Composite carrier for loading zinc oxide, preparation method and loaded zinc oxide

Abstract

The invention discloses a composite carrier for loading zinc oxide, a preparation method of the composite carrier and loaded zinc oxide, and relates to the technical field of carrier preparation, the preparation method of the composite carrier for loading zinc oxide comprises the following steps: providing a mesoporous carrier, and activating the mesoporous carrier through a metal additive; adding polymer ligand molecules into the mesoporous carrier to prepare a premix; and calcining the premix through gradient heating to obtain the composite carrier. The process of increasing the loading capacity of zinc oxide on the carrier is realized.

Description

Technical Field

[0001] This application relates to the field of carrier preparation technology, and in particular to composite carriers for loading zinc oxide and their preparation methods, and loaded zinc oxide. Background Technology

[0002] Zinc oxide is a crucial raw material in the automotive tire manufacturing industry, primarily used as a rubber vulcanization accelerator and reinforcing agent. However, the zinc oxide-containing microplastic particles (particle size <5mm) generated during tire use can be washed into water bodies by rainwater or dispersed by wind, causing environmental pollution. Therefore, supported zinc oxide can be prepared using dispersion technology.

[0003] However, existing carriers have low zinc oxide loading capacity during the zinc oxide loading process, which limits the practical application of zinc oxide in automobile tire manufacturing. Summary of the Invention

[0004] The main objective of this application is to provide a composite support for loading zinc oxide and its preparation method, as well as a supported zinc oxide. This aims to solve the technical problem of low zinc oxide loading on existing supports.

[0005] To achieve the above objectives, embodiments of this application provide a method for preparing a composite support for loading zinc oxide, the method comprising the following steps: A mesoporous carrier is provided, wherein the mesoporous carrier is activated by a metal additive; A premix was prepared by adding polymeric ligand molecules to the mesoporous carrier. The premix was calcined by gradient heating to obtain a composite carrier.

[0006] In one feasible embodiment, the mesoporous carrier comprises at least one of carbon black, lignin, and alumina.

[0007] In one feasible embodiment, the polymer ligand molecule comprises: polyether polyol or polyvinylpyrrolidone.

[0008] In one feasible embodiment, the metal additive includes at least one selected from sodium bicarbonate, ammonium bicarbonate, sodium silicate, and sodium carbonate.

[0009] In one feasible embodiment, the gradient heating calcination process includes: The reaction temperature is raised to 100~200℃ at a heating rate of less than or equal to 2℃ / min, and calcined for 1~3h; Calcination at 400-500℃ for 2-4 hours.

[0010] In one feasible embodiment, after the step of calcining at 400-500°C for 2-4 hours, the method further includes: The reaction temperature is increased to a third preset temperature at a heating rate of 5~10℃ / min, and calcined for 0.5~1h, wherein the third preset temperature is greater than 500℃.

[0011] In one feasible embodiment, prior to the step of obtaining the composite carrier by gradient temperature calcination of the premix, the method further includes: A first auxiliary agent is added to the premix to adjust the pH, wherein the first auxiliary agent includes at least one of sodium carbonate solution, sodium silicate solution, sodium hydroxide solution, sodium carbonate, sodium bicarbonate, ammonium bicarbonate, and potassium hydroxide.

[0012] In one feasible embodiment, the pH of the premix is ​​adjusted to 9-10 after the first adjuvant is added.

[0013] This application also provides a composite carrier for loading zinc oxide, which is prepared by the method described above.

[0014] This application also provides a supported zinc oxide, wherein the support for the supported zinc oxide is a composite support prepared by the method described above, or the composite support described above.

[0015] One or more technical solutions proposed in this application have at least the following technical effects: A mesoporous support is provided, which has a high specific surface area and a porous structure, providing space for subsequent creation of anchoring sites for binding with polymeric ligand molecules. The mesoporous support is activated by a metal additive to obtain more active sites on its surface. A premix is ​​prepared by adding polymeric ligand molecules to the mesoporous support. One end of the polymeric ligand molecule can interact with the support surface and be bonded to the support surface; the polymeric ligand molecule has active functional groups for binding with zinc ions in zinc oxide. The premix is ​​calcined by gradient heating to obtain a composite support. The slow, staged heating during gradient calcination allows the organic matter to decompose gradually, avoiding pore wall collapse caused by a sudden increase in vapor pressure within the pores. In this embodiment, polymer ligand molecules are used as active molecules to introduce functional groups with higher density, more uniformity, and stronger binding ability into the mesoporous support, thereby increasing the binding sites of zinc ions. Furthermore, a composite support is prepared through a gradient calcination process, and the staged heating increases the stability of the composite support structure during the preparation process and increases the loading of zinc oxide on the support. Attached Figure Description

[0016] Figure 1 This is a flowchart illustrating the preparation method of the composite carrier for loading zinc oxide involved in the embodiments of this application; Figure 2 This is a schematic diagram illustrating the steps of the composite carrier preparation method involved in the embodiments of this application; Figure 3This is an electron microscopy energy dispersive spectral distribution analysis diagram of carbon black-supported zinc oxide involved in the embodiments of this application; Figure 4 This is an electron microscopy energy-dispersive spectral distribution analysis diagram of zinc oxide loaded on a composite carrier according to the embodiments of this application.

[0017] The realization of the purpose, functional features and advantages of this application will be further explained in conjunction with the embodiments and with reference to the accompanying drawings. Detailed Implementation

[0018] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions in the embodiments of this application will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0019] The composite carrier for supporting zinc oxide and its preparation method, as well as embodiments of the supported zinc oxide, are disclosed in detail below with appropriate reference to the accompanying drawings. However, unnecessary detailed descriptions may be omitted. For example, detailed descriptions of well-known matters and repetitive descriptions of practically identical structures may be omitted. This is to avoid unnecessarily lengthy descriptions and to facilitate understanding by those skilled in the art. Furthermore, the accompanying drawings and the following description are provided to enable those skilled in the art to fully understand this application and are not intended to limit the subject matter of the claims.

[0020] The "range" disclosed in this application is defined by a lower limit and an upper limit. A given range is defined by selecting a lower limit and an upper limit, which define the boundaries of a particular range. Ranges defined in this way can include or exclude endpoints and can be arbitrarily combined; that is, any lower limit can be combined with any upper limit to form a range. For example, if ranges of 60~120 and 80~110 are listed for a specific parameter, it is also expected that ranges of 60~110 and 80~120 are also included. Furthermore, if minimum range values ​​of 1 and 2 are listed, and if maximum range values ​​of 3, 4, and 5 are listed, then the following ranges are all expected: 1~3, 1~4, 1~5, 2~3, 2~4, and 2~5. In this application, unless otherwise stated, the numerical range "a~b" represents a shortened representation of any combination of real numbers between a and b, where a and b are real numbers. For example, the numerical range "0~5" indicates that all real numbers between "0~5" have been listed in this article; "0~5" is simply a shortened representation of these numerical combinations. Furthermore, when a parameter is stated as an integer ≥2, it is equivalent to disclosing that the parameter is, for example, an integer such as 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, etc.

[0021] Unless otherwise specified, all embodiments and optional embodiments of this application can be combined to form new technical solutions.

[0022] Unless otherwise specified, all technical features and optional technical features of this application may be combined to form new technical solutions.

[0023] Unless otherwise specified, all steps in this application may be performed sequentially or randomly, preferably sequentially. For example, the method includes steps (a) and (b), indicating that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order. For example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc.

[0024] Unless otherwise specified, the terms "comprising" and "including" as used in this application can be open-ended or closed-ended. For example, "comprising" and "including" can mean that other components not listed may also be included, or that only the listed components may be included.

[0025] Unless otherwise specified, the term "or" is inclusive in this application. For example, the phrase "A or B" means "A, B, or both A and B". More specifically, the condition "A or B" is satisfied by any of the following conditions: A is true (or exists) and B is false (or does not exist); A is false (or does not exist) and B is true (or exists); or both A and B are true (or exist).

[0026] To make the above-mentioned objectives, features, and advantages of this application more apparent and understandable, the technical solution of this application is further described below in conjunction with the accompanying drawings and embodiments. However, this application is not limited to the listed embodiments, but should also include any other well-known modifications within the scope of the claims made in this application.

[0027] The term "an embodiment" or "embodiment" as used herein refers to a specific feature, structure, or characteristic that may be included in at least one implementation of this application. The phrase "in one embodiment" appearing in different places throughout this specification does not necessarily refer to the same embodiment, nor is it a single or selective embodiment that is mutually exclusive with other embodiments.

[0028] To better understand the technical solution of this application, a detailed description will be provided below in conjunction with the accompanying drawings and specific implementation methods.

[0029] Zinc oxide is a crucial raw material in the automotive tire manufacturing industry, primarily used as a rubber vulcanization accelerator and reinforcing agent. However, during the use of tires, zinc oxide-containing microplastic particles (particle size <5mm) can be washed into water bodies by rainwater or dispersed by wind, causing environmental pollution. Therefore, methods for preparing supported zinc oxide using dispersion technology have emerged. However, existing carriers exhibit low zinc oxide loading during the loading process, limiting the practical application of zinc oxide in automotive tire manufacturing. Therefore, a carrier capable of increasing the zinc oxide loading is needed.

[0030] This application provides a solution, specifically, a mesoporous support, wherein the mesoporous support is activated by a metal additive. The mesoporous support possesses a high specific surface area and porous structure, providing space for subsequent creation of anchoring sites for binding with polymeric ligand molecules. The activation treatment of the mesoporous support with the metal additive creates more active sites on its surface. A premix is ​​prepared by adding polymeric ligand molecules to the mesoporous support; one end of the polymeric ligand molecule can interact with the support surface and be bonded thereto; the polymeric ligand molecule possesses active functional groups for binding with zinc ions in zinc oxide. The premix is ​​calcined using a gradient heating method to obtain a composite support. The slow, staged heating during gradient calcination allows for the gradual decomposition of organic matter, avoiding pore wall collapse caused by a sudden increase in vapor pressure within the pores. In this embodiment, polymer ligand molecules are used as active molecules to introduce functional groups with higher density, more uniformity, and stronger binding ability into the mesoporous support, thereby increasing the binding sites of zinc ions. Furthermore, a composite support is prepared through a gradient calcination process, and the staged heating increases the stability of the composite support structure during the preparation process and increases the loading of zinc oxide on the support.

[0031] Reference Figure 1 The first aspect of this application provides a method for preparing a composite carrier for loading zinc oxide, comprising the following steps: Step S10: Provide a mesoporous support, wherein the mesoporous support is activated by a metal additive; In one feasible embodiment, the mesoporous support is the matrix used for loading zinc oxide. The mesoporous support has a high specific surface area and uniform pore size, which is beneficial for the subsequent loading and dispersion of zinc oxide, improving the stability and performance of the composite support. After activation treatment with metal additives, more active functional groups or defects can be introduced as active sites on the surface of the mesoporous support. These active sites can interact more strongly with polymer ligand molecules, increasing the adsorption capacity and adsorption stability of polymer ligand molecules on the surface of the mesoporous support. Activation treatment can also change the charge distribution on the surface of the mesoporous support, making its surface charge more conducive to the interaction with polymer ligand molecules.

[0032] In one feasible embodiment, the mesoporous carrier includes at least one of carbon black, lignin, and alumina.

[0033] Optionally, carbon black has a small particle size, a large specific surface area, and a large number of active groups on its surface, which provides sufficient space and attachment sites for zinc oxide loading, facilitating the high dispersion of zinc oxide on its surface. In addition, carbon black has good chemical stability, and can withstand certain temperature and chemical environment changes during the preparation of composite carriers, such as calcination, without easily undergoing chemical reactions that would affect its own structure and performance, thus ensuring the stability of the composite carrier structure.

[0034] Optionally, lignin possesses a three-dimensional network structure with numerous pores and channels, providing suitable space for zinc oxide loading. Furthermore, lignin is abundant and renewable, reducing the preparation cost of the composite carrier. Lignin molecules contain various functional groups, such as hydroxyl and methoxy groups, which possess a certain degree of activity and can interact with polymer ligand molecules and the primary auxiliary agent, helping to improve the surface properties of the composite carrier and enhance the binding force between zinc oxide and the carrier.

[0035] Optionally, alumina has various crystal forms, the most common being γ-alumina, which possesses a good mesoporous structure and a large specific surface area. The relatively uniform pore size distribution of alumina provides a stable and suitable loading environment for zinc oxide. Alumina exhibits high thermal stability, maintaining its structural and performance stability during gradient-heating calcination without significant structural changes or decomposition due to high temperatures, thus ensuring the quality and performance of the composite carrier during high-temperature preparation.

[0036] Optionally, the carbon black particle size is 30-50 nm. Carbon black with a particle size of 30-50 nm has a larger specific surface area and more surface active sites, thereby enhancing the performance of the composite support. Carbon black in this particle size range exhibits good dispersibility when mixed with polymeric ligand molecules, primary additives, etc. Good dispersibility ensures uniform distribution of carbon black throughout the system, avoiding agglomeration and facilitating the subsequent formation of a structurally uniform composite support. If the carbon black particle size is too large, agglomeration is likely to occur, leading to uneven zinc oxide loading and affecting the performance of the composite support; while if the particle size is too small, although the specific surface area is larger, it may increase the difficulty of preparation and dispersion.

[0037] Optionally, the lignin particle size is 200-300 mesh. Lignin with a particle size of 200-300 mesh possesses suitable particle size and pore structure, containing numerous mesopores and micropores, providing sufficient loading space. Simultaneously, the suitable particle size ensures the dispersion of lignin in the system, allowing zinc oxide to be uniformly loaded onto the pores and surface of the lignin, improving loading efficiency and stability. If the lignin particle size is too large, its internal pores may be difficult to fully utilize, and the reactivity of surface functional groups will decrease; while if the particle size is too small, although the reactivity may be higher, it may increase the tendency of lignin to aggregate, affecting the preparation and performance of the composite carrier.

[0038] Optionally, the alumina particle size is 20–50 nm. Alumina with a particle size of 20–50 nm has a larger specific surface area and higher surface activity, providing more loading sites for zinc oxide and improving the loading and dispersion of zinc oxide. Alumina in this particle size range has suitable pore structure and diffusion properties. Its mesoporous structure is beneficial for the loading and diffusion of zinc oxide, allowing zinc oxide to better enter the pores of the alumina and form a uniform loading system. If the alumina particle size is too large, the pore structure may not be well-developed, affecting the loading and diffusion of zinc oxide; while if the particle size is too small, it may lead to pore blockage and reduce diffusion performance.

[0039] In one feasible embodiment, the metal additive includes at least one of sodium bicarbonate, ammonium bicarbonate, sodium silicate, and sodium carbonate.

[0040] Alternatively, sodium bicarbonate and ammonium bicarbonate decompose to produce gases during the activation of the mesoporous support. When the gases escape from the inside of the support pores, they exert a slight physical scouring and etching effect on the pore walls, creating more nanoscale defects and roughness on the smooth pore wall surface. These defects can serve as high-energy active sites.

[0041] Optionally, sodium carbonate can deprotonate mesoporous supports containing hydroxyl groups on their surface, thereby enhancing the surface charge of the mesoporous supports, increasing their binding ability with polymer ligand molecules, and increasing the stability of the composite supports.

[0042] Optionally, the silicic acid and silicate ions generated by sodium silicate can be adsorbed or chemically bonded to the surface of the mesoporous support, increasing the number of silanol groups as new active sites. These silanol groups can act as hydrogen bond donors / acceptors, forming strong hydrogen bonds with polymer ligand molecules (such as the ether oxygen bonds of polyether polyols). Dehydration condensation may also occur during subsequent heat treatment, forming strong chemical bonds. This increases the stability of the composite support.

[0043] Step S20: Polymer ligand molecules are added to the mesoporous support to prepare a premix. In one feasible embodiment, polymeric ligand molecules can modify the surface properties of the mesoporous support. By interacting with functional groups on the surface of the mesoporous support, the polymeric ligand molecules can alter the surface charge distribution, hydrophilicity, and other properties, making the mesoporous support surface more suitable for zinc oxide loading and enhancing the binding force between zinc oxide and the mesoporous support. The polymeric ligand molecules contain multiple coordinating atoms or functional groups, providing a large number of coordination sites for zinc oxide. These sites can coordinate with zinc oxide, promoting more uniform dispersion of zinc oxide on the composite support surface, preventing zinc oxide aggregation, and thus improving the loading capacity and stability of zinc oxide.

[0044] In one feasible embodiment, the polymeric ligand molecule includes: polyether polyol or polyvinylpyrrolidone.

[0045] In step S30, the premix is ​​calcined by gradient heating to obtain a composite carrier.

[0046] In one feasible embodiment, calcination in stages, at specific heating rates and holding times, can induce a series of physical and chemical changes in the material at different temperatures, thereby improving the material's structure and properties and removing impurities. In the preparation of composite supports, gradient calcination helps to form a stable structure, optimize pore distribution, and improve the purity and activity of the composite support.

[0047] In one feasible embodiment, prior to the step of obtaining the composite carrier by gradient temperature calcination of the premix, the method further includes: A first auxiliary agent is added to the premix to adjust the pH, wherein the first auxiliary agent includes at least one of sodium carbonate solution, sodium silicate solution, sodium hydroxide solution, sodium carbonate, sodium bicarbonate, ammonium bicarbonate, and potassium hydroxide.

[0048] In one feasible embodiment, a first auxiliary agent is added to adjust the pH of the premix, causing a change in the surface charge of the polymer ligand molecules. Under alkaline conditions, negatively charged functional groups are exposed, resulting in a composite support that promotes subsequent binding with zinc ions in zinc oxide. The exposed negatively charged functional groups possess strong chemical activity and can bind with zinc ions (ZnO2) in zinc oxide. 2+ Electrostatic attraction occurs. This electrostatic attraction is the basis for subsequent binding processes, which facilitates the tight binding of zinc ions with polymer ligand molecules, thereby loading zinc ions onto the composite support.

[0049] Optionally, the first auxiliary agent includes at least one of sodium carbonate solution, sodium silicate solution, sodium hydroxide solution, sodium carbonate, sodium bicarbonate, ammonium bicarbonate, and potassium hydroxide.

[0050] In one feasible implementation, the pH of the premix is ​​adjusted to 9-10 after the first adjuvant is added.

[0051] Optionally, the pH of the premix after adding the first additive can be adjusted to 9.0, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, or 10.0. Different pH values ​​will affect the degree of change in the surface charge of the polymer ligand molecules and the number of exposed negatively charged functional groups. If the pH value is below 9, the dissociation of acidic functional groups in the polymer ligand molecules may be insufficient, resulting in insufficient exposure of negatively charged functional groups and weaker binding capacity with zinc ions. If the pH value is above 10, it may have adverse effects on other components in the premix, such as causing the dissolution or decomposition of certain substances, thereby affecting the quality and performance of the composite carrier.

[0052] In one feasible implementation, the gradient heating calcination process includes: The reaction temperature is raised to 100~200℃ at a heating rate of less than or equal to 2℃ / min, and calcined for 1~3h; Calcination at 400-500℃ for 2-4 hours; In one feasible embodiment, after the step of calcining at 400-500°C for 2-4 hours, the method further includes: The reaction temperature is increased to the third preset temperature at a heating rate of 5~10℃ / min, and calcined for 0.5~1h, wherein the third preset temperature is greater than 500℃.

[0053] In one feasible embodiment, calcination in stages, at specific heating rates and holding times, can induce a series of physical and chemical changes in the material at different temperatures, thereby improving the material's structure and properties and removing impurities. In the preparation of composite supports, gradient calcination helps to form a stable structure, optimize pore distribution, and improve the purity and activity of the composite support.

[0054] Optionally, the reaction temperature is increased to 100-200℃ at a heating rate of less than or equal to 2℃ / min. Temperatures can be 100℃, 110℃, 120℃, 130℃, 140℃, 150℃, 160℃, 170℃, 180℃, 190℃, 200℃, etc. The slow heating rate is to avoid thermal stress caused by rapid temperature changes, preventing defects such as cracks and deformation. Especially at lower temperatures, the material may still contain a certain amount of moisture and volatile substances; slow heating allows these substances to gradually volatilize, reducing structural damage caused by rapid volatilization. After heating to 100-200℃, calcination is carried out for 1-3 hours. This process mainly removes adsorbed water and some volatile impurities from the material, allowing the mesoporous support and polymer ligand molecules to undergo preliminary bonding, forming a preliminary network structure. During this process, the moisture physically adsorbed on the material surface and in the pores gradually evaporates, and some low-boiling-point impurities also volatilize. Appropriate calcination time can ensure that moisture and impurities are fully removed, creating favorable conditions for subsequent high-temperature calcination.

[0055] Optionally, calcination is performed at 400-500℃ for 2-4 hours. Calcination temperatures can be 400℃, 420℃, 440℃, 460℃, 480℃, 500℃, etc. Within this temperature range, the material undergoes a series of chemical changes. For example, some organic substances may decompose and carbonize, and metal salts may thermally decompose into metal oxides. A longer calcination time helps these chemical reactions to proceed fully, making the material structure more stable. Simultaneously, medium-temperature calcination can also promote the carbonization process, resulting in a more complete material structure and improved purity and activity.

[0056] Optionally, the reaction temperature is increased to the third preset temperature at a heating rate of 5~10℃ / min. This heating rate is faster than the first stage. This is because after the first two stages of treatment, the material structure is relatively stable and can withstand a certain rate of temperature change. A faster heating rate can improve production efficiency, and at the same time, appropriate rapid heating at this stage helps to form specific structures and pore structures. The third preset temperature is greater than 500℃, and calcination is carried out for 0.5~1h. High-temperature calcination can further promote the sintering process of the material, making the material structure more compact and improving the mechanical strength and chemical stability of the material. At the same time, high temperature can also remove some impurities that are difficult to decompose in the medium-temperature stage, further improving the purity of the material. The shorter calcination time is to avoid over-sintering, which would lead to a decrease in the specific surface area of ​​the material and damage to the pore structure.

[0057] Optionally, the mesoporous support is a mixture of lignin and alumina. Lignin powder and alumina are mixed at a mass ratio of 2:1 and ball-milled for 3 hours. Then, the mixture is placed in a tube furnace and pre-oxidized in air at 250°C for 1 hour. After removal, it is immersed in a 0.1 mol / L sodium hydroxide solution and sonicated at 80°C for 1 hour. It is then washed with deionized water until neutral, dried at 80°C, and then placed back into the tube furnace for carbonization in an argon atmosphere at 600°C for 2 hours to obtain the mesoporous support. Polyvinylpyrrolidone and Tween 80 are dissolved in an ethanol-water mixture (volume ratio 2:1) at a mass ratio of 3:2, and ammonium bicarbonate is added to adjust the pH to 10. The obtained mesoporous support is immersed in this solution and gently stirred at 40°C for 5 hours. After centrifugation, it is washed with ethanol and vacuum dried at 60°C to obtain the premix. After drying, the premix was placed in a high-pressure reactor and heated to 100°C at a rate of 2°C / min for 3 hours in a CO2 atmosphere (5 MPa). The premix was then transferred to a muffle furnace and calcined at 400°C for 2 hours to obtain the composite carrier.

[0058] This embodiment provides a mesoporous support with a high specific surface area and porous structure, providing space for subsequent creation of anchoring sites for binding with polymeric ligand molecules. The mesoporous support is activated with a metal additive to create more active sites on its surface. A premix is ​​prepared by adding polymeric ligand molecules to the mesoporous support. One end of the polymeric ligand molecule can interact with the support surface and be bonded thereto; the polymeric ligand molecule has active functional groups for binding with zinc ions in zinc oxide. The premix is ​​then calcined using a gradient temperature increase to obtain a composite support. The slow, staged temperature increase during gradient calcination allows for the gradual decomposition of organic matter, avoiding pore wall collapse caused by a sudden increase in vapor pressure within the pores. This embodiment introduces higher density, more uniformity, and stronger binding capacity functional groups onto the mesoporous support by using polymeric ligand molecules as active molecules, thereby increasing the number of zinc ion binding sites. Furthermore, the composite support is prepared through a gradient calcination process; the staged temperature increase increases the stability of the composite support structure during preparation and increases the loading of zinc oxide on the support.

[0059] In order to enable those skilled in the art to clearly understand the details and operations of the above embodiments of this application, and to demonstrate the significant improvement in performance of the embodiments of this application, the above technical solutions are illustrated below through multiple embodiments.

[0060] Example A mesoporous support, carbon black, was provided. Carbon black and sodium bicarbonate were dry-mixed at a 5:1 mass ratio and treated under an argon atmosphere (50 Pa) for 25 min to introduce oxygen-containing defects and active sites on the surface. The treated carbon black was immediately immersed in 0.5 mol / L hydrochloric acid and sonicated for 30 min at 70 °C. Afterward, it was washed until neutral and dried at 100 °C.

[0061] Polyether polyol and ammonium bicarbonate were mixed at a volume ratio of 1:4 and stirred at 50°C for 5 hours to form a transparent colloidal solution. Then, 3 parts of potassium hydroxide were added to the solution and stirring was continued for 3 hours.

[0062] The carrier was added to the colloid of polymer ligand molecules in three batches, heated to 70°C, and sodium carbonate solution was injected every 15 minutes while mechanically stirring at 800 rpm. After centrifugation, the premix was surface cross-linked and cured in a vacuum drying oven at 280°C, and then transferred to a tube furnace. The gradient calcination process is as follows: The temperature was increased to 200℃ at 2℃ / min and calcined for 1 hour; then increased to 400℃ and calcined for 2 hours; finally increased to 600℃ at 5℃ / min and calcined for 1 hour. The composite carrier was then cooled to room temperature.

[0063] By using a composite carrier to support zinc oxide, supported zinc oxide is obtained.

[0064] Reference Figure 3 and Figure 4 This application embodiment realizes the preparation of a composite support for loading zinc oxide, and finds that the composite support prepared by using carbon black as a mesoporous support, treating it with sodium bicarbonate as a metal additive, and combining it with polyether polyol as a polymer ligand molecule has a BET specific surface area of ​​25±4 m². 2 / g, which is greater than the case where carbon black is used directly as a carrier; the BET specific surface area of ​​carbon black is 18±3 m². 2 / g. The composite carrier prepared in this embodiment has a large specific surface area, allowing it to load more zinc oxide. Furthermore, Figure 3 When zinc oxide was directly loaded onto medium carbon black as a carrier, the results showed that there was no chemical interaction between the zinc oxide and the carrier, and the zinc oxide was randomly dispersed. Figure 4 The composite carrier prepared by this method was used to load zinc oxide, and the results showed that the zinc element was highly uniformly distributed on the carrier due to the anchoring effect.

[0065] The above are merely preferred embodiments of this application and do not limit the patent scope of this application. Various modifications and variations can be made to this application by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the patent protection scope of this application.

Claims

1. A method for preparing a composite carrier for loading zinc oxide, characterized in that, The method includes the following steps: A mesoporous carrier is provided, wherein the mesoporous carrier is activated by a metal additive; A premix was prepared by adding polymeric ligand molecules to the mesoporous carrier. The premix was calcined by gradient heating to obtain a composite carrier.

2. The method for preparing the composite carrier for loading zinc oxide as described in claim 1, characterized in that, The mesoporous carrier includes at least one of carbon black, lignin, and alumina.

3. The method for preparing the composite carrier for loading zinc oxide as described in claim 1, characterized in that, The polymer ligand molecules include: polyether polyols or polyvinylpyrrolidone.

4. The method for preparing the composite carrier for loading zinc oxide as described in claim 1, characterized in that, The metal additives include at least one of sodium bicarbonate, ammonium bicarbonate, sodium silicate, and sodium carbonate.

5. The method for preparing the composite carrier for loading zinc oxide as described in claim 1, characterized in that, The gradient heating calcination process includes: The reaction temperature is raised to 100~200℃ at a heating rate of less than or equal to 2℃ / min, and calcined for 1~3h; Calcination at 400-500℃ for 2-4 hours.

6. The method for preparing the composite carrier for loading zinc oxide as described in claim 5, characterized in that, After the step of calcining at 400~500℃ for 2~4 hours, the method further includes: The reaction temperature is increased to a third preset temperature at a heating rate of 5~10℃ / min, and calcined for 0.5~1h, wherein the third preset temperature is greater than 500℃.

7. The method for preparing the composite carrier for loading zinc oxide as described in claim 1, characterized in that, Before the step of obtaining the composite carrier by gradient temperature calcination of the premix, the method further includes: A first auxiliary agent is added to the premix to adjust the pH, wherein the first auxiliary agent includes at least one of sodium carbonate solution, sodium silicate solution, sodium hydroxide solution, sodium carbonate, sodium bicarbonate, ammonium bicarbonate, and potassium hydroxide.

8. The method for preparing the composite carrier for loading zinc oxide as described in claim 7, characterized in that, The pH of the premix is ​​adjusted to 9-10 after the first auxiliary agent is added.

9. A composite carrier for loading zinc oxide, characterized in that, The composite carrier for loading zinc oxide is prepared by the method described in any one of claims 1 to 8.

10. A supported zinc oxide, characterized in that, The support for the supported zinc oxide is a composite support prepared by the method described in any one of claims 1 to 8, or a composite support as described in claim 9.

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