CN115262280B - Fiber paper and preparation method and application thereof - Google Patents

Abstract

The invention provides fiber paper, a preparation method and application thereof, wherein the fiber paper comprises a three-dimensional network structure formed by oxide ceramic fibers and titanium particles and/or titanium sheets on the surfaces of the oxide ceramic fibers. The preparation method of the fiber paper comprises the following steps: (1) Uniformly mixing oxide sol, polymer and solvent, and then carrying out electrostatic spinning to obtain an oxide ceramic fiber paper green body; (2) And (3) carrying out hydrothermal reaction on the oxide ceramic fiber paper green body obtained in the step (1) and the titanium solution in an acidic environment, and sintering the obtained product to obtain the fiber paper. The fiber paper has super-strong hydrophilicity and good flexibility, and can be used in oil-water separation materials.

Description

Fiber paper and preparation method and application thereof

Technical field

The invention belongs to the technical field of oil-water separation materials, and specifically relates to a fiber paper and its preparation method and application.

Background technique

During the extraction, transportation and use of oil products and in people's daily lives, a large amount of oily wastewater will inevitably be generated. According to incomplete statistics, global oily wastewater emissions have reached more than 10 billion tons in 2020, and are still rising year by year. Oily sewage has high chemical oxygen consumption and is directly discharged into the environment, causing serious pollution to soil, rivers and oceans. In order to reduce the harm of oil pollution, reasonable oil-water separation technology must be used to remove oil pollutants in oily wastewater. At present, commonly used oil-water separation technologies such as gravity separation, flotation, oil separation, flocculation, etc. all have problems such as low separation efficiency, high energy consumption, complicated operations, or causing secondary pollution. In addition, oil substances in water are also valuable resources. Commonly used oil-water separation technologies are difficult to achieve direct recovery of oil resources in water at the same time. Therefore, the research on oil-water separation technology has important application significance.

Based on the difference in affinity to oil and water, the technology of using materials with special surface wettability to separate oil and water driven by gravity can effectively alleviate the shortcomings of traditional oil and water separation methods. It is an emerging oily wastewater treatment technology. CN107456879A discloses a nanosilica/nanofiber membrane oil-water separation composite membrane and a preparation method thereof. This method uses nanosilica and fiber membranes as raw materials to prepare super-hydrophilic nanofiber membrane materials, but the use temperature is not high. and the problem of pressure penetration caused by the accumulation of trapped oil phase; CN110327663A discloses a super hydrophilic TiO ₂ film and its preparation method. The method uses tetrabutyl titanate and deionized water as precursors, and passes through the plasma Deposition technology deposits TiO2 thin films on stainless steel mesh to improve the hydrophilicity of the material, but has the disadvantages of low filtration efficiency, high cost and uncontrollable material structure. In particular, oxide ceramic materials have good corrosion resistance, high temperature resistance, high flexibility and adjustable wettability, and have high application potential in the field of oily wastewater treatment. Therefore, it is of great research significance to use oxide ceramic materials to prepare an oil-water separation material with super hydrophilicity, high temperature resistance and good flexibility.

Contents of the invention

In view of the shortcomings of the existing technology, the purpose of the present invention is to provide a fiber paper and its preparation method and application. The present invention prepares a ceramic fiber material with high temperature resistance, high flexibility and adjustable wettability. Fiber paper material with a three-dimensional network structure, and then introducing titanium particles and/or titanium sheet nanostructures to the surface of the fiber paper to improve its roughness and enhance the hydrophilicity of the material to achieve efficient filtration of oily wastewater and at the same time make the fiber paper It has the advantages of high temperature resistance and good flexibility.

To achieve this goal, the present invention adopts the following technical solutions:

In a first aspect, the present invention provides a fiber paper that includes a three-dimensional network structure composed of oxide ceramic fibers and titanium particles and/or titanium sheets on the surface of the oxide ceramic fibers.

Oxide ceramic materials have the advantages of high temperature resistance, high flexibility and adjustable wettability. The present invention prepares fiber paper with a three-dimensional network structure by selecting oxide ceramic materials, and introduces titanium particles and/or titanium It is attached to the surface of the fiber paper to increase its roughness and enhance the hydrophilicity of the material, thus giving the fiber paper the characteristics of high temperature resistance, good flexibility and super hydrophilicity.

In the present invention, the mass percentage of oxide ceramic fibers in the fiber paper is 80-90%, for example, it can be 82%, 83%, 84%, 85%, 86%, 87%, 88% or 89% , and the specific point values between the above-mentioned point values. Due to space limitations and for the sake of simplicity, the present invention will not exhaustively list the specific point values included in the stated range.

Preferably, the material of the oxide ceramic fiber is selected from any one or a combination of at least two of TiO ₂ , Al ₂ O ₃ , SiO ₂ or ZrO ₂ .

Preferably, the particle diameter of the titanium particles is 10 to 100nm, for example, it can be 20nm, 30nm, 40nm, 50nm, 60nm, 70nm, 80nm or 90nm, and the specific point value between the above point values is limited by space and for the sake of For the sake of simplicity, the present invention does not exhaustively list the specific points included in the stated range.

Preferably, the diameter of the titanium sheet is 100 to 500nm, for example, it can be 150nm, 200nm, 250nm, 300nm, 350nm, 400nm or 450nm, and specific points between the above points are limited by space and for the sake of simplicity. It is contemplated that the present invention is not intended to be an exhaustive list of specific points included in the stated range.

Preferably, the material of the titanium particles and/or titanium sheets is titanium oxide.

In a second aspect, the present invention provides a method for preparing fiber paper as described in the first aspect, the preparation method comprising the following steps:

(1) Mix the oxide sol, polymer and solvent evenly, and perform electrospinning to obtain a green oxide ceramic fiber paper;

(2) The oxide ceramic fiber paper green body obtained in step (1) and the titanium solution are subjected to a hydrothermal reaction in an acidic environment, and the obtained product is sintered to obtain the fiber paper.

In the present invention, the oxide sol is prepared from a precursor solution.

Preferably, the temperature of the preparation is 60-80°C, for example, it can be 62°C, 65°C, 68°C, 70°C, 72°C, 75°C, 78°C or 79°C, as well as specific points between the above points. Values, due to space limitations and for the sake of simplicity, the present invention will not exhaustively list the specific point values included in the stated range.

Preferably, the oxide sol is selected from any one of TiO ₂ sol, Al ₂ O ₃ sol, SiO ₂ sol or ZrO ₂ sol.

Preferably, the mass percentage of oxide in the oxide sol is 3 to 50%, for example, it can be 5%, 10%, 12%, 15%, 18%, 20%, 22%, 25%, 30% %, 35%, 40%, 42%, 45% or 48%, as well as specific points between the above points. Due to space limitations and for the sake of simplicity, the present invention will not exhaustively list the specific points included in the range. value.

Preferably, the precursor of the _TiO sol is selected from tetrabutyl titanate and/or isopropyl titanate.

Preferably, the precursor of the Al ₂ O ₃ sol is aluminum chloride.

Preferably, the precursor of the SiO _sol is ethyl orthosilicate.

Preferably, the precursor of the _ZrO sol is zirconium n-propoxide.

Preferably, the solvent of the precursor solution includes an acid solution and optionally ethanol and/or N,N-dimethylformamide.

Preferably, the acid solution is selected from any one or a combination of at least two of acetic acid solution, hydrochloric acid solution, sulfuric acid solution or nitric acid solution.

Preferably, the mass ratio of oxide to polymer in the oxide sol is 1: (0.5-1.5), for example, it can be 1:0.6, 1:0.7, 1:0.8, 1:0.9, 1:1, 1 :1.2, 1:1.3 or 1:1.4 etc.

Preferably, the polymer is selected from any one or a combination of at least two of polyvinylpyrrolidone, polyacrylonitrile, polyvinyl alcohol or polycaprolactone.

Preferably, the weight average molecular weight of the polymer is 70,000 to 1,300,000, for example, it can be 80,000, 100,000, 200,000, 300,000, 500,000, 800,000, 1,000,000, 1,100,000 or 1,200,000, and specific points between the above points are limited by space. And for the sake of simplicity, the present invention does not exhaustively list the specific point values included in the stated range.

In the present invention, the solvent in step (1) is selected from any one or a combination of at least two of water, alcohol, acetic acid or N,N-dimethylformamide.

Preferably, the titanium solution is selected from any one or a combination of at least two of tetrabutyl titanate solution, isopropyl titanate solution or TiO ₂ solution.

Preferably, the solvent of the titanium solution is selected from any one or a combination of at least two of water, ethanol, acetic acid or N,N-dimethylformamide.

Preferably, the mass percentage of the solute in the titanium solution is 20-40%, for example, it can be 22%, 24%, 25%, 28%, 30%, 32%, 34%, 35%, 36%, 37%, 38% or 39%, as well as specific point values between the above points. Due to space limitations and for the sake of simplicity, the present invention will not exhaustively list the specific point values included in the stated range.

Preferably, the mass ratio of the oxide in the oxide sol to the solute in the titanium solution is 1: (0.1-10.6), for example, it can be 1:0.2, 1:0.5, 1:1, 1:2, 1:4 , 1:6, 1:8, 1:9 or 1:10, etc.

In the present invention, the electrospinning voltage is 10-30KV, for example, it can be 12KV, 14KV, 15KV, 16KV, 18KV, 20KV, 22KV, 24KV, 26KV, 28KV or 29KV, as well as specific points between the above points. Values, due to space limitations and for the sake of simplicity, the present invention will not exhaustively list the specific point values included in the stated range.

Preferably, the electrospinning temperature is 20-45°C, for example, it can be 22°C, 24°C, 25°C, 28°C, 30°C, 32°C, 35°C, 38°C, 40°C, 42°C or 44°C. °C, as well as specific point values between the above points. Due to space limitations and for the sake of simplicity, the present invention will not exhaustively list the specific point values included in the stated range.

Preferably, the humidity of the electrospinning is 10 to 90%, for example, it can be 15%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 60%, 70%, 80 % or 85%, as well as specific point values between the above points. Due to space limitations and for the sake of simplicity, the present invention will not exhaustively list the specific point values included in the stated range.

Preferably, the acidic environment is provided by adding an acid solution prior to the hydrothermal reaction.

Preferably, the acid solution is selected from any one or a combination of at least two of hydrochloric acid solution, sulfuric acid solution or nitric acid solution.

Preferably, the mass percentage of the solute in the acid solution is 5 to 20%, for example, it can be 6%, 8%, 10%, 12%, 14%, 15%, 16%, 17%, 18% or 19%, and the specific point values between the above points. Due to space limitations and for the sake of simplicity, the present invention will not exhaustively list the specific point values included in the stated range.

Preferably, the mass ratio of the oxide sol to the acid solution is 1: (0.5-7), for example, it can be 1:1, 1:2, 1:3, 1:4, 1:5, 1:6 or 1:6.5 etc.

In the present invention, the temperature of the hydrothermal reaction is 120-200°C, for example, it can be 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C or 195°C, and between the above points. Due to space limitations and for the sake of simplicity, the present invention will not exhaustively list the specific point values included in the range.

Preferably, the time of the hydrothermal reaction is 2 to 10 h, for example, it can be 3h, 4h, 5h, 6h, 7h, 8h or 9h, and specific points between the above points are limited by space and for the sake of simplicity. It is contemplated that the present invention is not intended to be an exhaustive list of specific points included in the stated range.

Preferably, the sintering temperature is 600-1500°C, for example, it can be 700°C, 800°C, 900°C, 1000°C, 1100°C, 1200°C, 1300°C or 1400°C, as well as specific points between the above points. Values, due to space limitations and for the sake of simplicity, the present invention will not exhaustively list the specific point values included in the stated range.

Preferably, the sintering time is 2 to 12h, for example, it can be 3h, 4h, 5h, 6h, 7h, 8h, 9h, 10h or 11h, and specific points between the above points are limited by space and reasons. For the sake of simplicity, the present invention does not exhaustively list the specific points included in the stated range.

Preferably, the sintering is performed in an air atmosphere.

As a preferred technical solution of the present invention, the preparation method specifically includes the following steps:

(1) Prepare a precursor solution to obtain an oxide sol;

(2) After mixing the oxide sol, polymer and solvent obtained in step (1) evenly, perform electrospinning under the conditions of a voltage of 10 to 30KV, a temperature of 20 to 45°C, and a humidity of 10 to 90%. Obtain oxide ceramic fiber paper green body; the mass ratio of oxide and polymer in the oxide sol is 1: (0.5-1.5);

(3) Mix the oxide ceramic fiber paper green body obtained in step (2), the titanium solution and the acid solution, and perform a hydrothermal reaction at 120 to 200°C for 2 to 10 hours. The obtained product is heated in an air atmosphere at a temperature of 600 to The fiber paper is obtained by sintering at 1500°C for 2 to 12 hours; the mass ratio of the oxide in the oxide sol to the solute in the titanium solution is 1: (0.1 to 10.6), and the mass ratio of the oxide sol to the acid solution is is 1: (0.5-7), and the titanium solution is selected from any one or a combination of at least two of tetrabutyl titanate solution, isopropyl titanate solution or TiO ₂ nanometer solution.

In a third aspect, the present invention provides an application of the fiber paper as described in the first aspect in oil-water separation materials.

Compared with the existing technology, the present invention has the following beneficial effects:

The present invention prepares fiber paper materials with a three-dimensional network structure by selecting ceramic fiber materials with high temperature resistance, high flexibility and adjustable wettability, and then introduces titanium particles and/or titanium sheet nanostructures to the surface of the fiber paper. To improve its roughness and enhance the oleophobicity of the material, through the specific ratio of oxide ceramics and titanium particles and/or titanium sheets, the oil droplet contact angle of fiber paper can reach more than 155°, and the oil-water separation efficiency can reach more than 99%. , the bending stiffness can reach 0.0098gf/cm, has good flexibility, and can withstand high temperatures up to 1450°C.

Description of the drawings

Figure 1 is a scanning electron microscope image of the surface of the fiber paper provided in Embodiment 1 of the present invention;

Figure 2 is a diagram showing the effect of using the fiber paper provided in Embodiment 1 of the present invention for oil-water separation.

Detailed ways

The technical solution of the present invention will be further described below through specific implementations. Those skilled in the art should understand that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

The materials used in the following examples and comparative examples of the present invention include:

Polyvinyl alcohol: Shanghai Merrill, PVA-224.

Example 1

This embodiment provides a fiber paper and a preparation method thereof. The fiber paper includes a three-dimensional network structure composed of TiO ₂ ceramic fibers and titanium particles and/or titanium sheets on the surface of the TiO ₂ ceramic fibers. The mass percentage of TiO ₂ ceramic fibers in the fiber paper is 85%.

The preparation method of the fiber paper includes the following steps:

(1) Prepare a solution of tetrabutyl titanate, acetic acid and ethanol in a ratio of 26:7:7 to obtain a TiO ₂ sol with a TiO ₂ mass fraction of 30%;

(2) After mixing the TiO sol, polyvinyl alcohol and ethanol obtained in step (1) evenly, perform electrospinning at a voltage of 20KV, a temperature of 30 _° C and a humidity of 50% to obtain TiO ₂ ceramic fibers. Paper green body; the mass ratio of TiO ₂ and polymer in the TiO ₂ sol is 1:1;

(3) Mix the TiO ₂ ceramic fiber paper green body obtained in step (2), a 30% by mass tetrabutyl titanate solution and a 10% by mass hydrochloric acid solution, and hydrotherm it at a temperature of 160°C. The reaction was carried out for 6 hours, and the obtained product was sintered in an air atmosphere at a temperature of 1000°C for 7 hours to obtain the fiber paper. The mass ratio of TiO ₂ to tetrabutyl titanate in the TiO sol is 1:0.75, and the mass ratio _of the _TiO sol to the hydrochloric acid solution is 1:4.

Example 2

This embodiment provides a fiber paper and a preparation method thereof. The fiber paper includes a three-dimensional network structure composed of TiO ₂ ceramic fibers and titanium particles and/or titanium sheets on the surface of the TiO ₂ ceramic fibers. The mass percentage of TiO ₂ ceramic fibers in the fiber paper is 90%.

The preparation method of the fiber paper includes the following steps:

(1) Prepare a solution of tetrabutyl titanate, acetic acid and ethanol in a ratio of 17:18:18 to obtain a TiO ₂ sol with a TiO ₂ mass fraction of 10%;

(2) After mixing the TiO sol, polyvinyl alcohol and ethanol obtained in step (1) evenly, perform electrospinning under the conditions of a voltage of 10KV, a temperature of 20° _C and a humidity of 10% to obtain TiO ₂ ceramic fibers Paper green body; the mass ratio of TiO ₂ and polymer in the TiO ₂ sol is 1:1.5;

(2) Mix the TiO ₂ ceramic fiber paper green body obtained in step (2), a TiO ₂ solution with a mass percentage of 40%, and a hydrochloric acid solution with a mass fraction of 12%, and conduct a hydrothermal reaction at 120°C for 2 hours. The product was sintered in an air atmosphere at a temperature of 600°C for 2 hours to obtain the fiber paper. The mass ratio of TiO _{2 to} tetrabutyl titanate in the TiO sol is 1:0.5, and the mass ratio of the _TiO sol to hydrochloric acid solution is 1:7.

Example 3

This embodiment provides a fiber paper and a preparation method thereof. The fiber paper includes a three-dimensional network structure composed of Al ₂ O ₃ ceramic fibers and titanium particles and/or titanium sheets on the surface of the Al ₂ O ₃ ceramic fibers. The mass percentage of Al ₂ O ₃ ceramic fiber in the fiber paper is 80%.

The preparation method of the fiber paper includes the following steps:

(1) Prepare a solution of aluminum chloride, acetic acid and ethanol in a ratio of 8:1:1 and heat it to 80°C to obtain an Al ₂ O ₃ sol with an Al ₂ O ₃ mass fraction of 50%;

(2) After mixing the Al ₂ O ₃ sol, polyvinyl alcohol and ethanol obtained in step (1) evenly, perform electrospinning under the conditions of a voltage of 30KV, a temperature of 45°C and a humidity of 90% to obtain Al ₂ O ₃ ceramic fiber paper green body;

(3) Mix the Al ₂ O ₃ ceramic fiber paper green body obtained in step (2), the mass fraction of 20% tetrabutyl titanate and the mass fraction of 20% hydrochloric acid, and conduct a hydrothermal reaction at 300°C for 2 hours to obtain The product was sintered in an air atmosphere at a temperature of 1500°C for 12 hours to obtain the fiber paper. The mass ratio of Al ₂ O ₃ to tetrabutyl titanate in the Al ₂ O ₃ sol is 1:1.1, and the mass ratio of the Al ₂ O ₃ sol to the hydrochloric acid solution is 1:7.

Example 4

This embodiment provides a fiber paper and a preparation method thereof. The fiber paper includes a three-dimensional network structure composed of Al ₂ O ₃ ceramic fibers and titanium particles and/or titanium sheets on the surface of the Al ₂ O ₃ ceramic fibers. The mass percentage of Al ₂ O ₃ ceramic fibers in the fiber paper is 85%.

(1) Prepare a solution of aluminum chloride, acetic acid and water in a ratio of 5:3:3 and heat it to 80°C to obtain an Al ₂ O ₃ sol with an Al ₂ O ₃ mass fraction of 25%;

(2) After mixing the Al ₂ O ₃ sol, polyvinyl alcohol and ethanol obtained in step (1) evenly, perform electrospinning under the conditions of a voltage of 15KV, a temperature of 25°C and a humidity of 55% to obtain Al ₂ O ₃ ceramic fiber paper green body;

(3) Mix the Al ₂ O ₃ ceramic fiber paper green body obtained in step (1), a solution of 20% mass fraction of tetrabutyl titanate and 10% mass fraction of hydrochloric acid, and perform a hydrothermal reaction at 150°C. 2h, the obtained product was dried at 110°C for 24h and sintered at 1450°C for 2h in an air atmosphere to obtain the fiber paper. The mass ratio of Al ₂ O ₃ to tetrabutyl titanate in the Al ₂ O ₃ sol is 1:1.1, and the mass ratio of the Al ₂ O ₃ sol to the hydrochloric acid solution is 1:4.

Example 5

(1) Prepare a solution of tetrabutyl titanate, acetic acid and ethanol in a mass ratio of 1:3:3 to obtain a TiO ₂ sol with a TiO ₂ mass fraction of 3%;

(2) After mixing the TiO sol, polyvinyl alcohol and ethanol obtained in step (1) evenly, perform electrospinning at a voltage of 20KV, a temperature of 25 _° C and a relative humidity of 45% to obtain TiO ₂ ceramics Fiber paper green body;

(3) Mix the TiO ₂ ceramic fiber paper green body obtained in step (2) with a 30% mass fraction of tetrabutyl titanate solution and a 12% mass fraction of hydrochloric acid, and perform a hydrothermal reaction at 180°C for 3 hours. , and finally the obtained material was dried at 110°C for 12 hours and sintered at 600°C for 2 hours in an air atmosphere to obtain the fiber paper. The mass ratio of TiO ₂ to tetrabutyl titanate in the TiO sol is 1:1.1, and the mass ratio _of the _TiO sol to hydrochloric acid solution is 1:4.

Example 6

This embodiment provides a fiber paper and a preparation method thereof. The difference between the fiber paper and Example 1 is that the mass percentage of TiO2 ceramic fibers in the fiber paper is 60%. In step (2) of the preparation method, The mass ratio of TiO _{2 to} tetrabutyl titanate in the TiO sol is 1:2.8, and other raw materials, dosages and preparation processes are the same as in Example 1.

Example 7

This embodiment provides a fiber paper and a preparation method thereof. The difference between the fiber paper and Example 1 is that the mass percentage of TiO ₂ ceramic fibers in the fiber paper is 95%, and the step (2) of the preparation method is The mass ratio of TiO ₂ and tetrabutyl titanate in the TiO ₂ sol described in is 1:0.2, and other raw materials, dosages and preparation processes are the same as in Example 1.

Example 8

This embodiment provides a fiber paper and a preparation method thereof. The only difference between the preparation method and Example 1 is that the mass ratio of TiO ₂ to polymer in the TiO ₂ sol in step (1) is 1:0.2, and the other The raw materials, dosage and preparation process are the same as in Example 1.

Example 9

This embodiment provides a fiber paper and a preparation method thereof. The only difference between the preparation method and Example 1 is that the mass ratio of TiO ₂ to polymer in the TiO ₂ sol in step (1) is 1:2, and the other The raw materials, dosage and preparation process are the same as in Example 1.

Comparative example 1

This comparative example provides a fiber paper and a preparation method thereof. The fiber paper includes a three-dimensional network structure composed of TiO2 ceramic fibers.

The preparation method of the fiber paper includes the following steps:

(1) Prepare a solution of tetrabutyl titanate, acetic acid and ethanol in a ratio of 6:7:7 to obtain a TiO ₂ sol with a TiO ₂ mass fraction of 30%;

(2) After mixing the TiO sol, polyvinyl alcohol and ethanol obtained in step (1) evenly, perform electrospinning at a voltage of 20KV, a temperature of 30 _° C and a humidity of 50% to obtain TiO ₂ ceramic fibers. Paper green;

(3) The obtained TiO ₂ ceramic fiber paper green body was sintered in an air atmosphere at a temperature of 1000°C for 7 hours to obtain the fiber paper.

Comparative example 2

This comparative example provides a fiber paper and a preparation method thereof. The fiber paper includes a three-dimensional network structure composed of polyvinyl alcohol fibers and titanium particles and/or titanium sheets on the surface of the polyvinyl alcohol fibers. The mass percentage of polyvinyl alcohol fiber in the fiber paper is 85%.

The preparation method of the fiber paper includes the following steps:

(1) Electrospinning a polyvinyl alcohol solution with a solute mass percentage of 85% at a voltage of 20KV, a temperature of 30°C, and a humidity of 50% to obtain a green polyvinyl alcohol fiber paper;

(2) Hydrothermally react the polyvinyl alcohol fiber paper green body obtained in step (1), a tetrabutyl titanate solution with a mass percentage of 30% and a hydrochloric acid solution with a mass fraction of 12% at 160°C for 6 hours to obtain The fiber paper. The mass ratio of the polyvinyl alcohol to tetrabutyl titanate is 1:0.75, and the mass ratio of the polyvinyl alcohol solution to the hydrochloric acid solution is 1:4.

Performance Testing:

(1) Scanning electron microscope test: The surface morphology of the fiber paper provided in Example 1 was tested using a scanning electron microscope (Hitachi Scientific Instruments Co., Ltd., Japan, model SU8020); the test results are shown in Figure 1.

(2) Bulk density test: Bulk density test was performed on the fiber papers provided in Examples 1-9 and Comparative Examples 1-3. The test results are shown in Table 1.

(3) Bending stiffness test: Use a bending stiffness tester (Japanese KATO company, KES-FB2S model) to conduct a bending stiffness test on the fiber paper provided in Examples 1-9 and Comparative Examples 1-3 to characterize its flexibility. The test results See Table 1.

(4) Oleophobicity test: Use a contact angle meter (Kruss, Germany, K100 type) to conduct an oleophobic property test on the fiber papers provided in Examples 1-9 and Comparative Examples 1-3. The test results are shown in Table 1.

(5) Oil-water separation efficiency test: According to the marine oil-water separability determination method SH/T 0619-1995, the oil-water separation efficiency test was performed on the fiber paper provided in Examples 1-9 and Comparative Examples 1-3. The test results are shown in Table 1; The effect diagram of the fiber paper provided in Example 1 for oil-water separation is shown in Figure 2. A large number of oil droplets can be observed in the mixed liquid before oil-water separation under an optical microscope. The aqueous phase liquid after oil-water separation is observed under an optical microscope. , it can be observed that there are only a few oil droplets in the photo, and the size of the oil droplets is very small, indicating that the oil-water separation efficiency of the fiber paper provided in the embodiment is very high. The scales of the optical micrographs before and after separation in Figure 2 are the same.

(6) High temperature resistance test: According to the national standard GB/T7322-2017, the fiber paper provided in Examples 1-9 and Comparative Examples 1-3 was tested for high temperature resistance. The test results are shown in Table 1.

Table 1

According to the data in Table 1, it can be seen from the comparison between Example 1 and Examples 6 and 7 that when the content of oxide ceramics in the fiber paper is higher, the flexibility of the fiber paper will increase, that is, the bending stiffness will decrease; when When the content of titanium particles and/or titanium flakes in the fiber paper is too high, the pore size of the network formed by the oxide ceramic fibers will be too small, thus affecting the oleophobicity of the fiber paper and the throughput of the water-oil mixture, reducing the efficiency of oil-water separation. ; When the content of titanium particles and/or titanium flakes in the fiber paper is too low or the content is 0 (Comparative Example 1), the network holes formed by the oxide ceramic fibers are too large, thereby affecting the oleophobicity of the fiber paper, causing oil and water The efficiency of separation is reduced. It can be seen from the comparison between Example 1 and Comparative Example 2 that compared to fiber paper prepared from organic matter, fiber paper prepared using oxide ceramics has excellent high temperature resistance.

Through the specific ratio of oxide ceramics and titanium particles and/or titanium sheets, the invention makes the oil droplet contact angle of the fiber paper reach more than 155°, the oil-water separation efficiency can be as high as more than 99%, and the bending stiffness is as low as 0.0098gf/cm. , and can withstand high temperatures of 600°C. Compared with the separation efficiency of current commercial fiber materials (96.76%), the fiber paper prepared in the present invention has higher separation performance.

The applicant declares that the present invention illustrates the process method of the present invention through the above embodiments, but the present invention is not limited to the above process steps, that is, it does not mean that the present invention must rely on the above process steps to be implemented. Those skilled in the art should understand that any improvements to the present invention, equivalent replacement of raw materials selected in the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims (22)

1. A fiber paper for oil-water separation, characterized in that the fiber paper includes a three-dimensional network structure composed of oxide ceramic fibers and titanium particles and/or titanium sheets on the surface of the oxide ceramic fibers; The mass percentage of oxide ceramic fibers in the fiber paper is 80 to 90%; The fiber paper is prepared by the following method, which method includes the following steps: (1) Mix the oxide sol, polymer and solvent evenly, and perform electrospinning to obtain a green oxide ceramic fiber paper; (2) The oxide ceramic fiber paper green body obtained in step (1) and the titanium solution are subjected to a hydrothermal reaction in an acidic environment, and the obtained product is sintered to obtain the fiber paper; The mass ratio of oxide to polymer in the oxide sol is 1: (0.5~1.5); The oxide sol is selected from any one of TiO ₂ sol, Al ₂ O ₃ sol, SiO ₂ sol or ZrO ₂ sol; The polymer is selected from any one or a combination of at least two of polyvinylpyrrolidone, polyacrylonitrile, polyvinyl alcohol or polycaprolactone; The titanium solution is selected from any one or a combination of at least two of tetrabutyl titanate solution, isopropyl titanate solution or TiO ₂ solution. 2. The fiber paper according to claim 1, wherein the material of the oxide ceramic fiber is selected from any one or a combination of at least two of TiO ₂ , Al ₂ O ₃ , SiO ₂ or ZrO ₂ . 3. The fiber paper according to claim 1, wherein the titanium particles have a particle size of 10 to 100 nm. 4. The fiber paper according to claim 1, wherein the titanium sheet has a sheet diameter of 100 to 500 nm. 5. The fiber paper according to claim 1, wherein the material of the titanium particles and/or titanium sheets is titanium oxide. 6. A method for preparing fiber paper according to any one of claims 1 to 5, characterized in that the preparation method includes the following steps: (1) Mix the oxide sol, polymer and solvent evenly, and perform electrospinning to obtain a green oxide ceramic fiber paper; (2) The oxide ceramic fiber paper green body obtained in step (1) and the titanium solution are subjected to a hydrothermal reaction in an acidic environment, and the obtained product is sintered to obtain the fiber paper. 7. The preparation method of claim 6, wherein the oxide sol is prepared from a precursor solution; The preparation temperature is 60-80°C. 8. The preparation method according to claim 6, characterized in that the mass percentage of oxide in the oxide sol is 3 to 50%. 9. The preparation method as claimed in claim 7, characterized in that the precursor of _the TiO sol is selected from tetrabutyl titanate and/or isopropyl titanate; The precursor of the Al ₂ O ₃ sol is aluminum chloride; The precursor of the SiO _sol is ethyl orthosilicate; The precursor of the ZrO sol is zirconium _n -propoxide. 10. The preparation method according to claim 7, wherein the solvent of the precursor solution includes an acid solution and optionally ethanol and/or N,N-dimethylformamide; The acid solution is selected from any one or a combination of at least two of acetic acid solution, hydrochloric acid solution, sulfuric acid solution or nitric acid solution. 11. The preparation method according to claim 6, wherein the weight average molecular weight of the polymer is 70,000 to 1,300,000. 12. The preparation method according to claim 6, wherein the solvent in step (1) is selected from any one or at least two of water, alcohol, acetic acid or N,N-dimethylformamide. combination. 13. The preparation method according to claim 6, wherein the solvent of the titanium solution is selected from any one or a combination of at least two of water, ethanol, acetic acid or N,N-dimethylformamide. . 14. The preparation method according to claim 6, characterized in that the mass percentage of solute in the titanium solution is 20-40%. 15. The preparation method of claim 6, wherein the mass ratio of the oxide in the oxide sol to the solute in the titanium solution is 1: (0.1-10.6). 16. The preparation method according to claim 6, characterized in that the voltage of the electrospinning is 10-30KV; The temperature of the electrospinning is 20-45°C; The humidity of the electrospinning is 10-90%. 17. The preparation method of claim 6, wherein the acidic environment is provided by adding an acid solution before the hydrothermal reaction; The acid solution is selected from any one or a combination of at least two of hydrochloric acid solution, sulfuric acid solution or nitric acid solution; The mass percentage of solute in the acid solution is 5-20%. 18. The preparation method according to claim 6, wherein the mass ratio of the oxide sol to the acid solution is 1: (0.5-7). 19. The preparation method according to claim 6, characterized in that the temperature of the hydrothermal reaction is 120-200°C; The hydrothermal reaction time is 2 to 10 hours. 20. The preparation method according to claim 6, characterized in that the sintering temperature is 600-1500°C; The sintering time is 2 to 12 hours; The sintering is performed in an air atmosphere. 21. The preparation method according to claim 6, characterized in that the preparation method specifically includes the following steps: (1) Prepare a precursor solution to obtain an oxide sol; (2) After mixing the oxide sol, polymer and solvent obtained in step (1) evenly, perform electrospinning under the conditions of a voltage of 10 to 30KV, a temperature of 20 to 45°C, and a humidity of 10 to 90%. Obtain oxide ceramic fiber paper green body; the mass ratio of oxide and polymer in the oxide sol is 1: (0.5-1.5); (3) Mix the oxide ceramic fiber paper green body obtained in step (2), the titanium solution and the acid solution, and perform a hydrothermal reaction at 120 to 200°C for 2 to 10 hours. The obtained product is heated in an air atmosphere at a temperature of 600 to The fiber paper is obtained by sintering at 1500°C for 2 to 12 hours; the mass ratio of the oxide in the oxide sol to the solute in the titanium solution is 1: (0.1 to 10.6), and the mass ratio of the oxide sol to the acid solution is is 1: (0.5-7), and the titanium solution is selected from any one or a combination of at least two of tetrabutyl titanate solution, isopropyl titanate solution or TiO ₂ nanometer solution. 22. Application of the fiber paper according to any one of claims 1 to 5 in oil-water separation materials.