 24h, and counting viable bacteria according to GB/T4789.2-2003 "determination of total number of bacterial colonies for food hygiene microorganism test". The antibacterial rate is calculated by comparing the number of colonies of the prepared membrane with that of the blank membrane. Through three groups of parallel tests, the film antibacterial rate of the silver cluster particle-free film obtained in the step 3) is 0, the antibacterial rate of the silver cluster particle-loaded film obtained in the step 5) to escherichia coli is 100%, and the antibacterial rate to staphylococcus aureus is 99.0%.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. A preparation method of an oil-water separation membrane with underwater super oleophobic property and antibacterial property is characterized by comprising the following steps:
1) dissolving sodium alginate in water to prepare a sodium alginate aqueous solution, and then coating the sodium alginate aqueous solution to control the film thickness to be 20-200 mu m;
2) screening water-soluble inorganic salt with the particle size of 20-500 mu m on the surface of the sodium alginate film obtained in the step 1) by using a screen to obtain a mixed film, and controlling the mass ratio of the sodium alginate to the water-soluble inorganic salt to be 1: (0.1-2);
3) immediately placing the mixed membrane obtained in the step 2) in a cross-linking agent aqueous solution for ultrasonic oscillation for 30-180 s, then soaking in the cross-linking agent aqueous solution to fully cross-link the membrane, and then cleaning with deionized water to obtain the sodium alginate porous membrane, wherein the cross-linking agent is any one or a mixture of more of zinc chloride, barium chloride, ferric chloride, aluminum chloride, calcium dihydrogen phosphate, calcium nitrate and hydrochloric acid;
4) soaking the sodium alginate porous membrane obtained in the step 3) in a soluble silver salt aqueous solution, taking out and then washing with deionized water;
5) and (3) soaking the porous membrane obtained in the step 4) in a reducing agent water solution, taking out the porous membrane, and washing the porous membrane with deionized water to obtain the porous membrane.
2. The method according to claim 1, wherein the water-soluble inorganic salt in step 2) is any one of sodium salt, potassium salt, and ammonium salt, or a mixture of two or more thereof.
3. The method according to claim 2, wherein the water-soluble inorganic salt is any one of sodium chloride, sodium sulfate, sodium carbonate, sodium nitrate, potassium chloride, potassium sulfate, and potassium carbonate, or a mixture of two or more thereof.
4. The preparation method according to claim 1 or 2, wherein the mass concentration of the aqueous solution of the crosslinking agent in the step 3) is 0.01 to 10 wt%.
5. The method according to claim 1 or 2, wherein the soluble silver salt in step 4) is silver nitrate.
6. The method according to claim 5, wherein the concentration of the soluble silver salt aqueous solution in the step 4) is 0.05 to 0.5 mol/L.
7. The method according to claim 1 or 2, wherein the reducing agent in step 5) is any one or a mixture of two or more of tyrosine, ascorbic acid, sodium borohydride and sodium hypophosphite.
8. The method according to claim 7, wherein the concentration of the aqueous solution of the reducing agent in the step 5) is 0.05 to 0.5 mol/L.
9. The preparation method according to claim 1 or 2, wherein the mass concentration of the sodium alginate aqueous solution in the step 1) is 0.5-10 wt%.
10. The preparation method according to claim 1 or 2, wherein the soaking time in the steps 3), 4) and 5) is 1-12 h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810144838.6A CN108273397B (en) | 2018-02-12 | 2018-02-12 | Preparation method of oil-water separation membrane with underwater super-oleophobic property and antibacterial property |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810144838.6A CN108273397B (en) | 2018-02-12 | 2018-02-12 | Preparation method of oil-water separation membrane with underwater super-oleophobic property and antibacterial property |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108273397A CN108273397A (en) | 2018-07-13 |
| CN108273397B true CN108273397B (en) | 2020-12-29 |
Family
ID=62808469
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810144838.6A Active CN108273397B (en) | 2018-02-12 | 2018-02-12 | Preparation method of oil-water separation membrane with underwater super-oleophobic property and antibacterial property |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108273397B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109794172B (en) * | 2019-01-25 | 2021-05-14 | 广东省医疗器械研究所 | Preparation method of antibacterial hollow fiber membrane for blood purification |
| CN114797485B (en) * | 2021-01-27 | 2023-03-10 | 中国科学院宁波材料技术与工程研究所 | Aerogel membrane for oil-water separation and heavy metal ion adsorption and preparation method and application thereof |
| CN114682099B (en) * | 2022-03-25 | 2022-12-09 | 湖北大学 | Preparation method and application of Janus film material for realizing oil-water on-demand separation |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103446898A (en) * | 2013-09-13 | 2013-12-18 | 天津工业大学 | Alginate-base organic-inorganic composite hydrogel filtering membrane and preparation method thereof |
| CN103446897A (en) * | 2013-09-13 | 2013-12-18 | 天津工业大学 | Chemical and ionic cross-linked alginate hydrogel flat membrane for filtration and preparation method thereof |
| CN103585788A (en) * | 2013-11-18 | 2014-02-19 | 天津理工大学 | Preparation method of super-hydrophilic oleophobic net film and application thereof in oil water separation |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2850442A1 (en) * | 2011-09-28 | 2013-04-04 | King Abdullah University Of Science And Technology | Grafted membranes and substrates having surfaces with switchable superoleophilicity and superoleophobicity and applications thereof |
-
2018
- 2018-02-12 CN CN201810144838.6A patent/CN108273397B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103446898A (en) * | 2013-09-13 | 2013-12-18 | 天津工业大学 | Alginate-base organic-inorganic composite hydrogel filtering membrane and preparation method thereof |
| CN103446897A (en) * | 2013-09-13 | 2013-12-18 | 天津工业大学 | Chemical and ionic cross-linked alginate hydrogel flat membrane for filtration and preparation method thereof |
| CN103585788A (en) * | 2013-11-18 | 2014-02-19 | 天津理工大学 | Preparation method of super-hydrophilic oleophobic net film and application thereof in oil water separation |
Non-Patent Citations (1)
| Title |
|---|
| 高疏油超亲水材料的制备及其在油水分离中的应用;姬悄悄;《中国优秀硕士学位论文全文数据库》;中国学术期刊（光盘版）电子杂志社;20150315(第3期);第34页第1段 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108273397A (en) | 2018-07-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108273397B (en) | Preparation method of oil-water separation membrane with underwater super-oleophobic property and antibacterial property | |
| CN108905296B (en) | Preparation method of biodegradable double-network oil-water separation net film with high stability | |
| You et al. | Direct coating of a DKGM hydrogel on glass fabric for multifunctional oil-water separation in harsh environments | |
| Dai et al. | Oil/water interfaces of guar gum-based biopolymer hydrogels and application to their separation | |
| Zhu et al. | Durability evaluation of superhydrophobic copper foams for long-term oil-water separation | |
| CN107722343B (en) | Preparation method of super-hydrophobic melamine sponge modified by dopamine and carbon nano tubes | |
| CN108421421B (en) | Fabric mesh with underwater super-oleophobic composite coating and preparation method thereof | |
| CN104562709A (en) | Preparation method of durable super-hydrophobic fabric | |
| CN107080975A (en) | The preparation method of oil-water separation mesh film with superhydrophilic superoleophobic property | |
| CN105568330B (en) | A kind of preparation method of base steel antiscale superficial layer | |
| CN114073897B (en) | Preparation method of nanofiber filtering membrane modified by zinc oxide nanowires | |
| CN109011701B (en) | Oil-water separation material with pH responsiveness and preparation method and application thereof | |
| CN111663330B (en) | Plant tannin mediated super-hydrophobic cellulose material and preparation method and application thereof | |
| CN104841287A (en) | Preparing method for multifunctional graded oil-water separation composite film material | |
| CN111530126A (en) | Preparation method and application of super-hydrophobic foam iron | |
| CN112029146B (en) | Protein particle-based super-hydrophobic coating and preparation method thereof | |
| CN112755795B (en) | Anti-wetting and anti-pollution amphiphobic membrane for membrane distillation process and preparation method and application thereof | |
| CN108978200A (en) | A kind of super-hydrophobic and perfusion lubricating fluid smooth type woven fabric preparation method for anti-pollution and freezing | |
| CN110791785B (en) | Electrodeposition layer-lyophobic-super-slippery triple film with composite anticorrosion function and preparation method and application thereof | |
| CN111171717B (en) | Environment-friendly bio-based organic silicon epoxy/nano silver composite coating, preparation method and application | |
| CN105061798A (en) | Super-hydrophobic LLDPE (linear low density polyethylene) film and preparation method thereof | |
| CN110029380B (en) | Preparation method of super-hydrophobic zinc-iron composite coating on surface of carbon steel | |
| CN114452838B (en) | Asymmetric hydrophilic/hydrophobic composite fiber membrane and preparation method thereof | |
| CN114891400A (en) | Nano-cellulose composite antifouling coating and preparation method thereof | |
| CN108970421A (en) | A kind of carbon nanotube-cellulose acetate film and preparation method efficiently to desalinize seawater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right | ||
| PE01 | Entry into force of the registration of the contract for pledge of patent right |
Denomination of invention: A preparation method of oil-water separation membrane with underwater super oleophobic and antibacterial properties Effective date of registration: 20211216 Granted publication date: 20201229 Pledgee: Yantai financing guarantee Group Co.,Ltd. Pledgor: LUDONG University Registration number: Y2021980015152 |
|
| PC01 | Cancellation of the registration of the contract for pledge of patent right | ||
| PC01 | Cancellation of the registration of the contract for pledge of patent right |
Date of cancellation: 20220317 Granted publication date: 20201229 Pledgee: Yantai financing guarantee Group Co.,Ltd. Pledgor: LUDONG University Registration number: Y2021980015152 |