WO2022016601A1 - Preparation method for graphene-tio 2 composite nanomaterial loaded with nickel mesh - Google Patents

Preparation method for graphene-tio 2 composite nanomaterial loaded with nickel mesh Download PDF

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WO2022016601A1
WO2022016601A1 PCT/CN2020/106355 CN2020106355W WO2022016601A1 WO 2022016601 A1 WO2022016601 A1 WO 2022016601A1 CN 2020106355 W CN2020106355 W CN 2020106355W WO 2022016601 A1 WO2022016601 A1 WO 2022016601A1
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nickel mesh
tio
graphene
sol
soaking
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PCT/CN2020/106355
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Chinese (zh)
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袁亮
袁振
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江苏万贤环境工程有限公司
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    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
    • B01J23/8933—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/8946—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals also combined with metals, or metal oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with alkali or alkaline earth metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • B01J37/0205—Impregnation in several steps
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B33/00—Clay-wares
    • C04B33/02—Preparing or treating the raw materials individually or as batches
    • C04B33/13—Compounding ingredients
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F23—COMBUSTION APPARATUS; COMBUSTION PROCESSES
    • F23G—CREMATION FURNACES; CONSUMING WASTE PRODUCTS BY COMBUSTION
    • F23G7/00—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals
    • F23G7/06—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases
    • F23G7/07—Incinerators or other apparatus for consuming industrial waste, e.g. chemicals of waste gases or noxious gases, e.g. exhaust gases in which combustion takes place in the presence of catalytic material
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3418—Silicon oxide, silicic acids, or oxide forming salts thereof, e.g. silica sol, fused silica, silica fume, cristobalite, quartz or flint
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/02—Composition of constituents of the starting material or of secondary phases of the final product
    • C04B2235/30—Constituents and secondary phases not being of a fibrous nature
    • C04B2235/34—Non-metal oxides, non-metal mixed oxides, or salts thereof that form the non-metal oxides upon heating, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
    • C04B2235/3427—Silicates other than clay, e.g. water glass
    • C04B2235/3463—Alumino-silicates other than clay, e.g. mullite
    • C04B2235/3472—Alkali metal alumino-silicates other than clay, e.g. spodumene, alkali feldspars such as albite or orthoclase, micas such as muscovite, zeolites such as natrolite
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2235/00—Aspects relating to ceramic starting mixtures or sintered ceramic products
    • C04B2235/65—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes
    • C04B2235/656—Aspects relating to heat treatments of ceramic bodies such as green ceramics or pre-sintered ceramics, e.g. burning, sintering or melting processes characterised by specific heating conditions during heat treatment

Definitions

  • the invention relates to the field of oxide catalysts, in particular to a method for preparing a graphene-TiO 2 composite nanomaterial loaded with nickel mesh.
  • Photocatalytic oxidation technology is widely used in the field of VOCs waste gas treatment.
  • the efficiency and stability of photocatalytic oxidation technology in the process of VOCs waste gas treatment are affected by many factors such as pollutant adsorption performance, photocatalytic oxidation contact time, humidity, catalyst activity, photon utilization efficiency, and catalyst adhesion stability.
  • zeolite runners are usually used to concentrate organic waste gas with low concentration and large air volume into organic waste gas with high concentration and small air volume, thereby reducing equipment investment costs and operating costs, and realizing economical and effective organic waste gas treatment;
  • CO furnace is a catalytic
  • the oxidation reaction furnace enters the heat exchanger, and then is sent to the heating chamber, through the heating device, the gas reaches the combustion reaction temperature, and then through the action of the catalytic bed, the organic matter is converted into harmless carbon dioxide and water, so as to remove pollutants.
  • object, wherein the graphene supported nickel mesh -TiO 2 CO nanocomposite furnace is located, is the core of the catalytic combustion catalyst technology.
  • the existing oxide catalysts have low activity and cannot be applied to various organic waste gases.
  • the selectivity ratio of combustion to CO2 is low, the coating is not strong, and the active components are easy to fall off. is sintered, it can not maintain a high activity of the catalyst surface area, high mechanical strength, high thermal stability, the use of the process to bring it to a certain extent, for which we propose the graphene of a supported nickel mesh -TiO 2 composite nano Method of preparation of materials.
  • the main object of the present invention to provide a supported nickel mesh graphene Preparation of -TiO 2 composite nano material can effectively solve the existing background art the oxide catalyst, the activity is not high, can not be applied to all types of organic waste, The selectivity ratio of combustion to CO2 is low, the coating is not strong, and the active components are easy to fall off. Due to the reasons of the carrier, it is impossible to ensure that the catalyst will not be sintered, and it is impossible to maintain the catalyst with high active specific surface area, high mechanical strength, and high thermal stability. The problem.
  • the technical scheme adopted in the present invention is:
  • a preparation method of a graphene-TiO 2 composite nanomaterial loaded with nickel mesh the graphene-TiO 2 composite nanomaterial is made of the following raw materials by weight: 25-35% of noble metal oxide, 10-10% of clay 20%, quartz 5-10%, potassium albite 5-10%, graphene 30-50%, TiO 2 30-40% and nickel mesh;
  • Step 1 Preparation of ceramic nickel mesh carrier: According to the above weight percentage ratio, mix clay 10-20%, quartz 5-10%, potassium albite 5-10%, add water and stir to form a mixture, and evenly spread it on the nickel mesh , all wrap the nickel mesh and then bake it on the kiln, so that the ceramic carrier is baked on the nickel mesh to produce a ceramic nickel mesh carrier;
  • Step 2 Gel loading: The ceramic nickel mesh carrier prepared in step 1 is first soaked in the first soaking sol, then dried, and then soaked in the second soaking sol, to obtain a loaded precious metal oxide, graphene and TiO 2 . Nickel mesh catalyst.
  • TiO 2 has a three-dimensional ordered macroporous structure, the pore size of the macropores is 100nm-20 ⁇ m, the macropores are connected by pores of 20-100nm, and the pore size of the nickel mesh is 40-60 meshes.
  • the noble metal oxide may be one or both of Pt or Pd.
  • the coating thickness of the mixture is 1-3 mm, which does not affect the aperture size of the nickel mesh.
  • the baking temperature of the kiln in the first step is divided into three zones: a preheating zone of 0-1000°C, a firing zone of 1000-1200°C, and a cooling zone of 1280-20°C.
  • the sol is divided into a first soaking sol and a second soaking sol, and the first soaking sol and the second soaking sol have exactly the same components, and the second soaking sol is added with precious metal oxide, graphene and TiO 2.
  • the ratio of raw materials in the second soaking sol is noble metal oxide, graphene and TiO 2 in a ratio of 2.5:3:3.
  • the present invention can ensure that the catalyst is not sintered by baking the ceramic carrier on the nickel mesh, maintain the catalyst with high active specific surface area, high mechanical strength and high thermal stability, and at the same time add precious metal oxides, Graphene and TiO 2 , high dispersion of precious metal active sites, high catalytic activity, long service life, small pressure loss, reduced energy consumption, high activity, broad-spectrum activity for various organic waste gases, and complete combustion.
  • the selectivity to CO2 reaches 98 % or more, the catalytic removal efficiency is high, the reaction activation energy is significantly reduced, and the catalyst operates at medium and low temperatures; the temperature resistance is good, the thermal shock resistance is strong, and the maximum working temperature is about 650 ° C.
  • the prepared ceramic nickel mesh carrier is first soaked in the first soaking sol, then dried, and then soaked in the second soaking sol, so that the coating can be firm and ensured.
  • the active components do not fall off, improve the service life, and the normal operating life is more than 3 years.
  • a graphene-TiO 2 composite nanomaterial loaded with nickel mesh is made of the following raw materials by weight: 25% of noble metal oxides, 10% of clay, 5% of quartz, 5% of potassium albite, graphene 30%, TiO 2 30% and nickel mesh, TiO 2 has a three-dimensional ordered macroporous structure, the pore size of the macropore is 100nm, the macropores are connected by 20nm pores, the pore size of the nickel mesh is 40 mesh, and the noble metal oxide can for Pt.
  • the present invention further provides a method for preparing a supported nickel mesh graphene in the nanocomposite -TiO 2, comprising the steps of:
  • Step 1 Preparation of ceramic nickel mesh carrier: According to the above weight percentage ratio, mix 10% of clay, 5% of quartz, and 5% of potassium albite with water and stir to form a mixture, spread evenly on the nickel mesh, and completely wrap the nickel mesh It is then baked in a kiln, so that a ceramic carrier is baked on the nickel mesh to produce a ceramic nickel mesh carrier.
  • the coating thickness of the mixture is 1mm, which does not affect the aperture size of the nickel mesh.
  • the baking temperature of the kiln is divided into three Zone: preheating zone 0-1000°C, firing zone 1000-1200°C, cooling zone 1280-20°C;
  • Step 2 Gel loading: The ceramic nickel mesh carrier prepared in Step 1 is first soaked in the first soaking sol, then dried, and then soaked in the second soaking sol, to obtain a loaded precious metal oxide, graphene and TiO 2 .
  • Nickel mesh catalyst the sol is divided into a first soaking sol and a second soaking sol, and the first soaking sol and the second soaking sol have exactly the same components, the second soaking sol is added with precious metal oxides, graphene and TiO 2 , and the first soaking sol and the second soaking sol have the same components.
  • the ratio of raw materials in the second soaking sol is noble metal oxide, graphene and TiO 2 in a ratio of 2.5:3:3.
  • the graphene-TiO 2 composite nanomaterial loaded with nickel mesh is made from the following raw materials by weight: 25% of noble metal oxide, 10% of clay, 5% of quartz, 5% of potassium albite, Graphene 30%, TiO 2 30% and nickel mesh, TiO 2 has a three-dimensional ordered macroporous structure, the pore size of the macropore is 100nm, the macropores are connected by 20nm pores, the pore size of the nickel mesh is 40 mesh, and the noble metal is oxidized
  • the material can be in Pt.
  • the gas After the catalyst is installed in the CO furnace, the gas reaches the combustion reaction temperature through the heating device, and then through the action of the catalytic bed, the organic matter is converted into harmless carbon dioxide and water, so as to achieve the removal of The purpose of pollutants, through experimental comparison, in which the ceramic carrier is baked on the nickel mesh to ensure that the catalyst is not sintered, and the catalyst has a high active specific surface area, high mechanical strength, and high thermal stability.
  • the ceramic carrier is baked on the nickel mesh to ensure that the catalyst is not sintered, and the catalyst has a high active specific surface area, high mechanical strength, and high thermal stability.
  • noble metal oxides are added to the catalyst. , Graphene and TiO 2 , noble metal active site dispersion is high, catalytic activity is high, service life is long, pressure loss is small, energy consumption is reduced, high activity has broad-spectrum activity on various organic waste gases, and combustion is completely effective.
  • the CO2 selectivity reaches more than 96%, the catalytic removal efficiency is high, the reaction activation energy is significantly reduced, and the catalyst operates at medium and low temperatures; good temperature resistance, strong thermal shock resistance, and the maximum working temperature is about 600 °C;
  • the coating can be firm, ensure that the active components do not fall off, improve the service life and normal operation life greater than 2.5 years.
  • a graphene nickel screen -TiO 2 composite nano material loading the raw material made of the following weight percentages: 30% of noble metal oxide, clay 15%, 8% silica, 8% potassium sodium feldspar, graphene 40%, TiO 2 35% and nickel mesh, TiO 2 has a three-dimensional ordered macroporous structure, the pore size of the macropores is 1 ⁇ m, the macropores are connected by 60nm pores, the pore size of the nickel mesh is 50 mesh, and the noble metal oxide can for Pd.
  • the present invention further provides a method for preparing a supported nickel mesh graphene in the nanocomposite -TiO 2, comprising the steps of:
  • Step 1 Preparation of ceramic nickel mesh carrier: According to the above weight percentage ratio, mix clay 15%, quartz 8%, potassium albite 8%, add water and stir to form a mixture, spread evenly on the nickel mesh, and completely wrap the nickel mesh After baking in the kiln, the ceramic carrier is baked on the nickel mesh to produce a ceramic nickel mesh carrier.
  • the coating thickness of the mixture is 2mm, which does not affect the aperture size of the nickel mesh.
  • the baking temperature of the kiln is divided into three Zone: preheating zone 0-1000°C, firing zone 1000-1200°C, cooling zone 1280-20°C;
  • Step 2 Gel loading: The ceramic nickel mesh carrier prepared in step 1 is first soaked in the first soaking sol, then dried, and then soaked in the second soaking sol, to obtain a loaded precious metal oxide, graphene and TiO 2 .
  • Nickel mesh catalyst the sol is divided into a first soaking sol and a second soaking sol, and the first soaking sol and the second soaking sol have exactly the same components, the second soaking sol is added with precious metal oxides, graphene and TiO 2 , and the first soaking sol and the second soaking sol have the same components.
  • the ratio of raw materials in the second soaking sol is noble metal oxide, graphene and TiO 2 in a ratio of 2.5:3:3.
  • the graphene-TiO 2 composite nanomaterial loaded with nickel mesh is made from the following raw materials by weight: 30% of noble metal oxide, 15% of clay, 8% of quartz, 8% of potassium albite, Graphene 40%, TiO 2 35% and nickel mesh, TiO 2 has a three-dimensional ordered macroporous structure, the pore size of the macropore is 1 ⁇ m, the macropores are connected by 60 nm pores, the pore size of the nickel mesh is 50 mesh, and the noble metal is oxidized The compound can be Pd. After the catalyst is installed in the CO furnace, the gas reaches the combustion reaction temperature through the heating device, and then through the action of the catalytic bed, the organic matter is converted into harmless carbon dioxide and water, so as to remove pollution.
  • the ceramic carrier is baked on the nickel mesh to ensure that the catalyst is not sintered, and the catalyst has a high active specific surface area, high mechanical strength, and high thermal stability.
  • adding precious metal oxides, Graphene and TiO 2 have higher active site dispersion of noble metals, higher catalytic activity, longer service life, lower pressure loss, lower energy consumption, high activity, and have broad-spectrum activity for various organic waste gases, and the combustion is completely effective for CO2
  • the selectivity reaches more than 97%, the catalytic removal efficiency is high, the reaction activation energy is significantly reduced, and the catalyst operates at medium and low temperatures; good temperature resistance, strong thermal shock resistance, and the maximum working temperature is about 620 °C; when the gel is loaded , the prepared ceramic nickel mesh carrier is first soaked in the first soaking sol, then dried, and then soaked in the second soaking sol, which can achieve a firm coating, ensure that the active components do not fall off, and improve the service life.
  • the normal operating life is longer than 2.5 years.
  • a graphene-TiO 2 composite nanomaterial loaded with nickel mesh is made of the following raw materials by weight percentage: noble metal oxide 35%, clay 20%, quartz 10%, potassium albite 10%, graphene 50%, TiO 2 40% and nickel mesh, TiO 2 has a three-dimensional ordered macroporous structure, the pore size of the macropore is 20 ⁇ m, and the macropores are connected by 100 nm pores, the pore size of the nickel mesh is 60 mesh, and the noble metal oxide can For Pt and Pd.
  • the present invention further provides a method for preparing a supported nickel mesh graphene in the nanocomposite -TiO 2, comprising the steps of:
  • Step 1 Preparation of ceramic nickel mesh carrier: According to the above weight percentage ratio, mix 20% of clay, 10% of quartz, and 10% of potassium albite, add water and stir to form a mixture, spread evenly on the nickel mesh, and completely wrap the nickel mesh After baking in the kiln, the ceramic carrier is baked on the nickel mesh to produce a ceramic nickel mesh carrier.
  • the coating thickness of the mixture is 3mm, which does not affect the aperture size of the nickel mesh.
  • the baking temperature of the kiln is divided into three Zone: preheating zone 0-1000°C, firing zone 1000-1200°C, cooling zone 1280-20°C;
  • Step 2 Gel loading: The ceramic nickel mesh carrier prepared in Step 1 is first soaked in the first soaking sol, then dried, and then soaked in the second soaking sol, to obtain a loaded precious metal oxide, graphene and TiO 2 .
  • Nickel mesh catalyst the sol is divided into a first soaking sol and a second soaking sol, and the first soaking sol and the second soaking sol have exactly the same components, the second soaking sol is added with precious metal oxides, graphene and TiO 2 , and the first soaking sol and the second soaking sol have the same components.
  • the ratio of raw materials in the second soaking sol is noble metal oxide, graphene and TiO 2 in a ratio of 2.5:3:3.
  • the graphene-TiO 2 composite nanomaterial loaded with nickel mesh is made from the following raw materials by weight: 35% of noble metal oxide, 20% of clay, 10% of quartz, 10% of potassium albite, Graphene 50%, TiO 2 40% and nickel mesh, TiO 2 has a three-dimensional ordered macroporous structure, the pore size of the macropore is 20 ⁇ m, the macropores are connected by 100 nm pores, the pore size of the nickel mesh is 60 mesh, and the noble metal is oxidized
  • the compounds can be Pt and Pd.
  • the gas After the catalyst is installed in the CO furnace, the gas reaches the combustion reaction temperature through the heating device, and then the organic matter is converted into harmless carbon dioxide and water through the action of the catalytic bed, so as to achieve For the purpose of removing pollutants, through experimental comparison, the ceramic carrier is baked on the nickel mesh to ensure that the catalyst is not sintered, and the catalyst has a high active specific surface area, high mechanical strength, and high thermal stability.
  • the catalytic removal efficiency is high, the reaction activation energy is significantly reduced, and the catalyst operates at medium and low temperatures; good temperature resistance, strong thermal shock resistance, and the maximum working temperature is about 650 ° C; when the gel is loaded, the The prepared ceramic nickel mesh carrier is first soaked in the first soaking sol, then dried, and then soaked in the second soaking sol, which can achieve a firm coating, ensure that the active components do not fall off, and improve the service life, and the normal operating life is more than 3 years. .
  • the present invention can ensure that the catalyst is not sintered by baking the ceramic carrier on the nickel mesh, and maintain the catalyst with high active specific surface area, high mechanical strength, and high thermal stability.
  • TiO 2 high dispersion of precious metal active sites, high catalytic activity, long service life, small pressure loss, reduced energy consumption, high activity, broad-spectrum activity on various organic waste gases, and complete combustion to CO2 selectivity above 96% , the catalytic removal efficiency is high, the reaction activation energy is significantly reduced, and the catalyst operates at medium and low temperatures; the temperature resistance is good, the thermal shock resistance is strong, and the maximum working temperature is above 600 ° C.
  • the prepared The ceramic nickel mesh carrier is first soaked in the first soaking sol, then dried, and then soaked in the second soaking sol, which can achieve a firm coating, ensure that the active components do not fall off, and improve the service life.
  • the normal operating life is greater than 2.5 years, among which Example 3 is the best option.

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Abstract

Disclosed is a graphene-TiO2 composite nanomaterial loaded with a nickel mesh. The composite nanomaterial is prepared from the following raw materials, in weight percentage: 25-35% of precious metal oxide, 10-20% of clay, 5-10% of quartz, 5-10% of potassium sodium feldspar, 30-50% of graphene, 30-40% of TiO 2 and a nickel mesh. Baking a ceramic carrier on a nickel mesh can ensure that a catalyst is not sintered, such that the high active specific surface area, high mechanical strength, and high thermal stability of the catalyst are maintained. In addition, a noble metal oxide, graphene and TiO 2 are added to the catalyst. The precious metal has an active site with high distribution and high catalytic activity. When loading a gel, a prepared ceramic nickel mesh carrier is first immersed in a first immersion sol-gel. The ceramic nickel mesh carrier is then dried and immersed in a second immersion sol-gel, thereby achieving a firm coating without releasing active components and having an increased service life, where a normal operating life is more than 3 years.

Description

一种负载镍网的石墨烯-TiO 2复合纳米材料的制备方法 A kind of graphene-TiO supported nickel mesh 2. Preparation method of composite nanomaterials 技术领域technical field
本发明涉及氧化物催化剂领域，特别涉及一种负载镍网的石墨烯-TiO 2复合纳米材料的制备方法。 The invention relates to the field of oxide catalysts, in particular to a method for preparing a graphene-TiO 2 composite nanomaterial loaded with nickel mesh.
背景技术Background technique
光催化氧化技术在VOCs废气治理领域有较为广泛的应用。光催化氧化技术在VOCs废气治理过程中的效率和稳定性受污染物吸附性能、光催化氧化接触时间、湿度、催化剂活性、光子利用效率、催化剂附着稳定性等诸多因素影响。Photocatalytic oxidation technology is widely used in the field of VOCs waste gas treatment. The efficiency and stability of photocatalytic oxidation technology in the process of VOCs waste gas treatment are affected by many factors such as pollutant adsorption performance, photocatalytic oxidation contact time, humidity, catalyst activity, photon utilization efficiency, and catalyst adhesion stability.
在VOCs的治理中，通常采用沸石转轮将低浓度大风量的有机废气浓缩成高浓度小风量的有机废气，从而减低设备投资费用和运行成本，实现经济有效的有机废气处理；CO炉为催化氧化反应炉，进入换热器，再送入到加热室，通过加热装置，使气体达到燃烧反应温度，再通过催化床的作用，将有机物转化为无害的二氧化碳和水，从而达到去除污染物的目的，其中负载镍网的石墨烯-TiO 2复合纳米材料就位于CO炉中，催化剂是催化燃烧技术的核心。 In the treatment of VOCs, zeolite runners are usually used to concentrate organic waste gas with low concentration and large air volume into organic waste gas with high concentration and small air volume, thereby reducing equipment investment costs and operating costs, and realizing economical and effective organic waste gas treatment; CO furnace is a catalytic The oxidation reaction furnace enters the heat exchanger, and then is sent to the heating chamber, through the heating device, the gas reaches the combustion reaction temperature, and then through the action of the catalytic bed, the organic matter is converted into harmless carbon dioxide and water, so as to remove pollutants. object, wherein the graphene supported nickel mesh -TiO 2 CO nanocomposite furnace is located, is the core of the catalytic combustion catalyst technology.
现有的氧化物催化剂，活性不高，无法适用于各类有机废气，燃烧对CO2的选择性占比较低，涂层不牢固，活性组分易于脱落，由于负载体的原因，无法保证催化剂不被烧结，无法保持催化剂高活性的比表面积、高机械强度、高热稳定性，给人们的使用过程带来了一定的影响，为此，我们提出一种负载镍网的石墨烯-TiO 2复合纳米材料的制备方法。 The existing oxide catalysts have low activity and cannot be applied to various organic waste gases. The selectivity ratio of combustion to CO2 is low, the coating is not strong, and the active components are easy to fall off. is sintered, it can not maintain a high activity of the catalyst surface area, high mechanical strength, high thermal stability, the use of the process to bring it to a certain extent, for which we propose the graphene of a supported nickel mesh -TiO 2 composite nano Method of preparation of materials.
发明内容SUMMARY OF THE INVENTION
本发明的主要目的在于提供一种负载镍网的石墨烯-TiO 2复合纳米材料的制备方法，可以有效解决背景技术中现有的氧化物催化剂，活性不高，无法适用于各类有机废气，燃烧对CO2的选择性占比较低，涂层不牢固，活性组 分易于脱落，由于负载体的原因，无法保证催化剂不被烧结，无法保持催化剂高活性的比表面积、高机械强度、高热稳定性的问题。 The main object of the present invention to provide a supported nickel mesh graphene Preparation of -TiO 2 composite nano material, can effectively solve the existing background art the oxide catalyst, the activity is not high, can not be applied to all types of organic waste, The selectivity ratio of combustion to CO2 is low, the coating is not strong, and the active components are easy to fall off. Due to the reasons of the carrier, it is impossible to ensure that the catalyst will not be sintered, and it is impossible to maintain the catalyst with high active specific surface area, high mechanical strength, and high thermal stability. The problem.
为实现上述目的，本发明采取的技术方案为：To achieve the above object, the technical scheme adopted in the present invention is:
一种负载镍网的石墨烯-TiO 2复合纳米材料的制备方法，该石墨烯-TiO 2复合纳米材料由下述重量百分含量的原料制成：贵金属氧化物25-35％、粘土10-20％、石英5-10％、钾钠长石5-10％、石墨烯30-50％、TiO 230-40％与镍网； A preparation method of a graphene-TiO 2 composite nanomaterial loaded with nickel mesh, the graphene-TiO 2 composite nanomaterial is made of the following raw materials by weight: 25-35% of noble metal oxide, 10-10% of clay 20%, quartz 5-10%, potassium albite 5-10%, graphene 30-50%, TiO 2 30-40% and nickel mesh;
该石墨烯-TiO 2复合纳米材料的制备方法具体步骤如下： The specific steps of the preparation method of the graphene-TiO 2 composite nanomaterial are as follows:
步骤一：制备陶瓷镍网载体：按照上述重量百分含量配比将粘土10-20％、石英5-10％、钾钠长石5-10％混合加水搅拌成混合料，均匀涂抹在镍网上，全部包裹住镍网后置于窑炉上烘烤，使得镍网上烤制出陶瓷载体，生产成陶瓷镍网载体；Step 1: Preparation of ceramic nickel mesh carrier: According to the above weight percentage ratio, mix clay 10-20%, quartz 5-10%, potassium albite 5-10%, add water and stir to form a mixture, and evenly spread it on the nickel mesh , all wrap the nickel mesh and then bake it on the kiln, so that the ceramic carrier is baked on the nickel mesh to produce a ceramic nickel mesh carrier;
步骤二：凝胶负载：将步骤一中制备的陶瓷镍网载体先浸泡在第一浸泡溶胶中，然后干燥，接着浸泡在第二浸泡溶胶中，得到负载贵金属氧化物、石墨烯与TiO 2的镍网催化剂。 Step 2: Gel loading: The ceramic nickel mesh carrier prepared in step 1 is first soaked in the first soaking sol, then dried, and then soaked in the second soaking sol, to obtain a loaded precious metal oxide, graphene and TiO 2 . Nickel mesh catalyst.
进一步的，TiO 2具有三维有序大孔结构，大孔的孔径为100nm～20μm，大孔之间通过20～100nm的孔连接，镍网孔径大小为40～60目。 Further, TiO 2 has a three-dimensional ordered macroporous structure, the pore size of the macropores is 100nm-20μm, the macropores are connected by pores of 20-100nm, and the pore size of the nickel mesh is 40-60 meshes.
进一步的，贵金属氧化物可以为Pt或Pd中的一种或两种。Further, the noble metal oxide may be one or both of Pt or Pd.
进一步的，所述步骤一中混合料的涂抹厚度为1-3mm，不影响镍网孔径大小。Further, in the step 1, the coating thickness of the mixture is 1-3 mm, which does not affect the aperture size of the nickel mesh.
进一步的，所述步骤一中窑炉的烘烤温度分为三个区：预热区0-1000℃，烧制区1000-1200℃，冷却区1280-20℃。Further, the baking temperature of the kiln in the first step is divided into three zones: a preheating zone of 0-1000°C, a firing zone of 1000-1200°C, and a cooling zone of 1280-20°C.
进一步的，所述步骤二中溶胶分为第一浸泡溶胶和第二浸泡溶胶，且第一浸泡溶胶和第二浸泡溶胶组分完全相同，第二浸泡溶胶中添加有贵金属氧化物、石墨烯与TiO 2。 Further, in the second step, the sol is divided into a first soaking sol and a second soaking sol, and the first soaking sol and the second soaking sol have exactly the same components, and the second soaking sol is added with precious metal oxide, graphene and TiO 2.
进一步的，所述步骤二中第二浸泡溶胶中的原料配比为贵金属氧化物、 石墨烯与TiO 2按照2.5∶3∶3的比例进行配比。 Further, in the second step, the ratio of raw materials in the second soaking sol is noble metal oxide, graphene and TiO 2 in a ratio of 2.5:3:3.
与现有技术相比，本发明通过在镍网上烤制陶瓷载体，能够确保催化剂不被烧结，保持催化剂高活性的比表面积、高机械强度、高热稳定性，同时在催化剂中添加贵金属氧化物、石墨烯与TiO 2，贵金属活性位分散度高，催化活性高，使用寿命长，压力损失小，降低了能耗，活性高具有对各类有机废气广谱活性，燃烧彻底对CO2选择性达到98％以上，催化去除效率高，显著降低反应活化能，使催化剂在中低温度下运行；耐温性好，耐热冲击性能强，最大工作温度约650℃。 Compared with the prior art, the present invention can ensure that the catalyst is not sintered by baking the ceramic carrier on the nickel mesh, maintain the catalyst with high active specific surface area, high mechanical strength and high thermal stability, and at the same time add precious metal oxides, Graphene and TiO 2 , high dispersion of precious metal active sites, high catalytic activity, long service life, small pressure loss, reduced energy consumption, high activity, broad-spectrum activity for various organic waste gases, and complete combustion. The selectivity to CO2 reaches 98 % or more, the catalytic removal efficiency is high, the reaction activation energy is significantly reduced, and the catalyst operates at medium and low temperatures; the temperature resistance is good, the thermal shock resistance is strong, and the maximum working temperature is about 650 ° C.
与现有技术相比，本发明在凝胶负载时，将制备的陶瓷镍网载体先浸泡在第一浸泡溶胶中，然后干燥，接着浸泡在第二浸泡溶胶中，能够实现涂层牢固，保证活性组分不脱落，提高使用寿命，正常运行寿命大于3年。Compared with the prior art, when the gel is loaded in the present invention, the prepared ceramic nickel mesh carrier is first soaked in the first soaking sol, then dried, and then soaked in the second soaking sol, so that the coating can be firm and ensured. The active components do not fall off, improve the service life, and the normal operating life is more than 3 years.
具体实施方式detailed description
为使本发明实现的技术手段、创作特征、达成目的与功效易于明白了解，下面结合具体实施方式，进一步阐述本发明。In order to make the technical means, creative features, achievement goals and effects realized by the present invention easy to understand, the present invention will be further described below with reference to the specific embodiments.
实施例1Example 1
一种负载镍网的石墨烯-TiO 2复合纳米材料，由下述重量百分含量的原料制成：贵金属氧化物25％、粘土10％、石英5％、钾钠长石5％、石墨烯30％、TiO 230％与镍网，TiO 2具有三维有序大孔结构，大孔的孔径为100nm，大孔之间通过20nm的孔连接，镍网孔径大小为40目，贵金属氧化物可以为Pt。 A graphene-TiO 2 composite nanomaterial loaded with nickel mesh is made of the following raw materials by weight: 25% of noble metal oxides, 10% of clay, 5% of quartz, 5% of potassium albite, graphene 30%, TiO 2 30% and nickel mesh, TiO 2 has a three-dimensional ordered macroporous structure, the pore size of the macropore is 100nm, the macropores are connected by 20nm pores, the pore size of the nickel mesh is 40 mesh, and the noble metal oxide can for Pt.
本发明还提供了一种负载镍网的石墨烯-TiO 2复合纳米材料的制备方法，包括以下步骤： The present invention further provides a method for preparing a supported nickel mesh graphene in the nanocomposite -TiO 2, comprising the steps of:
步骤一：制备陶瓷镍网载体：按照上述重量百分含量配比将粘土10％、石英5％、钾钠长石5％混合加水搅拌成混合料，均匀涂抹在镍网上，全部包裹住镍网后置于窑炉上烘烤，使得镍网上烤制出陶瓷载体，生产成陶瓷镍网载体，混合料的涂抹厚度为1mm，不影响镍网孔径大小，窑炉的烘烤温度分为三个区： 预热区0-1000℃，烧制区1000-1200℃，冷却区1280-20℃；Step 1: Preparation of ceramic nickel mesh carrier: According to the above weight percentage ratio, mix 10% of clay, 5% of quartz, and 5% of potassium albite with water and stir to form a mixture, spread evenly on the nickel mesh, and completely wrap the nickel mesh It is then baked in a kiln, so that a ceramic carrier is baked on the nickel mesh to produce a ceramic nickel mesh carrier. The coating thickness of the mixture is 1mm, which does not affect the aperture size of the nickel mesh. The baking temperature of the kiln is divided into three Zone: preheating zone 0-1000℃, firing zone 1000-1200℃, cooling zone 1280-20℃;
步骤二：凝胶负载：将步骤一中制备的陶瓷镍网载体先浸泡在第一浸泡溶胶中，然后干燥，接着浸泡在第二浸泡溶胶中，得到负载贵金属氧化物、石墨烯与TiO 2的镍网催化剂，溶胶分为第一浸泡溶胶和第二浸泡溶胶，且第一浸泡溶胶和第二浸泡溶胶组分完全相同，第二浸泡溶胶中添加有贵金属氧化物、石墨烯与TiO 2，第二浸泡溶胶中的原料配比为贵金属氧化物、石墨烯与TiO 2按照2.5∶3∶3的比例进行配比。 Step 2: Gel loading: The ceramic nickel mesh carrier prepared in Step 1 is first soaked in the first soaking sol, then dried, and then soaked in the second soaking sol, to obtain a loaded precious metal oxide, graphene and TiO 2 . Nickel mesh catalyst, the sol is divided into a first soaking sol and a second soaking sol, and the first soaking sol and the second soaking sol have exactly the same components, the second soaking sol is added with precious metal oxides, graphene and TiO 2 , and the first soaking sol and the second soaking sol have the same components. The ratio of raw materials in the second soaking sol is noble metal oxide, graphene and TiO 2 in a ratio of 2.5:3:3.
本实施例中，负载镍网的石墨烯-TiO 2复合纳米材料通过下述重量百分含量的原料制成：贵金属氧化物25％、粘土10％、石英5％、钾钠长石5％、石墨烯30％、TiO 230％与镍网，TiO 2具有三维有序大孔结构，大孔的孔径为100nm，大孔之间通过20nm的孔连接，镍网孔径大小为40目，贵金属氧化物可以为Pt中，制成后的催化剂安装在CO炉中后，通过加热装置，使气体达到燃烧反应温度，再通过催化床的作用，将有机物转化为无害的二氧化碳和水，从而达到去除污染物的目的，经过实验对比，其中通过在镍网上烤制陶瓷载体，能够确保催化剂不被烧结，保持催化剂高活性的比表面积、高机械强度、高热稳定性，同时在催化剂中添加贵金属氧化物、石墨烯与TiO 2，贵金属活性位分散度较高，催化活性较高，使用寿命较长，压力损失较小，降低了能耗，活性高具有对各类有机废气广谱活性，燃烧彻底对CO2选择性达到96％以上，催化去除效率高，显著降低反应活化能，使催化剂在中低温度下运行；耐温性好，耐热冲击性能强，最大工作温度约600℃；在凝胶负载时，将制备的陶瓷镍网载体先浸泡在第一浸泡溶胶中，然后干燥，接着浸泡在第二浸泡溶胶中，能够实现涂层牢固，保证活性组分不脱落，提高使用寿命，正常运行寿命大于2.5年。 In this embodiment, the graphene-TiO 2 composite nanomaterial loaded with nickel mesh is made from the following raw materials by weight: 25% of noble metal oxide, 10% of clay, 5% of quartz, 5% of potassium albite, Graphene 30%, TiO 2 30% and nickel mesh, TiO 2 has a three-dimensional ordered macroporous structure, the pore size of the macropore is 100nm, the macropores are connected by 20nm pores, the pore size of the nickel mesh is 40 mesh, and the noble metal is oxidized The material can be in Pt. After the catalyst is installed in the CO furnace, the gas reaches the combustion reaction temperature through the heating device, and then through the action of the catalytic bed, the organic matter is converted into harmless carbon dioxide and water, so as to achieve the removal of The purpose of pollutants, through experimental comparison, in which the ceramic carrier is baked on the nickel mesh to ensure that the catalyst is not sintered, and the catalyst has a high active specific surface area, high mechanical strength, and high thermal stability. At the same time, noble metal oxides are added to the catalyst. , Graphene and TiO 2 , noble metal active site dispersion is high, catalytic activity is high, service life is long, pressure loss is small, energy consumption is reduced, high activity has broad-spectrum activity on various organic waste gases, and combustion is completely effective. The CO2 selectivity reaches more than 96%, the catalytic removal efficiency is high, the reaction activation energy is significantly reduced, and the catalyst operates at medium and low temperatures; good temperature resistance, strong thermal shock resistance, and the maximum working temperature is about 600 °C; When the prepared ceramic nickel mesh carrier is first soaked in the first soaking sol, then dried, and then soaked in the second soaking sol, the coating can be firm, ensure that the active components do not fall off, improve the service life and normal operation life greater than 2.5 years.
实施例2Example 2
一种负载镍网的石墨烯-TiO 2复合纳米材料，由下述重量百分含量的原料 制成：贵金属氧化物30％、粘土15％、石英8％、钾钠长石8％、石墨烯40％、TiO 235％与镍网，TiO 2具有三维有序大孔结构，大孔的孔径为1μm，大孔之间通过60nm的孔连接，镍网孔径大小为50目，贵金属氧化物可以为Pd。 A graphene nickel screen -TiO 2 composite nano material loading, the raw material made of the following weight percentages: 30% of noble metal oxide, clay 15%, 8% silica, 8% potassium sodium feldspar, graphene 40%, TiO 2 35% and nickel mesh, TiO 2 has a three-dimensional ordered macroporous structure, the pore size of the macropores is 1 μm, the macropores are connected by 60nm pores, the pore size of the nickel mesh is 50 mesh, and the noble metal oxide can for Pd.
本发明还提供了一种负载镍网的石墨烯-TiO 2复合纳米材料的制备方法，包括以下步骤： The present invention further provides a method for preparing a supported nickel mesh graphene in the nanocomposite -TiO 2, comprising the steps of:
步骤一：制备陶瓷镍网载体：按照上述重量百分含量配比将粘土15％、石英8％、钾钠长石8％混合加水搅拌成混合料，均匀涂抹在镍网上，全部包裹住镍网后置于窑炉上烘烤，使得镍网上烤制出陶瓷载体，生产成陶瓷镍网载体，混合料的涂抹厚度为2mm，不影响镍网孔径大小，窑炉的烘烤温度分为三个区：预热区0-1000℃，烧制区1000-1200℃，冷却区1280-20℃；Step 1: Preparation of ceramic nickel mesh carrier: According to the above weight percentage ratio, mix clay 15%, quartz 8%, potassium albite 8%, add water and stir to form a mixture, spread evenly on the nickel mesh, and completely wrap the nickel mesh After baking in the kiln, the ceramic carrier is baked on the nickel mesh to produce a ceramic nickel mesh carrier. The coating thickness of the mixture is 2mm, which does not affect the aperture size of the nickel mesh. The baking temperature of the kiln is divided into three Zone: preheating zone 0-1000℃, firing zone 1000-1200℃, cooling zone 1280-20℃;
步骤二：凝胶负载：将步骤一中制备的陶瓷镍网载体先浸泡在第一浸泡溶胶中，然后干燥，接着浸泡在第二浸泡溶胶中，得到负载贵金属氧化物、石墨烯与TiO 2的镍网催化剂，溶胶分为第一浸泡溶胶和第二浸泡溶胶，且第一浸泡溶胶和第二浸泡溶胶组分完全相同，第二浸泡溶胶中添加有贵金属氧化物、石墨烯与TiO 2，第二浸泡溶胶中的原料配比为贵金属氧化物、石墨烯与TiO 2按照2.5∶3∶3的比例进行配比。 Step 2: Gel loading: The ceramic nickel mesh carrier prepared in step 1 is first soaked in the first soaking sol, then dried, and then soaked in the second soaking sol, to obtain a loaded precious metal oxide, graphene and TiO 2 . Nickel mesh catalyst, the sol is divided into a first soaking sol and a second soaking sol, and the first soaking sol and the second soaking sol have exactly the same components, the second soaking sol is added with precious metal oxides, graphene and TiO 2 , and the first soaking sol and the second soaking sol have the same components. The ratio of raw materials in the second soaking sol is noble metal oxide, graphene and TiO 2 in a ratio of 2.5:3:3.
本实施例中，负载镍网的石墨烯-TiO 2复合纳米材料通过下述重量百分含量的原料制成：贵金属氧化物30％、粘土15％、石英8％、钾钠长石8％、石墨烯40％、TiO 235％与镍网，TiO 2具有三维有序大孔结构，大孔的孔径为1μm，大孔之间通过60nm的孔连接，镍网孔径大小为50目，贵金属氧化物可以为Pd，制成后的催化剂安装在CO炉中后，通过加热装置，使气体达到燃烧反应温度，再通过催化床的作用，将有机物转化为无害的二氧化碳和水，从而达到去除污染物的目的，经过实验对比，其中通过在镍网上烤制陶瓷载体，能够确保催化剂不被烧结，保持催化剂高活性的比表面积、高机械强度、高热稳定性，同时在催化剂中添加贵金属氧化物、石墨烯与TiO 2，贵金属活性位 分散度较高，催化活性较高，使用寿命较长，压力损失较小，降低了能耗，活性高具有对各类有机废气广谱活性，燃烧彻底对CO2选择性达到97％以上，催化去除效率高，显著降低反应活化能，使催化剂在中低温度下运行；耐温性好，耐热冲击性能强，最大工作温度约620℃；在凝胶负载时，将制备的陶瓷镍网载体先浸泡在第一浸泡溶胶中，然后干燥，接着浸泡在第二浸泡溶胶中，能够实现涂层牢固，保证活性组分不脱落，提高使用寿命，正常运行寿命大于2.5年。 In this embodiment, the graphene-TiO 2 composite nanomaterial loaded with nickel mesh is made from the following raw materials by weight: 30% of noble metal oxide, 15% of clay, 8% of quartz, 8% of potassium albite, Graphene 40%, TiO 2 35% and nickel mesh, TiO 2 has a three-dimensional ordered macroporous structure, the pore size of the macropore is 1 μm, the macropores are connected by 60 nm pores, the pore size of the nickel mesh is 50 mesh, and the noble metal is oxidized The compound can be Pd. After the catalyst is installed in the CO furnace, the gas reaches the combustion reaction temperature through the heating device, and then through the action of the catalytic bed, the organic matter is converted into harmless carbon dioxide and water, so as to remove pollution. Through the experimental comparison, the ceramic carrier is baked on the nickel mesh to ensure that the catalyst is not sintered, and the catalyst has a high active specific surface area, high mechanical strength, and high thermal stability. At the same time, adding precious metal oxides, Graphene and TiO 2 have higher active site dispersion of noble metals, higher catalytic activity, longer service life, lower pressure loss, lower energy consumption, high activity, and have broad-spectrum activity for various organic waste gases, and the combustion is completely effective for CO2 The selectivity reaches more than 97%, the catalytic removal efficiency is high, the reaction activation energy is significantly reduced, and the catalyst operates at medium and low temperatures; good temperature resistance, strong thermal shock resistance, and the maximum working temperature is about 620 °C; when the gel is loaded , the prepared ceramic nickel mesh carrier is first soaked in the first soaking sol, then dried, and then soaked in the second soaking sol, which can achieve a firm coating, ensure that the active components do not fall off, and improve the service life. The normal operating life is longer than 2.5 years.
实施例3Example 3
一种负载镍网的石墨烯-TiO 2复合纳米材料，由下述重量百分含量的原料制成：贵金属氧化物35％、粘土20％、石英10％、钾钠长石10％、石墨烯50％、TiO 240％与镍网，TiO 2具有三维有序大孔结构，大孔的孔径为20μm，大孔之间通过100nm的孔连接，镍网孔径大小为60目，贵金属氧化物可以为Pt与Pd。 A graphene-TiO 2 composite nanomaterial loaded with nickel mesh is made of the following raw materials by weight percentage: noble metal oxide 35%, clay 20%, quartz 10%, potassium albite 10%, graphene 50%, TiO 2 40% and nickel mesh, TiO 2 has a three-dimensional ordered macroporous structure, the pore size of the macropore is 20 μm, and the macropores are connected by 100 nm pores, the pore size of the nickel mesh is 60 mesh, and the noble metal oxide can For Pt and Pd.
本发明还提供了一种负载镍网的石墨烯-TiO 2复合纳米材料的制备方法，包括以下步骤： The present invention further provides a method for preparing a supported nickel mesh graphene in the nanocomposite -TiO 2, comprising the steps of:
步骤一：制备陶瓷镍网载体：按照上述重量百分含量配比将粘土20％、石英10％、钾钠长石10％混合加水搅拌成混合料，均匀涂抹在镍网上，全部包裹住镍网后置于窑炉上烘烤，使得镍网上烤制出陶瓷载体，生产成陶瓷镍网载体，混合料的涂抹厚度为3mm，不影响镍网孔径大小，窑炉的烘烤温度分为三个区：预热区0-1000℃，烧制区1000-1200℃，冷却区1280-20℃；Step 1: Preparation of ceramic nickel mesh carrier: According to the above weight percentage ratio, mix 20% of clay, 10% of quartz, and 10% of potassium albite, add water and stir to form a mixture, spread evenly on the nickel mesh, and completely wrap the nickel mesh After baking in the kiln, the ceramic carrier is baked on the nickel mesh to produce a ceramic nickel mesh carrier. The coating thickness of the mixture is 3mm, which does not affect the aperture size of the nickel mesh. The baking temperature of the kiln is divided into three Zone: preheating zone 0-1000℃, firing zone 1000-1200℃, cooling zone 1280-20℃;
步骤二：凝胶负载：将步骤一中制备的陶瓷镍网载体先浸泡在第一浸泡溶胶中，然后干燥，接着浸泡在第二浸泡溶胶中，得到负载贵金属氧化物、石墨烯与TiO 2的镍网催化剂，溶胶分为第一浸泡溶胶和第二浸泡溶胶，且第一浸泡溶胶和第二浸泡溶胶组分完全相同，第二浸泡溶胶中添加有贵金属氧化物、石墨烯与TiO 2，第二浸泡溶胶中的原料配比为贵金属氧化物、石墨烯 与TiO 2按照2.5∶3∶3的比例进行配比。 Step 2: Gel loading: The ceramic nickel mesh carrier prepared in Step 1 is first soaked in the first soaking sol, then dried, and then soaked in the second soaking sol, to obtain a loaded precious metal oxide, graphene and TiO 2 . Nickel mesh catalyst, the sol is divided into a first soaking sol and a second soaking sol, and the first soaking sol and the second soaking sol have exactly the same components, the second soaking sol is added with precious metal oxides, graphene and TiO 2 , and the first soaking sol and the second soaking sol have the same components. The ratio of raw materials in the second soaking sol is noble metal oxide, graphene and TiO 2 in a ratio of 2.5:3:3.
本实施例中，负载镍网的石墨烯-TiO 2复合纳米材料通过下述重量百分含量的原料制成：贵金属氧化物35％、粘土20％、石英10％、钾钠长石10％、石墨烯50％、TiO 240％与镍网，TiO 2具有三维有序大孔结构，大孔的孔径为20μm，大孔之间通过100nm的孔连接，镍网孔径大小为60目，贵金属氧化物可以为Pt与Pd，制成后的催化剂安装在CO炉中后，通过加热装置，使气体达到燃烧反应温度，再通过催化床的作用，将有机物转化为无害的二氧化碳和水，从而达到去除污染物的目的，经过实验对比，其中通过在镍网上烤制陶瓷载体，能够确保催化剂不被烧结，保持催化剂高活性的比表面积、高机械强度、高热稳定性，同时在催化剂中添加贵金属氧化物、石墨烯与TiO 2，贵金属活性位分散度高，催化活性高，使用寿命长，压力损失小，降低了能耗，活性高具有对各类有机废气广谱活性，燃烧彻底对CO2选择性达到98％以上，催化去除效率高，显著降低反应活化能，使催化剂在中低温度下运行；耐温性好，耐热冲击性能强，最大工作温度约650℃；在凝胶负载时，将制备的陶瓷镍网载体先浸泡在第一浸泡溶胶中，然后干燥，接着浸泡在第二浸泡溶胶中，能够实现涂层牢固，保证活性组分不脱落，提高使用寿命，正常运行寿命大于3年。 In this embodiment, the graphene-TiO 2 composite nanomaterial loaded with nickel mesh is made from the following raw materials by weight: 35% of noble metal oxide, 20% of clay, 10% of quartz, 10% of potassium albite, Graphene 50%, TiO 2 40% and nickel mesh, TiO 2 has a three-dimensional ordered macroporous structure, the pore size of the macropore is 20 μm, the macropores are connected by 100 nm pores, the pore size of the nickel mesh is 60 mesh, and the noble metal is oxidized The compounds can be Pt and Pd. After the catalyst is installed in the CO furnace, the gas reaches the combustion reaction temperature through the heating device, and then the organic matter is converted into harmless carbon dioxide and water through the action of the catalytic bed, so as to achieve For the purpose of removing pollutants, through experimental comparison, the ceramic carrier is baked on the nickel mesh to ensure that the catalyst is not sintered, and the catalyst has a high active specific surface area, high mechanical strength, and high thermal stability. At the same time, adding precious metals to the catalyst to oxidize TiO 2 , high dispersion of noble metal active sites, high catalytic activity, long service life, small pressure loss, reduced energy consumption, high activity, broad-spectrum activity to various organic waste gases, and complete combustion to CO2 selectivity Reaching more than 98%, the catalytic removal efficiency is high, the reaction activation energy is significantly reduced, and the catalyst operates at medium and low temperatures; good temperature resistance, strong thermal shock resistance, and the maximum working temperature is about 650 ° C; when the gel is loaded, the The prepared ceramic nickel mesh carrier is first soaked in the first soaking sol, then dried, and then soaked in the second soaking sol, which can achieve a firm coating, ensure that the active components do not fall off, and improve the service life, and the normal operating life is more than 3 years. .
经过对比发现，本发明通过在镍网上烤制陶瓷载体，能够确保催化剂不被烧结，保持催化剂高活性的比表面积、高机械强度、高热稳定性，同时在催化剂中添加贵金属氧化物、石墨烯与TiO 2，贵金属活性位分散度高，催化活性高，使用寿命长，压力损失小，降低了能耗，活性高具有对各类有机废气广谱活性，燃烧彻底对CO2选择性均达到96％以上，催化去除效率高，显著降低反应活化能，使催化剂在中低温度下运行；耐温性好，耐热冲击性能强，最大工作温度均在600℃以上，在凝胶负载时，将制备的陶瓷镍网载体先浸泡在第一浸泡溶胶中，然后干燥，接着浸泡在第二浸泡溶胶中，能够实现涂层 牢固，保证活性组分不脱落，提高使用寿命，正常运行寿命大于2.5年，其中实施例3为最优选项。 Through comparison, it is found that the present invention can ensure that the catalyst is not sintered by baking the ceramic carrier on the nickel mesh, and maintain the catalyst with high active specific surface area, high mechanical strength, and high thermal stability. TiO 2 , high dispersion of precious metal active sites, high catalytic activity, long service life, small pressure loss, reduced energy consumption, high activity, broad-spectrum activity on various organic waste gases, and complete combustion to CO2 selectivity above 96% , the catalytic removal efficiency is high, the reaction activation energy is significantly reduced, and the catalyst operates at medium and low temperatures; the temperature resistance is good, the thermal shock resistance is strong, and the maximum working temperature is above 600 ° C. When the gel is loaded, the prepared The ceramic nickel mesh carrier is first soaked in the first soaking sol, then dried, and then soaked in the second soaking sol, which can achieve a firm coating, ensure that the active components do not fall off, and improve the service life. The normal operating life is greater than 2.5 years, among which Example 3 is the best option.
以上显示和描述了本发明的基本原理和主要特征和本发明的优点。本行业的技术人员应该了解，本发明不受上述实施例的限制，上述实施例和说明书中描述的只是说明本发明的原理，在不脱离本发明精神和范围的前提下，本发明还会有各种变化和改进，这些变化和改进都落入要求保护的本发明范围内。本发明要求保护范围由所附的权利要求书及其等效物界定。The basic principles and main features of the present invention and the advantages of the present invention have been shown and described above. Those skilled in the art should understand that the present invention is not limited by the above-mentioned embodiments. The above-mentioned embodiments and descriptions only illustrate the principle of the present invention. Without departing from the spirit and scope of the present invention, the present invention will also have Various changes and modifications fall within the scope of the claimed invention. The claimed scope of the present invention is defined by the appended claims and their equivalents.

Claims (7)

  1. 一种负载镍网的石墨烯-TiO 2复合纳米材料的制备方法，其特征在于：该石墨烯-TiO 2复合纳米材料由下述重量百分含量的原料制成：贵金属氧化物25-35％、粘土10-20％、石英5-10％、钾钠长石5-10％、石墨烯30-50％、TiO 230-40％与镍网； A method for preparing a graphene-TiO 2 composite nanomaterial loaded with nickel mesh, characterized in that: the graphene-TiO 2 composite nanomaterial is made from the following raw materials by weight percentage: 25-35% of noble metal oxides , clay 10-20%, quartz 5-10%, potassium albite 5-10%, graphene 30-50%, TiO 2 30-40% and nickel mesh;
    该石墨烯-TiO 2复合纳米材料的制备方法具体步骤如下： The specific steps of the preparation method of the graphene-TiO 2 composite nanomaterial are as follows:
    步骤一：制备陶瓷镍网载体：按照上述重量百分含量配比将粘土10-20％、石英5-10％、钾钠长石5-10％混合加水搅拌成混合料，均匀涂抹在镍网上，全部包裹住镍网后置于窑炉上烘烤，使得镍网上烤制出陶瓷载体，生产成陶瓷镍网载体；Step 1: Preparation of ceramic nickel mesh carrier: According to the above weight percentage ratio, mix clay 10-20%, quartz 5-10%, potassium albite 5-10%, add water and stir to form a mixture, and evenly spread it on the nickel mesh , all wrap the nickel mesh and then bake it on the kiln, so that the ceramic carrier is baked on the nickel mesh to produce a ceramic nickel mesh carrier;
    步骤二：凝胶负载：将步骤一中制备的陶瓷镍网载体先浸泡在第一浸泡溶胶中，然后干燥，接着浸泡在第二浸泡溶胶中，得到负载贵金属氧化物、石墨烯与TiO 2的镍网催化剂。 Step 2: Gel loading: The ceramic nickel mesh carrier prepared in Step 1 is first soaked in the first soaking sol, then dried, and then soaked in the second soaking sol, to obtain a loaded precious metal oxide, graphene and TiO 2 . Nickel mesh catalyst.
  2. 根据权利要求1所述的一种负载镍网的石墨烯-TiO 2复合纳米材料的制备方法，其特征在于：所述TiO 2具有三维有序大孔结构，大孔的孔径为100nm～20μm，大孔之间通过20～100nm的孔连接，镍网孔径大小为40～60目。 The method for preparing a nickel mesh-loaded graphene-TiO 2 composite nanomaterial according to claim 1, wherein the TiO 2 has a three-dimensional ordered macroporous structure, and the pore size of the macropores is 100 nm to 20 μm, The macropores are connected by pores of 20-100 nm, and the pore size of the nickel mesh is 40-60 meshes.
  3. 根据权利要求1所述的一种负载镍网的石墨烯-TiO 2复合纳米材料的制备方法，其特征在于：所述贵金属氧化物可以为Pt或Pd中的一种或两种。 The method for preparing a nickel mesh-loaded graphene-TiO 2 composite nanomaterial according to claim 1, wherein the noble metal oxide can be one or both of Pt or Pd.
  4. 根据权利要求1所述的一种负载镍网的石墨烯-TiO 2复合纳米材料的制备方法，其特征在于：步骤一中所述混合料的涂抹厚度为1-3mm，不影响镍网孔径大小。 The graphene 1 according to a supported nickel mesh as claimed in claim 2 -TiO method for preparing the nanocomposite, wherein: a step in the thickness of the applied mixture is 1-3mm, does not affect the pore size of nickel mesh .
  5. 根据权利要求1所述的一种负载镍网的石墨烯-TiO 2复合纳米材料的制备方法，其特征在于：步骤一中所述窑炉的烘烤温度分为三个区：预热区0-1000℃，烧制区1000-1200℃，冷却区1280-20℃。 A kind of graphene-TiO 2 composite nanomaterial preparation method of a kind of loaded nickel mesh according to claim 1, is characterized in that: the baking temperature of the kiln described in step 1 is divided into three zones: preheating zone 0 -1000℃, firing zone 1000-1200℃, cooling zone 1280-20℃.
  6. 根据权利要求1所述的一种负载镍网的石墨烯-TiO 2复合纳米材料的制 备方法，其特征在于：步骤二中所述溶胶分为第一浸泡溶胶和第二浸泡溶胶，且第一浸泡溶胶和第二浸泡溶胶组分完全相同，第二浸泡溶胶中添加有贵金属氧化物、石墨烯与TiO 2。 The graphene -TiO 2 nanocomposite production method according to claim 1 of a supported nickel mesh as claimed in claim, wherein: said step two into a first sol and the second sol soak soak sol, and the first The components of the soaking sol and the second soaking sol are exactly the same, and noble metal oxide, graphene and TiO 2 are added to the second soaking sol.
  7. 根据权利要求1所述的一种负载镍网的石墨烯-TiO 2复合纳米材料的制备方法，其特征在于：步骤二中所述第二浸泡溶胶中的原料配比为贵金属氧化物、石墨烯与TiO 2按照2.5∶3∶3的比例进行配比。 The graphene -TiO 2 nanocomposite production method according to claim 1 of a supported nickel mesh as claimed in claim, characterized in that: two second soaking step in the ratio of raw materials for the sol noble metal oxide, the graphene It is mixed with TiO 2 in a ratio of 2.5:3:3.
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