WO2022267335A1 - Filter material, preparation method therefor, and application thereof - Google Patents

Filter material, preparation method therefor, and application thereof Download PDF

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Publication number
WO2022267335A1
WO2022267335A1 PCT/CN2021/133271 CN2021133271W WO2022267335A1 WO 2022267335 A1 WO2022267335 A1 WO 2022267335A1 CN 2021133271 W CN2021133271 W CN 2021133271W WO 2022267335 A1 WO2022267335 A1 WO 2022267335A1
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Prior art keywords
filter material
solution
preparation
metal salt
substrate
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PCT/CN2021/133271
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French (fr)
Chinese (zh)
Inventor
张振
郭晓蓓
高政
王屹
尹奕玲
徐涛
费传军
余佳彬
匡新波
吴涛
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南京玻璃纤维研究设计院有限公司
中材科技股份有限公司
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Priority to KR1020237039027A priority Critical patent/KR20230170740A/en
Publication of WO2022267335A1 publication Critical patent/WO2022267335A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
    • B01D46/0001—Making filtering elements
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8628—Processes characterised by a specific catalyst
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/8621—Removing nitrogen compounds
    • B01D53/8625—Nitrogen oxides
    • B01D53/8631—Processes characterised by a specific device
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/04—Additives and treatments of the filtering material
    • B01D2239/0407—Additives and treatments of the filtering material comprising particulate additives, e.g. adsorbents
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/10—Filtering material manufacturing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2258/00—Sources of waste gases
    • B01D2258/02—Other waste gases
    • B01D2258/0283—Flue gases

Definitions

  • the invention belongs to the technical field of filter material preparation, and in particular relates to a filter material and its preparation method and application.
  • bag filter In the field of industrial flue gas post-treatment, bag filter has been widely used in coal-fired power plants, waste incineration, cement and other fields due to its high dust removal efficiency, good operation stability, and easy recycling.
  • the filter material is the core of the bag filter, such as glass fiber, PTFE and so on.
  • the use temperature of conventional bag filter media (about 150-200°C) is far lower than the temperature of catalytic reaction, which limits the development of multifunctional filter media with denitrification.
  • the integrated filter material for denitrification and dust removal is a material that enables the filter material to intercept dust and at the same time has the function of catalytically removing pollutants such as nitrogen oxides, sulfur oxides or heavy metals. It can realize the coordinated removal of multiple pollutions and effectively avoid the above problems.
  • the realization of integrated filter material for denitrification and dust removal is mainly to assemble the catalyst and the filter material base material by impregnation or coating.
  • This method is difficult to solve the problem of low bonding fastness and uneven dispersion of catalyst powder and filter material base material
  • the disadvantages are that the service life of the filter material and the catalytic stability are insufficient.
  • the treated metal fiber felt is immersed in a metal salt solution, and the in-situ deposition agent is added to adjust the pH and then calcined to obtain a filter material.
  • the catalyst and filter The surface bonding fastness of the material base material is high, but the air permeability of the obtained filter material is not good, and it is easy to harden, resulting in a low service life of the filter material. At the same time, the catalyst will also have the problem of uneven dispersion on the filter material base material.
  • the technical problem to be solved in the present invention is to overcome the defects that the integrated filter material for denitrification and dust removal in the prior art cannot simultaneously ensure the high binding fastness between the filter material and the catalyst, the uniform distribution of the catalyst, and the good air permeability of the integrated filter material. Therefore, a filter material and its preparation method and application are provided.
  • the present invention provides the following technical solutions.
  • the invention provides a kind of preparation method of filter material, comprises the following steps,
  • the mass concentration of the urea solution is 5-40%
  • the volume concentration of the ammonia solution is 35-60%;
  • the volume concentration of the hydrogen peroxide is 10-45%.
  • step (2) spray urea solution and/or ammonia solution on the surface of the filter material substrate under the condition of 55-80°C, and then spray the hydrogen peroxide solution on the surface of the filter material substrate under the condition of 55-80°C;
  • the spraying amount of ammonia solution is 150-330ml/m 2 ;
  • the amount of urea solution sprayed is 150-230ml/m 2 in terms of per square meter of filter material substrate;
  • the spraying amount of the hydrogen peroxide solution is 120-300ml/m 2 .
  • step (1) the time for the filter substrate to be immersed in the metal salt solution is greater than 30s;
  • the metal salt solution includes at least one of titanium salt, cerium salt and manganese salt;
  • the mass concentration of the metal salt solution is 30-35%.
  • the metal salt solution includes titanium salt, cerium salt and manganese salt
  • the molar ratio of titanium, cerium and manganese in the metal salt solution is (10-12):(0.7-1.3):(4-5).
  • the temperature of the heat treatment is 250-300° C., and the time is 20-30 minutes.
  • the heat treatment step also includes the step of spraying polytetrafluoroethylene composite emulsion on the surface of the filter material base material, and after sintering, heat-press lamination with polytetrafluoroethylene expanded microporous membrane.
  • the process parameters of the hot-press lamination the temperature is 260-380°C, the vehicle speed is 1-10m/min, and the pressure is 0.2-0.5MPa;
  • the polytetrafluoroethylene composite emulsion includes a mass ratio of (20-50): (10-20): (0.5-1.5): (1.5-5) polytetrafluoroethylene emulsion, fluorine-containing silane waterproofing agent, coupling agent and inorganic water repellent;
  • the sintering temperature is 260-320° C., and the sintering time is 4-10 minutes.
  • a drying step is also included between the steps of heat treatment and spraying the polytetrafluoroethylene composite emulsion; wherein, the drying temperature is 100-120°C.
  • the present invention also provides a filter material prepared by the above method.
  • the filter material is an integrated filter material for dust removal and denitrification, which can have the functions of dust removal and denitrification at the same time.
  • the present invention also provides a filter material prepared by the above method or an application of the above filter material in catalytic denitrification.
  • the invention provides a kind of preparation method of filter material, comprising, (1) at 55-70 °C, filter material substrate is immersed in metal salt solution; (2) filter material substrate surface after dipping Spraying urea solution and/or ammonia solution, and then spraying hydrogen peroxide solution on the surface of the filter material substrate; (3) obtaining the filter material after heat treatment.
  • the denitrification and dust removal integrated filter material obtained by the method can ensure high binding fastness between the filter material base material and the catalyst, and can also make the catalyst evenly distributed on the filter material base material, and the presence of the catalyst does not affect the air permeability of the filter material.
  • the base material of the filter material is immersed in the metal salt solution under the condition of 55-70°C.
  • the metal salt solution can ensure that the metal salt solution is in a uniform state, so that the metal ions are evenly loaded on the surface of the fiber of the filter material base material.
  • the catalyst particles will not block the pores of the filter material and affect the air permeability of the filter material; on the other hand, at this temperature, the metal salt solution is in a stable state and will not form a suspension. It has good wettability to the base material of the filter material, so that the metal salt solution can evenly cover the base material of the filter material, and the base material of the filter material has good wettability.
  • the urea solution and/or ammonia solution is sprayed on the surface of the filter substrate by spraying, so that the urea and/or ammonia react with the metal ions on the surface of the filter substrate to form catalyst particles on the surface of the filter substrate, making the catalyst particles Firmly attached to the surface of the filter material base material, the bonding fastness is strong; compared with the direct dipping method adopted in the prior art, the spraying method adopted in the present invention has little influence on the air permeability of the filter material and the denitrification efficiency of the catalyst, and the catalyst is formed on the surface of the filter material Particles, reducing the phenomenon of particles inside the filter material blocking the pores and the phenomenon of filter material compaction, improving the filtering effect and service life.
  • Spraying urea solution and/or ammonia solution has a good reduction effect and a wide range of sources, and can be popularized and applied to the removal of nitrogen oxides in industrial flue gas.
  • Spraying the hydrogen peroxide solution on the filter base material by spraying can further improve the stability of the metal ion valence state in the metal complex and improve the denitrification efficiency of the catalyst. During use, no other metal ions will be introduced and the stability of the catalytic system will not be affected. , low price, no pollution.
  • the preparation method of the filter material provided by the invention is suitable for high-temperature-resistant filter material substrates such as glass fiber, polytetrafluoroethylene, polyimide, aramid fiber, and metal fiber.
  • the preparation method of the filter material provided by the present invention is under the condition of 55-80 °C, sprays reductant and oxidizing agent on the surface of filter material base material, can prevent the metal ion in the metal salt solution from separating out, settling, metal
  • sprays reductant and oxidizing agent on the surface of filter material base material can prevent the metal ion in the metal salt solution from separating out, settling, metal
  • the salt solution reacts with the reducing agent, there will be no problem of agglomeration, so that the metal salt solution, the reducing agent and the oxidizing agent can fully contact and react, and an integrated filter material with uniform catalyst distribution can be obtained.
  • this method metal salt solution comprises titanium salt, cerium salt and manganese salt, can improve the catalytic efficiency of catalyst on the one hand, when this filter material is used for catalytic denitrification on the other hand, can Lower the reaction temperature.
  • the heat treatment temperature is reduced while the integrated filter material for dedusting and denitrification is prepared, thereby saving energy and protecting the environment.
  • Fig. 1 is a scanning electron microscope image of the filter material in Example 1 of the present invention.
  • the coupling agent used in the comparative example is KH1100
  • the fluorine-containing silane waterproofing agent is FLW-99 type
  • the inorganic waterproofing agent is nano inorganic silicon waterproofing agent.
  • the present embodiment provides a kind of preparation method of filter material, comprises the following steps,
  • the metal salt solution includes titanyl sulfate, cerium nitrate and acetic acid in a molar ratio of 11:1:4.5 Manganese, the mass concentration of the metal salt solution is 15wt%.
  • the glass fiber base material is placed under the atmosphere of 65 °C, and the volume concentration of 40% ammonia solution and the hydrogen peroxide solution of 30% volume concentration are sprayed successively on the surface of the glass fiber base material after immersion, and the per square meter filter Based on the base material, the spraying amount of ammonia solution is 220ml/m 2 , and the spraying amount of hydrogen peroxide solution is 160ml/m 2 . After spraying, dry the glass fiber substrate at 120°C to remove excess water and other liquids. .
  • the polytetrafluoroethylene composite emulsion includes polytetrafluoroethylene emulsion with a mass ratio of 45:15:1.5:1.5:37, fluorine-containing silane waterproofing agent, coupling agent, inorganic waterproofing agent and water, and the spraying amount is glass fiber-based 4% of the material mass; the temperature of hot-press lamination is 345°C, the pressure is 0.3MPa, and the vehicle speed is 4m/min.
  • Figure 1 is a topographical view of the filter material of this embodiment, from which it can be seen that the catalyst is evenly distributed on the surface of the filter material substrate.
  • the present embodiment provides a kind of preparation method of filter material, comprises the following steps,
  • the metal salt solution includes sulfuric acid oxygen with a molar ratio of 11:1:4.5 Titanium, cerium nitrate and manganese acetate, the concentration of the metal salt solution is 10wt%.
  • the polyimide needle felt base material is placed under the atmosphere of 70 °C, and the polyimide needle felt base material surface after dipping is sprayed successively that mass concentration is 40% urea aqueous solution and volume concentration is 12 % hydrogen peroxide solution, in terms of per square meter of filter material base material, the spraying amount of urea aqueous solution is 200ml/m 2 , the spraying amount of hydrogen peroxide solution is 140ml/m 2 , after spraying, the polyimide needle felt base The material is dried at 120°C to remove excess water and other liquids.
  • the polytetrafluoroethylene composite emulsion includes polytetrafluoroethylene emulsion with a mass ratio of 40:15:1:2:42, fluorine-containing silane waterproofing agent, coupling agent, inorganic waterproofing agent and water, and the spraying amount is polyimide 4wt% of the mass of the amine needle felt substrate; the temperature of hot-press lamination is 328°C, the pressure is 0.45MPa, and the vehicle speed is 5m/min.
  • the present embodiment provides a kind of preparation method of filter material, comprises the following steps,
  • the glass fiber and polyimide composite needle felt substrate were immersed in the metal salt solution, and the immersion time was 0.8min; wherein, the metal salt solution included a molar ratio of 11:1: 4.5 titanyl sulfate, cerium nitrate and manganese acetate, the concentration of the metal salt solution is 35wt%.
  • the composite needle felt base material is then placed in an atmosphere of 70° C., and the volume concentration of 40% ammonia solution and the volume concentration of 40% hydrogen peroxide solution are sprayed on the surface of the impregnated composite needle felt base material successively, with Calculated per square meter of filter material substrate, the spraying amount of ammonia solution is 320ml/m 2 , and the spraying amount of hydrogen peroxide solution is 270ml/m 2 . After spraying, put the composite needle felt substrate at 120°C to dry , to remove excess water and other liquids.
  • the polytetrafluoroethylene composite emulsion includes polytetrafluoroethylene emulsion with a mass ratio of 50:10:1.5:1.5:37, a fluorine-containing silane waterproofing agent, a coupling agent, an inorganic waterproofing agent and water, and the spraying amount is the composite acupuncture 4wt% of the mass of the felt substrate; the temperature of hot-press lamination is 320° C., the pressure is 0.5 MPa, and the vehicle speed is 10 m/min.
  • the present embodiment provides a kind of preparation method of filter material, comprises the following steps,
  • the metal salt solution includes titanyl sulfate, cerium nitrate and Manganese acetate, the concentration of the metal salt solution is 10wt%.
  • the glass fiber substrate is placed in an atmosphere of 60°C, and the volume concentration of 35% ammonia solution and 20% hydrogen peroxide solution are sprayed on the surface of the impregnated glass fiber substrate successively.
  • the spraying amount of ammonia solution is 160ml/m 2
  • the spraying amount of hydrogen peroxide solution is 120ml/m 2 .
  • the polytetrafluoroethylene composite emulsion includes polytetrafluoroethylene emulsion with a mass ratio of 50:10:1:2:36, fluorine-containing silane waterproofing agent, coupling agent, inorganic waterproofing agent and water, and the spraying amount is glass fiber-based 4wt% of the material weight; the temperature of hot-press lamination is 340°C, the pressure is 0.35MPa, and the vehicle speed is 6m/min.
  • This comparative example provides a kind of preparation method of filter material, comprises the following steps,
  • the metal salt solution includes titanyl sulfate, cerium nitrate and acetic acid in a molar ratio of 11:1:4.5 Manganese, the concentration of the metal salt solution is 15wt%.
  • the glass fiber substrate is placed in an atmosphere of 70°C, and the volume concentration of 40% ammonia solution and 30% hydrogen peroxide solution are sprayed on the surface of the impregnated glass fiber substrate successively.
  • the spraying amount of ammonia solution is 220ml/m 2
  • the spraying amount of hydrogen peroxide solution is 160ml/m 2 .
  • the polytetrafluoroethylene composite emulsion includes polytetrafluoroethylene emulsion with a mass ratio of 45:15:1.5:1.5:37, fluorine-containing silane waterproofing agent, coupling agent, inorganic waterproofing agent and water, and the spraying amount is glass fiber-based 4wt% of the material mass; the temperature of hot-press lamination is 345°C, the pressure is 0.3MPa, and the vehicle speed is 4m/min.
  • This comparative example provides a kind of preparation method of filter material, comprises the following steps,
  • the metal salt solution includes titanyl sulfate, cerium nitrate and manganese acetate in a molar ratio of 11:1:4.5, and the mass concentration of the metal salt solution is 15 wt%.
  • the polytetrafluoroethylene composite emulsion includes polytetrafluoroethylene emulsion with a mass ratio of 45:15:1.5:1.5:37, fluorine-containing silane waterproofing agent, coupling agent, inorganic waterproofing agent and water, and the spraying amount is glass fiber-based 4wt% of the material mass; the temperature of hot-press lamination is 345°C, the pressure is 0.3MPa, and the vehicle speed is 4m/min.
  • This test example provides the performance tests and test results of the filter materials prepared in Examples 1-4 and Comparative Examples 1-2.
  • the test methods are as follows, and the test results are shown in Table 1.
  • the weight deviation of the catalyst loaded on the filter material per square meter is in accordance with Section 9.1 of the standard GB/T6719-2009c;
  • the air permeability of the filter material is in accordance with the standard GB/T6719-2009c section 9.2;
  • the filtration resistance of the filter material is in accordance with section 9.5 of the standard GB/T6719-2009c.
  • the test method for the catalytic denitrification efficiency of the filter material is: test the denitrification efficiency at 250°C, specifically, after the nitrogen oxide gas meter passes through the disc-shaped filter material with a diameter of 10cm at a speed of 0.5m/min, the concentration of nitrogen oxides decreases by the percentage.
  • the catalyst prepared by the present invention has a small deviation in the loaded square meter gram weight, indicating that the catalyst is evenly distributed on the filter material substrate, and the filter material is used for denitrification, and the denitrification efficiency is high; the smaller the filtration resistance, the more breathable The greater the permeability, the better the air permeability of the filter material.
  • the filter material prepared in Example 1-4 of the present invention with both dust removal and catalytic denitrification functions is not easy to fall off during use, and the filter material prepared in Comparative Example 1-2 is not easy to fall off during use.
  • the filter material prepared by the present invention has higher binding fastness to the catalyst, and on the basis of ensuring the binding fastness, the distribution uniformity and air permeability of the catalyst are further improved.

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Abstract

A filter material, a preparation method therefor, and an application thereof. The preparation method comprises: (1) soaking a filter material substrate in a metal salt solution at 55-70°C; (2) spraying a urea solution and/or an ammonia water solution on the surface of the soaked filter material substrate, and then spraying a hydrogen peroxide solution on the surface of the filter material substrate; and (3) performing heat treatment to obtain the filter material.

Description

一种滤料及其制备方法和应用A kind of filter material and its preparation method and application 技术领域technical field
本发明属于过滤材料制备技术领域，具体涉及一种滤料及其制备方法和应用。The invention belongs to the technical field of filter material preparation, and in particular relates to a filter material and its preparation method and application.
背景技术Background technique
能源是经济社会发展和提高人民生活水平的重要物质基础，随着经济的快速发展，我国对能源的需求急剧上升，污染严重的重工业，如冶炼行业和发电行业迅速发展，这些行业大部分都以煤炭作为主要燃烧材料，导致了严重的煤烟污染，给人类的生命健康造成了极大威胁。我国对烟尘的排放有严格的限制，且标准越来越严格。Energy is an important material basis for economic and social development and improvement of people's living standards. With the rapid development of the economy, my country's demand for energy has risen sharply, and heavy industries with serious pollution, such as the smelting industry and power generation industry, have developed rapidly. Most of these industries are based on Coal, as the main combustion material, has caused serious soot pollution, posing a great threat to human life and health. my country has strict restrictions on the emission of smoke and dust, and the standards are becoming more and more stringent.
在工业烟气后处理领域，袋式除尘器由于除尘效率高，运行稳定性好，易于回收等特点已被广泛应用于燃煤电厂、垃圾焚烧、水泥等领域。其中，滤料是袋式除尘器的核心，如玻璃纤维、PTFE等。常规布袋滤料的使用温度(150-200℃左右)，远远低于催化反应的温度，这限制了具有脱硝多功能滤料的发展。脱硝除尘一体化滤料是使滤料拦截粉尘的同时具有催化脱除氮氧化物、硫氧化物或重金属等污染物功能的材料，可以实现多污染协同脱除，有效避免上述问题。In the field of industrial flue gas post-treatment, bag filter has been widely used in coal-fired power plants, waste incineration, cement and other fields due to its high dust removal efficiency, good operation stability, and easy recycling. Among them, the filter material is the core of the bag filter, such as glass fiber, PTFE and so on. The use temperature of conventional bag filter media (about 150-200°C) is far lower than the temperature of catalytic reaction, which limits the development of multifunctional filter media with denitrification. The integrated filter material for denitrification and dust removal is a material that enables the filter material to intercept dust and at the same time has the function of catalytically removing pollutants such as nitrogen oxides, sulfur oxides or heavy metals. It can realize the coordinated removal of multiple pollutions and effectively avoid the above problems.
目前，脱硝除尘一体化滤料的实现方式主要为通过浸渍或者涂覆的方式将催化剂与滤料基材组装，这种方法难以解决催化剂粉末与滤料基材表面结合牢度低、分散不均匀的缺点，滤料使用寿命及催化稳定性不足。现有技术中，在制备具有脱硝脱汞多功能复合滤料时，将处理后的金属纤维毡浸渍在金属盐溶液中，加原位沉积剂调pH后煅烧，得到滤料，虽然催化剂与滤料基材表面结合牢度高，但是得到的滤料的透气性不好，易板结，导致滤料使用寿命低，同 时，该催化剂在滤料基材上还会出现分散不均匀的问题。At present, the realization of integrated filter material for denitrification and dust removal is mainly to assemble the catalyst and the filter material base material by impregnation or coating. This method is difficult to solve the problem of low bonding fastness and uneven dispersion of catalyst powder and filter material base material The disadvantages are that the service life of the filter material and the catalytic stability are insufficient. In the prior art, when preparing a multifunctional composite filter material with denitrification and mercury removal, the treated metal fiber felt is immersed in a metal salt solution, and the in-situ deposition agent is added to adjust the pH and then calcined to obtain a filter material. Although the catalyst and filter The surface bonding fastness of the material base material is high, but the air permeability of the obtained filter material is not good, and it is easy to harden, resulting in a low service life of the filter material. At the same time, the catalyst will also have the problem of uneven dispersion on the filter material base material.
发明内容Contents of the invention
因此，本发明要解决的技术问题在于克服现有技术中的脱硝除尘一体化滤料不能同时保证滤料与催化剂的结合牢度高，催化剂分布均匀，一体化滤料的透气性好等缺陷，从而提供一种滤料及其制备方法和应用。Therefore, the technical problem to be solved in the present invention is to overcome the defects that the integrated filter material for denitrification and dust removal in the prior art cannot simultaneously ensure the high binding fastness between the filter material and the catalyst, the uniform distribution of the catalyst, and the good air permeability of the integrated filter material. Therefore, a filter material and its preparation method and application are provided.
为此，本发明提供了以下技术方案。For this reason, the present invention provides the following technical solutions.
本发明提供了一种滤料的制备方法，包括以下步骤，The invention provides a kind of preparation method of filter material, comprises the following steps,
(1)在55-70℃下，将滤料基材浸渍于金属盐溶液中；(1) At 55-70°C, immerse the filter material base material in the metal salt solution;
(2)在浸渍后的滤料基材表面喷洒尿素溶液和/或氨水溶液，然后再在滤料基材表面喷洒双氧水溶液；(2) Spray urea solution and/or ammonia solution on the surface of the impregnated filter material substrate, and then spray hydrogen peroxide solution on the surface of the filter material substrate;
(3)经热处理后得到滤料。(3) The filter material is obtained after heat treatment.
所述尿素溶液的质量浓度为5-40％；The mass concentration of the urea solution is 5-40%;
所述氨水溶液的体积浓度为35-60％；The volume concentration of the ammonia solution is 35-60%;
所述双氧水的体积浓度为10-45％。The volume concentration of the hydrogen peroxide is 10-45%.
所述步骤(2)中，在55-80℃的条件下在滤料基材表面喷洒尿素溶液和/或氨水溶液，再在55-80℃的条件下在滤料基材表面喷洒双氧水溶液；In the step (2), spray urea solution and/or ammonia solution on the surface of the filter material substrate under the condition of 55-80°C, and then spray the hydrogen peroxide solution on the surface of the filter material substrate under the condition of 55-80°C;
以每平方米滤料基材计，氨水溶液的喷洒量为150-330ml/m 2； In terms of per square meter of filter material base material, the spraying amount of ammonia solution is 150-330ml/m 2 ;
以每平方米滤料基材计，尿素溶液的喷洒量为150-230ml/m 2； The amount of urea solution sprayed is 150-230ml/m 2 in terms of per square meter of filter material substrate;
以每平方米滤料基材计，双氧水溶液的喷洒量为120-300ml/m 2。 Calculated per square meter of filter material substrate, the spraying amount of the hydrogen peroxide solution is 120-300ml/m 2 .
步骤(1)中，滤料基材浸渍于金属盐溶液中的时间大于30s；In step (1), the time for the filter substrate to be immersed in the metal salt solution is greater than 30s;
所述金属盐溶液包括钛盐、铈盐和锰盐中的至少一种；The metal salt solution includes at least one of titanium salt, cerium salt and manganese salt;
所述金属盐溶液的质量浓度为30-35％。The mass concentration of the metal salt solution is 30-35%.
所述金属盐溶液包括钛盐、铈盐和锰盐；The metal salt solution includes titanium salt, cerium salt and manganese salt;
所述金属盐溶液中钛、铈、和锰的摩尔比为(10-12)：(0.7-1.3)：(4-5)。The molar ratio of titanium, cerium and manganese in the metal salt solution is (10-12):(0.7-1.3):(4-5).
所述热处理的温度为250-300℃，时间为20-30min。The temperature of the heat treatment is 250-300° C., and the time is 20-30 minutes.
在所述热处理步骤之后还包括在滤料基材表面喷洒聚四氟乙烯复合乳液，经烧结后再与聚四氟乙烯膨化微孔膜进行热压覆合的步骤。After the heat treatment step, it also includes the step of spraying polytetrafluoroethylene composite emulsion on the surface of the filter material base material, and after sintering, heat-press lamination with polytetrafluoroethylene expanded microporous membrane.
所述热压覆合的工艺参数：温度为260-380℃，车速为1-10m/min，压力为0.2-0.5MPa；The process parameters of the hot-press lamination: the temperature is 260-380°C, the vehicle speed is 1-10m/min, and the pressure is 0.2-0.5MPa;
所述聚四氟乙烯复合乳液包括质量比为(20-50)：(10-20)：(0.5-1.5)：(1.5-5)的聚四氟乙烯乳液、含氟硅烷防水剂、偶联剂和无机防水剂；The polytetrafluoroethylene composite emulsion includes a mass ratio of (20-50): (10-20): (0.5-1.5): (1.5-5) polytetrafluoroethylene emulsion, fluorine-containing silane waterproofing agent, coupling agent and inorganic water repellent;
所述烧结的温度为260-320℃，烧结时间为4-10min。The sintering temperature is 260-320° C., and the sintering time is 4-10 minutes.
在热处理和喷洒聚四氟乙烯复合乳液步骤之间还包括烘干的步骤；其中，烘干的温度为100-120℃。A drying step is also included between the steps of heat treatment and spraying the polytetrafluoroethylene composite emulsion; wherein, the drying temperature is 100-120°C.
本发明还提供了一种上述方法制备得到的滤料。The present invention also provides a filter material prepared by the above method.
该滤料为除尘脱硝一体化滤料，可以同时兼具除尘和脱硝的功能。The filter material is an integrated filter material for dust removal and denitrification, which can have the functions of dust removal and denitrification at the same time.
此外，本发明还提供了一种上述方法制备得到的滤料或上述滤料在催化脱硝中的应用。In addition, the present invention also provides a filter material prepared by the above method or an application of the above filter material in catalytic denitrification.
本发明技术方案，具有如下优点：The technical solution of the present invention has the following advantages:
1.本发明提供了一种滤料的制备方法，包括，(1)在55-70℃下，将滤料基材浸渍于金属盐溶液中；(2)在浸渍后的滤料基材表面喷洒尿素溶液和/或氨水溶液，然后再在滤料基材表面喷洒双氧水溶液；(3)经热处理后得到滤料。该方法得到的脱硝除尘一体化滤料可以保证滤料基材与催化剂具有高结合牢度的同时，还可以使催化剂均匀分布在滤料基材，且催化剂的存在不影响滤料的透气性。滤料基材在55-70℃的条件下浸渍于金属盐溶液中，一方面可以保证金 属盐溶液呈均一状态，使金属离子均匀负载在滤料基材纤维表层，加入尿素和/或氨水后，在滤料基材纤维表层形成催化剂时，催化剂颗粒不会堵塞滤料孔隙以及影响滤料透气性；另一方面，在该温度下，金属盐溶液呈现稳定状态，不会形成悬浊液，对滤料基材具有较好的浸润性，使金属盐溶液对滤料基材均匀包覆，滤料基材具有较好的浸润性。采用喷洒的方式将尿素溶液和/或氨水溶液喷洒在滤料基材表面，使尿素和/或氨水与滤料基材表层的金属离子反应，在滤料基材表层形成催化剂颗粒，使催化剂颗粒牢固附着在滤料基材表面，结合牢度强；与现有技术采用的直接浸渍法相比，本发明采用的喷洒方法对滤料的透气性、催化剂脱硝效率影响小，在滤料表层生成催化剂颗粒，减少滤料内部颗粒堵塞孔隙的现象以及滤料出现板结的情况，提高了过滤效果和使用寿命。1. The invention provides a kind of preparation method of filter material, comprising, (1) at 55-70 ℃, filter material substrate is immersed in metal salt solution; (2) filter material substrate surface after dipping Spraying urea solution and/or ammonia solution, and then spraying hydrogen peroxide solution on the surface of the filter material substrate; (3) obtaining the filter material after heat treatment. The denitrification and dust removal integrated filter material obtained by the method can ensure high binding fastness between the filter material base material and the catalyst, and can also make the catalyst evenly distributed on the filter material base material, and the presence of the catalyst does not affect the air permeability of the filter material. The base material of the filter material is immersed in the metal salt solution under the condition of 55-70°C. On the one hand, it can ensure that the metal salt solution is in a uniform state, so that the metal ions are evenly loaded on the surface of the fiber of the filter material base material. After adding urea and/or ammonia water , when the catalyst is formed on the surface of the filter material substrate fiber, the catalyst particles will not block the pores of the filter material and affect the air permeability of the filter material; on the other hand, at this temperature, the metal salt solution is in a stable state and will not form a suspension. It has good wettability to the base material of the filter material, so that the metal salt solution can evenly cover the base material of the filter material, and the base material of the filter material has good wettability. The urea solution and/or ammonia solution is sprayed on the surface of the filter substrate by spraying, so that the urea and/or ammonia react with the metal ions on the surface of the filter substrate to form catalyst particles on the surface of the filter substrate, making the catalyst particles Firmly attached to the surface of the filter material base material, the bonding fastness is strong; compared with the direct dipping method adopted in the prior art, the spraying method adopted in the present invention has little influence on the air permeability of the filter material and the denitrification efficiency of the catalyst, and the catalyst is formed on the surface of the filter material Particles, reducing the phenomenon of particles inside the filter material blocking the pores and the phenomenon of filter material compaction, improving the filtering effect and service life.
喷洒尿素溶液和/或氨水溶液，还原效果好，来源广泛，可以推广应用于工业烟气氮氧化物脱除。Spraying urea solution and/or ammonia solution has a good reduction effect and a wide range of sources, and can be popularized and applied to the removal of nitrogen oxides in industrial flue gas.
采用喷洒的方式将滤料基材上喷洒双氧水溶液可以进一步提升金属络合物中金属离子价态稳定性，提升催化剂脱硝效率，在使用过程中不会引入其他金属离子，不影响催化体系稳定性，价格低廉，没有污染性。Spraying the hydrogen peroxide solution on the filter base material by spraying can further improve the stability of the metal ion valence state in the metal complex and improve the denitrification efficiency of the catalyst. During use, no other metal ions will be introduced and the stability of the catalytic system will not be affected. , low price, no pollution.
本发明提供的滤料的制备方法适用于玻璃纤维、聚四氟乙烯、聚酰亚胺、芳纶、金属纤维等耐高温滤料基材。The preparation method of the filter material provided by the invention is suitable for high-temperature-resistant filter material substrates such as glass fiber, polytetrafluoroethylene, polyimide, aramid fiber, and metal fiber.
2.本发明提供的滤料的制备方法，本发明在55-80℃的条件下，在滤料基材表面喷洒还原剂和氧化剂，可以防止金属盐溶液中的金属离子析出，发生沉降，金属盐溶液与还原剂反应时，不会出现团聚的问题，使金属盐溶液与还原剂、氧化剂可以充分接触反应，得到催化剂分布均匀的一体化滤料。2. The preparation method of the filter material provided by the present invention, the present invention is under the condition of 55-80 ℃, sprays reductant and oxidizing agent on the surface of filter material base material, can prevent the metal ion in the metal salt solution from separating out, settling, metal When the salt solution reacts with the reducing agent, there will be no problem of agglomeration, so that the metal salt solution, the reducing agent and the oxidizing agent can fully contact and react, and an integrated filter material with uniform catalyst distribution can be obtained.
3.本发明提供的滤料的制备方法，该方法金属盐溶液包括钛盐、铈盐和锰盐，一方面可以提高催化剂的催化效率，另一方面将该滤料用于催化脱硝时，可以降低反应温度。3. the preparation method of filter material provided by the invention, this method metal salt solution comprises titanium salt, cerium salt and manganese salt, can improve the catalytic efficiency of catalyst on the one hand, when this filter material is used for catalytic denitrification on the other hand, can Lower the reaction temperature.
通过控制热处理温度为250-280℃，在制备得到除尘脱硝一体化滤料的同时降低了热处理的温度，节能环保。By controlling the heat treatment temperature to 250-280° C., the heat treatment temperature is reduced while the integrated filter material for dedusting and denitrification is prepared, thereby saving energy and protecting the environment.
附图说明Description of drawings
为了更清楚地说明本发明具体实施方式或现有技术中的技术方案，下面将对具体实施方式或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图是本发明的一些实施方式，对于本领域普通技术人员来讲，在不付出创造性劳动的前提下，还可以根据这些附图获得其他的附图。In order to more clearly illustrate the specific implementation of the present invention or the technical solutions in the prior art, the following will briefly introduce the accompanying drawings that need to be used in the specific implementation or description of the prior art. Obviously, the accompanying drawings in the following description The drawings show some implementations of the present invention, and those skilled in the art can obtain other drawings based on these drawings without any creative work.
图1是本发明实施例1中滤料的扫描电镜图。Fig. 1 is a scanning electron microscope image of the filter material in Example 1 of the present invention.
具体实施方式detailed description
提供下述实施例是为了更好地进一步理解本发明，并不局限于所述最佳实施方式，不对本发明的内容和保护范围构成限制，任何人在本发明的启示下或是将本发明与其他现有技术的特征进行组合而得出的任何与本发明相同或相近似的产品，均落在本发明的保护范围之内。The following examples are provided in order to further understand the present invention better, are not limited to the best implementation mode, and do not limit the content and protection scope of the present invention, anyone under the inspiration of the present invention or use the present invention Any product identical or similar to the present invention obtained by combining features of other prior art falls within the protection scope of the present invention.
实施例中未注明具体实验步骤或条件者，按照本领域内的文献所描述的常规实验步骤的操作或条件即可进行。所用试剂或仪器未注明生产厂商者，均为可以通过市购获得的常规试剂产品。If no specific experimental steps or conditions are indicated in the examples, it can be carried out according to the operation or conditions of the conventional experimental steps described in the literature in this field. The reagents or instruments used, whose manufacturers are not indicated, are all commercially available conventional reagent products.
在以下实施例中对比例中用到的偶联剂为KH1100，含氟硅烷防水剂为FLW-99型，无机防水剂为纳米无机硅防水剂。In the following examples, the coupling agent used in the comparative example is KH1100, the fluorine-containing silane waterproofing agent is FLW-99 type, and the inorganic waterproofing agent is nano inorganic silicon waterproofing agent.
实施例1Example 1
本实施例提供了一种滤料的制备方法，包括以下步骤，The present embodiment provides a kind of preparation method of filter material, comprises the following steps,
(1)在65℃的条件下，将玻璃纤维基材浸渍于金属盐溶液中，浸渍时间为1min；其中，金属盐溶液包括摩尔比为11:1:4.5的硫酸氧钛、硝酸铈和乙酸锰，所述金属盐溶液的质量浓度为15wt％。(1) Under the condition of 65°C, immerse the glass fiber substrate in the metal salt solution for 1 min; wherein, the metal salt solution includes titanyl sulfate, cerium nitrate and acetic acid in a molar ratio of 11:1:4.5 Manganese, the mass concentration of the metal salt solution is 15wt%.
(2)然后将玻璃纤维基材置于65℃的气氛下，在浸渍后的玻璃纤维基材表面依次喷洒体积浓度为40％氨水溶液和体积浓度为30％的双氧水溶液，以每平方米滤料基材计，氨水溶液的喷洒量为220ml/m 2，双氧水溶液的喷洒量为160ml/m 2，喷洒结束后，将玻璃纤维基材置于120℃条件下烘干，去除多余水分等液体。 (2) Then the glass fiber base material is placed under the atmosphere of 65 ℃, and the volume concentration of 40% ammonia solution and the hydrogen peroxide solution of 30% volume concentration are sprayed successively on the surface of the glass fiber base material after immersion, and the per square meter filter Based on the base material, the spraying amount of ammonia solution is 220ml/m 2 , and the spraying amount of hydrogen peroxide solution is 160ml/m 2 . After spraying, dry the glass fiber substrate at 120°C to remove excess water and other liquids. .
(3)将烘干后的玻璃纤维基材置于300℃下热处理20min，然后在其表面喷洒一层聚四氟乙烯复合乳液，在300℃下烧结7min，与聚四氟乙烯膨化微孔膜热压覆合后得到滤料。其中，聚四氟乙烯复合乳液包括质量比为45:15:1.5:1.5:37的聚四氟乙烯乳液、含氟硅烷防水剂、偶联剂、无机防水剂和水，喷洒量为玻璃纤维基材质量的4％；热压覆合的温度为345℃，压力为0.3MPa，车速为4m/min。(3) heat-treat the dried glass fiber substrate at 300°C for 20 minutes, then spray a layer of polytetrafluoroethylene composite emulsion on its surface, sinter at 300°C for 7 minutes, and combine with polytetrafluoroethylene expanded microporous membrane The filter material is obtained after hot pressing lamination. Among them, the polytetrafluoroethylene composite emulsion includes polytetrafluoroethylene emulsion with a mass ratio of 45:15:1.5:1.5:37, fluorine-containing silane waterproofing agent, coupling agent, inorganic waterproofing agent and water, and the spraying amount is glass fiber-based 4% of the material mass; the temperature of hot-press lamination is 345°C, the pressure is 0.3MPa, and the vehicle speed is 4m/min.
图1是本实施例滤料的形貌图，从图中可以看出催化剂在滤料基材表面分布均匀。Figure 1 is a topographical view of the filter material of this embodiment, from which it can be seen that the catalyst is evenly distributed on the surface of the filter material substrate.
实施例2Example 2
本实施例提供了一种滤料的制备方法，包括以下步骤，The present embodiment provides a kind of preparation method of filter material, comprises the following steps,
(1)在60℃的条件下，将聚酰亚胺针刺毡基材浸渍于金属盐溶液中，浸渍时间为1.5min；其中，金属盐溶液包括摩尔比为11:1:4.5的硫酸氧钛、硝酸铈和乙酸锰，所述金属盐溶液的浓度为10wt％。(1) Under the condition of 60°C, immerse the polyimide needle felt substrate in the metal salt solution for 1.5 minutes; wherein, the metal salt solution includes sulfuric acid oxygen with a molar ratio of 11:1:4.5 Titanium, cerium nitrate and manganese acetate, the concentration of the metal salt solution is 10wt%.
(2)然后将聚酰亚胺针刺毡基材置于70℃的气氛下，在浸渍后的聚酰亚胺针刺毡基材表面依次喷洒质量浓度为40％尿素水溶液和体积浓度为12％的双氧水溶液，以每平方米滤料基材计，尿素水溶液的喷洒量为200ml/m 2，双氧水溶液的喷洒量为140ml/m 2，喷洒结束后，将聚酰亚胺针刺毡基材置于120℃条件下烘干，去除多余水分等液体。 (2) then the polyimide needle felt base material is placed under the atmosphere of 70 ℃, and the polyimide needle felt base material surface after dipping is sprayed successively that mass concentration is 40% urea aqueous solution and volume concentration is 12 % hydrogen peroxide solution, in terms of per square meter of filter material base material, the spraying amount of urea aqueous solution is 200ml/m 2 , the spraying amount of hydrogen peroxide solution is 140ml/m 2 , after spraying, the polyimide needle felt base The material is dried at 120°C to remove excess water and other liquids.
(3)将烘干后的聚酰亚胺针刺毡基材置于260℃下热处理25min，然后在其表面喷洒一层聚四氟乙烯复合乳液，在280℃下烧结10min，与聚四氟乙烯膨化微孔膜热压覆合后得到滤料。其中，聚四氟乙烯复合乳液包括质量比为40:15:1:2:42的聚四氟乙烯乳液、含氟硅烷防水剂、偶联剂、无机防水剂和水，喷洒量为聚酰亚胺针刺毡基材质量的4wt％；热压覆合的温度为328℃，压力为0.45MPa，车速为5m/min。(3) heat-treat the dried polyimide needle felt substrate at 260°C for 25 minutes, then spray a layer of polytetrafluoroethylene composite emulsion on its surface, sinter at 280°C for 10 minutes, and mix with polytetrafluoroethylene The ethylene expanded microporous membrane is hot-pressed and laminated to obtain a filter material. Among them, the polytetrafluoroethylene composite emulsion includes polytetrafluoroethylene emulsion with a mass ratio of 40:15:1:2:42, fluorine-containing silane waterproofing agent, coupling agent, inorganic waterproofing agent and water, and the spraying amount is polyimide 4wt% of the mass of the amine needle felt substrate; the temperature of hot-press lamination is 328°C, the pressure is 0.45MPa, and the vehicle speed is 5m/min.
实施例3Example 3
本实施例提供了一种滤料的制备方法，包括以下步骤，The present embodiment provides a kind of preparation method of filter material, comprises the following steps,
(1)在70℃的条件下，将玻璃纤维和聚酰亚胺复合针刺毡基材浸渍于金属盐溶液中，浸渍时间为0.8min；其中，金属盐溶液包括摩尔比为11:1:4.5的硫酸氧钛、硝酸铈和乙酸锰，所述金属盐溶液的浓度为35wt％。(1) Under the condition of 70°C, the glass fiber and polyimide composite needle felt substrate were immersed in the metal salt solution, and the immersion time was 0.8min; wherein, the metal salt solution included a molar ratio of 11:1: 4.5 titanyl sulfate, cerium nitrate and manganese acetate, the concentration of the metal salt solution is 35wt%.
(2)然后将复合针刺毡基材置于70℃的气氛下，在浸渍后的复合针刺毡基材表面依次喷洒体积浓度为40％氨水溶液和体积浓度为40％的双氧水溶液，以每平方米滤料基材计，氨水溶液的喷洒量为320ml/m 2，双氧水溶液的喷洒量为270ml/m 2，喷洒结束后，将复合针刺毡基材置于120℃条件下烘干，去除多余水分等液体。 (2) The composite needle felt base material is then placed in an atmosphere of 70° C., and the volume concentration of 40% ammonia solution and the volume concentration of 40% hydrogen peroxide solution are sprayed on the surface of the impregnated composite needle felt base material successively, with Calculated per square meter of filter material substrate, the spraying amount of ammonia solution is 320ml/m 2 , and the spraying amount of hydrogen peroxide solution is 270ml/m 2 . After spraying, put the composite needle felt substrate at 120°C to dry , to remove excess water and other liquids.
(3)将烘干后的复合针刺毡基材置于280℃下热处理20min，然后在其表面喷洒一层聚四氟乙烯复合乳液，在380℃下烧结5min，与聚四氟乙烯膨化微孔膜热压覆合后得到滤料。其中，聚四氟乙烯复合乳液包括质量比为50:10:1.5:1.5:37的聚四氟乙烯乳液、含氟硅烷防水剂、偶联剂、无机防水剂和水，喷洒量为复合针刺毡基材质量的4wt％；热压覆合的温度为320℃，压力为0.5MPa，车速为10m/min。(3) heat-treat the dried composite needle felt substrate at 280°C for 20 minutes, then spray a layer of polytetrafluoroethylene composite emulsion on its surface, sinter at 380°C for 5 minutes, and mix with polytetrafluoroethylene expanded micro The filter material is obtained after hot-press lamination of the porous film. Among them, the polytetrafluoroethylene composite emulsion includes polytetrafluoroethylene emulsion with a mass ratio of 50:10:1.5:1.5:37, a fluorine-containing silane waterproofing agent, a coupling agent, an inorganic waterproofing agent and water, and the spraying amount is the composite acupuncture 4wt% of the mass of the felt substrate; the temperature of hot-press lamination is 320° C., the pressure is 0.5 MPa, and the vehicle speed is 10 m/min.
实施例4Example 4
本实施例提供了一种滤料的制备方法，包括以下步骤，The present embodiment provides a kind of preparation method of filter material, comprises the following steps,
(1)在55℃的条件下，将玻璃纤维基材浸渍于金属盐溶液中，浸渍时间为1.5min；其中，金属盐溶液包括摩尔比为11:1:4.5的硫酸氧钛、硝酸铈和乙酸锰，所述金属盐溶液的浓度为10wt％。(1) Under the condition of 55°C, immerse the glass fiber substrate in the metal salt solution for 1.5 minutes; wherein, the metal salt solution includes titanyl sulfate, cerium nitrate and Manganese acetate, the concentration of the metal salt solution is 10wt%.
(2)然后将玻璃纤维基材置于60℃的气氛下，在浸渍后的玻璃纤维基材表面依次喷洒体积浓度为35％氨水溶液和体积浓度为20％的双氧水溶液，以每平方米滤料基材计，氨水溶液的喷洒量为160ml/m 2，双氧水溶液的喷洒量为120ml/m 2，喷洒结束后，将玻璃纤维基材置于120℃条件下烘干，去除多余水分等液体。 (2) Then the glass fiber substrate is placed in an atmosphere of 60°C, and the volume concentration of 35% ammonia solution and 20% hydrogen peroxide solution are sprayed on the surface of the impregnated glass fiber substrate successively. Based on the base material, the spraying amount of ammonia solution is 160ml/m 2 , and the spraying amount of hydrogen peroxide solution is 120ml/m 2 . After spraying, dry the glass fiber substrate at 120°C to remove excess water and other liquids. .
(3)将烘干后的玻璃纤维基材置于250℃下热处理20min，然后在其表面喷洒一层聚四氟乙烯复合乳液，在300℃下烧结4min，与聚四氟乙烯膨化微孔膜热压覆合后得到滤料。其中，聚四氟乙烯复合乳液包括质量比为50:10:1:2:36的聚四氟乙烯乳液、含氟硅烷防水剂、偶联剂、无机防水剂和水，喷洒量为玻璃纤维基材质量的4wt％；热压覆合的温度为340℃，压力为0.35MPa，车速为6m/min。(3) heat-treat the dried glass fiber substrate at 250°C for 20 minutes, then spray a layer of polytetrafluoroethylene composite emulsion on its surface, sinter at 300°C for 4 minutes, and combine with polytetrafluoroethylene expanded microporous membrane The filter material is obtained after heat-compression lamination. Among them, the polytetrafluoroethylene composite emulsion includes polytetrafluoroethylene emulsion with a mass ratio of 50:10:1:2:36, fluorine-containing silane waterproofing agent, coupling agent, inorganic waterproofing agent and water, and the spraying amount is glass fiber-based 4wt% of the material weight; the temperature of hot-press lamination is 340°C, the pressure is 0.35MPa, and the vehicle speed is 6m/min.
对比例1Comparative example 1
本对比例提供了一种滤料的制备方法，包括以下步骤，This comparative example provides a kind of preparation method of filter material, comprises the following steps,
(1)在80℃的条件下，将玻璃纤维基材浸渍于金属盐溶液中，浸渍时间为1min；其中，金属盐溶液包括摩尔比为11:1:4.5的硫酸氧钛、硝酸铈和乙酸锰，所述金属盐溶液的浓度为15wt％。(1) Under the condition of 80°C, immerse the glass fiber substrate in the metal salt solution for 1 min; wherein, the metal salt solution includes titanyl sulfate, cerium nitrate and acetic acid in a molar ratio of 11:1:4.5 Manganese, the concentration of the metal salt solution is 15wt%.
(2)然后将玻璃纤维基材置于70℃的气氛下，在浸渍后的玻璃纤维基材表面依次喷洒体积浓度为40％氨水溶液和体积浓度为30％的双氧水溶液，以每平方米滤料基材计，氨水溶液的喷洒量为220ml/m 2，双氧水溶液的喷洒量为160ml/m 2，喷洒结束后，将玻璃纤维基材置于120℃条件下烘干，去除多余水分等液体。 (2) Then the glass fiber substrate is placed in an atmosphere of 70°C, and the volume concentration of 40% ammonia solution and 30% hydrogen peroxide solution are sprayed on the surface of the impregnated glass fiber substrate successively. Based on the base material, the spraying amount of ammonia solution is 220ml/m 2 , and the spraying amount of hydrogen peroxide solution is 160ml/m 2 . After spraying, dry the glass fiber substrate at 120°C to remove excess water and other liquids. .
(3)将烘干后的玻璃纤维基材置于280℃下热处理20min，然后在其表面喷洒一层聚四氟乙烯复合乳液，在300℃下烧结20min，与聚四氟乙烯膨化微孔膜热压覆合后得到滤料。其中，聚四氟乙烯复合乳液包括质量比为45:15:1.5:1.5:37的聚四氟乙烯乳液、含氟硅烷防水剂、偶联剂、无机防水剂和水，喷洒量为玻璃纤维基材质量的4wt％；热压覆合的温度为345℃，压力为0.3MPa，车速为4m/min。(3) heat-treat the dried glass fiber substrate at 280°C for 20min, then spray a layer of polytetrafluoroethylene composite emulsion on its surface, sinter at 300°C for 20min, and combine with polytetrafluoroethylene expanded microporous membrane The filter material is obtained after hot pressing lamination. Among them, the polytetrafluoroethylene composite emulsion includes polytetrafluoroethylene emulsion with a mass ratio of 45:15:1.5:1.5:37, fluorine-containing silane waterproofing agent, coupling agent, inorganic waterproofing agent and water, and the spraying amount is glass fiber-based 4wt% of the material mass; the temperature of hot-press lamination is 345°C, the pressure is 0.3MPa, and the vehicle speed is 4m/min.
对比例2Comparative example 2
本对比例提供了一种滤料的制备方法，包括以下步骤，This comparative example provides a kind of preparation method of filter material, comprises the following steps,
(1)在65℃的条件下，将玻璃纤维基材浸渍于金属盐溶液中，再加入氨水溶液调金属盐溶液pH至9-10，取出滤料基材置于反应器中，在60℃下反应1h，经下烘干去除多余水分等液体。其中，金属盐溶液包括摩尔比为11:1:4.5的硫酸氧钛、硝酸铈和乙酸锰，所述金属盐溶液的质量浓度为15wt％。(1) Under the condition of 65°C, immerse the glass fiber base material in the metal salt solution, then add ammonia solution to adjust the pH of the metal salt solution to 9-10, take out the filter material base material and place it in the reactor, at 60°C The reaction was carried out for 1 hour, and the excess water and other liquids were removed by drying at the bottom. Wherein, the metal salt solution includes titanyl sulfate, cerium nitrate and manganese acetate in a molar ratio of 11:1:4.5, and the mass concentration of the metal salt solution is 15 wt%.
(2)将烘干后的玻璃纤维基材置于280℃下热处理20min，然后在其表面喷洒一层聚四氟乙烯复合乳液，在300℃下烧结7min，与聚四氟乙烯膨化微孔膜热压覆合后得到滤料。其中，聚四氟乙烯复合乳液包括质量比为45:15:1.5:1.5:37的聚四氟乙烯乳液、含氟硅烷防水剂、偶联剂、无机防水剂和水，喷洒量为玻璃纤维基材质量的4wt％；热压覆合的温度为345℃，压力为0.3MPa，车速为4m/min。(2) heat-treat the dried glass fiber substrate at 280°C for 20 minutes, then spray a layer of polytetrafluoroethylene composite emulsion on its surface, sinter at 300°C for 7 minutes, and combine with polytetrafluoroethylene expanded microporous membrane The filter material is obtained after heat-compression lamination. Among them, the polytetrafluoroethylene composite emulsion includes polytetrafluoroethylene emulsion with a mass ratio of 45:15:1.5:1.5:37, fluorine-containing silane waterproofing agent, coupling agent, inorganic waterproofing agent and water, and the spraying amount is glass fiber-based 4wt% of the material mass; the temperature of hot-press lamination is 345°C, the pressure is 0.3MPa, and the vehicle speed is 4m/min.
试验例Test case
本试验例提供了实施例1-4和对比例1-2制得的滤料的性能测试及测试结果，测试方法如下，测试结果见表1。This test example provides the performance tests and test results of the filter materials prepared in Examples 1-4 and Comparative Examples 1-2. The test methods are as follows, and the test results are shown in Table 1.
滤料催化剂负载平方米克重偏差按照标准GB/T6719-2009c 9.1节；The weight deviation of the catalyst loaded on the filter material per square meter is in accordance with Section 9.1 of the standard GB/T6719-2009c;
滤料的透气性按照标准GB/T6719-2009c 9.2节；The air permeability of the filter material is in accordance with the standard GB/T6719-2009c section 9.2;
滤料的过滤阻力按照标准GB/T6719-2009c 9.5节。The filtration resistance of the filter material is in accordance with section 9.5 of the standard GB/T6719-2009c.
滤料催化脱硝效率的测试方法为：在250℃下测试脱硝效率，具体为，含氮氧化物气体仪0.5m/min速度通过直径10cm圆片形滤料后，氮氧化物浓度减少百分比。The test method for the catalytic denitrification efficiency of the filter material is: test the denitrification efficiency at 250°C, specifically, after the nitrogen oxide gas meter passes through the disc-shaped filter material with a diameter of 10cm at a speed of 0.5m/min, the concentration of nitrogen oxides decreases by the percentage.
表1滤料的性能测试结果The performance test result of table 1 filter material
Figure PCTCN2021133271-appb-000001
Figure PCTCN2021133271-appb-000001
通过表1可以看出，本发明制备得到的催化剂负载平方米克重偏差小，说明催化剂在滤料基材上分布均匀，将该滤料用于脱硝，脱硝效率高；过滤阻力越小，透气性越大，说明滤料的透气性越好。As can be seen from Table 1, the catalyst prepared by the present invention has a small deviation in the loaded square meter gram weight, indicating that the catalyst is evenly distributed on the filter material substrate, and the filter material is used for denitrification, and the denitrification efficiency is high; the smaller the filtration resistance, the more breathable The greater the permeability, the better the air permeability of the filter material.
另外，发明人在应用中发现，本发明实施例1-4制备得到同时兼具除尘和催化脱硝作用的滤料在使用过程中不易脱落，对比例1-2制备得到的滤料在使用过程中会出现不同程度的脱落现象，本发明制备得到的滤料与催化剂的结合牢度更高，在保证结合牢度的基础上，进一步提高了催化剂的分布均匀性以及透气性。In addition, the inventor found in the application that the filter material prepared in Example 1-4 of the present invention with both dust removal and catalytic denitrification functions is not easy to fall off during use, and the filter material prepared in Comparative Example 1-2 is not easy to fall off during use. There will be different degrees of falling off, and the filter material prepared by the present invention has higher binding fastness to the catalyst, and on the basis of ensuring the binding fastness, the distribution uniformity and air permeability of the catalyst are further improved.
显然，上述实施例仅仅是为清楚地说明所作的举例，而并非对实施方式的限定。对于所属领域的普通技术人员来说，在上述说明的基础上还可以做出其它不同形式的变化或变动。这里无需也无法对所有的实施方式予以穷举。而由此所引申出的显而易见的变化或变动仍处于本发明创造的保护范围之中。Apparently, the above-mentioned embodiments are only examples for clear description, rather than limiting the implementation. For those of ordinary skill in the art, other changes or changes in different forms can be made on the basis of the above description. It is not necessary and impossible to exhaustively list all the implementation manners here. However, the obvious changes or changes derived therefrom are still within the scope of protection of the present invention.

Claims (10)

  1. 一种滤料的制备方法，其特征在于，包括以下步骤，A kind of preparation method of filter material, is characterized in that, comprises the following steps,
    (1)在55-70℃下，将滤料基材浸渍于金属盐溶液中；(1) At 55-70°C, immerse the filter material base material in the metal salt solution;
    (2)在浸渍后的滤料基材表面喷洒尿素溶液和/或氨水溶液，然后再在滤料基材表面喷洒双氧水溶液；(2) Spray urea solution and/or ammonia solution on the surface of the impregnated filter material substrate, and then spray hydrogen peroxide solution on the surface of the filter material substrate;
    (3)经热处理后得到滤料。(3) The filter material is obtained after heat treatment.
  2. 根据权利要求1所述的制备方法，其特征在于，所述尿素溶液的质量浓度为5-40％；The preparation method according to claim 1, characterized in that, the mass concentration of the urea solution is 5-40%;
    所述氨水溶液的体积浓度为35-60％；The volume concentration of the ammonia solution is 35-60%;
    所述双氧水的体积浓度为10-45％。The volume concentration of the hydrogen peroxide is 10-45%.
  3. 根据权利要求1或2所述的制备方法，其特征在于，所述步骤(2)中，在55-80℃的条件下在滤料基材表面喷洒尿素溶液和/或氨水溶液，再在55-80℃的条件下在滤料基材表面喷洒双氧水溶液；The preparation method according to claim 1 or 2, characterized in that, in the step (2), urea solution and/or ammonia solution are sprayed on the surface of the filter material substrate under the condition of 55-80° C. Spray a hydrogen peroxide solution on the surface of the filter substrate at -80°C;
    以每平方米滤料基材计，氨水溶液的喷洒量为150-330ml/m 2； In terms of per square meter of filter material base material, the spraying amount of ammonia solution is 150-330ml/m 2 ;
    尿素溶液的喷洒量为150-230ml/m 2； The spraying amount of urea solution is 150-230ml/m 2 ;
    双氧水溶液的喷洒量为120-300ml/m 2。 The spraying amount of hydrogen peroxide solution is 120-300ml/m 2 .
  4. 根据权利要求1-3任一项所述的制备方法，其特征在于，步骤(1)中，滤料基材浸渍于金属盐溶液中的时间大于30s；According to the preparation method described in any one of claims 1-3, it is characterized in that, in step (1), the time for the filter substrate to be immersed in the metal salt solution is greater than 30s;
    所述金属盐溶液包括钛盐、铈盐和锰盐中的至少一种；The metal salt solution includes at least one of titanium salt, cerium salt and manganese salt;
    所述金属盐溶液的质量浓度为30-35％。The mass concentration of the metal salt solution is 30-35%.
  5. 根据权利要求4所述的制备方法，其特征在于，所述金属盐溶液包括钛盐、铈盐和锰盐；The preparation method according to claim 4, wherein the metal salt solution comprises titanium salt, cerium salt and manganese salt;
    所述金属盐溶液中钛、铈、和锰的摩尔比为(10-12)：(0.7-1.3)：(4-5)。The molar ratio of titanium, cerium and manganese in the metal salt solution is (10-12):(0.7-1.3):(4-5).
  6. 根据权利要求1-5任一项所述的制备方法，其特征在于，所述热处理的温度为250-300℃，时间为20-30min。The preparation method according to any one of claims 1-5, characterized in that the temperature of the heat treatment is 250-300° C. and the time is 20-30 min.
  7. 根据权利要求1-6任一项所述的制备方法，其特征在于，在所述热处理步骤之后还包括在滤料基材表面喷洒聚四氟乙烯复合乳液，经烧结后再与聚四氟乙烯膨化微孔膜进行热压覆合的步骤。According to the preparation method described in any one of claims 1-6, it is characterized in that, after the heat treatment step, it also includes spraying polytetrafluoroethylene composite emulsion on the surface of the filter material base material, and after sintering, it is combined with polytetrafluoroethylene The step of hot-press laminating the expanded microporous membrane.
  8. 根据权利要求7所述的制备方法，其特征在于，所述热压覆合的工艺参数：温度为260-380℃，车速为1-10m/min，压力为0.2-0.5MPa；The preparation method according to claim 7, characterized in that, the process parameters of the hot press lamination: temperature is 260-380°C, vehicle speed is 1-10m/min, pressure is 0.2-0.5MPa;
    所述聚四氟乙烯复合乳液包括质量比为(20-50)：(10-20)：(0.5-1.5)：(1.5-5)的聚四氟乙烯乳液、含氟硅烷防水剂、偶联剂和无机防水剂；The polytetrafluoroethylene composite emulsion includes a mass ratio of (20-50): (10-20): (0.5-1.5): (1.5-5) polytetrafluoroethylene emulsion, fluorine-containing silane waterproofing agent, coupling agent and inorganic water repellent;
    所述烧结的温度为260-320℃，烧结时间为4-10min。The sintering temperature is 260-320° C., and the sintering time is 4-10 minutes.
  9. 权利要求1-8任一项所述方法制备得到的滤料。The filter material prepared by the method described in any one of claims 1-8.
  10. 权利要求1-8任一项所述方法制备得到的滤料或权利要求9所述的滤料在催化脱硝中的应用。Application of the filter material prepared by the method according to any one of claims 1-8 or the filter material according to claim 9 in catalytic denitrification.
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