Ceramic-based oil-water separation membrane, and preparation method and application thereof

Abstract

This invention belongs to the field of membrane separation technology, and provides a ceramic-based oil-water separation membrane, its preparation method, and its application. This invention utilizes Ti3C2T... x Particles are peeled into sheets of Ti3C2T x Next, ZIF-62 was synthesized in situ on Ti3C2T sheets. x In the Ti3C2T, ZIF-62... x The interlayer acts as a pillar support, stabilizing Ti3C2T. x Interlayer spacing to prevent Ti3C2T x Excessive expansion in aqueous solution improves separation performance; then ZIF-62 / Ti3C2T x Calcination is performed on ZIF-62 / Ti3C2T. x The ZIF-62 crystal grains in the glass were vitrified to obtain a g ZIF-62 enhances its performance on lamellar Ti3C2T. x The supporting effect of the columns and the stability of the interlayer spacing. Then, regarding a... g ZIF-62 / Ti3C2T x The modification enhances the surface wettability of the ceramic-based oil-water separation membrane, thereby improving its oil-water separation performance.

Description

Technical Field

[0001] This invention relates to the field of membrane separation technology, and in particular to a ceramic-based oil-water separation membrane, its preparation method, and its application. Background Technology

[0002] In recent years, the petrochemical, metal smelting, and pharmaceutical industries have developed rapidly, generating large amounts of oily wastewater. Discharging this wastewater into the environment can have serious consequences, making oil-water separation a major challenge within these industries. Floating oil wastewater and oil-in-water emulsion wastewater are common types of oily wastewater. During crude oil extraction and transportation, operational errors can lead to crude oil leaks, generating large amounts of floating oil, which then forms floating oil wastewater. This wastewater contains a large amount of oil and is difficult to treat. Oil-in-water emulsion wastewater mainly originates from industrial production processes in oil refineries, petrochemical plants, and metal manufacturing. Because it forms stable oil-in-water emulsion droplets, it is also difficult to treat.

[0003] Membrane separation technology has advantages such as low energy consumption, simple operation, and high efficiency, and is widely regarded as an effective water treatment technology. However, existing oil-water separation membranes have poor oil-water separation effects on floating oil wastewater and oil-in-water emulsion wastewater, especially for oily wastewater that is micro- or nano-sized and stable. Summary of the Invention

[0004] In view of this, the purpose of this invention is to provide a ceramic-based oil-water separation membrane, its preparation method, and its application. The ceramic-based oil-water separation membrane prepared by the method provided by this invention has good oil-water separation effect in oil-in-water emulsion wastewater and floating oil wastewater.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution:

[0006] This invention provides a method for preparing a ceramic-based oil-water separation membrane, comprising the following steps:

[0007] Ti3C2T x The particles were peeled off to obtain lamellar Ti3C2T. x ;

[0008] The Ti3C2T sheet x Zinc salt and organic solvent are mixed to obtain zinc salt solution;

[0009] Imidazole and benzimidazole were dissolved to obtain a ligand solution;

[0010] The ligand solution was added to the zinc salt solution, and an ultrasonic synthesis reaction was performed to obtain ZIF-62 / Ti3C2T. x Material;

[0011] The ZIF-62 / Ti3C2T x The material is calcined to obtain a g ZIF-62 / Ti3C2T x Material;

[0012] a g ZIF-62 / Ti3C2T x The material, modifier, and water are mixed and then modified and film-formed sequentially to obtain the ceramic-based oil-water separation membrane.

[0013] Preferably, the stripping includes: removing the Ti3C2T x The particles were dispersed in dimethyl sulfoxide and chemically intercalated to obtain the Ti3C2T sheet. x The Ti3C2T x The ratio of particles to dimethyl sulfoxide is 1 g: 10-20 mL; the chemical intercalation is carried out under stirring conditions, the stirring speed is 600-1200 rpm, and the time is 18-30 h.

[0014] Preferably, the zinc salt comprises zinc acetate or zinc nitrate; the Ti3C2T sheet x The mass ratio of zinc salt to zinc salt is 5 to 15:1.

[0015] Preferably, the mass ratio of imidazole to benzimidazole is 3 to 12:1.

[0016] Preferably, the ultrasonic synthesis reaction has an ultrasonic frequency of 30–60 Hz, a temperature of 20–60 °C, and a time of 2–6 h.

[0017] Preferably, the calcination temperature is 420–480°C, the heating rate to the calcination temperature is 5–15 K / min, and the holding time is 1–10 min.

[0018] Preferably, the modifier comprises one or more of carboxymethyl cellulose, polyethylene glycol, and chitosan, wherein a g ZIF-62 / Ti3C2T x The mass ratio of material to modifier is 1 to 10:1;

[0019] The modification time is 12 to 36 hours.

[0020] Preferably, the membrane formation method is vacuum filtration, and the filter membrane used in the vacuum filtration is a CMC membrane with a pore size of 0.45 μm.

[0021] The present invention also provides a ceramic-based oil-water separation membrane prepared by the preparation method described in the above technical solution.

[0022] This invention also provides the application of the ceramic-based oil-water separation membrane described above in oily wastewater and oil-in-water emulsion wastewater.

[0023] This invention provides a method for preparing a ceramic-based oil-water separation membrane.

[0024] The preparation method provided by this invention uses Ti3C2T x Using granules as raw material, Ti3C2T x The particle surface contains numerous functional groups, enabling it to composite well with other materials; next, this invention uses Ti3C2T x The particles were peeled off to obtain lamellar Ti3C2T. x (Laminated Ti3C2T) x (Single or multiple wafers), Ti3C2T layer x Its layered structure increases the specific surface area and allows the ZIF-62 synthesized in situ to be located within the Ti3C2T layers. x In the layered structure of Ti3C2T, ZIF-62 is present. x The interlayer acts as a pillar support, stabilizing Ti3C2T. x Interlayer spacing to prevent Ti3C2T x Excessive expansion in aqueous solution improves the separation performance of the ceramic-based oil-water separation membrane. Next, the ZIF-62 / Ti3C2T... x The material is calcined to form ZIF-62 / Ti3C2T x The ZIF-62 grains in the material vitrify, forming vitrified ZIF-62 (a g ZIF-62), a g ZIF-62 further enhances its performance on sheet-like Ti3C2T. x The supporting effect of the columns and the stability of the interlayer spacing. Then, regarding a... g ZIF-62 / Ti3C2T x The material was modified to further enhance the oil-water separation performance of the ceramic-based oil-water separation membrane. Furthermore, the preparation method provided by this invention uses simple raw materials and has a simple process flow, facilitating industrial-scale production.

[0025] Furthermore, the present invention specifies that the modifier includes one or more of carboxymethyl cellulose, polyethylene glycol, and chitosan, and utilizes one or more of carboxymethyl cellulose, polyethylene glycol, and chitosan to modify a g ZIF-62 / Ti3C2T x Material modification alters the hydrophilicity and hydrophobicity of ceramic-based oil-water separation membranes, thereby improving their oil-water separation efficiency. Moreover, the modifiers are widely available and inexpensive. Detailed Implementation

[0026] This invention provides a method for preparing a ceramic-based oil-water separation membrane, comprising the following steps:

[0027] Ti3C2T x The particles were peeled off to obtain lamellar Ti3C2T. x ;

[0028] The Ti3C2T sheet x Zinc salt and organic solvent are mixed to obtain zinc salt solution;

[0029] Imidazole and benzimidazole were dissolved to obtain a ligand solution;

[0030] The ligand solution was added to the zinc salt solution, and an ultrasonic synthesis reaction was performed to obtain ZIF-62 / Ti3C2T. x Material;

[0031] The ZIF-62 / Ti3C2T x The material is calcined to obtain a g ZIF-62 / Ti3C2T x Material;

[0032] a g ZIF-62 / Ti3C2T x The material, modifier, and water are mixed and then modified and film-formed sequentially to obtain the ceramic-based oil-water separation membrane.

[0033] Unless otherwise specified, the raw materials used in this invention are preferably commercially available products.

[0034] This invention uses Ti3C2T x The particles were peeled off to obtain lamellar Ti3C2T. x .

[0035] In this invention, the stripping preferably includes: stripping the Ti3C2T x The particles were dispersed in dimethyl sulfoxide and chemically intercalated to obtain the Ti3C2T sheet. x In this invention, the Ti3C2T xThe preferred ratio of particles to dimethyl sulfoxide is 1g:10-20mL, specifically 1g:10mL, 1g:15mL, or 1g:20mL. In this invention, the chemical intercalation is preferably carried out under stirring conditions, with the stirring speed preferably being 600-1200rpm, specifically 600rpm, 700rpm, 800rpm, 900rpm, 1000rpm, 1100rpm, or 1200rpm; the stirring time is preferably 16-32h, specifically 16h, 18h, 24h, 30h, or 32h. After the chemical intercalation, this invention preferably further includes: centrifuging the obtained chemical intercalation solution to collect the solid; and sequentially washing and drying the solid to obtain the Ti3C2T sheet. x In this invention, the sheet-like Ti3C2T x Preferred single-chip Ti3C2T x or multiple Ti3C2T chips x .

[0036] In this invention, Ti3C2T is used. x Particles as raw material, Ti3C2T x The surface of the particles contains a large number of functional groups, which makes it easy to form composite materials with ZIF-62.

[0037] Obtaining Ti3C2T sheets x Subsequently, the present invention will use the Ti3C2T sheet... x Zinc salt and organic solvent (denoted as the first organic solvent) are mixed to obtain a zinc salt solution.

[0038] In this invention, the zinc salt preferably comprises zinc acetate or zinc nitrate, and more preferably zinc acetate. In this invention, the first organic solvent preferably comprises N,N-dimethylformamide (DMF).

[0039] In this invention, the sheet Ti3C2T x The preferred mass ratio of Ti3C2T to zinc salt is 5–15:1, specifically preferably 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, or 15:1. In this invention, the sheet-like Ti3C2T... x The preferred ratio of the amount of organic solvent to the first organic solvent is 1g:50-100mL, and more preferably 1g:50mL, 1g:60mL, 1g:70mL, 1g:80mL, 1g:90mL or 1g:100mL.

[0040] In this invention, the sheet Ti3C2T xThe mixing of zinc salt and organic solvent is preferably carried out under stirring conditions. The stirring speed is preferably 600-1200 rpm, specifically 600 rpm, 700 rpm, 800 rpm, 900 rpm, 1000 rpm, 1100 rpm or 1200 rpm; the stirring time is preferably 1-12 h, more preferably 1 h, 2 h, 5 h, 6 h, 8 h, 9 h, 10 h or 12 h.

[0041] The present invention dissolves imidazole and benzimidazole to obtain a ligand solution.

[0042] In this invention, the solvent in which the imidazole and benzimidazole are dissolved is preferably an organic solvent (denoted as the second organic solvent), and the second organic solvent preferably includes N,N-dimethylformamide (DMF).

[0043] In this invention, the mass ratio of imidazole to benzimidazole is preferably 3 to 12:1, and more preferably 3:1, 4:1, 5:1, 5.2:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1 or 12:1.

[0044] In this invention, the preferred ratio of the imidazole to the second organic solvent is 1.463g:10-30mL, specifically preferably 1.463g:10mL, 1.463g:15mL, 1.463g:20mL, 1.463g:25mL or 1.463g:30mL.

[0045] After obtaining the zinc salt solution and the ligand solution, the present invention adds the ligand solution to the zinc salt solution and performs an ultrasonic synthesis reaction to obtain ZIF-62 / Ti3C2T. x Material.

[0046] In this invention, the mass ratio of zinc salt to imidazole is preferably 0.166:1 to 2, and more preferably 0.166:1, 0.166:1.463, 0.166:1.5 or 0.166:2.

[0047] In this invention, the addition of the ligand solution is preferably carried out under ultrasonic conditions, and the frequency and temperature of the ultrasound are preferably consistent with those of the ultrasonic synthesis reaction described below, which will not be repeated here.

[0048] In this invention, the ultrasonic frequency of the ultrasonic synthesis reaction is preferably 30–60 Hz, specifically 30 Hz, 40 Hz, 50 Hz, or 60 Hz; the temperature is preferably 20–60 °C, specifically 20 °C, 30 °C, 40 °C, 50 °C, or 60 °C; and the time is preferably 2–6 h, specifically 2 h, 3 h, 4 h, 5 h, or 6 h. In this invention, the timing of the ultrasonic synthesis reaction preferably begins after the ligand solution has been completely added.

[0049] Following the ultrasonic synthesis reaction, the present invention preferably further includes: sequentially washing, centrifuging, and drying the obtained ultrasonic synthesis reaction solution to obtain the ZIF-62 / Ti3C2T. x Materials. In this invention, the washing reagent is preferably N,N-dimethylformamide (DMF). In this invention, the drying temperature is preferably 60°C, the drying time is preferably 24 hours, and the drying is preferably carried out in a vacuum drying oven.

[0050] In this invention, the ultrasonic synthesis reaction enables imidazole, benzimidazole, and zinc salt to form ZIF-62 in situ and insert it into the Ti3C2T lamellar structure. x In the layers of Ti3C2T, ZIF-62 x The interlayer acts as a pillar support, stabilizing Ti3C2T. x Interlayer spacing to prevent Ti3C2T x Excessive expansion in aqueous solution improves separation performance.

[0051] ZIF-62 / Ti3C2T was obtained x Following the material, the present invention will use the ZIF-62 / Ti3C2T x The material is calcined to obtain a g ZIF-62 / Ti3C2T x Material.

[0052] In this invention, the calcination temperature is preferably 420–480°C, specifically 420°C, 430°C, 440°C, 450°C, 460°C, 470°C, or 480°C; the heating rate to the calcination temperature is preferably 5–15 K / min, preferably 5 K / min, 6 K / min, 7 K / min, 8 K / min, 9 K / min, 10 K / min, 11 K / min, 12 K / min, 13 K / min, 14 K / min, or 15 K / min; the holding time is preferably 1–10 min, specifically 1 min, 2 min, 3 min, 4 min, 5 min, 6 min, 7 min, 8 min, 9 min, or 10 min. In this invention, the calcination is preferably carried out under a protective atmosphere, preferably argon. In this invention, the calcination is preferably carried out in a tube furnace.

[0053] After calcination, the present invention preferably further includes: cooling the furnace to room temperature under a protective atmosphere to obtain the a. g ZIF-62 / Ti3C2T x Material.

[0054] In this invention, the calcination enables ZIF-62 / Ti3C2T to undergo oxidation. x The ZIF-62 crystal grains in the material vitrify, forming vitrified ZIF-62 (a g ZIF-62); a g ZIF-62 further enhances a g ZIF-62 / Ti3C2T x material a g ZIF-62 vs. Ti3C2T x The column bracing effect and interlayer spacing stability further prevent a g ZIF-62 / Ti3C2T x The material expands excessively in the aqueous solution, which improves the separation performance.

[0055] Get a g ZIF-62 / Ti3C2T x After the material, the present invention will use the a g ZIF-62 / Ti3C2T x The material, modifier, and water are mixed and then modified and film-formed sequentially to obtain the ceramic-based oil-water separation membrane.

[0056] In this invention, the a g ZIF-62 / Ti3C2T x Material preference is based on a g ZIF-62 / Ti3C2T x The material is used in powder form, wherein a g ZIF-62 / Ti3C2T x The particle size of the material powder is preferably less than or equal to 5 μm, and more specifically 5 μm.

[0057] In this invention, the modifier preferably includes one or more of carboxymethyl cellulose (CMC), polyethylene glycol and chitosan, and more preferably carboxymethyl cellulose.

[0058] In this invention, the water is preferably deionized water.

[0059] In this invention, the a g ZIF-62 / Ti3C2T x The mass ratio of material to modifier is preferably 1 to 10:1, more preferably 1 to 5:1, and specifically preferably 1:1, 1.6:1, 1.9:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1 or 10:1.

[0060] In this invention, the a g ZIF-62 / Ti3C2T xThe preferred ratio of material to water is 0.64–3.1 mg:50 mL, specifically 0.64 mg:50 mL, 1.33 mg:50 mL, or 3.1 mg:50 mL.

[0061] In this invention, the modification temperature is preferably room temperature, i.e., neither additional heating nor additional cooling is required. The modification time is preferably 12–36 hours, specifically 12 hours, 18 hours, 24 hours, 30 hours, or 36 hours. The modification is preferably carried out under stirring conditions, with the stirring speed preferably between 600 and 1200 rpm, specifically 600 rpm, 700 rpm, 800 rpm, 900 rpm, 1000 rpm, 1100 rpm, or 1200 rpm.

[0062] After modification, the present invention preferably uses the obtained modified liquid directly to form a film.

[0063] In this invention, the preferred method for forming the film is vacuum filtration, and the filter membrane used for vacuum filtration is preferably a CMC membrane with a pore size of 0.45 μm.

[0064] After film formation, the present invention preferably further includes drying.

[0065] The present invention also provides a ceramic-based oil-water separation membrane prepared by the preparation method described in the above technical solution.

[0066] In this invention, the ceramic-based oil-water separation membrane preferably comprises a base membrane and a composite material attached to the base membrane. In this invention, the base membrane is preferably a CMC membrane, and the pore size of the CMC membrane is preferably 0.45 μm. In this invention, the composite material is preferably modified with α-a... g ZIF-62 / Ti3C2T x Material.

[0067] This invention also provides the application of the ceramic-based oil-water separation membrane described above in oily wastewater and oil-in-water emulsion wastewater.

[0068] In this invention, the droplet size of the emulsion in the oil-in-water emulsion wastewater is preferably 50-200 nm, and the oil-in-water emulsion wastewater is a stable colloidal system.

[0069] The ceramic-based oil-water separation membrane, its preparation method, and its application provided by the present invention will be described in detail below with reference to the embodiments. However, these should not be construed as limiting the scope of protection of the present invention.

[0070] Example 1

[0071] 1g Ti3C2T xThe particles were added to 15 mL of dimethyl sulfoxide and stirred continuously at 800 rpm for 24 h. Then, the mixture was centrifuged, and the collected solids were washed with water and dried to obtain sheet-like Ti3C2T. x .

[0072] 1g of Ti3C2T flakes x Add 0.166 g of zinc acetate to 80 mL of N,N-dimethylformamide (DMF) and stir at 800 rpm for 2 h to obtain a zinc salt solution.

[0073] Weigh 1.463 g imidazole and 0.284 g benzimidazole and add them to 20 mL of LDM to dissolve, thus obtaining the ligand solution.

[0074] Under ultrasonic treatment conditions, the ligand solution was added to the zinc salt solution for ultrasonic synthesis. The ultrasonic synthesis reaction was carried out at a frequency of 40 Hz, a temperature of 20 °C, and a time of 4 h. After the ultrasonic synthesis reaction, the solution was washed with DMF and centrifuged. The obtained solid was dried in a vacuum drying oven at 60 °C for 24 h to obtain ZIF-62 / Ti3C2T. x Material.

[0075] Weigh 0.1g ZIF-62 / Ti3C2T x The material was placed in an argon-protected tubular furnace for calcination, and ZIF-62 / Ti3C2T was calcined using melt cold extraction technology. x The ZIF-62 crystal grains in the material are vitrified, thus obtaining a g ZIF-62 / Ti3C2T x The materials are as follows: the heating rate is controlled at 10K / min, the calcination temperature is 450℃, and the holding time is 5min; after calcination, the materials are cooled to room temperature in the furnace under an argon protective atmosphere and then taken out.

[0076] a g ZIF-62 / Ti3C2T x The material was ground to obtain a particle size of 5 μm. g ZIF-62 / Ti3C2T x Material powder.

[0077] Weigh 0.64 mg of a with a particle size of 5 μm. g ZIF-62 / Ti3C2T x The material powder and 0.34 mg CMC were added to 50 mL of deionized water and stirred at 800 rpm for 24 h for modification. After modification, the modified liquid was transferred to a vacuum filtration device, and a commercial CMC membrane with a pore size of 0.45 μm was vacuum filtered and dried to obtain a ceramic-based oil-water separation membrane.

[0078] 0.2g sodium dodecyl sulfate and 2g lubricating oil were added to 200mL of deionized water and stirred for 1h to obtain a stable oil-in-water emulsion wastewater, wherein the droplet size of the emulsion was 50-200nm.

[0079] Under vacuum filtration, the prepared ceramic-based oil-water separation membrane was used to treat oil-in-water emulsion wastewater.

[0080] Analysis of the TOC results revealed that the ceramic-based oil-water separation membrane achieved an oil-water separation efficiency of 98.34% and a flux of 882.00 L·m⁻¹. -2 ·h -1 .

[0081] Example 2

[0082] 1g Ti3C2T x The particles were added to 15 mL of dimethyl sulfoxide and stirred continuously at 800 rpm for 24 h. Then, the mixture was centrifuged, and the collected solids were washed with water and dried to obtain sheet-like Ti3C2T. x .

[0083] 1g of Ti3C2T flakes x Add 0.166 g of zinc acetate to 80 mL of N,N-dimethylformamide (DMF) solution and stir at 800 rpm for 2 h to obtain zinc salt solution.

[0084] Weigh 1.463 g imidazole and 0.284 g benzimidazole and add them to 20 mL of LDM to dissolve, thus obtaining the ligand solution.

[0085] Under ultrasonic treatment conditions, the ligand solution was added to the zinc salt solution for ultrasonic synthesis. The ultrasonic synthesis reaction was carried out at a frequency of 40 Hz, a temperature of 20 °C, and a time of 4 h. After the ultrasonic synthesis reaction, the solution was washed with DMF and centrifuged. The obtained solid was dried in a vacuum drying oven at 60 °C for 24 h to obtain ZIF-62 / Ti3C2T. x Material.

[0086] Weigh 0.1g ZIF-62 / Ti3C2T x The material was placed in an argon-protected tubular furnace for calcination, and ZIF-62 / Ti3C2T was calcined using melt cold extraction technology. x The ZIF-62 crystal grains in the material are vitrified, thus obtaining a g ZIF-62 / Ti3C2T x The materials are as follows: the heating rate is controlled at 10K / min, the calcination temperature is 450℃, the holding time is 5min, and after calcination, the materials are cooled to room temperature in the furnace under an argon protective atmosphere before being taken out.

[0087] ag ZIF-62 / Ti3C2T x The material was ground to obtain a particle size of 5 μm. g ZIF-62 / Ti3C2T x Material powder.

[0088] Weigh 3.1 mg of a with a particle size of 5 μm. g ZIF-62 / Ti3C2T x The material powder and 1.9 mg CMC were added to 50 mL of deionized water and stirred at 800 rpm for 24 h for modification. After modification, the modified liquid was transferred to a vacuum filtration device, and a commercial CMC membrane with a pore size of 0.45 μm was vacuum filtered and dried to obtain a ceramic-based oil-water separation membrane.

[0089] 0.25g sodium dodecyl sulfate and 1g lubricating oil were added to 200mL of deionized water and stirred for 1h to obtain a stable oil-in-water emulsion wastewater, wherein the droplet size of the emulsion was 50-200nm.

[0090] Under vacuum filtration, the prepared ceramic-based oil-water separation membrane was used to treat oil-in-water emulsion wastewater.

[0091] Analysis of the TOC results revealed that the ceramic-based oil-water separation membrane achieved an oil-water separation efficiency of 99.84% and a flux of 63.76 L·m⁻¹. -2 ·h -1 .

[0092] Example 3

[0093] 1g Ti3C2T x The particles were added to 15 mL of dimethyl sulfoxide and stirred continuously at 800 rpm for 24 h. Then, the mixture was centrifuged, and the collected solids were washed with water and dried to obtain sheet-like Ti3C2T. x .

[0094] 1g of Ti3C2T flakes x Add 0.166 g of zinc acetate to 80 mL of N,N-dimethylformamide (DMF) and stir at 800 rpm for 2 h to obtain a zinc salt solution.

[0095] Weigh 1.463 g imidazole and 0.284 g benzimidazole and add them to 20 mL of LDM to dissolve, thus obtaining the ligand solution.

[0096] Under ultrasonic treatment conditions, the ligand solution was added to the zinc salt solution for ultrasonic synthesis. The ultrasonic synthesis reaction was carried out at a frequency of 40 Hz, a temperature of 20 °C, and a time of 4 h. After the ultrasonic synthesis reaction, the solution was washed with DMF and centrifuged. The obtained solid was dried in a vacuum drying oven at 60 °C for 24 h to obtain ZIF-62 / Ti3C2T. x Material.

[0097] Weigh 0.1g ZIF-62 / Ti3C2T x The material was placed in an argon-protected tubular furnace for calcination, and ZIF-62 / Ti3C2T was calcined using melt cold extraction technology. x The ZIF-62 crystal grains in the material are vitrified, thus obtaining a g ZIF-62 / Ti3C2T x The materials are as follows: the heating rate is controlled at 10K / min, the calcination temperature is 450℃, the holding time is 5min, and after calcination, the materials are cooled to room temperature in the furnace under an argon protective atmosphere before being taken out.

[0098] a g ZIF-62 / Ti3C2T x The material was ground to obtain a particle size of 5 μm. g ZIF-62 / Ti3C2T x Material powder.

[0099] Weigh 1.33 mg of a with a particle size of 5 μm. g ZIF-62 / Ti3C2T x The material powder and 0.67 mg CMC were added to 50 mL of deionized water and stirred at 800 rpm for 24 h for modification. After modification, the modified liquid was transferred to a vacuum filtration device, and a commercial CMC membrane with a pore size of 0.45 μm was vacuum filtered and dried to obtain a ceramic-based oil-water separation membrane.

[0100] Dissolve 0.005g of Sudan III in 50mL of n-hexane and mix with 50mL of deionized water to obtain stratified oily wastewater.

[0101] Under vacuum filtration, the prepared ceramic-based oil-water separation membrane was used to treat stratified floating oil wastewater. It was found that water and n-hexane could be easily separated. By analyzing the TOC results, it was found that the oil-water separation efficiency of the ceramic-based oil-water separation membrane can reach 99.99%.

[0102] Comparative Example 1

[0103] 0.2g sodium dodecyl sulfate and 2g lubricating oil were added to 200mL of deionized water and stirred for 1h to obtain a stable oil-in-water emulsion wastewater, wherein the droplet size of the emulsion was 50-200nm.

[0104] Commercial CMC membranes are used to treat oil-in-water emulsion wastewater directly.

[0105] Analysis of the TOC results revealed that the CMC membrane achieved an oil-water separation efficiency of 71.36% and a flux of 140.50 L·m⁻¹. -2 ·h -1 .

[0106] Dissolve 0.005g of Sudan III in 50mL of n-hexane and mix with 50mL of deionized water to obtain stratified oily wastewater.

[0107] When commercial CMC membranes were used to treat stratified oily wastewater, it was found that the oil could not be separated well, and there was a colored oil phase in the aqueous phase.

[0108] Comparative Example 2

[0109] ZIF-62 / Ti3C2T was obtained according to the method in Example 1. x Material.

[0110] ZIF-62 / Ti3C2T x The material was ground to obtain ZIF-62 / Ti3C2T with a particle size of 5μm. x Material powder.

[0111] 5 mg of ZIF-62 / Ti3C2T with a particle size of 5 μm was added. x The material powder was dispersed in 100 mL of deionized water. After thorough dispersion, the dispersion was transferred to a vacuum filtration device, and a film was formed by vacuum filtration on a commercial CMC membrane with a pore size of 0.45 μm and then dried to obtain a ceramic-based oil-water separation membrane.

[0112] 0.2g sodium dodecyl sulfate and 2g lubricating oil were added to 200mL of deionized water and stirred for 1h to obtain a stable oil-in-water emulsion wastewater, wherein the droplet size of the emulsion was 50-200nm.

[0113] Analysis of the TOC results revealed that the ceramic-based oil-water separation membrane achieved an oil-water separation efficiency of 87.32% and a flux of 81.00 L·m⁻¹. -2 ·h -1 .

[0114] Comparative Example 3

[0115] Following the method in Example 1, a particle size of 5 μm was obtained. g ZIF-62 / Ti3C2T x Material powder.

[0116] 5 mg of a with a particle size of 5 μm was placed. gZIF-62 / Ti3C2T x The material powder was dispersed in 100 mL of deionized water. After thorough dispersion, the dispersion was transferred to a vacuum filtration device, and a film was formed by vacuum filtration on a commercial CMC membrane with a pore size of 0.45 μm and then dried to obtain a ceramic-based oil-water separation membrane.

[0117] 0.2g sodium dodecyl sulfate and 2g lubricating oil were added to 200mL of deionized water and stirred for 1h to obtain a stable oil-in-water emulsion wastewater, wherein the droplet size of the emulsion was 50-200nm.

[0118] Analysis of the TOC results revealed that the ceramic-based oil-water separation membrane achieved an oil-water separation efficiency of 91.07% and a flux of 90.07 L·m⁻¹. -2 ·h -1 .

[0119] In summary, the ceramic-based oil-water separation membrane prepared by this invention is suitable for the efficient separation of oil and water in stable emulsified wastewater and floating oil wastewater. Furthermore, the raw materials for preparing the ceramic-based oil-water separation membrane are widely available, and the operation method is simple, which can provide a new direction for the oil-water separation industry and make a positive contribution to reducing material consumption.

[0120] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A method for preparing a ceramic-based oil-water separation membrane, characterized in that, Includes the following steps: Ti3C2T x The particles were peeled off to obtain lamellar Ti3C2T. x ; The Ti3C2T sheet x Zinc salt and organic solvent are mixed to obtain zinc salt solution; Imidazole and benzimidazole were dissolved to obtain a ligand solution; The ligand solution was added to the zinc salt solution, and an ultrasonic synthesis reaction was performed to obtain ZIF-62 / Ti3C2T. x Material; The ZIF-62 / Ti3C2T x The material is calcined to obtain a g ZIF-62 / Ti3C2T x Material; a g ZIF-62 / Ti3C2T x The material, modifier, and water are mixed and then modified and film-formed sequentially to obtain the ceramic-based oil-water separation membrane. The calcination temperature is 420–480°C; The modifier includes one or more of carboxymethyl cellulose, polyethylene glycol, and chitosan.

2. The preparation method according to claim 1, characterized in that, The stripping includes: removing the Ti3C2T x The particles were dispersed in dimethyl sulfoxide and chemically intercalated to obtain the Ti3C2T sheet. x The Ti3C2T x The ratio of particles to dimethyl sulfoxide is 1 g: 10-20 mL; the chemical intercalation is carried out under stirring conditions, the stirring speed is 600-1200 rpm, and the time is 18-30 h.

3. The preparation method according to claim 1, characterized in that, The zinc salt includes zinc acetate or zinc nitrate; the Ti3C2T sheet x The mass ratio of zinc salt to zinc salt is 5 to 15:

1.

4. The preparation method according to claim 1, characterized in that, The mass ratio of imidazole to benzimidazole is 3 to 12:

1.

5. The preparation method according to claim 1, characterized in that, The ultrasonic synthesis reaction has an ultrasonic frequency of 30–60 Hz, a temperature of 20–60 °C, and a time of 2–6 h.

6. The preparation method according to claim 1, characterized in that, The heating rate to the calcination temperature is 5–15 K / min, and the holding time is 1–10 min.

7. The preparation method according to claim 1, characterized in that, The a g ZIF-62 / Ti3C2T x The mass ratio of material to modifier is 1 to 10:1; The modification time is 12 to 36 hours.

8. The preparation method according to claim 1, characterized in that, The membrane formation method is vacuum filtration, and the filter membrane used in the vacuum filtration is a CMC membrane with a pore size of 0.45 μm.

9. The ceramic-based oil-water separation membrane prepared by the preparation method according to any one of claims 1 to 8.

10. The application of the ceramic-based oil-water separation membrane according to claim 9 in oily wastewater and oil-in-water emulsion wastewater.