Oil-water separation mineralization net film as well as preparation method and application thereof

Abstract

The invention provides an oil-water separation mineralization net film as well as a preparation method and application thereof. The oil-water separation mineralization net film comprises an organic layer crosslinked on a grid substrate, the inorganic layer grows in the organic layer in an in-situ mineralization manner; the organic layer is a polymer layer formed by coating a polymer solution containing a cross-linking agent on the grid substrate for cross-linking; the inorganic layer is an inorganic mineral particle layer which grows on the surface of the organic layer in an in-situ mineralization mode. The mineralized net film for oil-water separation not only has excellent binding capacity with the grid substrate, but also has high chemical stability of acid resistance, alkali resistance and organic solvent resistance and excellent mechanical performance, and can be widely applied to oil-water separation under complex conditions.

Description

Technical Field

[0001] The present invention belongs to the technical fields of chemical engineering and functional materials, and specifically includes an oil-water separation mineralized membrane and its preparation method and application. Background Art

[0002] Offshore oil spills and industrial oil-containing wastewater pollution accidents occur frequently, posing great harm to human health and the ecological environment. To solve these problems, it is very important to develop efficient oil-water separation technologies. Traditional oil-water separation technologies, such as gravity separation, solidification, biological membrane, combustion, and oil absorption methods, are greatly limited due to low separation efficiency, high energy costs, complex equipment, poor selectivity, etc. Since oil-water separation is essentially an interfacial problem, designing advanced functional materials with special wettability is a simple and effective strategy.

[0003] In recent years, oil-water separation materials with superhydrophilicity and underwater superoleophobicity, namely "water-removing" materials, have attracted increasing attention. Due to their excellent water absorption and retention capabilities, hydrogel-based materials have become commonly used materials in the field of oil-water separation. For example, polyacrylamide hydrogel, cellulose hydrogel, polyvinyl alcohol hydrogel, and dimethylaminoethyl methacrylate hydrogel are often used to modify grids or porous substrates. However, the mechanical strength and chemical stability of these hydrogel-based materials are poor and are easily damaged in oil-water separation applications. Although the design of multi-network hydrogels and inorganic additive composite hydrogels can effectively enhance the mechanical strength of hydrogels, it is still insufficient for the harsh conditions actually faced. In recent years, calcium carbonate coatings prepared by a biomimetic mineralization strategy can significantly improve the mechanical properties of oil-water separation materials. However, these inorganic materials mainly composed of calcium carbonate have weak binding to the substrate and are easily decomposed under acidic and other conditions, limiting the application life and scenarios. In practical applications, the composition of oil-water mixtures is often complex. Therefore, improving the mechanical stability and chemical stability of materials is of great significance for their oil-water separation applications under complex conditions. Summary of the Invention

[0004] Aiming at the above problems existing in the prior art, the first object of the present invention is to provide an oil-water separation mineralized membrane. This oil-water separation mineralized membrane has the characteristics of superhydrophilicity in air and superoleophobicity underwater, with a water contact angle in air close to 0°, and the oil-water separation mineralized membrane has an oil droplet contact angle greater than 155° underwater, and has high separation efficiency for oil-water mixtures with complex properties. At the same time, it also has strong acid, alkali, and organic solvent resistance.

[0005] The second object of the present invention is to provide a preparation method for the above-mentioned oil-water separation mineralized membrane. This preparation method is simple to operate, easy to implement, low in cost, low in energy consumption, and can be prepared on a large scale.

[0006] The third object of the present invention is to provide an application of the oil-water separation mineralized mesh as described above in oil-water separation.

[0007] To achieve the above first object, the technical solution adopted by the present invention includes:

[0008] The present invention discloses an oil-water separation mineralized mesh, and the oil-water separation mineralized mesh includes

[0009] an organic layer crosslinked on a grid substrate; and

[0010] an inorganic layer in-situ mineralized and grown in the organic layer;

[0011] The organic layer is a polymer layer formed by coating a polymer solution containing a crosslinking agent on the grid substrate and crosslinking;

[0012] The inorganic layer is an inorganic mineral particle layer in-situ mineralized and grown on the surface of the organic layer;

[0013] Wherein, the inorganic mineral particles contained in the inorganic mineral particle layer are selected from one or more of metal sulfates, metal phosphates, and metal carbonates. When the inorganic mineral particles are selected from metal carbonates, the inorganic mineral particles are at least further selected from metal sulfates and / or metal phosphates.

[0014] Considering the problems of poor mechanical properties and chemical stability existing in traditional oil-water separation meshes, the present invention is based on a biomimetic mineralization strategy to form an inorganic mineral particle layer with acid, alkali, and organic solvent resistance characteristics on the surface of the organic layer. The organic layer containing a crosslinking agent not only acts as a "bridge" but also effectively controls the morphology and crystallization process of the inorganic layer, thereby realizing the firm integration of the grid substrate and the inorganic mineral layer, and finally obtaining an oil-water separation mineralized mesh with excellent performance. Due to its hierarchical micro-nano composite structure and the characteristics mainly composed of inorganic minerals, this oil-water separation mineralized mesh has the characteristics of superhydrophilicity in air and superoleophobicity underwater. Compared with the traditional oil-water separation materials prepared using organic or inorganic substances, the oil-water separation mineralized mesh provided by the present invention not only has an excellent binding ability with the substrate, showing high mechanical stability, with its hardness and Young's modulus reaching 2.5 GPa and 80 GPa respectively, and its mechanical properties being significantly superior to the traditional oil-water separation materials mainly prepared using organic substances, but also has strong chemical stability against acids, alkalis, and organic solvents, greatly increasing the service life and application environment of the oil-water separation mineralized mesh, and can be widely applied to oil-water separation under complex conditions.

[0015] Furthermore, the inorganic mineral particles are selected from one or more of calcium sulfate, barium sulfate, strontium sulfate, calcium phosphate, calcium carbonate, and magnesium carbonate.

[0016] Furthermore, the polymer contained in the polymer solution is selected from one or more of polyvinyl alcohol, cellulose, polyethyleneimine, chitosan, polyacrylamide, and chitin;

[0017] The crosslinking agent is selected from one or more of 3-glycidyloxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-acetoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane.

[0018] Furthermore, the grid base is selected from one of stainless steel mesh, copper mesh, iron mesh, aluminum mesh, polypropylene mesh, nylon mesh, polyester mesh, polyurethane mesh, and vinylon mesh.

[0019] Furthermore, the contact angle of the oil-water separation mineralized membrane to water in air is close to 0°, showing superhydrophilic properties, and the contact angle of the oil-water separation mineralized membrane to oil droplets underwater is greater than 155°, showing superoleophobic properties.

[0020] To achieve the above second purpose, the technical solutions adopted by the present invention include:

[0021] The present invention discloses a method for preparing the above-mentioned oil-water separation mineralized membrane, comprising the following steps:

[0022] 1) coating a polymer solution containing a cross-linking agent on a grid substrate and drying the solution to form an organic layer;

[0023] 2) Preparation of amorphous mineral aqueous solution:

[0024] A 1-100 mM aqueous solution of mineral cation A is prepared, the complexing molecule is added to the aqueous solution of mineral cation A, stirred and reacted for 0.1-1 hour, and then a 1-100 mM aqueous solution of anion B is added, stirred and reacted for 0.1-1 hour, and the pH is adjusted to 10-13 to obtain an amorphous mineral aqueous solution;

[0025] 3) Formation of mineralized retina:

[0026] The grid substrate containing the organic layer is immersed in an amorphous mineral aqueous solution and allowed to react at 20 to 50° C. for 2 to 24 hours to obtain an oil-water separation mineralized mesh membrane;

[0027] Wherein, the anion B contained in the anion B aqueous solution is selected from SO4 2- PO4 3- 、CO3 2- One or more of the following, and when the anion B aqueous solution contains CO3 2- When it contains at least SO4 2- PO4 3- Any one of .

[0028] Furthermore, the mineral cation A contained in the aqueous solution of mineral cation A is selected from one or more of Ca 2+ , Ba 2+ , Mg 2+ , Sr 2+ ;

[0029] The molar ratio of mineral cation A to anion B in the amorphous mineral aqueous solution is 0.1 - 5.0:1; Exemplarily, the molar ratio of mineral cation A to anion B can be 0.1:1, 0.5:1, 1:1, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, etc.

[0030] Furthermore, the metal salts contained in the aqueous solution of mineral cation A include one or more of BaCl2, CaCl2, MgCl2, SrCl2.

[0031] Furthermore, the complexing molecule is selected from one or more of polymaleic acid, polyvinyl acid, polyacrylic acid, polymethacrylic acid, polyvinyl acrylic acid, polyaspartic acid, polyglutamic acid, polyamic acid, polycrotonic acid, alginic acid;

[0032] The mass percentage content of the complexing molecule added to the aqueous solution of mineral cation A is 0.0001 - 0.5%; Exemplarily, the mass percentage content of the complexing molecule added to the aqueous solution of mineral cation A can be 0.0001%, 0.0002%, 0.0005%, 0.001%, 0.002%, 0.005%, 0.01%, 0.02%, 0.05%, etc.

[0033] Furthermore, in step 1, the drying condition is drying at 50 - 150 °C for 1 - 24 h.

[0034] Furthermore, in step 3, for the biomimetic mineralization process of the organic layer per square centimeter, the volume of the amorphous mineral aqueous solution added is 1.0 - 100.0 mL; Exemplarily, the added volume can be 1.0 mL, 2.0 mL, 3.0 mL, 4.0 mL, 5.0 mL, 6.0 mL, 7.0 mL, 8.0 mL, 9.0 mL, 10.0 mL, 20.0 mL, 30.0 mL, 40.0 mL, 50.0 mL, 60.0 mL, 70.0 mL, 80.0 mL, 90.0 mL, 100.0 mL, etc.

[0035] Furthermore, before coating the polymer solution on the grid substrate, it also includes cleaning and plasma treatment of the grid substrate.

[0036] To achieve the above - mentioned third objective, the technical solution adopted by the present invention includes:

[0037] The present invention discloses an application of the oil-water separation mineralized membrane as described above in the oil-water separation of oily sewage.

[0038] Advantages of the present invention:

[0039] 1. The oil-water separation mineralized membrane prepared by the present invention has the characteristics of superhydrophilicity in air and superoleophobicity underwater. The contact angle with water in air is close to 0°, and the contact angle of the oil-water separation mineralized membrane with oil droplets underwater is greater than 155°. It has high separation efficiency for oil-water mixtures with complex properties.

[0040] 2. The oil-water separation mineralized membrane prepared by the present invention is resistant to acids, alkalis, and various organic solvents, and has the properties of high chemical stability and high mechanical strength. Its hardness and Young's modulus are as high as 2.5 GPa and 80 GPa respectively, which are significantly superior to the oil-water separation materials prepared from traditional organic substances, and broaden the application of materials in oil-water separation under complex conditions.

[0041] 3. The oil-water separation mineralized membrane prepared by the present invention has low cost, low energy consumption, low pollution, easily available raw materials, and extremely simple equipment and manufacturing process, and can be used for large-scale preparation under room temperature conditions.

[0042] 4. The oil-water separation mineralized membrane prepared by the present invention can be applied to the surfaces of most grid substrates, and has no special requirements for the structure and components of the substrate surface.

[0043] 5. The oil-water separation mineralized membrane prepared by the present invention is mainly composed of natural inorganic mineral materials, which has high safety, long service life, wear resistance, high reuse rate, and is environmentally friendly. Description of the Drawings

[0044] The following further elaborates in detail the specific embodiments of the present invention with reference to the drawings.

[0045] Figure 1 Photograph of the contact angle of the underwater superoleophobic mineral membrane prepared in Example 1 with oil droplets (1,3-dichloroethane) underwater.

[0046] Figure 2 Scanning electron microscope photographs of the oil-water separation mineralized membrane prepared in Example 4 at different magnification ratios. Specific Embodiments

[0047] To illustrate the present invention more clearly, the present invention will be further described below in conjunction with preferred embodiments and the drawings. It should be clear that the described embodiments are only a part of the embodiments of the present invention, rather than all of the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0048] In addition, unless otherwise specified, the raw materials used in the present invention can be obtained through commercial purchase. Any range described in the present invention includes the end values, any numerical value between the end values, and any sub-range constituted by any numerical value between the end values or the end values.

[0049] Example 1

[0050] (1) Ultrasonically clean a nylon mesh (5×5 cm 2 ) with absolute ethanol and deionized water for 30 min, put it in an oven at 50 °C for 1 h to dry, and treat it with a plasma cleaner in high-power mode for 10 min;

[0051] (2) Spray the pre-prepared 1.0 wt% polyvinyl alcohol solution onto the above nylon mesh. Control the spraying distance at 10 cm, spray both the front and back sides three times, and then put it in an oven at 80 °C for 6 h to dry to obtain a nylon mesh modified with an organic layer. The polyvinyl alcohol solution contains 0.1 wt% 3-glycidoxypropyltrimethoxysilane;

[0052] (3) Prepare 100 mL of a 15 mM aqueous BaCl2 solution with deionized water, stir and dissolve it at room temperature for 30 min, then add 0.05 g of sodium polyacrylate, continue to stir and dissolve for 30 min, then slowly add 100 mL of a 15 mM aqueous Na2SO4 solution, continue to stir and mix evenly for 30 min, and adjust the pH of the mixed solution to 10.0 with 0.1 mol / L sodium hydroxide aqueous solution and 0.1 mol / L hydrochloric acid aqueous solution to obtain an amorphous mineral aqueous solution;

[0053] (4) Immerse the above nylon mesh modified with an organic layer in 100 mL of the amorphous mineral solution, let it stand and react in a water bath at 27 °C for 8 h, take it out and dry it at room temperature, and an oil-water separation mineralized mesh with underwater superoleophobic properties can be obtained on the surface of the nylon grid.

[0054] The water contact angle of this oil-water separation mineralized mesh in air is about 0°, and the contact angle with an oil droplet (i.e., 1,3-dichloroethane) underwater is 160°. The separation efficiency for the mixture of mineral oil and water can reach 99.9%.

[0055] Figure 1 This is a photo of the contact angle of the oil-water separation mineralized mesh with an oil droplet (i.e., 1,3-dichloroethane) underwater, indicating its superoleophobic performance underwater.

[0056] Example 2

[0057] (1) Ultrasonically clean a stainless steel mesh (5×5 cm 2) Clean it thoroughly by ultrasonic cleaning for 30 min, then put it in an oven at 50 °C for 1 h to dry, and treat it with a plasma cleaner in high-power mode for 12 min;

[0058] (2) Immerse the above-mentioned stainless steel mesh in a pre-prepared 0.5 wt% polyvinyl alcohol solution. After soaking for 10 min, pull it vertically to form a film at a speed of 10 mm / min, and then put it in an oven at 120 °C for 4 h to obtain a stainless steel mesh modified with an organic layer, wherein the polyvinyl alcohol solution contains 0.2 wt% 3-isocyanatopropyltrimethoxysilane;

[0059] (3) Prepare 100 mL of 30 mM CaCl₂ aqueous solution with deionized water, stir and dissolve it at room temperature for 30 min, then add 0.05 g of sodium polyacrylate, continue to stir and dissolve for 30 min, then slowly add 100 mL of 30 mM Na₂SO₄ aqueous solution, continue to stir and mix evenly for 30 min, and adjust the pH of the mixed solution to 11.0 with 0.1 mol / L sodium hydroxide aqueous solution and 0.1 mol / L hydrochloric acid aqueous solution to obtain an amorphous mineral aqueous solution;

[0060] (4) Immerse the above-mentioned stainless steel mesh modified with an organic layer in 100 mL of amorphous mineral solution, let it stand and react in a water bath at 30 °C for 8 h, then take it out and air-dry at room temperature to obtain an oil-water separation mineralized mesh with underwater superoleophobic properties on the surface of the stainless steel grid.

[0061] The water contact angle of this oil-water separation mineralized mesh in air is about 0°, the contact angle of underwater oil droplets (i.e., 1,3-dichloroethane) is 161°, and the separation efficiency for the mixture of cyclohexane and water can reach 99.7%.

[0062] Example 3

[0063] (1) Clean the copper mesh (5×5 cm 2 ) thoroughly by ultrasonic cleaning with absolute ethanol and deionized water for 30 min, then put it in an oven at 50 °C for 1 h to dry, and treat it with a plasma cleaner in high-power mode for 12 min;

[0064] (2) Immerse the above-mentioned copper mesh in a pre-prepared 0.5 wt% chitosan solution. After soaking for 10 min, pull it vertically to form a film at a speed of 5 mm / min, and then put it in an oven at 60 °C for 4 h to obtain a copper mesh modified with an organic layer, wherein the chitosan solution contains 0.4 wt% 3-glycidoxypropyltrimethoxysilane;

[0065] (3) Prepare 100 mL of 10 mM aqueous BaCl₂ solution with deionized water. After stirring and dissolving it at room temperature for 30 min, add 0.05 g of sodium polyacrylate, continue to stir and dissolve for 30 min, then slowly add 100 mL of 30 mM aqueous Na₂SO₄ solution. After continuing to stir and mix evenly for 20 min, adjust the pH of the mixed solution to 11.0 with 0.1 mol / L aqueous sodium hydroxide solution and 0.1 mol / L aqueous hydrochloric acid solution to obtain an amorphous mineral solution;

[0066] (4) Immerse the above copper mesh modified with the organic layer in 100 mL of the amorphous mineral solution. After standing and reacting in a 25 °C water bath for 8 h, take it out and dry it at room temperature to obtain an oil-water separation mineralized reticular membrane with underwater superoleophobic properties on the surface of the copper grid.

[0067] The water contact angle of this oil-water separation mineralized reticular membrane in air is about 0°, and the contact angle of underwater oil droplets (i.e., 1,2-dichloroethane) is 165°. The separation efficiency for the mixture of soybean oil and water can reach 99.8%.

[0068] Example 4

[0069] (1) Ultrasonically clean a stainless steel mesh (5×5 cm 2 ) with absolute ethanol and deionized water for 30 min respectively, then put it into an oven at 50 °C for 1 h to dry, and treat it with a plasma cleaner in high-power mode for 12 min;

[0070] (2) Coat the above grid substrate with the pre-prepared 0.5 wt% polyvinyl alcohol aqueous solution by spin coating, and keep the thickness of the solution layer controlled by the spin coater at 50 μm. After spin coating, put it into an oven at 120 °C and keep it for 4 h to obtain a copper mesh modified with an organic layer, where the polyvinyl alcohol aqueous solution contains 0.1 wt% 3-glycidoxypropyltrimethoxysilane;

[0071] (3) Prepare 100 mL of 30 mM aqueous BaCl₂ solution with deionized water. After stirring and dissolving it at room temperature for 20 min, add 0.06 g of sodium polyacrylate, continue to stir and dissolve for 20 min, then slowly add 100 mL of 20 mM aqueous Na₂SO₄ solution. After continuing to stir and mix evenly for 10 min, adjust the pH of the mixed solution to 11.0 with 0.1 mol / L aqueous sodium hydroxide solution and 0.1 mol / L aqueous hydrochloric acid solution to obtain an amorphous mineral solution;

[0072] (4) Immerse the above stainless steel mesh modified with the organic layer in 100 mL of the amorphous mineral solution. After standing and reacting in a 20 °C water bath for 8 h, take it out and dry it at room temperature to obtain an oil-water separation mineralized reticular membrane with underwater superoleophobic properties on the surface of the stainless steel grid.

[0073] The water-oil separation mineralized mesh has a water contact angle of approximately 0° in air and an oil droplet (i.e., 1,3-dichloroethane) contact angle of 165° underwater. The separation efficiency for a mixture of silicone oil and water can reach 99.6%. The hardness of the water-oil separation mineralized mesh is 2.5 GPa and the Young's modulus is 60.0 GPa as measured by nanoindentation test.

[0074] Figure 2 Figure shows the scanning electron microscope photos of the water-oil separation mineralized mesh at different magnification ratios, indicating that its inorganic layer is composed of mineral nanoparticles.

[0075] Example 5

[0076] (1) Ultrasonically clean the polyester mesh (5×5 cm 2 ) with anhydrous ethanol and deionized water for 30 min, put it in an oven at 50 °C for 1 h to dry, and treat it with a plasma cleaner in high-power mode for 10 min;

[0077] (2) Immerse the above polyester mesh in a pre-prepared 0.2 wt% polyvinyl alcohol solution. After soaking for 10 min, pull it vertically at a speed of 20 mm / min to form a film, and then put it in an oven at 60 °C for 5 h to obtain a polyester mesh modified with an organic layer, wherein the polyvinyl alcohol solution contains 0.05 wt% 3-glycidoxypropyltrimethoxysilane;

[0078] (3) Prepare 100 mL of a 20 mM aqueous BaCl2 solution with deionized water, stir and dissolve it at room temperature for 30 min, then add 0.05 g of sodium polyacrylate, continue to stir and dissolve for 30 min, then slowly add 100 mL of a 20 mM aqueous Na2SO4 solution, continue to stir and mix evenly for 30 min, and adjust the pH of the mixed solution to 12.0 with 0.1 mol / L sodium hydroxide aqueous solution and 0.1 mol / L hydrochloric acid aqueous solution to obtain an amorphous mineral solution;

[0079] (4) Immerse the above polyester mesh modified with an organic layer in 100 mL of the amorphous mineral solution, let it stand and react in a water bath at 26 °C for 10 h, then take it out and dry it at room temperature to obtain a water-oil separation mineralized mesh with underwater superoleophobic properties on the surface of the polyester grid.

[0080] The water-oil separation mineralized mesh has a water contact angle of approximately 0° in air and an oil droplet (i.e., 1,3-dichloroethane) contact angle of 167° underwater. The separation efficiency for a mixture of n-hexane and water can reach 99.9%.

[0081] Example 6

[0082] (1) Ultrasonically clean the stainless steel mesh (5×5 cm 2)Clean it thoroughly by ultrasonic cleaning for 30 min, then put it in an oven at 50 °C for 1 h to dry, and treat it with a plasma cleaner in high-power mode for 10 min;

[0083] (2) Immerse the above-mentioned stainless-steel mesh in a pre-prepared 0.2 wt% polyvinyl alcohol solution. After soaking for 5 min, pull it vertically to form a film at a speed of 12 mm / min, and then put it in an oven at 110 °C for 4 h to obtain a stainless-steel mesh modified with an organic layer, wherein the polyvinyl alcohol solution contains 0.05 wt% 3-isocyanatopropyltrimethoxysilane;

[0084] (3) Prepare 100 mL of a 20 mM CaCl₂ aqueous solution with deionized water. Stir and dissolve it at room temperature for 20 min, then add 0.06 g of sodium polyacrylate, continue to stir and dissolve for 20 min, then slowly add 100 mL of a 20 mM Na₂SO₄ aqueous solution, continue to stir and mix evenly for 10 min, and adjust the pH of the mixed solution to 11.0 with 0.1 mol / L sodium hydroxide aqueous solution and 0.1 mol / L hydrochloric acid aqueous solution to obtain an amorphous mineral solution;

[0085] (4) Immerse the above-mentioned stainless-steel mesh modified with an organic layer in 100 mL of the amorphous mineral solution. After standing and reacting in a water bath at 25 °C for 12 h, take it out and dry it at room temperature to obtain an oil-water separation mineralized mesh with underwater superoleophobic properties on the surface of the stainless-steel grid.

[0086] The water contact angle of this oil-water separation mineralized mesh in air is about 0°, the contact angle of an oil droplet (i.e., 1,3-dichloroethane) underwater is 158°, and the separation efficiency for the mixture of mineral oil and water can reach 99.7%.

[0087] Obviously, the above-mentioned embodiments of the present invention are merely examples for clearly explaining the present invention, rather than limitations on the implementation manners of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation manners here. Any obvious changes or modifications derived from the technical solutions of the present invention still fall within the protection scope of the present invention.

Claims

1. An oil-water separation mineralized mesh, characterized in that, The oil-water separation mineralized reticular membrane comprises an organic layer crosslinked on a grid substrate; and an inorganic layer in-situ mineralized and grown in the organic layer; The organic layer is a polymer layer formed by coating a polymer solution containing a crosslinking agent on the grid substrate and crosslinking; The inorganic layer is an inorganic mineral particle layer in-situ mineralized and grown on the surface of the organic layer; wherein, the inorganic mineral particles contained in the inorganic mineral particle layer are selected from one or more of metal sulfates, metal phosphates, and metal carbonates. When the inorganic mineral particles are selected from metal carbonates, the inorganic mineral particles are at least further selected from metal sulfates and / or metal phosphates.

2. The oil-water separation mineralized reticular membrane according to claim 1, characterized in that The inorganic mineral particles are selected from one or more of calcium sulfate, barium sulfate, strontium sulfate, calcium phosphate, calcium carbonate, and magnesium carbonate.

3. The oil-water separation mineralized reticular membrane according to claim 1, wherein The polymers contained in the polymer solution are selected from one or more of polyvinyl alcohol, cellulose, polyethyleneimine, chitosan, polyacrylamide, and chitin.

4. The oil-water separation mineralized reticular membrane according to claim 1, characterized in that, The crosslinking agent is selected from one or more of 3-glycidoxypropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-acetoxypropyltrimethoxysilane, 3-isocyanatopropyltrimethoxysilane, and 3-methacryloxypropyltrimethoxysilane.

5. The oil-water separation mineralized reticular membrane according to claim 1, wherein The oil-water separation mineralized reticular membrane has a water contact angle close to 0° in the air, showing superhydrophilic properties, and the oil-water separation mineralized reticular membrane has an oil droplet contact angle greater than 155° underwater, showing superoleophobic properties.

6. The preparation method of the oil-water separation mineralized reticular membrane according to any one of claims 1-5, characterized in that, It includes the following steps: 1) Coating a polymer solution containing a crosslinking agent on a grid substrate and drying to form an organic layer; 2) Preparation of an amorphous mineral aqueous solution: Preparing an aqueous solution of mineral cation A with a concentration of 1-100 mM, adding a complexing molecule to the aqueous solution of mineral cation A, stirring and reacting for 0.1-1 h, then adding an aqueous solution of anion B with a concentration of 1-100 mM, stirring and reacting for 0.1-1 h, and adjusting the pH to 10-13 to obtain an amorphous mineral aqueous solution; 3) Formation of the mineralized reticular membrane: Immersing the grid substrate with the organic layer in the amorphous mineral aqueous solution and standing and reacting at 20-50 °C for 2-24 h to obtain the oil-water separation mineralized reticular membrane; Among them, the anion B contained in the aqueous solution of anion B is selected from SO4 2- , PO4 3- , CO3 2- or one or more of them, and when the aqueous solution of anion B contains CO3 2- , it also contains at least any one of SO4 2- , PO4 3- .

7. The preparation method according to claim 6, characterized in that, The mineral cation A contained in the aqueous solution of the mineral cation A is selected from Ca 2+ , Ba 2+ , Mg 2+ , Sr 2+ or more than one of them; The molar ratio of mineral cation A to anion B in the amorphous mineral aqueous solution is 0.1-5.0:

1.

8. The preparation method according to claim 6, characterized in that, The grid substrate is selected from one of stainless steel mesh, copper mesh, iron mesh, aluminum mesh, polypropylene mesh, nylon mesh, polyester mesh, polyurethane mesh, and vinylon mesh.

9. The preparation method according to claim 6, wherein The complexing molecule is selected from one or more of polymaleic acid, polyvinyl acid, polyacrylic acid, polymethacrylic acid, polyvinyl acrylic acid, polyaspartic acid, polyglutamic acid, polyamic acid, polybutenoic acid, and alginic acid; The mass percentage content of the complexing molecule added to the aqueous solution of mineral cation A is 0.0001-0.5%.

10. The application of the oil-water separation mineralized reticular membrane according to any one of claims 1-5 in the oil-water separation of oily sewage.

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