CN112675576B - Oil-water separation membrane and preparation method and application thereof - Google Patents
Oil-water separation membrane and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an oil-water separation membrane and a preparation method and application thereof, wherein the preparation method comprises the following steps: uniformly mixing an alkaline substance, an oxidant and water to obtain an aqueous solution I, wherein the mass fraction of the alkaline substance in the aqueous solution I is 3-10%, and the mass fraction of the oxidant in the aqueous solution I is 1-5%; immersing the stainless steel mesh membrane in the aqueous solution I for 12-36 h, taking out the stainless steel mesh membrane, and washing with ultrapure water; and immersing the obtained stainless steel mesh membrane in the aqueous solution II for 2-12 h, taking out the stainless steel mesh membrane, and drying by using nitrogen to obtain the oil-water separation membrane. The oil-water separation membrane prepared by the preparation method has super-hydrophilic and underwater super-oleophobic performances, the retention rate of oil content is as high as 99.9%, and the hydrophilic and oleophobic performances and the friction resistance of the oil-water separation membrane are not affected after acid-base corrosion.
Description
Technical Field
The invention belongs to the technical field of oil-water separation, and particularly relates to an oil-water separation membrane and a preparation method and application thereof.
Background
Oily wastewater is one of the environmental pollutions troubling researchers in the current society, and improper treatment can cause the problems of water body deterioration, fish resource yield reduction, toxin enrichment, resource waste and the like. The traditional oil-water separation method comprises the following steps: chemical, biological, physicochemical, biochemical methods. However, these methods have problems such as low efficiency, high cost, complicated process, secondary pollution, and the like, and cannot cope with oil-containing wastewater whose discharge amount is increasing. The oil-water separation net membrane is generally composed of a supporting substrate and a surface coating with special wettability, and is a separation membrane which utilizes the special wettability of the surface to realize specific passing of an oil phase or a water phase. The super-hydrophilic oil-water separation net membrane has the advantages of high flux, easiness in cleaning and the like in practical application because the specific passing phase of the super-hydrophilic oil-water separation net membrane is a water phase.
The surface hydrophilic layer stability of present common hydrophilicity oil water separation net is not enough, causes the decline of hydrophilicity because of factors such as friction, long-time placing or soaking in the use, leads to the entrapment rate decline of oil content and loses the oil water separation function, and the separation net that even part adopted organic polymer to modify releases little plastics or toxic chemical substance to the environment because of the organic matter decomposes. The oil-water separation membrane has the characteristics of high separation efficiency, low separation cost and environmental-friendly and pollution-free separation process, and the emergence of the oil-water separation membrane makes the low-cost treatment of oil-containing wastewater possible. However, most of the current oil-water separation membranes have the problems of poor durability and short service life, and the problems also become key problems for restricting the development and application of the oil-water separation net membrane. In contrast, the main research at present is to adopt a method of coating a high polymer by surface modification, and by coating the high polymer, a special wetting substance on the surface of a substrate is not easy to fall off, so that the oil-water separation membrane can bear a certain degree of mechanical friction. However, once the surface of the separation membrane is rubbed vigorously or for a long time, wettability is reduced, and the retention function is lost.
Disclosure of Invention
In order to solve the technical problems of short service life, low durability, high preparation cost, complex process, poor chemical stability, unfavorable industrial production and the like of the existing product, the invention aims to provide a preparation method of an oil-water separation membrane, which is simple and environment-friendly.
The oil-water separation membrane obtained by the preparation method has the properties of super-hydrophilicity and super-lipophobicity under water, has the advantages of durability, long service life, abrasion resistance, good thermal stability and easiness in regeneration, and can be practically applied to oil pollution prevention and oily water treatment processes in the industries of food, petrifaction and the like and oil pollution treatment of oceans.
The purpose of the invention is realized by the following technical scheme.
A preparation method of an oil-water separation membrane comprises the following steps:
1) uniformly mixing an alkaline substance, an oxidant and water to obtain an aqueous solution I, wherein the mass fraction of the alkaline substance in the aqueous solution I is 3-10%, and the mass fraction of the oxidant in the aqueous solution I is 1-5%, wherein the oxidant is one or a mixture of more of potassium chlorate, sodium chlorate, potassium perchlorate, sodium perchlorate, potassium hypochlorite, sodium hypochlorite, potassium bromate, sodium bromate, potassium hypobromite, sodium hypobromite, ammonium persulfate, sodium persulfate, potassium persulfate and hydrogen peroxide, and the alkaline substance is one or a mixture of more of sodium hydroxide, potassium hydroxide and ammonia water;
2) immersing the stainless steel mesh membrane in the aqueous solution I for 12-36 h, taking out the stainless steel mesh membrane, and washing with ultrapure water;
in the step 2), the stainless steel mesh film is immersed in the aqueous solution I at the temperature of 20-50 ℃.
In the step 2), before the stainless steel mesh membrane is immersed in the aqueous solution I, the stainless steel mesh membrane is sequentially subjected to ultrasonic treatment in acetone, absolute ethyl alcohol and ultrapure water, and is dried by nitrogen.
In the step 2), the mesh number of the stainless steel net film is 300-2500 meshes.
In the step 2), the stainless steel net film is of a plain weave structure or a twill weave structure.
3) Immersing the stainless steel mesh membrane obtained in the step 2) in an aqueous solution II for 2-12 h, taking out a stainless steel mesh membrane, and drying the stainless steel mesh membrane by using nitrogen to obtain an oil-water separation membrane, wherein the pH of the aqueous solution II is 1.5-3.0, the aqueous solution II is formed by mixing macromolecular organic acid, inorganic acid and water, the mass fraction of the macromolecular organic acid in the aqueous solution II is 1-5%, the macromolecular organic acid is humic acid, alginic acid, citric acid, hydroxycitric acid, dihydrocholine citrate, 2-acetyl triethyl citrate, gallic acid, gallotannic acid, theaflavin-3, 3' -digallic acid, di (p-methylbenzoyl) tartaric acid, di-p-toluoyl-D-tartaric acid, 2- (4-dibutylamino-2-hydroxybenzoyl), 1, 2-cyclohexanediamine L-tartrate, 4-nitrosalicylic acid, 2-phosphonobutane-1, 2, 4-tricarboxylic acid, 1, 8-dihydroxynaphthalene-3, 6-disulfonic acid, pamoic acid, ascorbic acid, hyaluronic acid, deoxycholic acid, diponic acid, 2-acrylamide-2-methylpropanesulfonic acid, diethylenetriamine pentamethylenephosphonic acid, the inorganic acid is one or a mixture of more of sodium hexametaphosphate, sodium tripolyphosphate, phytic acid, ethylenediamine tetramethylene phosphonic acid, aminotrimethylene phosphonic acid, 5, 3-triphosphonyl valeric acid, 4-diphosphonic acid-1, 7-pimelic acid, 1-amino-ethylidene-1, 1-diphosphonic acid and 1-hydroxy-ethylidene-1, 1-diphosphonic acid, and the inorganic acid is hydrochloric acid, phosphoric acid or sulfuric acid.
In the step 3), the mass fraction of the inorganic acid in the aqueous solution II is 5-15%
In the step 3), the stainless steel mesh film obtained in the step 2) is immersed in the aqueous solution II at the temperature of 20-50 ℃.
The oil-water separation membrane obtained by the preparation method.
The application of the preparation method in super-hydrophilicity.
The preparation method is applied to underwater super oleophobic property.
Compared with the prior art, the invention has the following beneficial effects:
1. the oil-water separation membrane prepared by the preparation method has better super-hydrophilic and underwater super-oleophobic performances, the retention rate of oil content is as high as 99.9%, and the super-hydrophilic and underwater super-oleophobic performances are not affected after acid-base corrosion, and the oil-water separation membrane is friction-resistant. After the stainless steel mesh membrane is soaked in the aqueous solution I containing the oxidant, the surface of the stainless steel mesh membrane is uniformly oxidized and is easily chelated with the polybasic acid of the aqueous solution II to be modified, and the formed structure has uniform and stable properties;
2. the super-hydrophilic and underwater super-oleophobic performances and the durability of the stainless steel net film can be regulated and controlled by parameters such as the composition of an aqueous solution, the concentration, the immersion time, the immersion temperature and the like;
3. the preparation method is simple, the preparation conditions are mild, the application range is wide, the amplification and the popularization are easy, the durability is good, the practical application value is high, and the stainless steel mesh membrane can be recycled.
Drawings
FIG. 1 is a scanning electron micrograph of the front 300 times of an unmodified stainless steel mesh film (example 1);
FIG. 2 is a scanning electron micrograph of the front surface of an unmodified stainless steel mesh film at 10k times (example 1);
FIG. 3 is a scanning electron micrograph of the front surface of the oil-water separation membrane obtained in example 1 magnified 300 times;
FIG. 4 is a scanning electron micrograph of the front surface of the oil-water separation membrane obtained in example 1, the front surface being 10k times;
FIG. 5 is the contact angle of the unmodified stainless steel mesh membrane surface with water (example 1);
FIG. 6 shows the contact angle of the unmodified stainless steel mesh membrane surface with carbon tetrachloride under water (example 1);
FIG. 7 is a contact angle of the surface of the oil-water separation membrane obtained in example 1 with water;
FIG. 8 is a view showing a contact angle between the surface of the oil-water separation membrane obtained in example 1 and carbon tetrachloride under water.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples.
The purity and manufacturer of the drug products referred to in the following examples are as follows:
ethanol (analytical grade), acetone (analytical grade), carbon tetrachloride (analytical grade), n-hexane (analytical grade), hydrochloric acid (analytical grade), sulfuric acid (analytical grade), nitric acid (analytical grade), phosphoric acid (analytical grade), ammonia water (chemical grade), ammonium persulfate (analytical grade) and the like are purchased from Tianjin Jiangtian reagent company; macromolecular organic acids such as tannic acid (analytically pure) are purchased from Shanghai Allantin reagent company; the rapeseed oil is goldfish transgenic rapeseed oil; crude oil and 0#The diesel oil is obtained from oil and gas group of China.
The test methods involved in the examples below were as follows:
detection of contact angle: a hanging drop mode of a Dataphysics OCA15EC video optical contact angle measuring instrument is adopted to test the water contact angle and the underwater carbon tetrachloride liquid drop contact angle, the volume of the carbon tetrachloride liquid drop in the test is 2 mu L, and the stable morphology and the contact angle value (oil drop contact angle) of the carbon tetrachloride liquid drop are recorded after the carbon tetrachloride liquid drop contacts a stainless steel mesh film for 10 seconds.
Detection of flux and oil rejection: the effective test area of the sample to be tested is 8cm2The tested oil-water mixed liquid is a mixed liquid of normal hexane and water (the volume ratio of normal hexane to water is 1:1), a mixed liquid of engine oil and water (the volume ratio of engine oil to water is 1:1), a mixed liquid of diesel oil and water (the volume ratio of diesel oil to water is 1:1), a mixed liquid of rapeseed oil and water (the volume ratio of rapeseed oil to water is 1:1) or crude oilAnd water (crude oil to water volume ratio 1: 1). The method for testing the retention rate of the oil comprises the following steps: and pouring the oil-water mixed solution onto a sample to be detected for separation, and dividing the mass fraction difference of the oil in the solution before and after separation by the mass fraction of the oil in the solution before separation. And determining the mass fraction of the oil in the separated solution by an infrared oil detector.
Rub test (test of rub resistance): adopt the self-control friction test platform in laboratory, level be fixed in the laboratory bench with abrasive paper, place the stainless steel net membrane on the abrasive paper surface, at the upper surface of stainless steel net membrane fixed 1 Kg's weight, horizontal pulling weight 20cm, the weight drives the stainless steel nethike embrane and removes on abrasive paper. The procedure was repeated 60 times, and then the stainless steel mesh membrane was tested for flux and oil rejection.
Acid-base salt soaking experiment (test of acid-base salt resistance): an aqueous solution having a pH of 1, an aqueous solution having a pH of 14, artificial seawater, and ultrapure water were prepared and used as soaking solutions. Wherein, the pH value of the aqueous solution of 1 is adjusted by hydrochloric acid; aqueous solution at pH 14 was adjusted with sodium hydroxide; the artificial seawater is prepared according to Mocledon artificial seawater standard. After the sample is soaked in the four soaking solutions for 16 days (24 hours per day), a water contact angle, a contact angle of an underwater carbon tetrachloride liquid drop, flux of a mixed solution of diesel oil and water and an oil content retention rate are taken out for testing.
Long-term seawater corrosion test (test of long-term seawater corrosion resistance): preparing artificial seawater according to Mocledon artificial seawater standard, soaking a sample in the artificial seawater at 35 ℃ for 120 days (24 hours per day), taking out the sample, and testing the water contact angle of the sample, the contact angle of underwater carbon tetrachloride liquid drops, the flux of a mixed solution of diesel oil and water and the retention rate of oil content.
Example 1
A preparation method of an oil-water separation membrane comprises the following steps:
1) uniformly mixing an alkaline substance, an oxidant and water to obtain an aqueous solution I, wherein the oxidant is a mixture of potassium chlorate, sodium chlorate, potassium perchlorate, sodium perchlorate and ammonium persulfate, and the alkaline substance is sodium hydroxide; the mass fraction of the alkaline substance in the aqueous solution I is 8 percent, and the mass fraction of the oxidant in the aqueous solution I is 2 percent of ammonium persulfate, 0.2 percent of potassium chlorate, 0.1 percent of sodium chlorate, 1 percent of potassium perchlorate and 0.5 percent of sodium perchlorate.
2) Preparing a stainless steel net film with 800 meshes, wherein the stainless steel net film is of a twill weave structure. Sequentially subjecting the stainless steel mesh membrane to ultrasonic treatment in acetone, anhydrous ethanol and ultrapure water for 10min, and blowing with nitrogen gas. Immersing the stainless steel net film in an aqueous solution I at 30 ℃ for 12h, taking out the stainless steel net film, and washing with ultrapure water;
3) immersing the stainless steel mesh membrane obtained in the step 2) in an aqueous solution II at 30 ℃ for 8h, taking out the stainless steel mesh membrane, and drying by using nitrogen to obtain the oil-water separation membrane, wherein the pH of the aqueous solution II is 2.3, and the aqueous solution II is formed by mixing macromolecular organic acid, inorganic acid (for adjusting the pH) and water. The macromolecular organic acid is a mixture of humic acid, gallotannic acid, diethylenetriamine pentamethylene phosphonic acid, sodium hexametaphosphate, sodium tripolyphosphate and phytic acid, and the inorganic acid is hydrochloric acid. The mass fraction of the inorganic acid in the aqueous solution II is 10%, and the mass fraction of the macromolecular organic acid in the aqueous solution II is 2% of gallic acid, 1% of humic acid, 0.2% of diethylenetriamine pentamethylene phosphonic acid, 0.5% of sodium hexametaphosphate, 0.1% of sodium tripolyphosphate and 1% of phytic acid in sequence.
According to the characterization, after the ultrasonic treatment is carried out on acetone, absolute ethyl alcohol and ultrapure water for 10min respectively (an unmodified stainless steel net film), the surface of the stainless steel net film is smooth (shown in figure 1), a rough structure is not seen after the amplification by 1 ten thousand times (shown in figure 2), a nano-cluster structure is present in gaps of the oil-water separation film (the modified stainless steel net film) (shown in figure 3), and a rough corrugated structure is obviously seen after the amplification by 1 ten thousand times (shown in figure 4).
The surface of the unmodified stainless steel mesh film was tested to have a water contact angle of 109 ° (shown in fig. 5) and an underwater oil drop contact angle of 112 ° (shown in fig. 6). The surface water contact angle of the oil-water separation membrane obtained in example 1 was 0 ° (shown in fig. 7), and the underwater oil drop contact angle was 159 ° (shown in fig. 8).
The oil-water separation experiment showed that the flux of the mixed solution of n-hexane and water in the oil-water separation membrane obtained in example 1 was 48k L.m-2.h-1The flux of the mixed liquid of the oil and the water is 44k L.m-2.h-1Opening of mixed liquid of diesel oil and waterThe amount is 38k L.m-2.h-1The flux of the mixed liquid of the rapeseed oil and the water is 40k L.m-2.h-1The flux of the mixed liquid of crude oil and water was 49k L.m-2.h-1The oil retention rate reaches 99.8%.
After the rubbing experiment, the surface water contact angle of the oil-water separation membrane obtained in example 1 was still 0 °, and the underwater oil drop contact angle was 112 °. The flux of the mixed liquid of the diesel oil and the water is 30k L.m-2.h-1The oil retention rate still reaches 99.8%.
After the acid soaking experiment, the surface water contact angle of the oil-water separation membrane obtained in example 1 is still 0 degrees, and the underwater oil drop contact angle is still 147 degrees. The flux of the mixed liquid of the diesel oil and the water is 35k L.m-2.h-1The oil retention rate still reaches 99.8%.
After the alkali soaking experiment, the surface water contact angle of the oil-water separation membrane obtained in example 1 is still 0 °, and the underwater oil drop contact angle is still 148 °. The flux of the mixed liquid of the diesel oil and the water is 36k L.m-2.h-1The oil retention rate still reaches 99.7%.
After long-term seawater corrosion test, the surface water contact angle of the oil-water separation membrane obtained in example 1 is still 0 °, and the underwater oil drop contact angle is still 150 °. The flux of the mixed solution of the diesel oil and the water is 36k L.m-2.h-1The oil retention rate still reaches 99.7%.
Before and after the soaking of the ultrapure water, the water contact angle, the underwater oil drop contact angle, the flux of the mixed liquid of the diesel oil and the water and the interception rate of the oil are not changed.
Example 2
A preparation method of an oil-water separation membrane comprises the following steps:
1) uniformly mixing an alkaline substance, an oxidant and water to obtain an aqueous solution I, wherein the oxidant is a mixture of potassium hypochlorite, sodium hypochlorite, ammonium persulfate and sodium persulfate, the alkaline substance is a mixture of sodium hydroxide and potassium hydroxide, the mass fractions of the alkaline substance in the aqueous solution I are 5% of potassium hydroxide and 3% of sodium hydroxide in sequence, and the mass fractions of the oxidant in the aqueous solution I are 1% of ammonium persulfate, 1% of sodium persulfate, 2% of potassium hypochlorite and 0.5% of sodium hypochlorite in sequence.
2) Preparing a stainless steel net film with 700 meshes, wherein the stainless steel net film is of a twill weave structure. Sequentially placing the stainless steel mesh film in acetone, anhydrous ethanol and ultrapure water, respectively, performing ultrasonic treatment for 10min, and drying with nitrogen. Immersing the stainless steel mesh membrane in the aqueous solution I at 20 ℃ for 36h, taking out the stainless steel mesh membrane, and washing with ultrapure water;
3) immersing the stainless steel mesh membrane obtained in the step 2) in an aqueous solution II at 20 ℃ for 12h, taking out the stainless steel mesh membrane, and drying by using nitrogen to obtain the oil-water separation membrane, wherein the pH value of the aqueous solution II is 1.5, and the aqueous solution II is formed by mixing macromolecular organic acid, inorganic acid and water. The macromolecular organic acid is a mixture of humic acid, citric acid, hydroxycitric acid, choline dihydrogen citrate, 2-triethyl acetylcitrate and gallotannic acid, the inorganic acid is sulfuric acid, the mass fractions of the macromolecular organic acid in the aqueous solution II are 1% of gallic acid and tannic acid, 1% of humic acid, 0.1% of citric acid, 0.1% of hydroxycitric acid, 0.1% of choline dihydrogen citrate and 0.1% of 2-triethyl acetylcitrate in sequence, and the mass fraction of the inorganic acid in the aqueous solution II is 15%.
Through testing, the surface water contact angle of the unmodified stainless steel mesh film is 109 degrees, and the underwater oil drop contact angle is 112 degrees. The surface water contact angle of the oil-water separation membrane obtained in example 2 was 0 °, and the underwater oil drop contact angle was 150 °.
The results of the oil-water separation experiments showed that the flux of the mixed solution of n-hexane and water in the oil-water separation membrane obtained in example 2 was 54k L.m-2.h-1The flux of the mixed liquid of the oil and the water is 48k L.m-2.h-1The flux of the mixed liquid of diesel oil and water is 43k L.m-2.h-1The flux of the mixed liquid of the rapeseed oil and the water is 45k L.m-2.h-1The flux of the mixed liquid of crude oil and water is 52k L.m-2.h-1The oil retention rate is higher than 99.8%.
After the rubbing experiment, the surface water contact angle of the oil-water separation membrane obtained in example 2 was still 0 °, and the underwater oil drop contact angle was 109 °. The flux of the mixed liquid of the diesel oil and the water is 42k L.m-2.h-1Oil content ofThe retention rate still reaches 99.8 percent.
After the acid soaking experiment, the surface water contact angle of the oil-water separation membrane obtained in example 2 is still 0 °, and the underwater oil drop contact angle is still 149 °. The flux of the mixed liquid of diesel oil and water is 43k L.m-2.h-1The oil retention rate still reaches 99.8%.
After the alkali soaking experiment, the surface water contact angle of the oil-water separation membrane obtained in example 2 is still 0 °, and the underwater oil drop contact angle is still 147 °. The flux of the mixed liquid of the diesel oil and the water is 44k L.m-2.h-1The oil retention rate still reaches 99.8%.
After long-term seawater corrosion test, the surface water contact angle of the oil-water separation membrane obtained in example 2 is still 0 °, and the underwater oil drop contact angle is still 150 °. The flux of the mixed solution of diesel oil and water is 43k L.m-2.h-1The oil retention rate still reaches 99.7%.
Before and after the soaking of the ultrapure water, the water contact angle, the underwater oil drop contact angle, the flux of the mixed liquid of the diesel oil and the water and the interception rate of the oil are not changed.
Example 3
A preparation method of an oil-water separation membrane comprises the following steps:
1) uniformly mixing an alkaline substance, an oxidant and water to obtain an aqueous solution I, wherein the oxidant is a mixture of potassium hypochlorite, sodium hypochlorite, ammonium persulfate, sodium persulfate and potassium persulfate, the alkaline substance is a mixture of sodium hydroxide and ammonia water, the mass fraction of the alkaline substance in the aqueous solution I is 4% of ammonia water and 4% of sodium hydroxide, and the mass fraction of the oxidant in the aqueous solution I is 1% of sodium persulfate, 0.5% of potassium persulfate, 1% of ammonium persulfate, 0.5% of potassium hypochlorite and 0.5% of sodium hypochlorite.
2) Preparing a stainless steel net film with the mesh number of 1400, wherein the stainless steel net film is of a twill weave structure. Sequentially subjecting the stainless steel mesh membrane to ultrasonic treatment in acetone, anhydrous ethanol and ultrapure water for 10min, and blowing with nitrogen gas. Immersing the stainless steel mesh membrane in the 40 ℃ aqueous solution I for 18h, taking out the stainless steel mesh membrane, and washing with ultrapure water;
3) immersing the stainless steel mesh membrane obtained in the step 2) in an aqueous solution II at 30 ℃ for 10h, taking out the stainless steel mesh membrane, and drying by using nitrogen to obtain the oil-water separation membrane, wherein the pH value of the aqueous solution II is 3, and the aqueous solution II is formed by mixing macromolecular organic acid, inorganic acid and water. The macromolecular organic acid is humic acid, gallotannic acid, di-p-toluoyl-D-tartaric acid, 2- (4-dibutylamino-2-hydroxybenzoyl), 1, 2-cyclohexanediamine L-tartrate, a mixture of 4-nitrosalicylic acid and hyaluronic acid, the inorganic acid is phosphoric acid, the mass fraction of the macromolecular organic acid in the aqueous solution II is 1% of gallic acid, 1% of humic acid, 1% of hyaluronic acid, 0.5% of di-p-toluoyl-D-tartaric acid, 0.5% of 2- (4-dibutylamino-2-hydroxybenzoyl), 0.1% of 1, 2-cyclohexanediamine L-tartrate and 0.1% of 4-nitrosalicylic acid, and the mass fraction of the inorganic acid in the aqueous solution II is 5%.
Through testing, the surface water contact angle of the unmodified stainless steel mesh film is 109 degrees, and the underwater oil drop contact angle is 112 degrees. The surface water contact angle of the oil-water separation membrane obtained in this example was 0 °, and the underwater oil drop contact angle was 157 °.
The oil-water separation experiment result showed that the flux of the mixed solution of n-hexane and water in the oil-water separation membrane obtained in example 3 was 36k L.m-2.h-1The flux of the mixed liquid of the engine oil and the water is 38k L.m-2.h-1The flux of the mixed liquid of diesel oil and water is 35k L.m-2.h-1The flux of the mixed liquid of the rapeseed oil and the water is 34k L.m-2.h-1Flux of mixed liquid of crude oil and water was 40k L.m-2.h-1The oil retention rate is higher than 99.9%.
After a friction experiment, the surface water contact angle of the oil-water separation membrane obtained in example 3 is still 0 °, and the underwater oil drop contact angle is 112 °. The flux of the mixed solution of the diesel oil and the water is 29k L.m-2.h-1The oil retention rate still reaches 99.8%.
After the acid soaking experiment, the surface water contact angle of the oil-water separation membrane obtained in example 3 is still 0 °, and the underwater oil drop contact angle is still 152 °. The flux of the mixed liquid of the diesel oil and the water is 34k L.m-2.h-1The oil retention rate still reaches 99.8%.
After the alkali soaking experiment, the surface water contact angle of the oil-water separation membrane obtained in example 3 is still 0 °, and the underwater oil drop contact angle is still 153 °. The flux of the mixed liquid of the diesel oil and the water is 35k L.m-2.h-1The oil retention rate still reaches 99.7%.
After long-term seawater corrosion test, the surface water contact angle of the oil-water separation membrane obtained in example 3 is still 0 °, and the underwater oil drop contact angle is still 155 °. The flux of the mixed liquid of the diesel oil and the water is 35k L.m-2.h-1The oil retention rate still reaches 99.7%.
Before and after the soaking of the ultrapure water, the water contact angle, the underwater oil drop contact angle, the flux of the mixed liquid of the diesel oil and the water and the interception rate of the oil are not changed.
Example 4
A preparation method of an oil-water separation membrane comprises the following steps:
1) uniformly mixing an alkaline substance, an oxidant and water to obtain an aqueous solution I, wherein the oxidant is a mixture of potassium bromate, sodium bromate, potassium hypobromite, sodium hypobromite and sodium persulfate, the alkaline substance is ammonia water, the mass fraction of the alkaline substance in the aqueous solution I is 6%, and the mass fraction of the oxidant in the aqueous solution I is 2% of sodium persulfate, 0.5% of potassium bromate, 0.1% of sodium bromate, 1% of potassium hypobromite and 1% of sodium hypobromite;
2) preparing a stainless steel net film with the mesh number of 600 meshes, wherein the stainless steel net film is of a twill weave structure. Sequentially subjecting the stainless steel mesh membrane to ultrasonic treatment in acetone, anhydrous ethanol and ultrapure water for 10min, and blowing with nitrogen gas. Immersing the stainless steel mesh membrane in the aqueous solution I at the temperature of 45 ℃ for 20h, taking out the stainless steel mesh membrane, and washing with ultrapure water;
3) immersing the stainless steel mesh membrane obtained in the step 2) in a 35 ℃ water solution II for 12h, taking out the stainless steel mesh membrane, and drying by using nitrogen to obtain the oil-water separation membrane, wherein the pH value of the water solution II is 2.2, and the water solution II is formed by mixing macromolecular organic acid, inorganic acid and water. The macromolecular organic acid is a mixture of gallic acid, gallotannic acid, theaflavin-3, 3 '-digallic acid, diethylenetriamine pentamethylene phosphonic acid and sodium hexametaphosphate, the inorganic acid is phosphoric acid, the mass fraction of the macromolecular organic acid in the aqueous solution II is 1% of gallic acid tannic acid, 0.5% of gallic acid, 1% of theaflavin-3, 3' -digallic acid, 1% of diethylenetriamine pentamethylene phosphonic acid and 0.5% of sodium hexametaphosphate, and the mass fraction of the inorganic acid in the aqueous solution II is 12%.
Through testing, the surface water contact angle of the unmodified stainless steel mesh film is 109 degrees, and the underwater oil drop contact angle is 112 degrees. The water contact angle of the oil-water separation membrane obtained in this example was 0 °, and the contact angle of an underwater oil drop was 159 °.
The results of the oil-water separation experiments showed that the flux of the mixed solution of n-hexane and water in the oil-water separation membrane obtained in example 4 was 49k L.m-2.h-1The flux of the mixed liquid of the oil and the water was 46k L.m-2.h-1The flux of the mixed solution of diesel oil and water is 40k L.m-2.h-1The flux of the mixed liquid of the rapeseed oil and the water is 41k L.m-2.h-1The flux of the mixed liquid of crude oil and water is 48k L.m-2.h-1The oil retention rate is higher than 99.9%.
After the rubbing experiment, the surface water contact angle of the oil-water separation membrane obtained in example 4 was still 0 °, and the underwater oil drop contact angle was 110 °. The flux of the mixed solution of the diesel oil and the water is 36k L.m-2.h-1The oil retention rate still reaches 99.8%.
After the acid soaking experiment, the surface water contact angle of the oil-water separation membrane obtained in example 4 is still 0 °, and the underwater oil drop contact angle is still 156 °. The flux of the mixed liquid of the diesel oil and the water is 40k L.m-2.h-1The oil retention rate still reaches 99.8%.
After the alkali immersion experiment, the surface water contact angle of the oil-water separation membrane obtained in example 4 is still 0 °, and the underwater oil drop contact angle is still 155 °. The flux of the mixed liquid of the diesel oil and the water is 41k L.m-2.h-1The oil retention rate still reaches 99.7%.
After long-term seawater corrosion test, the surface water contact angle of the oil-water separation membrane obtained in example 4 is still 0 °, and the underwater oil drop contact angle is still 157 °. The flux of the mixed liquid of the diesel oil and the water is 40k L.m-2.h-1The oil retention rate still reaches 99.7 percent
Before and after the soaking of the ultrapure water, the water contact angle, the underwater oil drop contact angle, the flux of the mixed liquid of the diesel oil and the water and the interception rate of the oil are not changed.
Example 5
A preparation method of an oil-water separation membrane comprises the following steps:
1) uniformly mixing an alkaline substance, an oxidant and water to obtain an aqueous solution I, wherein the oxidant is a mixture of potassium hypochlorite, sodium persulfate and potassium persulfate, the alkaline substance is ammonia water, the mass fraction of the alkaline substance in the aqueous solution I is 7%, and the mass fraction of the oxidant in the aqueous solution I is 3% of sodium persulfate, 0.5% of potassium persulfate, 0.1% of potassium hypochlorite and 0.5% of sodium hypochlorite;
2) preparing a stainless steel net film with the mesh number of 600 meshes, wherein the stainless steel net film is of a twill weave structure. Sequentially subjecting the stainless steel mesh membrane to ultrasonic treatment in acetone, anhydrous ethanol and ultrapure water for 10min, and blowing with nitrogen gas. Immersing the stainless steel net film in an aqueous solution I at 30 ℃ for 32h, taking out the stainless steel net film, and washing with ultrapure water;
3) immersing the stainless steel mesh membrane obtained in the step 2) in an aqueous solution II at 35 ℃ for 12h, taking out the stainless steel mesh membrane, and drying by using nitrogen to obtain the oil-water separation membrane, wherein the pH value of the aqueous solution II is 1.5, and the aqueous solution II is formed by mixing macromolecular organic acid, inorganic acid and water. The macromolecular organic acid is a mixture of alginic acid, citric acid, gallotannic acid, theaflavin-3, 3 '-digallic acid, di (p-methylbenzoyl) tartaric acid, pamoic acid and ascorbic acid, the inorganic acid is hydrochloric acid, the mass fraction of the macromolecular organic acid in the aqueous solution II is 1% of gallic acid tannic acid, 0.1% of theaflavin-3, 3' -digallic acid, 1% of alginic acid, 0.5% of citric acid, 1% of di (p-methylbenzoyl) tartaric acid, 0.1% of pamoic acid and 0.1% of ascorbic acid, and the mass fraction of the inorganic acid in the aqueous solution II is 15%.
Through testing, the water contact angle of the surface of the unmodified stainless steel mesh film is 109 degrees, and the contact angle of underwater oil drops is 112 degrees. The water contact angle of the oil-water separation membrane obtained in this example was 0 °, and the contact angle of an underwater oil drop was 159 °.
Oil-water separation experimental resultsIt was found that the flux of the mixed solution of n-hexane and water in the oil-water separation membrane obtained in example 5 was 49k L.m-2.h-1The flux of the mixed liquid of the oil and the water was 46k L.m-2.h-1The flux of the mixed solution of diesel oil and water is 40k L.m-2.h-1The flux of the mixed liquid of the rapeseed oil and the water is 41k L.m-2.h-1The flux of the mixed liquid of crude oil and water is 48k L.m-2.h-1The oil retention rate is higher than 99%.
After the rubbing experiment, the surface water contact angle of the oil-water separation membrane obtained in example 5 was still 0 °, and the underwater oil drop contact angle was 110 °. The flux of the mixed liquid of the diesel oil and the water is 34k L.m-2.h-1The oil retention rate still reaches 99.7%.
After the acid soaking experiment, the surface water contact angle of the oil-water separation membrane obtained in example 5 is still 0 degrees, and the underwater oil drop contact angle is still 157 degrees. The flux of the mixed liquid of the diesel oil and the water is 40k L.m-2.h-1The oil retention rate still reaches 99.8%.
After the alkali soaking experiment, the surface water contact angle of the oil-water separation membrane obtained in example 5 is still 0 °, and the underwater oil drop contact angle is still 155 °. The flux of the mixed solution of the diesel oil and the water is 40k L.m-2.h-1The oil retention rate still reaches 99.9%.
After long-term seawater corrosion test, the surface water contact angle of the oil-water separation membrane obtained in example 5 is still 0 °, and the underwater oil drop contact angle is still 157 °. The flux of the mixed liquid of the diesel oil and the water is 41k L.m-2.h-1The retention rate of oil content still reaches 99.9 percent
Before and after the soaking of the ultrapure water, the water contact angle, the underwater oil drop contact angle, the flux of the mixed liquid of the diesel oil and the water and the interception rate of the oil are not changed.
Example 6
A preparation method of an oil-water separation membrane comprises the following steps:
1) uniformly mixing an alkaline substance, an oxidant and water to obtain an aqueous solution I, wherein the oxidant is a mixture of potassium hypochlorite, sodium hypochlorite, ammonium persulfate and sodium persulfate, the alkaline substance is a mixture of sodium hydroxide and potassium hydroxide, the mass fractions of the alkaline substance in the aqueous solution I are 5% of potassium hydroxide and 3% of sodium hydroxide in sequence, and the mass fractions of the oxidant in the aqueous solution I are 1% of ammonium persulfate, 1% of sodium persulfate, 2% of potassium hypochlorite and 1% of sodium hypochlorite in sequence.
2) A stainless steel mesh film with 700 meshes is prepared, and the stainless steel mesh film is of a plain weave structure. Sequentially subjecting the stainless steel mesh membrane to ultrasonic treatment in acetone, anhydrous ethanol and ultrapure water for 10min, and blowing with nitrogen gas. Immersing the stainless steel mesh membrane in the aqueous solution I at 20 ℃ for 36h, taking out the stainless steel mesh membrane, and washing with ultrapure water;
3) immersing the stainless steel mesh membrane obtained in the step 2) in a 35 ℃ water solution II for 12h, taking out the stainless steel mesh membrane, and drying by using nitrogen to obtain the oil-water separation membrane, wherein the pH value of the water solution II is 2.2, and the water solution II is formed by mixing macromolecular organic acid, inorganic acid and water. The macromolecular organic acid is a mixture of humic acid, citric acid, hydroxycitric acid, choline dihydrogen citrate, 2-triethyl acetylcitrate and gallotannic acid, the inorganic acid is sulfuric acid, the mass fractions of the macromolecular organic acid in the aqueous solution II are 1% of gallic acid and tannic acid, 1% of humic acid, 0.1% of citric acid, 0.1% of hydroxycitric acid, 0.1% of choline dihydrogen citrate and 0.1% of 2-triethyl acetylcitrate in sequence, and the mass fraction of the inorganic acid in the aqueous solution II is 10%.
Through testing, the surface water contact angle of the unmodified stainless steel mesh film is 109 degrees, and the underwater oil drop contact angle is 112 degrees. The surface water contact angle of the oil-water separation membrane obtained in this example was 0 °, and the underwater oil drop contact angle was 159 °.
The oil-water separation experiment result shows that the flux of the mixed liquid of the normal hexane and the water is 49k L.m-2.h-1The flux of the mixed liquid of the oil and the water was 46k L.m-2.h-1The flux of the mixed solution of diesel oil and water is 40k L.m-2.h-1The flux of the mixed liquid of the rapeseed oil and the water is 41k L.m-2.h-1The flux of the mixed liquid of crude oil and water is 48k L.m-2.h-1The oil retention rate is higher than 99%.
After the rubbing experiment, the surface water contact angle of the oil-water separation membrane obtained in example 6 was still 0 °, and the underwater oil drop contact angle was 113 °.
After the acid soaking experiment, the surface water contact angle of the oil-water separation membrane obtained in example 6 is still 0 °, and the underwater oil drop contact angle is still 158 °. The flux of the mixed liquid of the diesel oil and the water is 42k L.m-2.h-1The oil retention rate still reaches 99.6%.
After the alkali immersion experiment, the surface water contact angle of the oil-water separation membrane obtained in example 6 is still 0 °, and the underwater oil drop contact angle is still 157 °. The flux of the mixed liquid of the diesel oil and the water is 42k L.m-2.h-1The oil retention rate still reaches 99.4%.
After long-term seawater corrosion test, the surface water contact angle of the oil-water separation membrane obtained in example 6 is still 0 °, and the underwater oil drop contact angle is still 157 °. The flux of the mixed liquid of diesel oil and water is 43k L.m-2.h-1The retention rate of oil content still reaches 99.6 percent
Before and after the soaking of the ultrapure water, the water contact angle, the underwater oil drop contact angle, the flux of the mixed liquid of the diesel oil and the water and the interception rate of the oil are not changed.
Comparative example 1
The stainless steel mesh membranes obtained in example 1 after ultrasonic treatment in acetone, absolute ethyl alcohol and ultrapure water for 10min were used as unmodified stainless steel mesh membranes, and the results were compared with the effect of improving the performance of the oil-water separation membrane of the present invention.
Through testing, the contact angle of the surface of the unmodified stainless steel mesh film is 109 degrees, and the contact angle of underwater oil drops is 112 degrees. The separation net has no separation effect on the mixed liquid of normal hexane and water, the mixed liquid of engine oil and water, the mixed liquid of diesel oil and water, the mixed liquid of rapeseed oil and water and the mixed liquid of crude oil and water, and the retention rate of oil content is 0%.
The following conclusions are drawn in conjunction with the above examples and comparative examples:
by contact angle characterization test results: compared with the comparative example 1, the contact angle of the water surface of the oil-water separation membrane is reduced, and the contact angle of oil drops under water is improved, which shows that the oil-water separation membrane has improved hydrophilicity and simultaneously has super oleophobic performance under water.
Obtained by a friction resistance test: the stainless steel net film still has the capability of completely cutting oil after being rubbed for 12 meters under the pressure of 1Kg, the bearing pressure is improved by 5-10 times compared with the pressure of 100-200 g commonly reported at present, and the friction distance is improved by 6-12 times compared with the friction distance of 1-2 meters commonly reported at present;
the material is obtained by acid and alkali resistance testing: the stainless steel net film can normally and continuously run for more than 2 weeks under the conditions of strong acid, strong alkali and high salinity;
the long-term soaking standing life test results show that: the contact angle, flux and oil retention rate of the water-based paint are not changed greatly after the water-based paint is used in seawater for a long time.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (5)
1. The preparation method of the oil-water separation membrane is characterized by comprising the following steps:
1) uniformly mixing an alkaline substance, an oxidant and water to obtain an aqueous solution I, wherein the mass fraction of the alkaline substance in the aqueous solution I is 3-10%, and the mass fraction of the oxidant in the aqueous solution I is 1-5%, wherein the oxidant is one or a mixture of more of potassium chlorate, sodium chlorate, potassium perchlorate, sodium perchlorate, potassium hypochlorite, sodium hypochlorite, potassium bromate, sodium bromate, potassium hypobromate, sodium hypobromate, ammonium persulfate, sodium persulfate, potassium persulfate and hydrogen peroxide, and the alkaline substance is one or a mixture of more of sodium hydroxide, potassium hydroxide and ammonia water;
2) immersing a stainless steel net membrane in the aqueous solution I at the temperature of 20-50 ℃ for 12-36 h, taking out the stainless steel net membrane, and washing with ultrapure water, wherein the mesh number of the stainless steel net membrane is 300-2500 meshes;
3) immersing the stainless steel mesh membrane obtained in the step 2) in an aqueous solution II at the temperature of 20-50 ℃ for 2-12 h, taking out the stainless steel mesh membrane, and drying the stainless steel mesh membrane by using nitrogen to obtain an oil-water separation membrane, wherein the pH of the aqueous solution II is 1.5-3.0, the aqueous solution II is formed by mixing macromolecular organic acid, inorganic acid and water, the mass fraction of the macromolecular organic acid in the aqueous solution II is 1-5%, the mass fraction of the inorganic acid in the aqueous solution II is 5-15%, the macromolecular organic acid is humic acid, alginic acid, citric acid, hydroxycitric acid, gallic acid, gallotannic acid, theaflavin-3, 3' -bisgallic acid, di (p-methylbenzoyl) tartaric acid, 4-nitro salicylic acid, 2-phosphonic butane-1, 2, 4-tricarboxylic acid and 1, 8-dihydroxynaphthalene-3, 6-disulfonic acid, pamoic acid, ascorbic acid, hyaluronic acid, deoxycholic acid, diprotic acid, 2-acrylamide-2-methylpropanesulfonic acid, diethylenetriamine pentamethylene phosphonic acid, phytic acid, ethylenediamine tetramethylene phosphonic acid, aminotrimethylene phosphonic acid, 5, 3-triphosphonyl valeric acid, 4-diphosphonic acid radical-1, 7-heptanedioic acid, 1-amino-ethylidene-1, 1-diphosphonic acid and 1-hydroxy-ethylidene-1, 1-diphosphonic acid, or a mixture of several of them, and the inorganic acid is hydrochloric acid, phosphoric acid or sulfuric acid.
2. The preparation method according to claim 1, wherein in the step 2), before the stainless steel mesh membrane is immersed in the aqueous solution I, the stainless steel mesh membrane is sequentially subjected to ultrasonic treatment in acetone, absolute ethyl alcohol and ultrapure water, and then is dried by blowing with nitrogen.
3. The manufacturing method according to claim 2, wherein in the step 2), the stainless steel mesh film has a plain weave structure or a twill weave structure.
4. An oil-water separation membrane obtained by the production method according to any one of claims 1 to 3.
5. The use of the oil-water separation membrane of claim 4 for underwater superoleophobic applications.
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