CN115069096A - Inorganic membrane and preparation method and application thereof - Google Patents
Inorganic membrane and preparation method and application thereof Download PDFInfo
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- CN115069096A CN115069096A CN202210804944.9A CN202210804944A CN115069096A CN 115069096 A CN115069096 A CN 115069096A CN 202210804944 A CN202210804944 A CN 202210804944A CN 115069096 A CN115069096 A CN 115069096A
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- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
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Abstract
The invention relates to the technical field of materials, in particular to an inorganic membrane and a preparation method and application thereof. The specific technical scheme is as follows: an inorganic membrane comprises a manganese hydrogen phosphate trihydrate micro-nano structure deposited on a metal mesh, wherein the manganese hydrogen phosphate trihydrate micro-nano structure is flower-shaped and has the size of 50 nm-10 mu m. The inorganic film prepared by the invention shows excellent crude oil pollution resistance and ultralow crude oil adhesion so as to separate an immiscible oil-water mixture and a crude oil-in-water emulsion stabilized by a surfactant.
Description
Technical Field
The invention relates to the technical field of materials, in particular to a micro-nano flower-like manganese hydrogen phosphate trihydrate inorganic membrane prepared on the surface of a metal mesh by microwave assistance and used for crude oil/water emulsion separation.
Background
The accidental oil leakage in the marine oil exploitation process and the frequent accidents in the transportation process cause a large amount of crude oil to enter the sea and seriously threaten the marine ecological environment and the human health, so the effective marine crude oil-containing wastewater treatment technology draws wide attention.
Depending on the size of the oil particles, the oil in oil/water mixtures is generally divided into free oil (diameter > 150 μm), dispersed oil (20 μm < diameter < 150 μm) and emulsified oil (diameter < 20 μm). However, the large amount of crude oil/water mixture to be treated is actually present in the form of an emulsion, which is difficult to handle due to the small size and easy deformation of the emulsified droplets with a stable emulsion, which remains a great challenge for the separation of crude oil/water emulsions.
The traditional oily water treatment methods, such as oil skimming, gravity treatment, ultrasonic separation, air flotation, electrocoagulation, biological treatment and the like, generally have the defects of low separation efficiency, high energy consumption, secondary pollutant generation, high cost and the like. The membrane technology has the advantages of low energy consumption, short time consumption, small occupied area, high separation efficiency, simple operation and the like, and is known as one of the most effective methods for treating various kinds of wastewater.
Crude oil has high viscosity and high adhesion, which makes it easy to contaminate the matrix and cause related instrument failures during the separation of crude oil. Therefore, there is a pressing need for efficient, energy-efficient, and economical crude oil separation processes, particularly for processing crude oil-in-water emulsions.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides an inorganic membrane which is prepared by depositing a manganese hydrogen phosphate trihydrate micro-nano structure on the surface of a metal mesh through a one-step electrodeposition method and has super-hydrophilicity and is used for separating oil-water and crude oil-in-water emulsions, wherein the prepared inorganic membrane has excellent crude oil pollution resistance and super-low crude oil adhesion so as to separate immiscible oil-water mixtures and crude oil-in-water emulsions stabilized by surfactants.
In order to realize the purpose, the invention is realized by the following technical scheme:
the invention discloses an inorganic membrane, which comprises a manganese hydrogen phosphate trihydrate micro-nano structure deposited on a metal mesh, wherein the manganese hydrogen phosphate trihydrate micro-nano structure is flower-shaped and has the size of 50 nm-10 mu m.
Preferably, the manganese hydrogen phosphate trihydrate micro-nano structure is deposited on the metal mesh by adopting an electrodeposition method.
Correspondingly, the preparation method of the inorganic film adopts an electrodeposition method to deposit the manganese hydrogen phosphate trihydrate micro-nano structure on the metal mesh.
Preferably, MnSO 4 And NaH 2 PO 4 Dissolving the components in deionized water, and stirring to obtain a transparent solution system; and putting the cleaned metal net into a transparent solution system to perform an electrodeposition reaction under the action of microwaves, and preparing the metal net film with the manganese hydrogen phosphate trihydrate micro-nano structure.
Preferably, the MnSO 4 The concentration of (A) is 0.25-0.35M, NaH 2 PO 4 The concentration of (A) is 0.08-0.12M.
Preferably, the current density in the electrodeposition process is-15 to-25 mA/cm 2 The electrodeposition time is 3-10 min, the electrodeposition process is carried out at room temperature-60 ℃, and a magnetic stirrer is used for stirring the electrodeposition solution.
Preferably, the frequency of the microwave is 2000-2600 MHz.
Preferably, the prepared metal mesh membrane is washed by deionized water and absolute ethyl alcohol and dried for 2-24 hours at the temperature of 40-90 ℃.
Accordingly, use of an inorganic membrane as described above in the separation of a crude oil/water emulsion.
Preferably, the application method comprises the following steps: pre-wetting a metal net film, placing the metal net film between two containers, adding a crude oil/water mixture, and separating the crude oil/water mixture, wherein v is 2: 3; or adding Tween 20 into the mixture of crude oil and water, performing ultrasonic treatment to obtain crude oil-in-water emulsion, pre-wetting the metal net film, placing between two containers, adding crude oil-in-water emulsion, and performing oil-water separation.
The invention has the following beneficial effects:
1. the invention successfully prepares the inorganic reticular membrane with excellent super-hydrophilicity and underwater crude oil pollution resistance by a simple and economic one-step electrodeposition method. The prepared inorganic membrane can effectively separate various oil-water mixtures and crude oil-in-water emulsions. In particular, the inorganic membrane can separate tween 20-stabilized high-viscosity crude oil-in-water emulsion, showing excellent flux and separation efficiency. Based on these results, the present invention provides a novel, low-cost, environmentally friendly material for treating crude oil wastewater.
2. The inorganic reticular membrane prepared by the electrodeposition method combines the rough structure of the manganese hydrogen phosphate trihydrate and the strong hydration capacity of the phosphate groups on the surface, and shows excellent super-hydrophilicity and underwater oil pollution resistance; at the same time, it has excellent environmental durability and mechanical stability. Separating an immiscible oil-water mixture and a crude oil-in-water emulsion, prewetting a membrane by using deionized water before separation, washing the membrane by using the deionized water after separation, and recycling the membrane for oil-water separation.
3. The inorganic membrane disclosed by the invention has self-cleaning capability, can be recycled, is applied to oil-water separation, keeps high flux and high separation efficiency, and can effectively get rid of oil stains in water to realize self-cleaning. Meanwhile, the inorganic membrane disclosed by the invention has strong hydration capability, can effectively separate high-viscosity crude oil/water mixture, and even can separate a crude oil-in-water emulsion with stable surfactant. The preparation process of the inorganic membrane disclosed by the invention is economic, simple, environment-friendly and easy for large-scale industrial production.
4. The preparation process of the inorganic membrane disclosed by the invention is simple, different from other methods, and the preparation process does not contain fluorine and chromium which are harmful to the environment, so that the inorganic membrane is a good choice for treating oily wastewater. The size of the flower-like manganese hydrogen phosphate trihydrate in the inorganic membrane can be controllably adjusted through microwave frequency, current density, voltage and electrodeposition time, so that the separation performance of the crude oil-water emulsion of the membrane can be accurately regulated and controlled.
Drawings
FIG. 1 is an SEM image of an inorganic film prepared in example 1;
FIG. 2 is a graph showing the permeation flux and separation efficiency of an inorganic membrane for a crude oil/water mixture in various examples;
FIG. 3(a) is a water contact angle in air of the inorganic film prepared in example 1; (b) crude oil contact angle under water for the inorganic membranes prepared for the different examples;
FIG. 4 is a graph of flux of Tween 20 stabilized crude oil-in-water emulsion prepared by inorganic membrane separation in different examples;
FIG. 5(a) shows the underwater oil contact angle of the inorganic film prepared in example 1 after treatment with an aqueous solution having a pH of 1 to 14; (b) the underwater oil contact angle of the inorganic membrane prepared for different examples after being soaked in seawater (3.5% NaCl) for 30 days;
FIG. 6 shows the underwater contact angle of crude oil after 30 times of abrasion with sandpaper for inorganic films prepared in different examples;
FIG. 7 is a photograph of the inorganic membrane prepared in example 1 separating a crude oil/water mixture.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Unless otherwise indicated, the technical means used in the examples are conventional means well known to those skilled in the art.
The invention discloses an inorganic membrane, which comprises the following steps:
(1) sequentially placing the metal net in absolute ethyl alcohol, acetone and deionized water, ultrasonically cleaning for 10-30 min to remove oil stains on the surface of the metal net, and drying for later use; metal meshes include, but are not limited to, brass mesh, red copper mesh, phosphor copper mesh, iron mesh, stainless steel mesh, aluminum mesh.
(2) Adding 0.25-0.35M MnSO 4 And 0.08-0.12M NaH 2 PO 4 Dissolving the components in deionized water, and magnetically stirring the components at room temperature for 5-10 min to obtain a transparent solution system.
(3) Using the treated metal net as a cathode, putting the metal net into a microwave reactor (the frequency of the microwave is 2000-2600 MHz) in the transparent solution system prepared in the step (2), and carrying out electrodeposition reaction to prepare the manganese hydrogen phosphate trihydrate micro-nano structureThe metal mesh film of (1). Wherein the current density in the electrodeposition process is-15 to-25 mA/cm 2 The electrodeposition time is 3-10 min, the electrodeposition process is carried out at room temperature-60 ℃, and a magnetic stirrer is used for stirring the electrodeposition solution.
(4) Washing the manganese hydrogen phosphate trihydrate inorganic membrane obtained after electrodeposition with deionized water and absolute ethyl alcohol, drying for 2-24 h at 40-90 ℃, and using the membrane for separating oil-water mixtures. The prepared manganese hydrogen phosphate trihydrate micro-nano structure is flower-shaped, and the size of micro-nano flower petals is 50 nm-10 mu m.
When oil-water mixture separation is carried out, the membrane is pre-wetted by deionized water, placed between two containers, and the crude oil/water mixture or crude oil-in-water emulsion is poured into the container for oil-water mixture separation, wherein the separation process is completely driven by gravity.
The invention is further illustrated below with reference to specific examples.
Example 1
The inorganic film was prepared as follows:
(1) sequentially placing a 200-mesh red copper net in absolute ethyl alcohol, acetone and deionized water, ultrasonically cleaning for 10min to remove oil stains on the surface of the metal net, and drying for 2h at 105 ℃ for later use;
(2) adding 0.30M MnSO 4 And 0.10M NaH 2 PO 4 Dissolving in deionized water, and magnetically stirring at room temperature for 5min to obtain transparent solution system.
(3) And (3) taking the treated red copper net as a cathode, putting the red copper net into a microwave reactor in a transparent solution system, and carrying out electrodeposition reaction at the microwave frequency of 2400MHz to prepare the metal net film with the manganese hydrogen phosphate trihydrate micro-nano structure. The current density in the electrodeposition process is-20 mA/cm 2 The electro-deposition time is 10min, the electro-deposition process is carried out at 40 ℃, and a magnetic stirrer is used for stirring the electro-deposition solution;
(4) washing the manganese hydrogen phosphate trihydrate inorganic membrane obtained after electrodeposition with deionized water and absolute ethyl alcohol, and drying at 60 ℃ for 12h for later use for separating an oil-water mixture.
The SEM image of the prepared inorganic membrane is shown in FIG. 1, from which the existence of flower-like morphology can be clearly seen, the size of the manganese hydrogen phosphate trihydrate flower is 3.2 μm, and the petal thickness is 500 nm.
The process of the inorganic membrane prepared for separating the oil-water mixture comprises the following steps:
mode 1, the membrane was pre-wetted with deionized water prior to separation, placed between two 20mm diameter glass containers, the crude oil used was a medium crude oil (used in the examples below), and the crude oil/water mixture (v: v ═ 2:3) was poured into one of the glass containers, with the separation process being driven entirely by gravity. The results are shown in fig. 7, where the filtrate is clear and free of oil droplets, while the crude oil is retained by the membrane. The flux and efficiency results are shown in FIG. 2, and show that the inorganic membrane prepared in this example shows a large permeation flux for different oil-water mixtures, the separation efficiency is 99.6%, and the permeation flux of the crude oil/water mixture is 2135L/(m) 2 ·h)。
The inorganic films prepared as described above were subjected to performance tests
(1) Wettability testing of inorganic films
The inorganic film was immersed in seawater (3.5% NaCl) for 30 days, then dried at 50 ℃ and tested for underwater oil contact angle. As shown in fig. 3, fig. 3(a) shows that the hydrophilic angle of the inorganic film prepared in this example in the air is 0 °, and fig. 3(b) shows that the underwater crude oil contact angle is 165 °.
(2) Acid and base resistance test of inorganic membranes
And (3) soaking the inorganic membrane in a solution with the pH value of 1-14 for 24h, drying at 50 ℃, and testing the underwater oil contact angle. The results are shown in fig. 5, wherein (a) is the underwater oil contact angle of the prepared inorganic film after being treated by an aqueous solution with the pH value of 1-14; (b) the underwater oil contact angle of the inorganic membrane prepared for the present example after being soaked in seawater (3.5% NaCl) for 30 days was 161 ℃. The final result shows that the inorganic membrane prepared by the invention has excellent salt resistance and acid and alkali resistance.
(3) Mechanical stability testing of inorganic membranes
Sandpaper (600 mesh) was mounted on a sample holder, the inorganic membrane was placed on the sandpaper and loaded with a weight of 200g, and then the inorganic membrane was pulled forward a distance of 20cm, rubbing back and forth once defined as one abrasion, and contact angle test for underwater oil. As shown in FIG. 6, the contact angle of crude oil under water after the inorganic film prepared in this example is abraded for 30 times is 152 degrees, and the super oleophobic property of the crude oil under water is maintained.
Example 2
The inorganic film was prepared as follows:
(1) sequentially placing a 200-mesh brass net in absolute ethyl alcohol, acetone and deionized water, ultrasonically cleaning for 10min to remove oil stains on the surface of the metal net, and drying for 2h at 105 ℃ for later use;
(2) adding 0.25M MnSO 4 And 0.10M NaH 2 PO 4 Dissolving in deionized water, and magnetically stirring at room temperature for 5min to obtain transparent solution system.
(3) And (3) taking the treated brass net as a cathode, putting the cathode into a microwave reactor in a transparent solution system, and carrying out electrodeposition reaction at the microwave frequency of 2200MHz to prepare the metal net film with the manganese hydrogen phosphate trihydrate micro-nano structure. The current density in the electrodeposition process is-20 mA/cm 2 The electrodeposition time was 9min, the electrodeposition process was carried out at 45 ℃ and the electrodeposition solution was stirred using a magnetic stirrer.
(4) Washing the manganese hydrogen phosphate trihydrate inorganic membrane obtained after electrodeposition with deionized water and absolute ethyl alcohol, and drying at 60 ℃ for 12h for later use for separating an oil-water mixture.
The size of the manganese hydrogen phosphate trihydrate flowers in the inorganic film prepared in this example was 2.6 μm with a petal thickness of 450 nm.
The process of the inorganic membrane prepared for separating the oil-water mixture comprises the following steps:
mode 1, membranes were pre-wetted with deionized water prior to separation, placed between two 20mm diameter glass containers, and crude oil/water mixture (v: v ═ 2:3) was poured into the upper glass container, with the separation process driven entirely by gravity. The results are shown in fig. 2, where the separation efficiency of the manganese hydrogen phosphate trihydrate inorganic membrane on the crude oil/water mixture is 99.5%, the filtrate is clear and free of oil droplets, and the crude oil is retained by the membrane. Meanwhile, the permeation flux of the crude oil/water mixture is 2230L/(m) 2 ·h)。
The inorganic film prepared in example 2 was subjected to the performance test, which was the same as in example 1.
The results show that: the hydrophilic angle of the inorganic membrane is 0 deg., and as shown in fig. 3, the contact angle of the underwater crude oil is 164 deg.. Meanwhile, the salt resistance and the acid and alkali resistance are excellent. Fig. 5(b) shows that the contact angle of the underwater crude oil after being soaked in seawater for 30d is 159 degrees, fig. 6 shows that the contact angle of the underwater crude oil after being abraded by sand paper for 30 times is 151 degrees, and the super oleophobic property of the underwater crude oil is kept underwater.
Example 3
The inorganic film was prepared as follows:
(1) sequentially placing a 200-mesh stainless steel net in absolute ethyl alcohol, acetone and deionized water, ultrasonically cleaning for 10min to remove oil stains on the surface of the metal net, and drying for 2h at 105 ℃ for later use;
(2) adding 0.25M MnSO 4 And 0.10M NaH 2 PO 4 Dissolving in deionized water, and magnetically stirring at room temperature for 5min to obtain transparent solution system.
(3) Using treated stainless steel net as cathode, placing in transparent solution systemAnd (3) putting the metal mesh membrane into a microwave reactor, wherein the microwave frequency is 2400MHz, and performing electrodeposition reaction to prepare the metal mesh membrane with the manganese hydrogen phosphate trihydrate micro-nano structure. The current density in the electrodeposition process is-20 mA/cm 2 The electrodeposition time was 8min, the electrodeposition process was carried out at 50 ℃ and the electrodeposition solution was stirred using a magnetic stirrer.
(4) Washing the manganese hydrogen phosphate trihydrate inorganic membrane obtained after electrodeposition with deionized water and absolute ethyl alcohol, and drying at 60 ℃ for 12h for later use for separating an oil-water mixture.
The size of the manganese hydrogen phosphate trihydrate flowers in the inorganic film prepared in this example was 3.4 μm with a petal thickness of 530 nm.
The process of the inorganic membrane prepared for separating the oil-water mixture comprises the following steps:
mode 1, membranes were pre-wetted with deionized water prior to separation, placed between two 20mm diameter glass containers, and crude oil/water mixture (v: v ═ 2:3) was poured into the upper glass container, with the separation process driven entirely by gravity. As a result, as shown in FIG. 2, the separation efficiency of the manganese hydrogen phosphate trihydrate inorganic membrane on the crude oil/water mixture was 99.6%, the filtrate was clear and free of oil droplets, and the crude oil was retained by the membrane. Meanwhile, the permeation flux of the crude oil/water mixture is 2300L/(m) 2 ·h)。
The inorganic film prepared in example 3 was subjected to the performance test, which was the same as in example 1.
The results show that: the hydrophilic angle of the inorganic film was 0 °, and as shown in fig. 3, the underwater crude oil contact angle was 161 °. Meanwhile, the coating has excellent salt resistance and acid and alkali resistance, and fig. 5(b) shows that the underwater oil contact angle after the seawater soaking treatment for 30d is 156 degrees. FIG. 6 shows that the contact angle of crude oil under water after 30 times of abrasion with sandpaper is 154 degrees, and the super-oleophobic property of the crude oil is maintained under water.
Example 4
The inorganic film was prepared as follows:
(1) sequentially placing 200 meshes of aluminum mesh in absolute ethyl alcohol, acetone and deionized water, ultrasonically cleaning for 30min to remove oil stains on the surface of the metal mesh, and drying for 2h at 105 ℃ for later use;
(2) adding 0.3M MnSO 4 And 0.10M NaH 2 PO 4 Dissolving in deionized water, and magnetically stirring at room temperature for 5min to obtain transparent solution system.
(3) And (3) taking the treated aluminum mesh as a cathode, putting the aluminum mesh into a microwave reactor in a transparent solution system, and carrying out electrodeposition reaction at the microwave frequency of 2400MHz to prepare the metal mesh membrane with the manganese hydrogen phosphate trihydrate micro-nano structure. The current density in the electrodeposition process is-15 mA/cm 2 The electrodeposition time was 10min, the electrodeposition process was carried out at 35 ℃ and the electrodeposition solution was stirred using a magnetic stirrer.
(4) Washing the manganese hydrogen phosphate trihydrate inorganic membrane obtained after electrodeposition with deionized water and absolute ethyl alcohol, and drying at 60 ℃ for 12h for later use for separating an oil-water mixture.
The size of the manganese hydrogen phosphate trihydrate flowers in the inorganic film prepared in this example was 2.5 μm with a petal thickness of 370 nm.
The process of the inorganic membrane prepared for separating the oil-water mixture comprises the following steps:
mode 1, membranes were pre-wetted with deionized water prior to separation, placed between two 20mm diameter glass containers, and crude oil/water mixture (v: v ═ 2:3) was poured into the upper glass container, with the separation process driven entirely by gravity. As a result, as shown in FIG. 2, the separation efficiency of the manganese hydrogen phosphate trihydrate inorganic membrane on the crude oil/water mixture was 99.5%, the filtrate was clear and free of oil droplets, and the crude oil was retained by the membrane. Meanwhile, the permeation flux of the crude oil/water mixture is 2100L/(m) 2 ·h)
The inorganic film prepared in example 4 was subjected to the performance test, which was the same as in example 1.
The results show that: the hydrophilic angle of the inorganic film was 0 °, and as shown in fig. 3, the underwater crude oil contact angle was 163 °. Meanwhile, the paint has excellent salt resistance and acid and alkali resistance, and the underwater oil contact angle of the paint after being soaked in seawater for 30d is 158 degrees as shown in fig. 5 (b). FIG. 6 shows that the contact angle of crude oil under water after 30 times of abrasion with sandpaper is 151 degrees, and the super oleophobic property of the crude oil is kept under water.
Example 5
The inorganic film was prepared as follows:
(1) sequentially placing a 300-mesh iron net in absolute ethyl alcohol, acetone and deionized water, ultrasonically cleaning for 30min to remove oil stains on the surface of the metal net, and drying for 2h at 105 ℃ for later use;
(2) adding 0.25M MnSO 4 And 0.10M NaH 2 PO 4 Dissolving in deionized water, and magnetically stirring at room temperature for 5min to obtain transparent solution system.
(3) And (3) taking the treated iron net as a cathode, putting the treated iron net into a microwave reactor in a transparent solution system, and performing electrodeposition reaction at the microwave frequency of 2300MHz to prepare the metal net film with the manganese hydrogen phosphate trihydrate micro-nano structure. The current density in the electrodeposition process is-15 mA/cm 2 The electrodeposition time was 5min, the electrodeposition process was carried out at 55 ℃ and the electrodeposition solution was stirred using a magnetic stirrer.
(4) Washing the manganese hydrogen phosphate trihydrate inorganic membrane obtained after electrodeposition with deionized water and absolute ethyl alcohol, and drying at 60 ℃ for 12h for later use for separating an oil-water mixture.
The size of the manganese hydrogen phosphate trihydrate flowers in the inorganic film prepared in this example was 3.7 μm with a petal thickness of 540 nm.
The process of the inorganic membrane prepared for separating the oil-water mixture comprises the following steps:
mode 1, membranes were pre-wetted with deionized water prior to separation, placed between two 20mm diameter glass containers, and crude oil/water mixture (v: v ═ 2:3) was poured into the upper glass container, with the separation process driven entirely by gravity. As a result, as shown in FIG. 2, the separation efficiency of the manganese hydrogen phosphate trihydrate inorganic membrane on the crude oil/water mixture was 99.8%, the filtrate was clear and free of oil droplets, and the crude oil was retained by the membrane. At the same time, the crude oil/water mixture has a permeation flux of 2210L/(m) 2 ·h)。
The inorganic film prepared in example 5 was subjected to the performance test, which was the same as in example 1.
The results show that: the hydrophilic angle of the inorganic membrane was 0 deg., and fig. 3 shows that the underwater crude oil contact angle was 158 deg.. Meanwhile, the paint has excellent salt resistance and acid and alkali resistance, and the contact angle of the underwater crude oil after being soaked in seawater for 30 days is 155 degrees as shown in figure 5 (b). FIG. 6 shows that the contact angle of crude oil under water after 30 times of abrasion with sandpaper is 152 degrees, and the super-oleophobic property of the crude oil is maintained under water.
Example 6
The inorganic film was prepared as follows:
(1) sequentially placing a 300-mesh phosphor-copper net in absolute ethyl alcohol, acetone and deionized water, ultrasonically cleaning for 20min to remove oil stains on the surface of the metal net, and drying for 2h at 105 ℃ for later use;
(2) adding 0.30M MnSO 4 And 0.10M NaH 2 PO 4 Dissolving in deionized water, and magnetically stirring at room temperature for 5min to obtain transparent solution system.
(3) Use ofAnd (3) taking the treated phosphor copper mesh as a cathode, putting the cathode into a microwave reactor in a transparent solution system, and carrying out electrodeposition reaction at the microwave frequency of 2450MHz to prepare the metal mesh film with the manganese hydrogen phosphate trihydrate micro-nano structure. The current density in the electrodeposition process is-15 mA/cm 2 The electrodeposition time was 3min, the electrodeposition process was carried out at 60 ℃ and the electrodeposition solution was stirred using a magnetic stirrer.
(4) Washing the manganese hydrogen phosphate trihydrate inorganic membrane obtained after electrodeposition with deionized water and absolute ethyl alcohol, and drying at 60 ℃ for 12h for later use for separating an oil-water mixture.
The inorganic film prepared in this example, manganese hydrogen phosphate trihydrate flower size was 6.5 μm with a petal thickness of 600 nm.
The process of the inorganic membrane prepared for separating the oil-water mixture comprises the following steps:
mode 1, membranes were pre-wetted with deionized water prior to separation, placed between two 20mm diameter glass containers, and crude oil/water mixture (v: v ═ 2:3) was poured into the upper glass container, with the separation process driven entirely by gravity. As a result, as shown in FIG. 2, the separation efficiency of the manganese hydrogen phosphate trihydrate inorganic membrane on the crude oil/water mixture was 99.7%, the filtrate was clear and free of oil droplets, and the crude oil was retained by the membrane. Meanwhile, the permeation flux of the crude oil/water mixture is 2040L/(m) 2 ·h)。
The inorganic film prepared in example 6 was subjected to the performance test, which was the same as in example 1.
The results show that: the hydrophilic angle of the inorganic film was 0 °, and fig. 3 shows that the underwater crude oil contact angle was 163 °. Meanwhile, the water has excellent salt resistance and acid and alkali resistance, and the underwater oil contact angle after being soaked in seawater for 30d is 160 degrees as shown in fig. 5 (b). FIG. 6 shows that the contact angle of crude oil under water after 30 times of abrasion with sandpaper is 156 degrees, and the super-oleophobic property of the crude oil is maintained under water.
The above-described embodiments are merely illustrative of the preferred embodiments of the present invention, and do not limit the scope of the present invention, and various modifications and improvements of the technical solutions of the present invention can be made by those skilled in the art without departing from the spirit of the present invention, and the technical solutions of the present invention are within the scope of the present invention defined by the claims.
Claims (10)
1. An inorganic film, characterized in that: the manganese hydrogen phosphate trihydrate particle comprises a manganese hydrogen phosphate trihydrate micro-nano structure deposited on a metal mesh, wherein the manganese hydrogen phosphate trihydrate micro-nano structure is flower-shaped and has the size of 50 nm-10 mu m.
2. The inorganic film of claim 1, wherein: and depositing the manganese hydrogen phosphate trihydrate micro-nano structure on the metal mesh by adopting an electrodeposition method.
3. A method of preparing an inorganic membrane, characterized by: and depositing the manganese hydrogen phosphate trihydrate micro-nano structure on the metal mesh by adopting an electrodeposition method.
4. The method of claim 1, wherein: mixing MnSO 4 And NaH 2 PO 4 Dissolving in deionized water, and stirring to obtain transparent solution system; and (3) putting the metal net into a transparent solution system to perform electrodeposition reaction under the action of microwaves to prepare the metal net film with the manganese hydrogen phosphate trihydrate micro-nano structure.
5. The method of claim 4, wherein: the MnSO 4 The concentration of (A) is 0.25-0.35M, NaH 2 PO 4 The concentration of (A) is 0.08-0.12M.
6. The method of claim 4A method of preparing an inorganic membrane, characterized by: the current density in the electrodeposition process is-15 to-25 mA/cm 2 The electrodeposition time is 3-10 min, the electrodeposition process is carried out at room temperature-60 ℃, and a magnetic stirrer is used for stirring the electrodeposition solution.
7. The method of claim 4, wherein: the frequency of the microwave is 2000-2600 MHz.
8. The method of claim 4, wherein: and washing the prepared metal net film by using deionized water and absolute ethyl alcohol, and drying for 2-24 hours at 40-90 ℃.
9. Use of the inorganic membrane according to any one of claims 1 to 2 or the inorganic membrane prepared by the preparation method according to any one of claims 3 to 8 in crude oil/water emulsion separation.
10. Use according to claim 9, characterized in that: the application method comprises the following steps: pre-wetting a metal net film, placing the metal net film between two containers, adding a crude oil/water mixture, and separating the crude oil/water mixture, wherein v is 2: 3; or adding Tween 20 into the mixture of crude oil and water, performing ultrasonic treatment to obtain crude oil-in-water emulsion, pre-wetting the metal net film, placing between two containers, adding crude oil-in-water emulsion, and performing oil-water separation.
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