WO2019010892A1 - Preparation method for high corrosion-resistance aluminum oxide ceramic membrane support - Google Patents

Preparation method for high corrosion-resistance aluminum oxide ceramic membrane support Download PDF

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WO2019010892A1
WO2019010892A1 PCT/CN2017/111548 CN2017111548W WO2019010892A1 WO 2019010892 A1 WO2019010892 A1 WO 2019010892A1 CN 2017111548 W CN2017111548 W CN 2017111548W WO 2019010892 A1 WO2019010892 A1 WO 2019010892A1
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ceramic membrane
membrane support
sintering
alumina
temperature
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PCT/CN2017/111548
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French (fr)
Chinese (zh)
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杨东亮
樊震坤
王磊
李泉
郭维娜
张伟
张超
张健
孟凡朋
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山东硅元新型材料股份有限公司
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Publication of WO2019010892A1 publication Critical patent/WO2019010892A1/en

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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
    • C04B35/10—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 aluminium oxide
    • 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
    • C04B35/62218—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products obtaining ceramic films, e.g. by using temporary supports
    • 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
    • C04B38/0051—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity
    • C04B38/0058—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof characterised by the pore size, pore shape or kind of porosity open porosity
    • 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
    • C04B2235/6562—Heating rate
    • 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
    • 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
    • C04B2235/9669—Resistance against chemicals, e.g. against molten glass or molten salts
    • C04B2235/9692—Acid, alkali or halogen resistance

Definitions

  • the invention relates to a preparation method of a high corrosion-resistant alumina ceramic membrane support, belonging to the technical field of ceramic membranes.
  • porous ceramic membrane Since the porous ceramic membrane was first applied in France in the 1980s, its high separation efficiency, high temperature resistance, solvent resistance, antimicrobial resistance, acid and alkali resistance, high mechanical strength and easy cleaning and regeneration have been gradually industrialized. It has been accepted and has been widely used. Inorganic ceramic membranes are used in gas separation, liquid separation and purification, and membrane reactors. They are widely used in the food industry, pharmaceutical and bioengineering, chemical and petrochemical industries, and environmental protection. At present, with the increasing demand for process industry energy conservation and emission reduction technologies worldwide, ceramic nanofiltration membranes, pervaporation membranes and gas separation membranes with nanostructures have become the research hotspots in the field of ceramic membranes and the important development direction in the future. One.
  • the porous ceramic membrane generally has a three-layer asymmetric structure, that is, a top layer, a transition layer, and a support layer that function as separation.
  • As the support layer it must have sufficient mechanical strength, high permeability, smooth surface and good acid and alkali resistance. The performance of the support directly affects the preparation of the subsequent porous ceramic membrane.
  • inorganic ceramic membrane supports are mostly made of alumina.
  • the inorganic ceramic membrane support can only reach a higher firing temperature (>1750°C). It has sufficient mechanical strength, high permeability, smooth surface and good acid and alkali resistance (the loss rate of acid and alkali corrosion resistance of domestic alumina support is ⁇ 10%).
  • the baking temperature of American Pall Company reaches 1800 ° C.
  • Ultra-high temperature sintering reduces the service life of the furnace by 60-70%; ultra-high temperature sintering requires heavy-duty high-temperature kiln with burning, low effective loading, short service life of kiln furniture, and high cost of kiln furniture. The high sintering cost has caused many support manufacturers to abandon the ultra-high temperature sintering process.
  • Ceramic membrane module in the process of use, on the one hand, due to the treatment of wastewater, waste liquid, there is long-term acid-base erosion; on the other hand, the cleaning ceramic membrane module uses a strong acid and alkali solution, there is a short-term strong acid and alkali corrosion. Therefore, the acid and alkali corrosion resistance of the ceramic membrane support is a key technical indicator that affects its service life and reliability of filtration performance.
  • An object of the present invention is to provide a method for preparing a highly corrosion-resistant alumina ceramic membrane support, which is effective for reducing the firing temperature of various molding processes and various appearance shapes of the alumina support, and significantly improving the above support The acid and alkali corrosion resistance of the body.
  • the preparation method of the high corrosion-resistant alumina ceramic membrane support body is characterized in that the alumina support is dried to a water content of ⁇ 2 wt%, and the rubber support is discharged at a low temperature of 1000-1200 ° C, and the alumina support after debinding is in a vacuum.
  • the product is sintered at a high temperature of 1550-1700 ° C under a pressurized atmosphere.
  • the alumina support is formed by grouting, dry pressing, plastic pressing, extrusion, and gel casting.
  • the alumina support is in the form of a sheet, a single tube, a multi-channel, a disk or a disk.
  • the weight of alumina is >90% by weight in the alumina support.
  • the kiln moisture of the alumina support is ⁇ 2 wt%.
  • the low temperature kiln used for low temperature debinding is continuous and intermittent, and the heating method is electric heating or gas heating.
  • the low temperature debinding time is 31-36 hours.
  • the high-temperature sintering kiln used for sintering is a vacuum atmosphere sintering furnace, and the heating method is electric heating and nitrogen gas is used for atmosphere protection.
  • the high temperature sintering time is 13-16 hours.
  • the vacuum atmosphere sintering furnace used for sintering is intermittent.
  • the present invention is applicable to a support having an alumina content (% by weight) of >90% by weight.
  • the continuous low temperature kiln is a roller kiln and a tunnel kiln
  • the intermittent low temperature kiln is a shuttle kiln.
  • the technical index test method of the invention is based on the marine industry standard of the People's Republic of China HY/T 064-2002 "Test Method for Tube Ceramic Microporous Membrane” and the National Standard of the People's Republic of China GB/T 1966-1996 "Polar Ceramic Porosity, Volumetric experimental method.
  • the invention adopts vacuum atmospheric pressure nitrogen gas atmosphere sintering, the sintering temperature of the alumina support body is reduced by 50-100 ° C, the firing time is shortened by 35-40%, the kiln furniture has long service life, and the comprehensive energy consumption is reduced by 30-50%.
  • the acid support corrosion resistance of the alumina support prepared by the invention is greatly improved, and the comparison is as follows:
  • Standard acid and alkali corrosion quality loss rate is 0.5%, and the acid loss and alkali corrosion quality loss rate of the invention is ⁇ 0.1%;
  • the present invention has the following beneficial effects:
  • the preparation method of the high corrosion-resistant alumina ceramic membrane support provided by the invention not only significantly improves the acid and alkali corrosion resistance of the product, but also has the service life of the kiln furniture is prolonged, the energy consumption is reduced, and the manufacturing cost is reduced by about 70%, which is a An innovative process route for the production of alumina ceramic membrane supports.
  • the preparation method of the high corrosion resistant alumina ceramic membrane support body is as follows:
  • the support body having an alumina content of 99% by weight was dried to a water content of 1.5% by weight.
  • the alumina support is formed by grouting, dry pressing, plastic pressing, extrusion, and gel casting.
  • the alumina support is in the shape of a disk.
  • the kiln moisture of the alumina support is ⁇ 2 wt%.
  • the low temperature furnace is continuous and the heating method is electric heating.
  • the high-temperature sintering kiln is a vacuum atmosphere sintering furnace, and the heating method is electric heating, and nitrogen gas is used for atmosphere protection.
  • the apparent porosity of the alumina support is 36%
  • the bending strength is 38 MPa
  • the acid loss quality loss rate is 0.05%
  • the alkali corrosion mass loss rate is 0.08%
  • the acid etching strength loss rate is measured. 1.80%
  • the alkali corrosion strength loss rate is 8.70%.
  • the preparation method of the high corrosion resistant alumina ceramic membrane support body is as follows:
  • the support body having an alumina content of 93% by weight was dried to a water content of 0.5% by weight.
  • the alumina support is formed by grouting, dry pressing, plastic pressing, extrusion, and gel casting.
  • the alumina support is in the form of a dish.
  • the kiln moisture of the alumina support is ⁇ 2 wt%.
  • the low temperature furnace is continuous and the heating method is electric heating.
  • the high-temperature sintering kiln is a vacuum atmosphere sintering furnace, and the heating method is electric heating, and nitrogen gas is used for atmosphere protection.
  • the apparent porosity of the alumina support is 50%
  • the bending strength is 35 MPa
  • the acid loss quality loss rate is 0.08%
  • the alkali corrosion mass loss rate is 0.10%
  • the acid etching strength loss rate is measured. 2.6%
  • the alkali corrosion strength loss rate was 6.8%.
  • the preparation method of the high corrosion resistant alumina ceramic membrane support body is as follows:
  • a support body having an alumina content of 97% by weight was dried to a water content of 1% by weight.
  • the alumina support is formed by grouting, dry pressing, plastic pressing, extrusion, and gel casting.
  • the alumina support is multi-channel.
  • the kiln moisture of the alumina support is ⁇ 2 wt%.
  • the low temperature furnace is continuous and the heating method is electric heating.
  • the high-temperature sintering kiln is a vacuum atmosphere sintering furnace, and the heating method is electric heating, and nitrogen gas is used for atmosphere protection.
  • the apparent porosity of the alumina support is 42%
  • the bending strength is 37 MPa
  • the acid loss quality loss rate is 0.06%
  • the alkali corrosion mass loss rate is 0.09%
  • the acid etching strength loss rate is measured. 2.0%
  • the alkali corrosion strength loss rate is 7.10%.
  • the preparation method of the high corrosion resistant alumina ceramic membrane support body is as follows:
  • the support body having an alumina content of 99% by weight was dried to a water content of 1.5% by weight.
  • the alumina support is formed by grouting, dry pressing, plastic pressing, extrusion, and gel casting.
  • the alumina support is a single tube.
  • the kiln moisture of the alumina support is ⁇ 2 wt%.
  • the low temperature furnace is continuous and the heating method is electric heating.
  • the high-temperature sintering kiln is a vacuum atmosphere sintering furnace, and the heating method is electric heating, and nitrogen gas is used for atmosphere protection.
  • the apparent porosity of the alumina support is 30%
  • the bending strength is 39 MPa
  • the acid loss quality loss rate is 0.02%
  • the alkali corrosion mass loss rate is 0.06%
  • the acid etching strength loss rate is measured. 1.2%
  • the alkali corrosion strength loss rate was 5.8%.
  • the preparation method of the high corrosion resistant alumina ceramic membrane support body is as follows:
  • the support body having an alumina content of 95% by weight was dried to a water content of 1% by weight.
  • the alumina support is formed by grouting, dry pressing, plastic pressing, extrusion, and gel casting.
  • the alumina support is in the form of a sheet.
  • the kiln moisture of the alumina support is ⁇ 2 wt%.
  • the low temperature furnace is continuous and the heating method is electric heating.
  • the high-temperature sintering kiln is a vacuum atmosphere sintering furnace, and the heating method is electric heating, and nitrogen gas is used for atmosphere protection.
  • the apparent porosity of the alumina support is 38%
  • the bending strength is 36 MPa
  • the acid loss quality loss rate is 0.05%
  • the alkali corrosion mass loss rate is 0.07%
  • the acid etching strength loss rate is measured. 2.2%
  • the alkali corrosion strength loss rate was 8.1%.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

A preparation method for a high corrosion-resistance aluminum oxide ceramic membrane support, comprising: drying an aluminum oxide support until the water content is less than 2 wt%, dumping at a low temperature of 1000-1200°C, and sintering the dumped aluminum oxide support at a high temperature of 1550-1700°C under vacuum and constant pressure atmosphere to obtain a product. According to the method, the acid and alkali resistance performance of the product is significantly improved, and the service life of a kiln furniture is prolonged; energy consumption is reduced, and the manufacturing cost is reduced by about 70%, and the method is an innovative process route for producing the aluminum oxide ceramic membrane support.

Description

高耐腐蚀性氧化铝陶瓷膜支撑体的制备方法Method for preparing highly corrosion-resistant alumina ceramic membrane support 技术领域Technical field
本发明涉及一种高耐腐蚀性氧化铝陶瓷膜支撑体的制备方法，属于陶瓷膜技术领域。The invention relates to a preparation method of a high corrosion-resistant alumina ceramic membrane support, belonging to the technical field of ceramic membranes.
背景技术Background technique
自从20世纪80年代多孔陶瓷膜首先在法国工业化应用以来，其所具有的高分离效率、耐高温、耐溶剂、抗微生物、耐酸碱性、高机械强度及易清洗再生等优异性能逐渐被工业界接受并已得到了广泛应用。无机陶瓷膜用于气体分离、液体分离净化和膜反应器，在食品工业、制药与生物工程、化学与石油化工工业以及环境保护等领域均有广泛的应用。当前，随着世界范围对过程工业节能减排技术需求的日益提高，具有纳米结构的陶瓷纳滤膜、渗透气化膜和气体分离膜已成为陶瓷膜领域的研究热点和未来重要的发展方向之一。Since the porous ceramic membrane was first applied in France in the 1980s, its high separation efficiency, high temperature resistance, solvent resistance, antimicrobial resistance, acid and alkali resistance, high mechanical strength and easy cleaning and regeneration have been gradually industrialized. It has been accepted and has been widely used. Inorganic ceramic membranes are used in gas separation, liquid separation and purification, and membrane reactors. They are widely used in the food industry, pharmaceutical and bioengineering, chemical and petrochemical industries, and environmental protection. At present, with the increasing demand for process industry energy conservation and emission reduction technologies worldwide, ceramic nanofiltration membranes, pervaporation membranes and gas separation membranes with nanostructures have become the research hotspots in the field of ceramic membranes and the important development direction in the future. One.
多孔陶瓷膜一般具有三层非对称结构，即由起分离作用的顶层、过渡层和支撑层。作为支撑层须具有足够的机械强度、较高的渗透性能、表面光滑和较好的耐酸碱性能。支撑体性能的好坏直接影响后续多孔陶瓷膜的制备。The porous ceramic membrane generally has a three-layer asymmetric structure, that is, a top layer, a transition layer, and a support layer that function as separation. As the support layer, it must have sufficient mechanical strength, high permeability, smooth surface and good acid and alkali resistance. The performance of the support directly affects the preparation of the subsequent porous ceramic membrane.
目前，国内外无机陶瓷膜支撑体多采用氧化铝材质，当配方中氧化铝的重量百分比不低于99wt％时，无机陶瓷膜支撑体只有达到较高的烧成温度(>1750℃)，才能拥有足够的机械强度、较高的渗透性能、表面光滑和较好的耐酸碱性能(国内氧化铝支撑体耐酸碱腐蚀强度损失率均≥10％)，例如美国Pall公司其烧成温度达到1800℃。超高温烧结使窑炉使用寿命降低了60-70％；超高温烧结需要重质高温窑具装烧，有效装载量低，窑具材料使用寿命短，窑具损耗费用高。高昂的烧结成本，使很多支撑体生产厂家放弃了超高温烧结的工艺路线。At present, inorganic ceramic membrane supports are mostly made of alumina. When the weight percentage of alumina in the formulation is not less than 99wt%, the inorganic ceramic membrane support can only reach a higher firing temperature (>1750°C). It has sufficient mechanical strength, high permeability, smooth surface and good acid and alkali resistance (the loss rate of acid and alkali corrosion resistance of domestic alumina support is ≥10%). For example, the baking temperature of American Pall Company reaches 1800 ° C. Ultra-high temperature sintering reduces the service life of the furnace by 60-70%; ultra-high temperature sintering requires heavy-duty high-temperature kiln with burning, low effective loading, short service life of kiln furniture, and high cost of kiln furniture. The high sintering cost has caused many support manufacturers to abandon the ultra-high temperature sintering process.
为达到工业化使用的机械强度，很多厂家在配方中添加1-8wt％的促烧结剂，使支撑体的烧结温度降低到1650℃以下。机械强度虽然达到标准，但支撑体的耐酸碱腐蚀性能大幅度降低，耐酸碱强度损失率在25-80％之间，使膜组件的使用寿命大幅降低。In order to achieve the mechanical strength of industrial use, many manufacturers add 1-8 wt% of a sintering aid to the formulation to lower the sintering temperature of the support to below 1650 °C. Although the mechanical strength meets the standard, the acid-base corrosion resistance of the support is greatly reduced, and the acid-base strength loss rate is between 25 and 80%, which greatly reduces the service life of the membrane module.
陶瓷膜组件，在使用过程中，一方面，由于处理的是废水、废液，存在长期的酸碱侵蚀；另一方面，清洗陶瓷膜组件采用强酸强碱溶液，存在短期强酸强碱的侵蚀。因此，陶瓷膜支撑体的耐酸碱腐蚀性能，是影响其使用寿命和过滤性能可靠性的关键性技术指标。Ceramic membrane module, in the process of use, on the one hand, due to the treatment of wastewater, waste liquid, there is long-term acid-base erosion; on the other hand, the cleaning ceramic membrane module uses a strong acid and alkali solution, there is a short-term strong acid and alkali corrosion. Therefore, the acid and alkali corrosion resistance of the ceramic membrane support is a key technical indicator that affects its service life and reliability of filtration performance.
发明内容Summary of the invention
本发明的目的是提供一种高耐腐蚀性氧化铝陶瓷膜支撑体的制备方法，该方法有效地降低各种成型工艺和各种外观形状的氧化铝支撑体的烧成温度，显著提高上述支撑体的耐酸碱腐蚀性能。 An object of the present invention is to provide a method for preparing a highly corrosion-resistant alumina ceramic membrane support, which is effective for reducing the firing temperature of various molding processes and various appearance shapes of the alumina support, and significantly improving the above support The acid and alkali corrosion resistance of the body.
所述的高耐腐蚀性氧化铝陶瓷膜支撑体的制备方法，将氧化铝支撑体干燥至含水量<2wt％，在1000-1200℃低温排胶，排胶后的氧化铝支撑体在真空常压气氛下，1550-1700℃高温烧结得产品。The preparation method of the high corrosion-resistant alumina ceramic membrane support body is characterized in that the alumina support is dried to a water content of <2 wt%, and the rubber support is discharged at a low temperature of 1000-1200 ° C, and the alumina support after debinding is in a vacuum. The product is sintered at a high temperature of 1550-1700 ° C under a pressurized atmosphere.
低温排胶，高温气氛烧结，适用于各种成型工艺和各种外观形状的氧化铝支撑体。Low temperature debinding, high temperature atmosphere sintering, suitable for various molding processes and various appearances of alumina support.
氧化铝支撑体通过注浆、干压、塑压、挤出和凝胶注成型。The alumina support is formed by grouting, dry pressing, plastic pressing, extrusion, and gel casting.
氧化铝支撑体为片状、单管、多通道、碟片形或盘形。The alumina support is in the form of a sheet, a single tube, a multi-channel, a disk or a disk.
氧化铝的重量在氧化铝支撑体中的重量百分比>90wt％。The weight of alumina is >90% by weight in the alumina support.
氧化铝支撑体的入窑水分<2wt％。The kiln moisture of the alumina support is <2 wt%.
低温排胶采用的低温窑炉为连续性和或间歇式，加热方式采用电加热和或燃气加热。The low temperature kiln used for low temperature debinding is continuous and intermittent, and the heating method is electric heating or gas heating.
低温排胶时间为31-36小时。The low temperature debinding time is 31-36 hours.
烧结采用的高温烧结窑炉为真空气氛烧结炉，加热方式采用电加热，充氮气进行气氛保护。The high-temperature sintering kiln used for sintering is a vacuum atmosphere sintering furnace, and the heating method is electric heating and nitrogen gas is used for atmosphere protection.
高温烧结时间13-16小时。The high temperature sintering time is 13-16 hours.
烧结采用的真空气氛烧结炉为间歇式。The vacuum atmosphere sintering furnace used for sintering is intermittent.
本发明适用于氧化铝含量(重量百分比)>90wt％的支撑体。The present invention is applicable to a support having an alumina content (% by weight) of >90% by weight.
连续性低温窑炉为辊道窑、隧道窑，间歇式低温窑炉为梭式窑。The continuous low temperature kiln is a roller kiln and a tunnel kiln, and the intermittent low temperature kiln is a shuttle kiln.
本发明技术指标测试方法，依据中华人民共和国海洋行业标准HY/T 064-2002《管式陶瓷微孔滤膜测试方法》和中华人民共和国国家标准GB/T 1966-1996《多孔陶瓷显气孔率、容重实验方法》。The technical index test method of the invention is based on the marine industry standard of the People's Republic of China HY/T 064-2002 "Test Method for Tube Ceramic Microporous Membrane" and the National Standard of the People's Republic of China GB/T 1966-1996 "Polar Ceramic Porosity, Volumetric experimental method.
本发明采用真空常压充氮气气氛烧结，氧化铝支撑体的烧结温度降低了50-100℃，烧成时间缩短了35-40％，窑具使用寿命长，综合能耗降低了30-50％，该发明制备的氧化铝支撑体耐酸碱腐蚀性能大幅度提高，对比如下：The invention adopts vacuum atmospheric pressure nitrogen gas atmosphere sintering, the sintering temperature of the alumina support body is reduced by 50-100 ° C, the firing time is shortened by 35-40%, the kiln furniture has long service life, and the comprehensive energy consumption is reduced by 30-50%. The acid support corrosion resistance of the alumina support prepared by the invention is greatly improved, and the comparison is as follows:
(1)标准：耐酸、碱腐蚀质量损失率0.5％，本发明耐酸、碱腐蚀质量损失率≤0.1％；(1) Standard: acid and alkali corrosion quality loss rate is 0.5%, and the acid loss and alkali corrosion quality loss rate of the invention is ≤0.1%;
(2)标准：耐酸、碱腐蚀强度损失率10％，本发明耐酸腐蚀强度损失率≤3％，耐碱腐蚀强度损失率≤9％。(2) Standard: acid and alkali corrosion strength loss rate is 10%, acid corrosion resistance loss rate ≤ 3%, and alkali corrosion resistance loss rate ≤ 9%.
与现有技术相比，本发明具有以下有益效果：Compared with the prior art, the present invention has the following beneficial effects:
本发明提供的高耐腐蚀性氧化铝陶瓷膜支撑体的制备方法，不仅显著提高了产品的耐酸碱腐蚀性能，而且窑具使用寿命延长，能耗降低，制造成本降低70％左右，是一种生产氧化铝陶瓷膜支撑体的创新工艺路线。The preparation method of the high corrosion-resistant alumina ceramic membrane support provided by the invention not only significantly improves the acid and alkali corrosion resistance of the product, but also has the service life of the kiln furniture is prolonged, the energy consumption is reduced, and the manufacturing cost is reduced by about 70%, which is a An innovative process route for the production of alumina ceramic membrane supports.
具体实施方式 Detailed ways
下面结合实施例对本发明作进一步的说明。The present invention will be further described below in conjunction with the embodiments.
实施例1Example 1
高耐腐蚀性氧化铝陶瓷膜支撑体的制备方法，步骤如下：The preparation method of the high corrosion resistant alumina ceramic membrane support body is as follows:
(1)将氧化铝含量为99wt％的支撑体坯体干燥至含水量1.5wt％。(1) The support body having an alumina content of 99% by weight was dried to a water content of 1.5% by weight.
(2)在5M3燃气梭式窑1200℃低温排胶，升温速率0.6℃/min，保温时间2小时。(2) Discharge at 1200 °C in 5M3 gas shuttle kiln at a low temperature of 0.6 °C/min and hold for 2 hours.
(3)在1M3真空常压气氛烧结炉高温烧结，烧结温度1700℃，升温速率2℃/min，保温时间1.5小时。(3) High temperature sintering in a 1M3 vacuum atmospheric pressure sintering furnace, sintering temperature 1700 ° C, heating rate 2 ° C / min, holding time 1.5 hours.
氧化铝支撑体通过注浆、干压、塑压、挤出和凝胶注成型。The alumina support is formed by grouting, dry pressing, plastic pressing, extrusion, and gel casting.
氧化铝支撑体为盘形。The alumina support is in the shape of a disk.
氧化铝支撑体的入窑水分<2wt％。The kiln moisture of the alumina support is <2 wt%.
低温窑炉为连续性，加热方式采用电加热。The low temperature furnace is continuous and the heating method is electric heating.
高温烧结窑炉为真空气氛烧结炉，加热方式采用电加热，充氮气进行气氛保护。The high-temperature sintering kiln is a vacuum atmosphere sintering furnace, and the heating method is electric heating, and nitrogen gas is used for atmosphere protection.
根据本发明所述技术指标测试方法，测试出氧化铝支撑体的显气孔率为36％，弯曲强度为38MPa，酸蚀质量损失率0.05％，碱蚀质量损失率0.08％，酸蚀强度损失率1.80％，碱蚀强度损失率8.70％。According to the technical index test method of the present invention, the apparent porosity of the alumina support is 36%, the bending strength is 38 MPa, the acid loss quality loss rate is 0.05%, the alkali corrosion mass loss rate is 0.08%, and the acid etching strength loss rate is measured. 1.80%, the alkali corrosion strength loss rate is 8.70%.
实施例2Example 2
高耐腐蚀性氧化铝陶瓷膜支撑体的制备方法，步骤如下：The preparation method of the high corrosion resistant alumina ceramic membrane support body is as follows:
(1)将氧化铝含量为93wt％的支撑体坯体干燥至含水量0.5wt％。(1) The support body having an alumina content of 93% by weight was dried to a water content of 0.5% by weight.
(2)在3M3燃气梭式窑1000℃低温排胶，升温速率0.5℃/min，保温时间1小时。(2) Discharge at a low temperature of 1000 ° C in a 3M3 gas shuttle kiln at a heating rate of 0.5 ° C / min and a holding time of 1 hour.
(3)在1M3真空常压气氛烧结炉高温烧结，烧结温度1550℃，升温速率2℃/min，保温时间0.5小时。(3) Sintering at a high temperature in a 1M3 vacuum atmospheric pressure sintering furnace at a sintering temperature of 1550 ° C, a heating rate of 2 ° C / min, and a holding time of 0.5 hours.
氧化铝支撑体通过注浆、干压、塑压、挤出和凝胶注成型。The alumina support is formed by grouting, dry pressing, plastic pressing, extrusion, and gel casting.
氧化铝支撑体为碟片形。The alumina support is in the form of a dish.
氧化铝支撑体的入窑水分<2wt％。The kiln moisture of the alumina support is <2 wt%.
低温窑炉为连续性，加热方式采用电加热。The low temperature furnace is continuous and the heating method is electric heating.
高温烧结窑炉为真空气氛烧结炉，加热方式采用电加热，充氮气进行气氛保护。The high-temperature sintering kiln is a vacuum atmosphere sintering furnace, and the heating method is electric heating, and nitrogen gas is used for atmosphere protection.
根据本发明所述技术指标测试方法，测试出氧化铝支撑体的显气孔率为50％，弯曲强度为35MPa，酸蚀质量损失率0.08％，碱蚀质量损失率0.10％，酸蚀强度损失率2.6％，碱蚀强度损失率6.8％。According to the technical index test method of the present invention, the apparent porosity of the alumina support is 50%, the bending strength is 35 MPa, the acid loss quality loss rate is 0.08%, the alkali corrosion mass loss rate is 0.10%, and the acid etching strength loss rate is measured. 2.6%, the alkali corrosion strength loss rate was 6.8%.
实施例3 Example 3
高耐腐蚀性氧化铝陶瓷膜支撑体的制备方法，步骤如下：The preparation method of the high corrosion resistant alumina ceramic membrane support body is as follows:
(1)将氧化铝含量为97wt％的支撑体坯体干燥至含水量1wt％。(1) A support body having an alumina content of 97% by weight was dried to a water content of 1% by weight.
(2)在3M3燃气梭式窑1100℃低温排胶，升温速率0.6℃/min，保温时间0.5小时。(2) Discharge at 1100 °C in 3M3 gas shuttle kiln at a low temperature of 0.6 °C/min and a holding time of 0.5 hours.
(3)在1M3真空常压气氛烧结炉高温烧结，烧结温度1650℃，升温速率2℃/min，保温时间2小时。(3) High temperature sintering in a 1M3 vacuum atmospheric pressure sintering furnace, sintering temperature 1650 ° C, heating rate 2 ° C / min, holding time 2 hours.
氧化铝支撑体通过注浆、干压、塑压、挤出和凝胶注成型。The alumina support is formed by grouting, dry pressing, plastic pressing, extrusion, and gel casting.
氧化铝支撑体为多通道。The alumina support is multi-channel.
氧化铝支撑体的入窑水分<2wt％。The kiln moisture of the alumina support is <2 wt%.
低温窑炉为连续性，加热方式采用电加热。The low temperature furnace is continuous and the heating method is electric heating.
高温烧结窑炉为真空气氛烧结炉，加热方式采用电加热，充氮气进行气氛保护。The high-temperature sintering kiln is a vacuum atmosphere sintering furnace, and the heating method is electric heating, and nitrogen gas is used for atmosphere protection.
根据本发明所述技术指标测试方法，测试出氧化铝支撑体的显气孔率为42％，弯曲强度为37MPa，酸蚀质量损失率0.06％，碱蚀质量损失率0.09％，酸蚀强度损失率2.0％，碱蚀强度损失率7.10％。According to the technical index test method of the present invention, the apparent porosity of the alumina support is 42%, the bending strength is 37 MPa, the acid loss quality loss rate is 0.06%, the alkali corrosion mass loss rate is 0.09%, and the acid etching strength loss rate is measured. 2.0%, the alkali corrosion strength loss rate is 7.10%.
实施例4Example 4
高耐腐蚀性氧化铝陶瓷膜支撑体的制备方法，步骤如下：The preparation method of the high corrosion resistant alumina ceramic membrane support body is as follows:
(1)将氧化铝含量为99wt％的支撑体坯体干燥至含水量1.5wt％。(1) The support body having an alumina content of 99% by weight was dried to a water content of 1.5% by weight.
(2)在5M3燃气梭式窑1200℃低温排胶，升温速率0.58℃/min，保温时1.5小时。(2) Discharge at 1200 °C in 5M3 gas shuttle kiln at a low temperature of 0.58 °C/min and 1.5 hours at the time of heat preservation.
(3)在1M3真空常压气氛烧结炉高温烧结，烧结温度1700℃，升温速率2℃/min，保温时间1.5小时。(3) High temperature sintering in a 1M3 vacuum atmospheric pressure sintering furnace, sintering temperature 1700 ° C, heating rate 2 ° C / min, holding time 1.5 hours.
氧化铝支撑体通过注浆、干压、塑压、挤出和凝胶注成型。The alumina support is formed by grouting, dry pressing, plastic pressing, extrusion, and gel casting.
氧化铝支撑体为单管。The alumina support is a single tube.
氧化铝支撑体的入窑水分<2wt％。The kiln moisture of the alumina support is <2 wt%.
低温窑炉为连续性，加热方式采用电加热。The low temperature furnace is continuous and the heating method is electric heating.
高温烧结窑炉为真空气氛烧结炉，加热方式采用电加热，充氮气进行气氛保护。The high-temperature sintering kiln is a vacuum atmosphere sintering furnace, and the heating method is electric heating, and nitrogen gas is used for atmosphere protection.
根据本发明所述技术指标测试方法，测试出氧化铝支撑体的显气孔率为30％，弯曲强度为39MPa，酸蚀质量损失率0.02％，碱蚀质量损失率0.06％，酸蚀强度损失率1.2％，碱蚀强度损失率5.8％。According to the technical index test method of the present invention, the apparent porosity of the alumina support is 30%, the bending strength is 39 MPa, the acid loss quality loss rate is 0.02%, the alkali corrosion mass loss rate is 0.06%, and the acid etching strength loss rate is measured. 1.2%, the alkali corrosion strength loss rate was 5.8%.
实施例5Example 5
高耐腐蚀性氧化铝陶瓷膜支撑体的制备方法，步骤如下：The preparation method of the high corrosion resistant alumina ceramic membrane support body is as follows:
(1)将氧化铝含量为95wt％的支撑体坯体干燥至含水量1wt％。 (1) The support body having an alumina content of 95% by weight was dried to a water content of 1% by weight.
(2)在3M3燃气梭式窑1100℃低温排胶，升温速率0.55℃/min，保温时1小时。(2) Discharge at 1100 °C in 3M3 gas shuttle kiln at a low temperature of 0.55 °C/min and hold for 1 hour.
(3)在1M3真空常压气氛烧结炉高温烧结，烧结温度1600℃，升温速率2℃/min，保温时间2小时。(3) High temperature sintering in a 1M3 vacuum atmospheric pressure sintering furnace, sintering temperature 1600 ° C, heating rate 2 ° C / min, holding time 2 hours.
氧化铝支撑体通过注浆、干压、塑压、挤出和凝胶注成型。The alumina support is formed by grouting, dry pressing, plastic pressing, extrusion, and gel casting.
氧化铝支撑体为片状。The alumina support is in the form of a sheet.
氧化铝支撑体的入窑水分<2wt％。The kiln moisture of the alumina support is <2 wt%.
低温窑炉为连续性，加热方式采用电加热。The low temperature furnace is continuous and the heating method is electric heating.
高温烧结窑炉为真空气氛烧结炉，加热方式采用电加热，充氮气进行气氛保护。The high-temperature sintering kiln is a vacuum atmosphere sintering furnace, and the heating method is electric heating, and nitrogen gas is used for atmosphere protection.
根据本发明所述技术指标测试方法，测试出氧化铝支撑体的显气孔率为38％，弯曲强度为36MPa，酸蚀质量损失率0.05％，碱蚀质量损失率0.07％，酸蚀强度损失率2.2％，碱蚀强度损失率8.1％。According to the technical index test method of the present invention, the apparent porosity of the alumina support is 38%, the bending strength is 36 MPa, the acid loss quality loss rate is 0.05%, the alkali corrosion mass loss rate is 0.07%, and the acid etching strength loss rate is measured. 2.2%, the alkali corrosion strength loss rate was 8.1%.
本发明获得的产品检测技术指标与市售产品性能对比见表1。The performance comparison between the product testing technical indicators obtained by the present invention and the commercially available products is shown in Table 1.
表1、产品检测技术指标表Table 1, product testing technical indicator table
性能指标Performance 本发明this invention 市售产品1Commercial products 1 市售产品2Commercial products 2 市售产品3Commercial products 3
氧化铝含量(wt％)Alumina content (wt%) ≥99≥99 9999 9595 9696
显气孔率(％)Apparent porosity(%) 30-5030-50 3535 4848 3232
弯曲强度(MPa)Bending strength (MPa) ≥35≥35 3535 3333 3636
酸蚀质量损失率(％)Acid erosion quality loss rate (%) ≤0.1≤0.1 0.50.5 0.20.2 0.30.3
碱蚀质量损失率(％)Alkali corrosion mass loss rate (%) ≤0.1≤0.1 0.50.5 4.54.5 0.40.4
酸蚀强度损失率(％)Acid erosion strength loss rate (%) ≤3≤3 1010 44 1616
碱蚀强度损失率(％)Alkali corrosion strength loss rate (%) ≤9≤9 1010 8080 21twenty one
从表1中明显看出，本发明的显气孔率和弯曲强度与同类型产品相当，耐酸碱腐蚀性能明显优于同类型产品。 It is apparent from Table 1 that the apparent porosity and flexural strength of the present invention are comparable to those of the same type, and the acid and alkali corrosion resistance is significantly superior to the same type of product.

Claims (10)

  1. 一种高耐腐蚀性氧化铝陶瓷膜支撑体的制备方法，其特征在于，将氧化铝支撑体干燥至含水量<2wt％，在1000-1200℃低温排胶，排胶后的氧化铝支撑体在真空常压气氛下，1550-1700℃高温烧结得产品。A method for preparing a highly corrosion-resistant alumina ceramic membrane support, characterized in that the alumina support is dried to a water content of <2 wt%, and the aluminum oxide support is discharged at a low temperature of 1000-1200 ° C. The product is sintered at a high temperature of 1550-1700 ° C under a vacuum atmosphere.
  2. 根据权利要求1所述的高耐腐蚀性氧化铝陶瓷膜支撑体的制备方法，其特征在于，氧化铝支撑体通过注浆、干压、塑压、挤出和凝胶注成型。The method for producing a highly corrosion-resistant alumina ceramic membrane support according to claim 1, wherein the alumina support is formed by grouting, dry pressing, plastic pressing, extrusion, and gel casting.
  3. 根据权利要求1所述的高耐腐蚀性氧化铝陶瓷膜支撑体的制备方法，其特征在于，氧化铝支撑体为片状、单管、多通道、碟片形或盘形。The method for producing a highly corrosion-resistant alumina ceramic membrane support according to claim 1, wherein the alumina support is in the form of a sheet, a single tube, a multichannel, a disk or a disk.
  4. 根据权利要求1所述的高耐腐蚀性氧化铝陶瓷膜支撑体的制备方法，其特征在于，氧化铝的重量在氧化铝支撑体中的重量百分比>90wt％。A method of producing a highly corrosion-resistant alumina ceramic membrane support according to claim 1, wherein the weight of alumina is >90% by weight in the alumina support.
  5. 根据权利要求1所述的高耐腐蚀性氧化铝陶瓷膜支撑体的制备方法，其特征在于，氧化铝支撑体的入窑水分<2wt％。The method for producing a highly corrosion-resistant alumina ceramic membrane support according to claim 1, wherein the alumina support has a kiln moisture content of <2 wt%.
  6. 根据权利要求1所述的高耐腐蚀性氧化铝陶瓷膜支撑体的制备方法，其特征在于，低温排胶采用的低温窑炉为连续性和或间歇式，加热方式采用电加热和或燃气加热。The method for preparing a highly corrosion-resistant alumina ceramic membrane support according to claim 1, wherein the low-temperature furnace used for low-temperature debinding is continuous and intermittent, and the heating method is electric heating or gas heating. .
  7. 根据权利要求1所述的高耐腐蚀性氧化铝陶瓷膜支撑体的制备方法，其特征在于，低温排胶时间为31-36小时。The method for producing a highly corrosion-resistant alumina ceramic membrane support according to claim 1, wherein the low-temperature discharge time is from 31 to 36 hours.
  8. 根据权利要求1所述的高耐腐蚀性氧化铝陶瓷膜支撑体的制备方法，其特征在于，烧结采用的高温烧结窑炉为真空气氛烧结炉，加热方式采用电加热，充氮气进行气氛保护。The method for preparing a highly corrosion-resistant alumina ceramic membrane support according to claim 1, wherein the high-temperature sintering kiln for sintering is a vacuum atmosphere sintering furnace, and the heating method is electric heating and nitrogen gas is used for atmosphere protection.
  9. 根据权利要求1所述的高耐腐蚀性氧化铝陶瓷膜支撑体的制备方法，其特征在于，高温烧结时间13-16小时。The method for producing a highly corrosion-resistant alumina ceramic membrane support according to claim 1, wherein the high-temperature sintering time is 13 to 16 hours.
  10. 根据权利要求9所述的高耐腐蚀性氧化铝陶瓷膜支撑体的制备方法，其特征在于，烧结采用的真空气氛烧结炉为间歇式。 The method for producing a highly corrosion-resistant alumina ceramic membrane support according to claim 9, wherein the vacuum atmosphere sintering furnace used for sintering is a batch type.
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CN104072111A (en) * 2013-03-29 2014-10-01 北京市理化分析测试中心 Preparation method of aluminium oxide honeycomb ceramics
CN103342543A (en) * 2013-06-28 2013-10-09 珠海微晶新材料科技有限公司 LED ceramic baseplate and preparation method thereof

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