Preparation method of sediment remediation materials and sediment remediation materials

Abstract

A method for preparing a sediment remediation material and the sediment remediation material thereof are disclosed. The preparation method involves uniformly dispersing a transition metal oxide in a silica-alumina carrier, adding a binder, drying the mixture in a mold, and then demolding it to obtain the sediment remediation material. The mass ratio of the transition metal oxide to the silica-alumina carrier is 1:10 to 10:1. The sediment remediation material contains a transition metal oxide dispersed in a silica-alumina carrier, wherein the mass ratio of the transition metal oxide to the silica-alumina carrier is 1:10 to 10:1. The sediment remediation material of this invention is safe and non-toxic, easy to apply, and can be used in conjunction with other remediation materials to continuously exert a remediation effect. It can be applied to the remediation of sediment in ponds, rivers, lakes, and other water bodies.

Description

Technical Field

[0001] This invention relates to the field of sediment treatment technology. Background Technology

[0002] Water pollution mainly originates from two sources: external and internal. External pollution primarily comes from industrial, agricultural, and domestic wastewater discharges; internal pollution mainly originates from the sediment at the bottom of the water body. When control measures are taken for external pollution, but the sediment environment changes, the deposited polluted sediment becomes a potential source of pollution, and dissolved pollutants are released again. Therefore, sediment is an internal source of pollution that must be addressed in water body remediation.

[0003] Among the relevant technologies, the commonly used methods for treating bottom sediment include bottom sediment dredging, bottom sediment aeration, and bottom sediment chemical remediation.

[0004] Seabed dredging refers to the mechanical removal of bottom sediment to reduce its internal load and pollution risk. However, due to the difficulty in determining the dredging area and required depth, the effectiveness of dredging is highly variable, and it also requires a significant amount of work.

[0005] Sediment aeration primarily relies on aeration combined with microbial remediation, using the aerobic metabolic activities of microorganisms to degrade pollutants. However, some technical bottlenecks exist. The presence of sediment leads to extremely low dissolved oxygen levels in the water, necessitating aeration to ensure the oxygen-rich environment required by aerobic microorganisms. However, aeration is unstable during water treatment; once aeration ceases, the sediment quickly deteriorates again under hypoxic conditions.

[0006] Chemical remediation of sediments utilizes chemical reagents to react with pollutants through oxidation, reduction, polymerization, and other reactions, causing the pollutants to separate from the sediment or be transformed into a low-pollution or non-pollution state. However, the stability of chemical remediation materials is very important; otherwise, they are prone to disintegration and cannot play a long-term remediation role.

[0007] Chinese patent application CN106477836A discloses a method for using a mixture of calcium peroxide, diatomaceous earth, iron-nickel hydrotalcite, and manganese dioxide as a sediment remediation agent. This method belongs to the category of chemical sediment remediation methods. However, this method only mechanically mixes the components, which is prone to disintegration in water. Furthermore, calcium peroxide reacts with water, accelerating the disintegration rate of the mixture, resulting in unstable effects and an inability to maintain its effectiveness over a long period.

[0008] Chinese patent application CN107262024A discloses a submerged biofilm method for purifying river water using a combined artificial aquatic plant facility. This method combines forced aeration with artificial aquatic plant filler and mainly consists of floats, artificial aquatic plants, a fixing system, weight anchors, and an aeration system. The aeration device alleviates the anaerobic black and odorous problem of riverbed sediment. However, this method also suffers from the problem that once aeration is stopped, the sediment quickly deteriorates again under anaerobic conditions.

[0009] Therefore, developing new sediment remediation materials and new methods for preparing sediment materials is of great significance. Summary of the Invention

[0010] The present invention aims to solve the problems of unstable treatment effect and high workload in related technologies, and provides a sediment treatment material and preparation method with stable treatment effect, which can be used for long-term treatment and saves workload.

[0011] To address the aforementioned limitations, this invention proposes a method for preparing sediment remediation materials and the sediment remediation materials themselves.

[0012] A method for preparing a sediment remediation material involves first uniformly dispersing a transition metal oxide in a silica-alumina carrier, then adding a binder, drying the mixture in a mold, and finally demolding it to obtain the sediment remediation material.

[0013] Further: the transition metal oxide is one or more of TiO2, MoO3, WO3, MnO2, Fe2O3, Fe3O4, CoO, Co3O4, NiO, CuO, Cu2O, and ZnO.

[0014] Further: the silicon oxide-alumina carrier is a powder obtained by calcining SiO2 and Al2O3 in a mass ratio of 3:1 to 1:3 at 300 to 500°C for 2 to 6 hours.

[0015] Further: the adhesive is one or more of polyacrylic acid, polyvinyl alcohol, water glass, epoxy resin, and polyvinylidene fluoride.

[0016] Furthermore, the drying temperature is 50–80°C, and the drying time is 6–18 hours.

[0017] Further: the mass ratio of the transition metal oxide to the silicon oxide-alumina carrier is 1:10 to 10:1.

[0018] Further: the mass ratio of the adhesive added is 1 / 10000 to 1 / 1000 of the sum of the masses of the transition metal oxide and the silicon oxide-alumina carrier.

[0019] Furthermore, the inner cavity of the mold is a cylinder with a diameter of 10-20cm and a height of 20-30cm.

[0020] A sediment remediation material, wherein the sediment remediation material contains a transition metal oxide dispersed in a silica-alumina carrier, and the mass ratio of the transition metal oxide to the silica-alumina carrier is 1:10 to 10:1.

[0021] Further: In the silicon oxide-alumina support, the mass ratio of SiO2 to Al2O3 is 3:1 to 1:3; the transition metal oxide is one or more of TiO2, MoO3, WO3, MnO2, Fe2O3, Fe3O4, CoO, Co3O4, NiO, CuO, Cu2O, and ZnO.

[0022] Furthermore, the sediment treatment material is prepared using the method described above.

[0023] Compared with related technologies, the present invention has the following advantages:

[0024] One aspect of the present invention relates to a method for preparing a sediment remediation material, which involves uniformly dispersing a transition metal oxide in a silica-alumina carrier, adding a binder, drying the material in a mold, and then demolding it to obtain the sediment remediation material. By utilizing the large work functions of the transition metal oxide, silica, and alumina, a strong contact potential difference and surface polarization are generated at the interface, causing spontaneous charge transfer, which is beneficial for the oxidative decomposition of pollutants in the sediment and can sustainably exert a remediation effect.

[0025] Another aspect of this invention relates to a sediment remediation material that utilizes the significantly different work functions of transition metal oxides, silicon dioxide, and aluminum oxide to generate a strong contact potential difference and surface polarization at the interface, leading to spontaneous charge transfer. This facilitates the oxidative decomposition of pollutants in the sediment and provides a sustainable remediation effect. The sediment remediation material of this invention is safe and non-toxic, simple to operate, saves on the construction costs of aeration equipment, does not cause water pollution, is beneficial to the protection of aquatic ecosystems, provides long-lasting and stable remediation effects, can be used in conjunction with other remediation materials to continuously enhance the remediation effect, and can be applied to the remediation of sediment in ponds, rivers, and lakes. Attached Figure Description

[0026] Figure 1 This is a schematic diagram of a method for preparing sediment treatment materials according to an embodiment of the present invention;

[0027] Figure 2 This is a physical image of a sediment treatment material according to an embodiment of the present invention. Detailed Implementation

[0028] To make the objectives, technical solutions, and advantages of this invention clearer, the invention will be further described in detail below. However, it should be understood that the description herein is merely illustrative and not intended to limit the scope of the invention.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains. The terminology used herein in the specification is for the purpose of describing particular embodiments only and is not intended to limit the invention. All characterization techniques mentioned herein can be found in relevant descriptions in the prior art, and will not be repeated here.

[0030] To further understand the present invention, the present invention will be described in detail below with reference to the preferred embodiments.

[0031] Example 1

[0032] like Figure 1-2 As shown, a method for preparing a sediment remediation material involves first uniformly dispersing a transition metal oxide in a silica-alumina carrier, then adding a binder, drying the mixture in a mold, and finally demolding it to obtain the sediment remediation material.

[0033] By utilizing the significant work functions of transition metal oxides, silicon dioxide, and aluminum oxide, a strong contact potential difference and surface polarization are generated at the formed interface, inducing spontaneous charge transfer. This facilitates the oxidative decomposition of pollutants in the sediment and provides a sustainable remediation effect. Silicon dioxide and aluminum oxide, as carrier materials, have the advantages of easy raw material preparation and high surface area ratio.

[0034] Example 2

[0035] Based on Example 1, the transition metal oxide is further described as one or more of TiO2, MoO3, WO3, MnO2, Fe2O3, Fe3O4, CoO, Co3O4, NiO, CuO, Cu2O, and ZnO.

[0036] Transition metals refer to metals that transition from an inner electron shell with 8 electrons to one with 18 electrons, or from one with 18 electrons to one with 32 electrons. The addition of transition metal oxides utilizes the significant difference in work functions between transition metal oxides, silicon oxide, and aluminum oxide to generate a strong contact potential difference and surface polarization at the interface, inducing spontaneous charge transfer. This facilitates the oxidative decomposition of pollutants in the sediment and provides a sustainable remediation effect. The work function is the difference between the Fermi level Ef and the energy level E0 of a stationary electron in a vacuum.

[0037] Further: The silicon oxide-alumina carrier is a powder obtained by calcining SiO2 and Al2O3 in a mass ratio of 3:1 to 1:3 at 300 to 500°C for 2 to 6 hours. The preferred mass ratio of SiO2 to Al2O3 is 1:2, 3:4, 4:5, 1:1, 1:3, 4:3, 3:2, 2:1, 3:1, or 5:2; however, it is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0038] Preferably, the powder is ground through a 50-80 mesh sieve, and more preferably, it is ground through a 50, 60, 70, or 80 mesh sieve. However, it is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0039] The preferred calcination temperature is 300℃, 310℃, 320℃, 330℃, 340℃, 350℃, 360℃, 370℃, 380℃, 390℃, 400℃, 410℃, 420℃, 430℃, 440℃, 450℃, 460℃, 470℃, 480℃, 490℃, or 500℃. The preferred calcination time is 2 hours, 3 hours, 4 hours, 5 hours, or 6 hours, but is not limited to the listed values; other unlisted values ​​within this range are also applicable.

[0040] Calcination can be carried out in a muffle furnace, also known as a box furnace. It is a general-purpose heating device with a box-shaped shape. The resistance wire is built into the box. The furnace body has a large wall thickness and is lined with heat insulation material. The temperature can be raised to 1200 degrees. It is often used for calcination, alkali melting of refractory metals and minerals, calcination and decomposition of organic matter, and removal of volatile components from inorganic matter.

[0041] Further: the adhesive is one or more of polyacrylic acid, polyvinyl alcohol, water glass, epoxy resin, and polyvinylidene fluoride.

[0042] Polyacrylic acid (PAA) is a water-soluble polymer, also known as acrylic homopolymer. It is a chain-like water-based polymer binder. PAA is a linear adhesive, which provides a higher degree of anchoring for particles and stronger cohesion in the electrode, thus contributing to structural stability.

[0043] Aqueous solutions of alkali metal silicates are commonly known as water glass, with the chemical formula R₂O·nSiO₂, where R₂O is an alkali metal oxide and n is the molar ratio of silicon dioxide to alkali metal oxide. Water glass has strong adhesive properties and is therefore often used as an adhesive.

[0044] Polyvinyl alcohol (PVA) is a colorless, water-soluble synthetic resin that is often used as a binder.

[0045] Epoxy resin is a substance that is cured and molded by reacting with epoxy groups. It has good dimensional stability, very stable chemical properties, and excellent adhesion to many materials, and is often used as an adhesive.

[0046] Polyvinylidene fluoride (PVDF), generally referring to polyvinylidene fluoride, is a highly non-reactive thermoplastic fluoropolymer. It possesses excellent properties such as anti-aging, chemical resistance, weather resistance, and UV radiation resistance.

[0047] Furthermore, the drying temperature is 50–80°C, and the drying time is 6–18 hours.

[0048] The preferred drying temperature is 50℃, 51℃, 52℃, 53℃, 54℃, 55℃, 56℃, 57℃, 58℃, 59℃, 60℃, 61℃, 62℃, 63℃, 64℃, 65℃, 66℃, 67℃, 68℃, 69℃, 70℃, 71℃, 72℃, 73℃, 74℃, 75℃, 76℃, 77℃, 78℃, 79℃, or 80℃; the preferred drying time is 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, or 18 hours; however, it is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0049] Further: the mass ratio of the transition metal oxide to the silicon oxide-alumina carrier is 1:10 to 10:1.

[0050] The preferred mass ratio of the transition metal oxide to the silica-alumina carrier is 1:10, 2:10, 3:10, 4:10, 5:10, 6:10, 7:10, 8:10, 9:10, 1:1, 1:9, 2:9, 3:9, 4:9, 5:9, 6:9, 7:9, 8:9, 9:9, 10:9, 1:8, 2:8, 3:8, 4:8, 5:8, 6:8, 7:8, 8:8, 9:8, 10:8, 1:7, 2:7, 3:7, 4:7, 5:7, 6:7, 7:7, 8:7, 9:7, 10:7, 1:6, 2:6, 3:6, 4:6, 5:6, 6:6, 7:6, 8:6, 9:6, 10 :6, 1:5, 2:5, 3:5, 4:5, 5:5, 6:5, 7:5, 8:5, 9:5, 10:5, 1:4, 2:4, 3:4, 4:4, 5:4, 6:4, 7:4, 8:4, 9:4, 10:4, 1:3, 2:3, 3:3, 4:3, 5:3, 6:3, 7:3, 8:3, 9:3, 10:3, 1:2, 2:2, 3:2, 4:2, 5:2, 6:2, 7:2, 8:2, 9:2, 10:2, 1:1, 2:1, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, or 10:1; but not limited to the listed values, other unlisted values ​​within this range also apply.

[0051] This invention utilizes the significant difference in work function between transition metal oxides, silicon oxide, and aluminum oxide to generate a strong contact potential difference and surface polarization at the interface, causing spontaneous charge transfer, which is beneficial for the oxidative decomposition of pollutants in the sediment. Therefore, the mass ratio of transition metal oxides to silicon oxide-alumina carrier needs to be within a suitable range. Too much transition metal oxide will increase costs, while too little will not achieve sufficient treatment effect.

[0052] Further: the mass ratio of the binder is 1 / 10000 to 1 / 1000 of the sum of the masses of the transition metal oxide and the silica-alumina carrier. Preferably, the mass ratio of the binder is 1 / 10000, 1 / 5000, 3 / 10000, 2 / 5000, 1 / 2000, 3 / 5000, 7 / 10000, 4 / 5000, 9 / 10000, or 1 / 1000 of the sum of the masses of the transition metal oxide and the silica-alumina carrier; however, it is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0053] Further: the inner cavity of the mold is a cylinder with a diameter of 10-20cm and a height of 20-30cm. The diameter is preferably 10cm, 11cm, 12cm, 13cm, 14cm, 15cm, 16cm, 17cm, 18cm, 19cm, or 20cm; the inner height of the mold is preferably 20cm, 21cm, 22cm, 23cm, 24cm, 25cm, 26cm, 27cm, 28cm, 29cm, or 30cm; but it is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0054] Furthermore, the inner cavity of the mold can be a cylinder, a regular triangular prism, a regular square prism, or a regular polygonal prism, so the shape of the substrate material can be a cylinder, a regular triangular prism, a regular square prism, or a regular polygonal prism.

[0055] Conventional chemical remediation techniques for riverbed sediments primarily involve adding chemicals to the riverbed, where the sediment reacts with the chemicals to adsorb and degrade pollutants. This method only requires the addition of chemicals, effectively oxidizing large amounts of pollutants and resolving black and odorous conditions. However, this method has drawbacks: small amounts of compounds are ineffective, while large amounts can damage the existing ecosystem and cause aquatic life death. The sediment remediation material of this invention is manufactured into a solid shape using a mold, such as... Figure 2 As shown, it is placed at the bottom of the water body to make full contact with the bottom sediment, and the sediment is treated in a targeted manner. The treatment effect of the sediment is good and it is not easy to cause water pollution, which is conducive to protecting the aquatic ecosystem.

[0056] Example 3

[0057] Based on Example 1 or 2, a sediment remediation material is provided, the sediment remediation material containing transition metal oxides dispersed in a silica-alumina carrier.

[0058] Further, the transition metal oxide is one or more of TiO2, MoO3, WO3, MnO2, Fe2O3, Fe3O4, CoO, Co3O4, NiO, CuO, Cu2O, and ZnO.

[0059] Further: The silicon oxide-alumina carrier is a powder obtained by calcining SiO2 and Al2O3 in a mass ratio of 3:1 to 1:3 at 300 to 500°C for 2 to 6 hours. The preferred mass ratio of SiO2 to Al2O3 is 1:2, 3:4, 4:5, 1:1, 4:3, 3:2, 2:1, 3:1, or 5:2; however, it is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0060] Further: the mass ratio of the transition metal oxide to the silicon oxide-alumina support is 1:10 to 10:1.

[0061] Furthermore, the sediment treatment material also contains a binder.

[0062] Further: the adhesive is one or more of polyacrylic acid, polyvinyl alcohol, water glass, epoxy resin, and polyvinylidene fluoride.

[0063] Further: the mass ratio of the binder is 1 / 10000 to 1 / 1000 of the sum of the masses of the transition metal oxide and the silica-alumina carrier; preferably, the mass ratio of the binder is 1 / 10000, 1 / 5000, 3 / 10000, 2 / 5000, 1 / 2000, 3 / 5000, 7 / 10000, 4 / 5000, 9 / 10000, or 1 / 1000 of the sum of the masses of the transition metal oxide and the silica-alumina carrier; but it is not limited to the listed values, and other unlisted values ​​within this range are also applicable.

[0064] Furthermore, the sediment treatment material is prepared using the method described in Example 1 or 2.

[0065] The sediment treatment material of this invention is safe and non-toxic, easy to operate, can save the construction cost of aeration equipment, will not cause water pollution, is conducive to protecting the aquatic ecosystem, has a long-lasting and stable treatment effect, can be used in conjunction with other treatment materials to continuously exert the treatment effect, and can be applied to the treatment of sediment in ponds, rivers and lakes.

[0066] Example 4

[0067] Experimental Example 1

[0068] (Sediment Remediation Material 1) Preparation method of sediment remediation material, such as Figure 1 As shown, it includes the following steps:

[0069] Step 1: Take SiO2 and Al2O3, calcine them, and grind them through a 70-mesh sieve. This powder is a silicon oxide-alumina carrier. The mass ratio of SiO2 to Al2O3 is 2:1. The calcination is carried out in a muffle furnace at 400°C for 3.5 hours.

[0070] Step 2: Take a transition metal oxide and a silica-alumina support and mix them evenly; the transition metal oxide is Fe2O3 and the mass ratio of Fe2O3 to the silica-alumina support is 1:10.

[0071] Step 3: Mix the binder with Fe2O3 and silica-alumina carrier evenly and add it to the mold; the binder is polyvinyl alcohol, and the ratio of its mass to the sum of the masses of Fe2O3 and silica-alumina carrier is 1 / 1000.

[0072] Step four: Place the mold in a 60℃ oven until the material is completely dry, approximately 15 hours. Remove from the mold to obtain the sediment treatment material. Figure 2 The mold is a cylinder with an inner diameter of 20cm and a height of 30cm.

[0073] Experiment Example 2

[0074] (Sediment Remediation Material 2) Preparation method of sediment remediation material, such as Figure 1 As shown, it includes the following steps:

[0075] Step 1: Take SiO2 and Al2O3 in a mass ratio of 1:2, calcine them in a muffle furnace at 480°C for 2.5 hours, and grind them through a 50-mesh sieve. This powder is a silicon oxide-alumina carrier.

[0076] Step 2: Mix TiO2 and silica-alumina support in a mass ratio of 1:1 evenly;

[0077] Step 3: Mix water glass with TiO2 and silica-alumina carrier evenly, and add it into a cylindrical mold with an inner diameter of 15cm and a height of 27cm; wherein the mass ratio of water glass to TiO2 and silica-alumina carrier is 1 / 2000.

[0078] Step 4: Place the mold in a 70℃ oven until the material is completely dried, which takes about 10 hours. Demold the mold to obtain the bottom mud treatment material.

[0079] Experimental Example 3

[0080] (Sediment Remediation Material 3) Preparation methods of sediment remediation materials, such as Figure 1 As shown, it includes the following steps:

[0081] Step 1: Take SiO2 and Al2O3 in a mass ratio of 3:1, calcine them in a muffle furnace at 500°C for 2 hours, and grind them through a 60-mesh sieve. This powder is a silicon oxide-alumina carrier.

[0082] Step 2: Mix MnO2 and silica-alumina carrier in a mass ratio of 3:1 evenly;

[0083] Step 3: Mix epoxy resin with MnO2 and silica-alumina carrier evenly, and add it into a cylindrical mold with an inner diameter of 12cm and a height of 23cm; the mass ratio of epoxy resin to MnO2 and silica-alumina carrier is 3 / 5000.

[0084] Step 4: Place the mold in an 80℃ oven until the material is completely dried, which takes about 6 hours. Demold the mold to obtain the bottom mud treatment material.

[0085] In Experiment 4, Pond 1 suffered from long-term, unscientific overfeeding, leading to the inability to decompose organic matter, resulting in bottom sediment accumulation, blue-green algae blooms, and fish deaths. Bottom sediment treatment materials 1, 2, and 3 were added to areas 1, 2, and 3 of Pond 1, respectively. The addition density was 1 material per 10m³. 2 The observation period was in January. Regions 1-3 were far enough away for the experiment.

[0086] The parameters of the pond before addition were as follows:

[0087] Zone 1 COD: 240.8 ppm, ammonia nitrogen: 21.4 ppm, total phosphorus: 3.4 ppm;

[0088] Zone 2 COD: 220.5 ppm, ammonia nitrogen: 23.5 ppm, total phosphorus: 2.8 ppm;

[0089] Zone 3 COD: 260.4 ppm, ammonia nitrogen: 19.8 ppm, total phosphorus: 3.3 ppm.

[0090] One month after the injection,

[0091] The test results for Area 1 were: COD 62.4 ppm, ammonia nitrogen 7.4 ppm, and total phosphorus 1.2 ppm.

[0092] The test results for Area 2 were: COD 61.3 ppm, ammonia nitrogen 7.8 ppm, and total phosphorus 1.6 ppm.

[0093] The test results for Zone 3 were: COD 58.4 ppm, ammonia nitrogen 7.5 ppm, and total phosphorus 1.2 ppm.

[0094] The test results above show that after one month of treatment with the sediment remediation material of this invention, the COD, ammonia nitrogen, and total phosphorus in pond 1 all decreased significantly to about one-third of their original levels, demonstrating a significant and efficient remediation effect. Using the method and sediment remediation material of this invention can reduce water treatment costs by approximately 30%.

[0095] The scope of protection of this invention is not limited to the above embodiments. It is understood that the sediment treatment materials and preparation methods of this invention are not limited to the above applications, but can also be used in all application scenarios suitable for the inventive concept of this invention.

[0096] The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention. Any modifications, equivalent substitutions or improvements made within the spirit and principles of the present invention should be included within the protection scope of the present invention.

Claims

1. A method for preparing a sediment remediation material, characterized in that: The transition metal oxide is first uniformly dispersed in a silica-alumina carrier, then a binder is added, and the mixture is dried in a mold. After demolding, the sediment treatment material is obtained. Due to the significant difference in work function between the transition metal oxide and the silicon oxide-alumina support, a strong contact potential difference and surface polarization are generated at the interface, leading to spontaneous charge transfer. The transition metal oxide is one or more of TiO2, MoO3, WO3, MnO2, Fe2O3, Fe3O4, CoO, Co3O4, NiO, CuO, Cu2O, and ZnO; The silicon oxide-alumina carrier is a powder made of SiO2 and Al2O3 in a mass ratio of 3:1 to 1:3, calcined at 300 to 500°C for 2 to 6 hours. The adhesive is one or more of polyacrylic acid, polyvinyl alcohol, water glass, epoxy resin, or polyvinylidene fluoride.

2. The preparation method according to claim 1, characterized in that: The drying temperature is 50~80℃, and the drying time is 6~18 hours.

3. The preparation method according to claim 1, characterized in that: The mass ratio of the transition metal oxide to the silicon oxide-alumina carrier is 1:10 to 10:

1.

4. The preparation method according to claim 1, characterized in that: The mass ratio of the binder added is 1 / 10000 to 1 / 1000 of the sum of the masses of the transition metal oxide and the silica-alumina carrier.

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