WO2020057097A1 - Fly ash-based mullite closed-cell ceramic and preparation method thereof - Google Patents

Fly ash-based mullite closed-cell ceramic and preparation method thereof Download PDF

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WO2020057097A1
WO2020057097A1 PCT/CN2019/080547 CN2019080547W WO2020057097A1 WO 2020057097 A1 WO2020057097 A1 WO 2020057097A1 CN 2019080547 W CN2019080547 W CN 2019080547W WO 2020057097 A1 WO2020057097 A1 WO 2020057097A1
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fly ash
closed
mullite
based mullite
pore
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Chinese (zh)
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马北越
苏畅
任鑫明
于景坤
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东北大学
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    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/16—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay
    • C04B35/18—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on silicates other than clay rich in aluminium oxide
    • C04B35/185—Mullite 3Al2O3-2SiO2
    • 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
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/64—Burning or sintering processes
    • 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
    • C04B38/00—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof
    • C04B38/02—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by adding chemical blowing agents
    • 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
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    • 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • 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
    • C04B2235/70—Aspects relating to sintered or melt-casted ceramic products
    • C04B2235/96—Properties of ceramic products, e.g. mechanical properties such as strength, toughness, wear resistance
    • C04B2235/9607—Thermal properties, e.g. thermal expansion coefficient

Definitions

  • the invention belongs to the technical field of high-value utilization of industrial solid waste resources, and particularly relates to a fly ash-based mullite closed-hole ceramic and a preparation method thereof.
  • Organic thermal insulation materials are mostly used in buildings in China, which have the advantages of light weight, good thermal insulation effect and easy processing.
  • organic thermal insulation materials have low strength, are easy to burn, and have poor ecological and environmental protection properties. Therefore, inorganic thermal insulation materials are a new research direction in the field of wall thermal insulation materials. Compared with developed countries, China's research and development of inorganic insulation materials is relatively backward. At present, China's industry and agriculture are booming and facing increasing environmental pollution. Therefore, how to use cheap raw materials to prepare inorganic thermal insulation materials with excellent performance is a hot research topic in the field of thermal insulation materials in China at this stage.
  • Mullite porous ceramic has low thermal conductivity, good chemical stability, and high hardness, and can be used as an excellent inorganic thermal insulation material. With the continuous rise in power generation, the emissions of coal ash from coal combustion have increased year by year, and the pollution to atmospheric rivers has become increasingly serious.
  • the main components of fly ash are SiO 2 and Al 2 O 3 , which are very suitable for preparing mullite ceramic materials. Therefore, the preparation of mullite closed-pore ceramics using fly ash as the main raw material can greatly improve the utilization rate and added value of fly ash, turn waste into treasure, and turn harm into profit.
  • the commonly used processes for preparing porous ceramics include: organic foam impregnation method, foaming method, pore-forming agent method, sol-gel method, and the like.
  • the process of adding a pore-forming agent is simple, and the preparation conditions are easy to control. It is the most commonly used porous ceramic preparation process.
  • the obtained material has a low closed porosity and a high thermal conductivity, which is not conducive to thermal insulation. Therefore, improving the closed porosity and reducing the thermal conductivity of mullite ceramic materials is the research focus in the field of mullite ceramic materials.
  • the purpose of the present invention is to overcome the shortcomings of the prior art described above, and provide a fly ash-based mullite closed-pore ceramic and a preparation method thereof.
  • the main steps of the method are as follows: first, the fly ash is pre-calcined to Obtain high-stability fly ash clinker; secondly, add an appropriate amount of correction material (aluminum-containing material, silicon-containing material) according to the composition of the fly ash; then, use the mixed fly ash and correction material as raw materials. An appropriate amount of a pore-forming agent and a flux are added thereto, and the mixture is mixed again uniformly; finally, mullite closed-pore ceramics are prepared by dry pressing and high-temperature sintering.
  • correction material aluminum-containing material, silicon-containing material
  • the present invention adopts the following technical solutions:
  • fly ash-based mullite closed-pore ceramic each component is proportioned by mass.
  • Fly ash clinker: corrector: pore-forming agent: flux 100: (100-200): (0-15): (10-20).
  • the fly ash clinker is prepared by calcining the fly ash, and the components of the fly ash are mainly SiO 2 and Al 2 O 3 .
  • the calibration material is one or more of an aluminum-containing raw material or a silicon-containing raw material.
  • the added amount of the calibration material should be calculated according to the mullite chemical composition.
  • the aluminum-containing raw material is one or more of aluminum powder, high-alumina bauxite, or alumina powder; and the silicon-containing raw material is silicon powder and / or silicon fine powder.
  • the pore-forming agent is one or more of silicon carbide, ammonium bicarbonate, ammonium bisulfate, or ammonium nitrate.
  • the flux is one or more of V 2 O 5 , aluminum chloride, aluminum fluoride, potassium feldspar or sodium feldspar.
  • the closed-pore porosity of the fly ash-based mullite closed-pore ceramic is 15 to 21%, the compressive strength at room temperature is 190 to 220 MPa, and the thermal conductivity is 0.21 to 0.29 w / (m ⁇ K).
  • the preparation method of the fly ash-based mullite closed-pore ceramic according to the present invention is performed according to the following steps:
  • Step 1 Raw material pretreatment
  • Step 2 Weighing and mixing
  • Step 3 Dry pressing and sintering
  • step 1 calcination is used to remove impurities in industrial silicon-based waste residue.
  • the calcining operation is performed in a calcining furnace, the calcining temperature is 1000 ° C, and the calcining time is 5 hours.
  • the calcining furnace is a box resistance wire furnace, a silicon carbon rod furnace, and a silicon molybdenum rod furnace. And one of the tunnel kiln.
  • the raw material is mixed in one or more of manual mixing, high-energy ball milling mixing, or mechanical stirring.
  • the forming pressure is 50 to 300 MPa, and the holding time is 3 to 5 minutes.
  • the high-temperature furnace is one of a box-type resistance furnace, a tube-type resistance furnace, and a tunnel kiln.
  • the sintering temperature is 1400-1600 ° C, and the sintering holding time is 2-8 hours.
  • the method for preparing closed-cell mullite ceramics proposed by the present invention realizes the efficient and comprehensive utilization of fly ash, not only reduces its environmental pollution, but also can produce high-performance closed-cell mullite ceramics, which has Better economic and environmental benefits.
  • the method for preparing mullite closed-hole ceramics according to the present invention has higher strength, better comprehensive performance and broad application prospects.
  • the method for preparing mullite closed-hole ceramics according to the present invention has simple operation and is convenient for industrialized production.
  • FIG. 1 is a process flow chart of an embodiment of the present invention.
  • fly ash-based mullite closed-pore ceramic Each component is proportioned by mass.
  • Fly ash clinker: high alumina vanadium: ammonium bicarbonate: potassium feldspar 100: 100: 5: 10.
  • FIG. 1 A method for preparing a fly ash-based mullite closed-cell ceramic is shown in FIG. 1 and is performed in the following steps:
  • Step 1 Raw material pretreatment
  • the fly ash is placed in a box-type resistance wire furnace and calcined at 1000 ° C for 5 hours to obtain a fly ash clinker with good stability;
  • Step 2 Weighing and mixing
  • Step 3 Sample preparation and sintering
  • the formed material is fully sintered in a high-temperature furnace at 1400 ° C for 4 hours, and the high-temperature furnace is cooled to room temperature to obtain fly ash-based mullite closed-hole ceramic.
  • the closed porosity of the obtained mullite closed-cell ceramic was 20%, the compressive strength at room temperature was 200 MPa, and the thermal conductivity was 0.23 W / (m ⁇ K).
  • fly ash-based mullite closed-pore ceramic Each component is proportioned by mass.
  • Fly ash clinker: high alumina vanadium: silicon carbide: potassium feldspar 100: 100: 5: 10.
  • FIG. 1 A method for preparing a fly ash-based mullite closed-cell ceramic is shown in FIG. 1 and is performed in the following steps:
  • Step 1 Raw material pretreatment
  • the fly ash is placed in a box-type resistance wire furnace and calcined at 1000 ° C for 5 hours to obtain a fly ash clinker with good stability;
  • Step 2 Weighing and mixing
  • Step 3 Sample preparation and sintering
  • the formed material is fully sintered in a high-temperature furnace at 1400 ° C for 8 hours, and the high-temperature furnace is cooled to room temperature to obtain fly ash-based mullite closed-hole ceramic.
  • the closed porosity of the obtained mullite closed-cell ceramic was 15%, the compressive strength at room temperature was 220 MPa, and the thermal conductivity was 0.29 W / (m ⁇ K).
  • fly ash-based mullite closed-pore ceramic Each component is in a mass ratio.
  • Fly ash clinker: alumina powder: ammonium bicarbonate: potassium feldspar 100: 100: 5: 10.
  • FIG. 1 A method for preparing a fly ash-based mullite closed-cell ceramic is shown in FIG. 1 and is performed in the following steps:
  • Step 1 Raw material pretreatment
  • the fly ash is placed in a box-type resistance wire furnace and calcined at 1000 ° C for 5 hours to obtain a fly ash clinker with good stability;
  • Step 2 Weighing and mixing
  • Step 3 Sample preparation and sintering
  • the formed material is placed in a high-temperature furnace at 1600 ° C for sufficient sintering and heat preservation for 4 hours, and the high-temperature furnace is cooled to room temperature to obtain a fly ash-based mullite closed-hole ceramic.
  • the closed porosity of the obtained mullite closed-cell ceramic was 21%, the compressive strength at room temperature was 190 MPa, and the thermal conductivity was 0.21 W / (m ⁇ K).
  • a fly ash-based mullite closed-pore ceramic Each component is in a mass ratio.
  • the fly ash clinker: high alumina vanadium: ammonium nitrate: aluminum fluoride 100: 200: 15: 15.
  • FIG. 1 A method for preparing a fly ash-based mullite closed-cell ceramic is shown in FIG. 1 and is performed in the following steps:
  • Step 1 Raw material pretreatment
  • the fly ash is placed in a box-type resistance wire furnace and calcined at 1000 ° C for 5 hours to obtain a fly ash clinker with good stability;
  • Step 2 Weighing and mixing
  • fly ash clinker, high alumina vanadium, ammonium nitrate and aluminum fluoride were weighed according to the mass ratio of 100: 200: 15: 15, and high energy ball milling was performed in an agate crucible for 30 minutes to obtain a mixed material;
  • Step 3 Sample preparation and sintering
  • the formed material is fully sintered in a high-temperature furnace at 1400 ° C for 4 hours, and the high-temperature furnace is cooled to room temperature to obtain fly ash-based mullite closed-hole ceramic.
  • the closed porosity of the obtained mullite closed-pore ceramic was 19%, the compressive strength at room temperature was 210 MPa, and the thermal conductivity was 0.28 W / (m ⁇ K).

Abstract

Provided are a fly ash-based mullite closed-cell ceramic and preparation method thereof, each component is formulated in mass ratio, fly ash clinker: calibrator: pore forming agent: flux = 100: (100-200): (0-15): (10-20). The preparation method comprises: step 1, calcining the fly ash to obtain the fly ash clinker; step 2, according to the mass ratio, uniformly mixing the raw materials to obtain the uniform mixture; step 3, (1) dry-pressing and molding the uniform mixture; (2) after sufficiently drying the molded mixture, placing the mixture in a high-temperature furnace, sinterring and insulating for a certain period of time to prepare the fly ash-based mullite closed-cell ceramic.

Description

一种粉煤灰基莫来石闭孔陶瓷及其制备方法Fly ash-based mullite closed-hole ceramic and preparation method thereof 技术领域：Technical field:
本发明属于工业固废资源高值化利用技术领域，具体涉及一种粉煤灰基莫来石闭孔陶瓷及其制备方法。The invention belongs to the technical field of high-value utilization of industrial solid waste resources, and particularly relates to a fly ash-based mullite closed-hole ceramic and a preparation method thereof.
背景技术：Background technique:
我国的建筑使用较多的是有机保温材料，其具有质轻、保温隔热效果好、便于加工等优点。但有机保温材料强度低、易燃烧、生态环保性差，因此，无机保温材料是墙体保温材料领域新的研究方向。相比发达国家，我国无机保温材料研发相对落后。目前，中国的工农业正蓬勃发展，面临环境污染日益加剧的问题。因此，如何利用廉价的原材料制备出性能优异的无机保温材料，是现阶段我国保温材料领域的研究热点。Organic thermal insulation materials are mostly used in buildings in China, which have the advantages of light weight, good thermal insulation effect and easy processing. However, organic thermal insulation materials have low strength, are easy to burn, and have poor ecological and environmental protection properties. Therefore, inorganic thermal insulation materials are a new research direction in the field of wall thermal insulation materials. Compared with developed countries, China's research and development of inorganic insulation materials is relatively backward. At present, China's industry and agriculture are booming and facing increasing environmental pollution. Therefore, how to use cheap raw materials to prepare inorganic thermal insulation materials with excellent performance is a hot research topic in the field of thermal insulation materials in China at this stage.
莫来石多孔陶瓷导热系数低、化学稳定性好、硬度大，可作为优良的无机保温材料。随着发电量不断上升，煤燃烧产生粉煤灰的排放量逐年增加，对大气河流造成的污染日趋严重。粉煤灰的主要组分是SiO 2和Al 2O 3，非常适合制备莫来石陶瓷材料。因此，以粉煤灰为主要原料制备莫来石闭孔陶瓷可大大提高粉煤灰利用率和附加值，变废为宝，变害为利。 Mullite porous ceramic has low thermal conductivity, good chemical stability, and high hardness, and can be used as an excellent inorganic thermal insulation material. With the continuous rise in power generation, the emissions of coal ash from coal combustion have increased year by year, and the pollution to atmospheric rivers has become increasingly serious. The main components of fly ash are SiO 2 and Al 2 O 3 , which are very suitable for preparing mullite ceramic materials. Therefore, the preparation of mullite closed-pore ceramics using fly ash as the main raw material can greatly improve the utilization rate and added value of fly ash, turn waste into treasure, and turn harm into profit.
目前常用的制备多孔陶瓷的工艺有：有机泡沫浸渍法、发泡法、添加造孔剂法、溶胶-凝胶法等。其中，添加造孔剂工艺步骤简单、制备条件易于控制，是最常用的多孔陶瓷制备工艺。然而，添加造孔剂工艺难以制得闭口气孔率较高的陶瓷材料，所制得材料闭口气孔率低、导热系数偏高，不利于保温隔热。因此，提高莫来石陶瓷材料的闭口气孔率，降低其热导率是莫来石陶瓷材料领域的研究重点。At present, the commonly used processes for preparing porous ceramics include: organic foam impregnation method, foaming method, pore-forming agent method, sol-gel method, and the like. Among them, the process of adding a pore-forming agent is simple, and the preparation conditions are easy to control. It is the most commonly used porous ceramic preparation process. However, it is difficult to obtain a ceramic material with a high closed porosity by adding a pore-forming agent. The obtained material has a low closed porosity and a high thermal conductivity, which is not conducive to thermal insulation. Therefore, improving the closed porosity and reducing the thermal conductivity of mullite ceramic materials is the research focus in the field of mullite ceramic materials.
发明内容：Summary of the invention:
本发明的目的是克服上述现有技术存在的不足，提供一种粉煤灰基莫来石闭孔陶瓷及其制备方法，该方法的主要工序如下：首先，对粉煤灰预先煅烧处理，以获得稳定性高的粉煤灰熟料；其次，根据粉煤灰组分掺入适量的校正料(含铝料、含硅料)；然后，以混合后的粉煤灰、校正料为原料，向其中加入适量造孔剂、熔剂，将混合料再次混合均匀；最后，经干压成型，高温烧结制得莫来石闭孔陶瓷。The purpose of the present invention is to overcome the shortcomings of the prior art described above, and provide a fly ash-based mullite closed-pore ceramic and a preparation method thereof. The main steps of the method are as follows: first, the fly ash is pre-calcined to Obtain high-stability fly ash clinker; secondly, add an appropriate amount of correction material (aluminum-containing material, silicon-containing material) according to the composition of the fly ash; then, use the mixed fly ash and correction material as raw materials. An appropriate amount of a pore-forming agent and a flux are added thereto, and the mixture is mixed again uniformly; finally, mullite closed-pore ceramics are prepared by dry pressing and high-temperature sintering.
为实现上述目的，本发明采用以下技术方案：To achieve the above objective, the present invention adopts the following technical solutions:
一种粉煤灰基莫来石闭孔陶瓷，各组分按质量配比，粉煤灰熟料∶校正剂∶造孔剂∶熔剂＝100∶(100～200)∶(0～15)∶(10～20)。A fly ash-based mullite closed-pore ceramic, each component is proportioned by mass. Fly ash clinker: corrector: pore-forming agent: flux = 100: (100-200): (0-15): (10-20).
所述的粉煤灰熟料由粉煤灰煅烧处理制得，所述的粉煤灰成分主要是SiO 2和Al 2O 3。 The fly ash clinker is prepared by calcining the fly ash, and the components of the fly ash are mainly SiO 2 and Al 2 O 3 .
所述的校正料为含铝原料或含硅原料中的一种或多种。The calibration material is one or more of an aluminum-containing raw material or a silicon-containing raw material.
所述的校正料添加量应按照莫来石化学组分进行计算。The added amount of the calibration material should be calculated according to the mullite chemical composition.
所述的含铝原料为铝粉、高铝矾土或氧化铝粉中的一种或多种；所述的含硅原料为硅粉和/或硅微粉。The aluminum-containing raw material is one or more of aluminum powder, high-alumina bauxite, or alumina powder; and the silicon-containing raw material is silicon powder and / or silicon fine powder.
所述的造孔剂为碳化硅、碳酸氢铵、硫酸氢铵或硝酸铵中的一种或多种。The pore-forming agent is one or more of silicon carbide, ammonium bicarbonate, ammonium bisulfate, or ammonium nitrate.
所述的熔剂为V 2O 5、氯化铝、氟化铝、钾长石或钠长石中的一种或多种。 The flux is one or more of V 2 O 5 , aluminum chloride, aluminum fluoride, potassium feldspar or sodium feldspar.
所述的粉煤灰基莫来石闭孔陶瓷闭口气孔率为15～21％，常温抗压强度为190～220MPa，热导率为0.21～0.29w/(m·K)。The closed-pore porosity of the fly ash-based mullite closed-pore ceramic is 15 to 21%, the compressive strength at room temperature is 190 to 220 MPa, and the thermal conductivity is 0.21 to 0.29 w / (m · K).
本发明的一种粉煤灰基莫来石闭孔陶瓷的制备方法，按以下步骤进行：The preparation method of the fly ash-based mullite closed-pore ceramic according to the present invention is performed according to the following steps:
步骤1：原料预处理Step 1: Raw material pretreatment
将粉煤灰进行煅烧处理，制得粉煤灰熟料；Calcining the fly ash to obtain a fly ash clinker;
步骤2：称料和混料Step 2: Weighing and mixing
按原料质量配比，粉煤灰熟料∶校正剂∶造孔剂∶熔剂＝100∶(100～200)∶(0～15)∶(10～20)，将原料混合均匀，制得混匀物料；According to the mass ratio of raw materials, fly ash clinker: calibrator: pore former: flux = 100: (100 ～ 200): (0 ～ 15): (10 ～ 20). materials;
步骤3：干压和烧结Step 3: Dry pressing and sintering
(1)将混匀物料干压成型；(1) dry pressing the mixed material;
(2)将成型后的物料充分干燥后，置于高温炉中，烧结并保温一定时间，制得粉煤灰基莫来石闭孔陶瓷。(2) After the formed materials are sufficiently dried, they are placed in a high-temperature furnace, sintered and held for a certain period of time to obtain fly ash-based mullite closed-hole ceramics.
所述的步骤1中，煅烧用于去除工业硅基废渣中的杂质。In said step 1, calcination is used to remove impurities in industrial silicon-based waste residue.
所述的步骤1中，所述的煅烧操作在煅烧炉中进行，煅烧温度为1000℃，煅烧时间为5h，所述的煅烧炉为箱式电阻丝炉、硅碳棒炉、硅钼棒炉和隧道窑中的一种。In the step 1, the calcining operation is performed in a calcining furnace, the calcining temperature is 1000 ° C, and the calcining time is 5 hours. The calcining furnace is a box resistance wire furnace, a silicon carbon rod furnace, and a silicon molybdenum rod furnace. And one of the tunnel kiln.
所述的步骤2中，所述的原料混合方式为手混、高能球磨混合或机械搅拌中的一种或多种。In the step 2, the raw material is mixed in one or more of manual mixing, high-energy ball milling mixing, or mechanical stirring.
所述的步骤3(1)中，所述的成型压力为50～300MPa，保压时间为3～5min。In the step 3 (1), the forming pressure is 50 to 300 MPa, and the holding time is 3 to 5 minutes.
所述的步骤3(2)中，所述的高温炉为箱式电阻炉、管式电阻炉和隧道窑中一种。In the step 3 (2), the high-temperature furnace is one of a box-type resistance furnace, a tube-type resistance furnace, and a tunnel kiln.
所述的步骤3(2)中，所述的烧结温度为1400～1600℃，烧结保温时间为2～8h。In the step 3 (2), the sintering temperature is 1400-1600 ° C, and the sintering holding time is 2-8 hours.
本发明的有益效果：The beneficial effects of the present invention:
1.本发明提出的制备莫来石闭孔陶瓷的方法，实现了粉煤灰的高效综合利用，不仅减少其对环境产生的污染，而且可制得高性能的莫来石闭孔陶瓷，具有较好的经济效益和环保效益。1. The method for preparing closed-cell mullite ceramics proposed by the present invention realizes the efficient and comprehensive utilization of fly ash, not only reduces its environmental pollution, but also can produce high-performance closed-cell mullite ceramics, which has Better economic and environmental benefits.
2.本发明的制备莫来石闭孔陶瓷的方法，制得材料的强度较高，综合性能较佳，应用前 景广阔。2. The method for preparing mullite closed-hole ceramics according to the present invention has higher strength, better comprehensive performance and broad application prospects.
3.本发明的制备莫来石闭孔陶瓷的方法，操作简单易行，便于工业化生产。3. The method for preparing mullite closed-hole ceramics according to the present invention has simple operation and is convenient for industrialized production.
附图说明：Brief description of the drawings:
图1是本发明实施例的工艺流程图。FIG. 1 is a process flow chart of an embodiment of the present invention.
具体实施方式：detailed description:
下面结合实施例对本发明作进一步的详细说明。The present invention will be further described in detail with reference to the following embodiments.
实施例1Example 1
一种粉煤灰基莫来石闭孔陶瓷，各组分按质量配比，粉煤灰熟料∶高铝钒土∶碳酸氢铵∶钾长石＝100∶100∶5∶10。A fly ash-based mullite closed-pore ceramic. Each component is proportioned by mass. Fly ash clinker: high alumina vanadium: ammonium bicarbonate: potassium feldspar = 100: 100: 5: 10.
一种粉煤灰基莫来石闭孔陶瓷的制备方法，其工艺流程图如图1所示，按以下步骤进行：A method for preparing a fly ash-based mullite closed-cell ceramic is shown in FIG. 1 and is performed in the following steps:
步骤1：原料预处理Step 1: Raw material pretreatment
(1)将粉煤灰置于箱式电阻丝炉中，在1000℃下煅烧5h，得到稳定性好的粉煤灰熟料；(1) The fly ash is placed in a box-type resistance wire furnace and calcined at 1000 ° C for 5 hours to obtain a fly ash clinker with good stability;
(2)按照莫来石的组分配比，配制高铝钒土；其中，高铝石土质量与粉煤灰熟料质量相同；(2) According to the group distribution ratio of mullite, prepare high-alumina vanadium; among them, the quality of high-alumina soil is the same as that of fly ash clinker;
步骤2：称料和混料Step 2: Weighing and mixing
按100∶100∶5∶10的质量配比称量粉煤灰熟料、高铝钒土、碳酸氢铵和钾长石，在玛瑙坩埚中混合手磨30min，制得混匀物料；Weigh fly ash clinker, high alumina vanadium, ammonium bicarbonate and potassium feldspar according to the mass ratio of 100: 100: 5: 10, and mix by hand grinding in an agate crucible for 30 minutes to obtain a mixed material;
步骤3：制样和烧结Step 3: Sample preparation and sintering
(1)将混匀物料置于压力机中干压成型，100MPa下保压5min；(1) Put the mixed material into a press for dry pressing, and hold the pressure for 5min at 100MPa;
(2)将成型后的物料置于1400℃的高温炉中充分烧结保温4h，待高温炉冷却至室温，得到粉煤灰基莫来石闭孔陶瓷。(2) The formed material is fully sintered in a high-temperature furnace at 1400 ° C for 4 hours, and the high-temperature furnace is cooled to room temperature to obtain fly ash-based mullite closed-hole ceramic.
经检测，所得莫来石闭孔陶瓷的闭口气孔率为20％，常温抗压强度为200MPa，热导率为0.23W/(m·K)。After inspection, the closed porosity of the obtained mullite closed-cell ceramic was 20%, the compressive strength at room temperature was 200 MPa, and the thermal conductivity was 0.23 W / (m · K).
实施例2Example 2
一种粉煤灰基莫来石闭孔陶瓷，各组分按质量配比，粉煤灰熟料∶高铝钒土∶碳化硅∶钾长石＝100∶100∶5∶10。A fly ash-based mullite closed-pore ceramic. Each component is proportioned by mass. Fly ash clinker: high alumina vanadium: silicon carbide: potassium feldspar = 100: 100: 5: 10.
一种粉煤灰基莫来石闭孔陶瓷的制备方法，其工艺流程图如图1所示，按以下步骤进行：A method for preparing a fly ash-based mullite closed-cell ceramic is shown in FIG. 1 and is performed in the following steps:
步骤1：原料预处理Step 1: Raw material pretreatment
(1)将粉煤灰置于箱式电阻丝炉中，在1000℃下煅烧5h，得到稳定性好的粉煤灰熟料；(1) The fly ash is placed in a box-type resistance wire furnace and calcined at 1000 ° C for 5 hours to obtain a fly ash clinker with good stability;
(2)按照莫来石的组分配比，配制高铝钒土；其中，高铝石土质量与粉煤灰熟料质量相同；(2) According to the group distribution ratio of mullite, prepare high-alumina vanadium; among them, the quality of high-alumina soil is the same as that of fly ash clinker;
步骤2：称料和混料Step 2: Weighing and mixing
按100∶100∶5∶10的质量配比称量粉煤灰熟料、高铝钒土、碳化硅和钾长石，在玛瑙坩埚 中混合手磨30min，制得混匀物料；Weigh fly ash clinker, high alumina vanadium, silicon carbide and potassium feldspar according to the mass ratio of 100: 100: 5: 10, and mix by hand grinding in an agate crucible for 30 minutes to obtain a mixed material;
步骤3：制样和烧结Step 3: Sample preparation and sintering
(1)将混匀物料置于压力机中干压成型，100MPa下保压5min；(1) Put the mixed material into a press for dry pressing, and hold the pressure for 5min at 100MPa;
(2)将成型后的物料置于1400℃的高温炉中充分烧结保温8h，待高温炉冷却至室温，得到粉煤灰基莫来石闭孔陶瓷。(2) The formed material is fully sintered in a high-temperature furnace at 1400 ° C for 8 hours, and the high-temperature furnace is cooled to room temperature to obtain fly ash-based mullite closed-hole ceramic.
经检测，所得莫来石闭孔陶瓷的闭口气孔率为15％，常温抗压强度为220MPa，热导率为0.29W/(m·K)。After testing, the closed porosity of the obtained mullite closed-cell ceramic was 15%, the compressive strength at room temperature was 220 MPa, and the thermal conductivity was 0.29 W / (m · K).
实施例3Example 3
一种粉煤灰基莫来石闭孔陶瓷，各组分按质量配比，粉煤灰熟料∶氧化铝粉∶碳酸氢铵∶钾长石＝100∶100∶5∶10。A fly ash-based mullite closed-pore ceramic. Each component is in a mass ratio. Fly ash clinker: alumina powder: ammonium bicarbonate: potassium feldspar = 100: 100: 5: 10.
一种粉煤灰基莫来石闭孔陶瓷的制备方法，其工艺流程图如图1所示，按以下步骤进行：A method for preparing a fly ash-based mullite closed-cell ceramic is shown in FIG. 1 and is performed in the following steps:
步骤1：原料预处理Step 1: Raw material pretreatment
(1)将粉煤灰置于箱式电阻丝炉中，在1000℃下煅烧5h，得到稳定性好的粉煤灰熟料；(1) The fly ash is placed in a box-type resistance wire furnace and calcined at 1000 ° C for 5 hours to obtain a fly ash clinker with good stability;
(2)按照莫来石的组分配比，配制高铝钒土；其中，高铝石土质量与粉煤灰熟料质量相同；(2) According to the group distribution ratio of mullite, prepare high-alumina vanadium; among them, the quality of high-alumina soil is the same as that of fly ash clinker;
步骤2：称料和混料Step 2: Weighing and mixing
按100∶100∶5∶10的质量配比称量粉煤灰熟料、氧化铝粉、碳酸氢铵和钾长石，在玛瑙坩埚中混合手磨30min，制得混匀物料；Weigh fly ash clinker, alumina powder, ammonium bicarbonate, and potassium feldspar according to the mass ratio of 100: 100: 5: 10, and mix and grind it in an agate crucible for 30 minutes to obtain a mixed material;
步骤3：制样和烧结Step 3: Sample preparation and sintering
(1)将混匀物料置于压力机中干压成型，100MPa下保压5min；(1) Put the mixed material into a press for dry pressing, and hold the pressure for 5min at 100MPa;
(2)将成型后的物料置于1600℃的高温炉中充分烧结保温4h，待高温炉冷却至室温，得到粉煤灰基莫来石闭孔陶瓷。(2) The formed material is placed in a high-temperature furnace at 1600 ° C for sufficient sintering and heat preservation for 4 hours, and the high-temperature furnace is cooled to room temperature to obtain a fly ash-based mullite closed-hole ceramic.
经检测，所得莫来石闭孔陶瓷的闭口气孔率为21％，常温抗压强度为190MPa，热导率为0.21W/(m·K)。After inspection, the closed porosity of the obtained mullite closed-cell ceramic was 21%, the compressive strength at room temperature was 190 MPa, and the thermal conductivity was 0.21 W / (m · K).
实施例4Example 4
一种粉煤灰基莫来石闭孔陶瓷，各组分按质量配比，粉煤灰熟料∶高铝钒土∶硝酸铵∶氟化铝＝100∶200∶15∶15。A fly ash-based mullite closed-pore ceramic. Each component is in a mass ratio. The fly ash clinker: high alumina vanadium: ammonium nitrate: aluminum fluoride = 100: 200: 15: 15.
一种粉煤灰基莫来石闭孔陶瓷的制备方法，其工艺流程图如图1所示，按以下步骤进行：A method for preparing a fly ash-based mullite closed-cell ceramic is shown in FIG. 1 and is performed in the following steps:
步骤1：原料预处理Step 1: Raw material pretreatment
(1)将粉煤灰置于箱式电阻丝炉中，在1000℃下煅烧5h，得到稳定性好的粉煤灰熟料；(1) The fly ash is placed in a box-type resistance wire furnace and calcined at 1000 ° C for 5 hours to obtain a fly ash clinker with good stability;
(2)按照莫来石的组分配比，配制高铝钒土；其中，高铝石土质量与粉煤灰熟料质量比为1∶2；(2) Preparation of high alumina vanadium according to the group distribution ratio of mullite; of which, the ratio of the quality of high alumina and the mass of fly ash clinker is 1: 2;
步骤2：称料和混料Step 2: Weighing and mixing
按100∶200∶15∶15的质量配比称量粉煤灰熟料、高铝钒土、硝酸铵和氟化铝，在玛瑙坩埚中高能球磨30min，制得混匀物料；The fly ash clinker, high alumina vanadium, ammonium nitrate and aluminum fluoride were weighed according to the mass ratio of 100: 200: 15: 15, and high energy ball milling was performed in an agate crucible for 30 minutes to obtain a mixed material;
步骤3：制样和烧结Step 3: Sample preparation and sintering
(1)将混匀物料置于压力机中干压成型，100MPa下保压5min；(1) Put the mixed material into a press for dry pressing, and hold the pressure for 5min at 100MPa;
(2)将成型后的物料置于1400℃的高温炉中充分烧结保温4h，待高温炉冷却至室温，得到粉煤灰基莫来石闭孔陶瓷。(2) The formed material is fully sintered in a high-temperature furnace at 1400 ° C for 4 hours, and the high-temperature furnace is cooled to room temperature to obtain fly ash-based mullite closed-hole ceramic.
经检测，所得莫来石闭孔陶瓷的闭口气孔率为19％，常温抗压强度为210MPa，热导率为0.28W/(m·K)。After testing, the closed porosity of the obtained mullite closed-pore ceramic was 19%, the compressive strength at room temperature was 210 MPa, and the thermal conductivity was 0.28 W / (m · K).

Claims (10)

  1. 一种粉煤灰基莫来石闭孔陶瓷，其特征在于，各组分按质量配比，粉煤灰熟料∶校正剂∶造孔剂∶熔剂＝100:(100～200):(0～15):(10～20)。A fly ash-based mullite closed-pore ceramic, characterized in that each component is in a mass ratio, and fly ash clinker: corrector: pore former: flux = 100: (100-200): (0 ~ 15): (10 ~ 20).
  2. 根据权利要求1所述的粉煤灰基莫来石闭孔陶瓷，其特征在于，所述的校正料为含铝原料或含硅原料中的一种或多种。The fly ash-based mullite closed-cell ceramic according to claim 1, wherein the correction material is one or more of an aluminum-containing raw material or a silicon-containing raw material.
  3. 根据权利要求2所述的粉煤灰基莫来石闭孔陶瓷，其特征在于，所述的含铝原料为铝粉、高铝矾土或氧化铝粉中的一种或多种；所述的含硅原料为硅粉和/或硅微粉。The fly ash-based mullite closed-cell ceramic according to claim 2, wherein the aluminum-containing raw material is one or more of aluminum powder, high-alumina bauxite, or alumina powder; The silicon-containing raw material is silicon powder and / or silicon fine powder.
  4. 根据权利要求1所述的粉煤灰基莫来石闭孔陶瓷，其特征在于，所述的造孔剂为碳化硅、碳酸氢铵、硫酸氢铵或硝酸铵中的一种或多种。The fly ash-based mullite closed-pore ceramic according to claim 1, wherein the pore-forming agent is one or more of silicon carbide, ammonium bicarbonate, ammonium bisulfate, or ammonium nitrate.
  5. 根据权利要求1所述的粉煤灰基莫来石闭孔陶瓷，其特征在于，所述的熔剂为V 2O 5、氯化铝、氟化铝、钾长石或钠长石中的一种或多种。 The fly ash-based mullite closed-cell ceramic according to claim 1, wherein the flux is one of V 2 O 5 , aluminum chloride, aluminum fluoride, potassium feldspar, or sodium feldspar. Or more.
  6. 根据权利要求1所述的粉煤灰基莫来石闭孔陶瓷，其特征在于，所述的粉煤灰基莫来石闭孔陶瓷闭口气孔率为15～21％，常温抗压强度为190～220MPa，热导率为0.21～0.29w/(m·K)。The fly ash-based mullite closed-cell ceramic according to claim 1, wherein the closed-pore porosity of the fly ash-based mullite closed-cell ceramic is 15 to 21%, and the compressive strength at room temperature is 190. ～ 220MPa, thermal conductivity is 0.21 ～ 0.29w / (m · K).
  7. 权利要求1所述的一种粉煤灰基莫来石闭孔陶瓷的制备方法，其特征在于，按以下步骤进行：The method for preparing fly ash-based mullite closed-pore ceramics according to claim 1, characterized in that, the following steps are performed:
    步骤1：原料预处理Step 1: Raw material pretreatment
    将粉煤灰进行煅烧处理，制得粉煤灰熟料；Calcining the fly ash to obtain a fly ash clinker;
    步骤2：称料和混料Step 2: Weighing and mixing
    按原料质量配比，粉煤灰熟料∶校正剂∶造孔剂∶熔剂＝100:(100～200):(0～15):(10～20)，将原料混合均匀，制得混匀物料；According to the mass ratio of the raw materials, the fly ash clinker: calibrator: pore former: flux = 100: (100 ～ 200): (0 ～ 15): (10 ～ 20), the raw materials are mixed uniformly to obtain a homogeneous mixture. materials;
    步骤3：干压和烧结Step 3: Dry pressing and sintering
    (1)将混匀物料干压成型；(1) dry pressing the mixed material;
    (2)将成型后的物料充分干燥后，置于高温炉中，烧结并保温一定时间，制得粉煤灰基莫来石闭孔陶瓷。(2) After the formed materials are sufficiently dried, they are placed in a high-temperature furnace, sintered and held for a certain period of time to obtain fly ash-based mullite closed-hole ceramics.
  8. 根据权利要求7所述的一种粉煤灰基莫来石闭孔陶瓷的制备方法，其特征在于，所述的步骤2中，所述的原料混合方式为手混、高能球磨混合或机械搅拌中的一种或多种。The method for preparing fly ash-based mullite closed-pore ceramics according to claim 7, characterized in that in said step 2, said raw material mixing method is manual mixing, high-energy ball milling mixing or mechanical stirring One or more of them.
  9. 根据权利要求7所述的一种粉煤灰基莫来石闭孔陶瓷的制备方法，其特征在于，所述的步骤3(1)中，所述的成型压力为50～300MPa，保压时间为3～5min。The method for preparing fly ash-based mullite closed-cell ceramics according to claim 7, characterized in that, in the step 3 (1), the forming pressure is 50-300 MPa, and the holding time is It is 3 ~ 5min.
  10. 根据权利要求7所述的一种粉煤灰基莫来石闭孔陶瓷的制备方法，其特征在于，所述的步骤3(2)中，所述的烧结温度为1400～1600℃，烧结保温时间为2～8h。The method for preparing fly ash-based mullite closed-cell ceramics according to claim 7, characterized in that, in the step 3 (2), the sintering temperature is 1400-1600 ° C, and the sintering temperature is maintained. The time is 2-8h.
PCT/CN2019/080547 2018-09-20 2019-03-29 Fly ash-based mullite closed-cell ceramic and preparation method thereof WO2020057097A1 (en)

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CN104159868A (en) * 2011-12-09 2014-11-19 新南创新私人有限公司 Percolated mullite and a method of forming same
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CN1844041A (en) * 2006-04-30 2006-10-11 中国地质科学院地质研究所 Method for preparing microporous mullite aerated head(plate) by fly ash
CN102557711A (en) * 2011-12-06 2012-07-11 天津大学 Porous filter material utilizing coal ash as raw material and preparation method thereof
CN104159868A (en) * 2011-12-09 2014-11-19 新南创新私人有限公司 Percolated mullite and a method of forming same
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