CN115215672B - Preparation method of mullite whisker-based ceramic fiber membrane - Google Patents
Preparation method of mullite whisker-based ceramic fiber membrane Download PDFInfo
- Publication number
- CN115215672B CN115215672B CN202211043180.2A CN202211043180A CN115215672B CN 115215672 B CN115215672 B CN 115215672B CN 202211043180 A CN202211043180 A CN 202211043180A CN 115215672 B CN115215672 B CN 115215672B
- Authority
- CN
- China
- Prior art keywords
- mullite
- powder
- whisker
- ceramic fiber
- aluminum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- 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
- C04B35/71—Ceramic products containing macroscopic reinforcing agents
- C04B35/78—Ceramic products containing macroscopic reinforcing agents containing non-metallic materials
- C04B35/80—Fibres, filaments, whiskers, platelets, or the like
-
- 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
- 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
- C04B38/06—Porous mortars, concrete, artificial stone or ceramic ware; Preparation thereof by burning-out added substances by burning natural expanding materials or by sublimating or melting out added substances
- C04B38/063—Preparing or treating the raw materials individually or as batches
- C04B38/0635—Compounding ingredients
- C04B38/0645—Burnable, meltable, sublimable materials
- C04B38/068—Carbonaceous materials, e.g. coal, carbon, graphite, hydrocarbons
-
- 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
- C04B2235/32—Metal oxides, mixed metal oxides, or oxide-forming salts thereof, e.g. carbonates, nitrates, (oxy)hydroxides, chlorides
- C04B2235/3217—Aluminum oxide or oxide forming salts thereof, e.g. bauxite, alpha-alumina
- C04B2235/3218—Aluminium (oxy)hydroxides, e.g. boehmite, gibbsite, alumina sol
-
- 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
- C04B2235/02—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
- C04B2235/349—Clays, e.g. bentonites, smectites such as montmorillonite, vermiculites or kaolines, e.g. illite, talc or sepiolite
-
- 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
- C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
- C04B2235/422—Carbon
-
- 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
- C04B2235/44—Metal salt constituents or additives chosen for the nature of the anions, e.g. hydrides or acetylacetonate
- C04B2235/444—Halide containing anions, e.g. bromide, iodate, chlorite
- C04B2235/445—Fluoride containing anions, e.g. fluosilicate
-
- 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
- C04B2235/50—Constituents or additives of the starting mixture chosen for their shape or used because of their shape or their physical appearance
- C04B2235/52—Constituents or additives characterised by their shapes
- C04B2235/5208—Fibers
- C04B2235/5216—Inorganic
- C04B2235/522—Oxidic
- C04B2235/5228—Silica and alumina, including aluminosilicates, e.g. mullite
-
- 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
- C04B2235/65—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
- C04B2235/6565—Cooling 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
- C04B2235/65—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
- C04B2235/6567—Treatment time
-
- 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
- C04B2235/74—Physical characteristics
- C04B2235/77—Density
-
- 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
Abstract
The invention discloses a preparation method of a mullite whisker-based ceramic fiber film, which takes mullite fiber as a main material, synchronously adds sintering aid, active carbon, aluminum-silicon sol and aluminum fluoride to prepare active powder, obtains a whisker film blank by a dry pressing molding method, and then obtains an asymmetric mullite whisker-based ceramic film by heat treatment. Mullite is the most stable aluminum-silicon compound, has a series of advantages of high temperature resistance, chemical corrosion resistance, high mechanical strength and the like, and the ceramic fiber membrane prepared by the method can meet the application of gas-solid separation in severe environments. Meanwhile, the membrane layer formed by the staggered whiskers not only reduces the phenomenon of infiltration, but also increases the contact area with dust-containing air flow in subsequent application, and improves the interception performance of the ceramic fiber membrane on nanoscale dust particles.
Description
Technical Field
The invention relates to a preparation method of a mullite whisker-based ceramic fiber membrane, which is applied to the preparation of a mullite whisker-based ceramic fiber membrane with low cost and high performance for gas-solid separation, and belongs to the field of membrane material preparation.
Background
In the face of generating a large amount of high-temperature dust-containing smoke in the traditional industries of chemical industry, energy source, metallurgy and the like, a ceramic fiber membrane prepared by taking ceramic fiber as a framework material is called one of ideal materials with high performance of a high-temperature smoke filter due to high porosity, good air permeability and excellent heat shock resistance. However, the biggest problem in ceramic fiber membrane applications is its low strength, particulate infiltration and susceptibility to breakage during long-term filtration dust removal and blowback ash removal. Therefore, the ceramic fiber membrane with high strength is developed, and has wide application prospect in the field of high-temperature flue gas purification.
Mullite is used as a stable aluminum-silicon compound, has the characteristics of high temperature resistance, chemical corrosion resistance, high mechanical strength and the like, can meet the application requirements in severe environments, and is considered as one of excellent materials for preparing ceramic fiber filtering membranes with high porosity and high air permeability.
In order to fully exert the function of mullite whisker in a ceramic fiber membrane, the structural advantage of high length-diameter ratio of the fiber is required to be fully exerted, the preparation process is optimized, the growth of mullite whisker on the fiber surface is promoted by adjusting the content of aluminum fluoride in a closed system, the change of the microporous structure of the whisker membrane is researched, and thus an asymmetric whisker membrane is prepared, and the stability of interface combination and the filtering performance of submicron dust are tested. Yang [ J Ceramics International, 2018, 44 (11) ] et al adopts vacuum filtration technology to prepare mullite fiber porous ceramic products, then uses zirconia sol as inorganic binder, and soaks the obtained sample in the sol in a vacuum impregnation mode, and the result shows that the addition of zirconia sol improves the compressive strength of the ceramic fiber products from 0.62 MPa to 3.44MPa. Jia [ J Ceramics International, 2019, 45 (2): 2474-2482] et al introduced propylene oxide to promote crosslinking of the organic molecules and thus more uniform distribution within the fibrous porous ceramic. The result shows that the addition of the propylene oxide effectively consolidates the mullite fiber skeleton and is beneficial to obtaining a uniform porous fiber structure. In addition, compared with mullite fiber porous ceramic prepared by adding no propylene oxide, the compressive strength of the mullite fiber porous ceramic is improved from 0.868 MPa to 1.489 MPa. Xu et al [ J Ceramics International, 2017, 43 (1): 228-233] using a gel casting method, adding mullite fiber and a sintering aid to a tertiary butanol-based gel premix solution, and polymerizing an organic monomer under the action of an initiator to solidify the slurry, thereby obtaining a green compact of high strength. And simultaneously, the thermal performance and the mechanical performance of the fiber porous ceramic material prepared by taking the silicon powder, the silicon dioxide powder and the boron-silicon mixture as sintering aids are examined.
Disclosure of Invention
The invention aims to improve the defects of the prior art and provides the preparation of an asymmetric ceramic fiber membrane by replacing common mullite short fibers with mullite fiber powder with low length-diameter ratio, and the problem of easy aggregation and difficult dispersion caused by the mullite short fibers is solved by using the mullite fiber powder with low length-diameter ratio. The mullite fiber powder is low in cost and good in dispersibility, and the prepared film layer has a higher pore structure, so that dust particles are trapped more easily.
The technical scheme of the invention is as follows: a preparation method of a mullite fiber-based asymmetric ceramic fiber membrane with low cost comprises the following specific steps: dispersing mullite fiber in water, fully stirring and drying to obtain mullite fiber powder with good dispersibility, mixing and grinding the mullite fiber powder, a composite sintering aid and activated carbon powder according to a certain proportion to obtain support powder, adding a binder, grinding uniformly again, and then carrying out dry pressing molding to obtain a mullite-based support; and B, uniformly coating mullite fibers by using an aluminum-silicon sol, putting the aluminum-silicon sol into an oven to dry the moisture of the aluminum-silicon sol, grinding the aluminum-silicon sol, a composite sintering aid, a pore-forming agent and a binder to prepare film active powder, removing agglomerated large particles by a 40-mesh standard sieve to obtain the film active powder with uniform size, pressing and forming the film active powder and a support together by using a certain pressure, and drying, sintering and the like to obtain the asymmetrical mullite whisker-based ceramic fiber film.
Preferably, the mullite fiber for preparing the mullite-based support powder and the additive amount of the composite sintering aid in the step A are prepared, wherein the composite sintering aid consists of kaolin and potassium feldspar, and the mass ratio of the kaolin to the potassium feldspar is 1:2, and the mullite fiber is prepared by the following steps: activated carbon powder: the mass ratio of the composite sintering auxiliary agent is as follows: (1-1.4): 1: (0.4-0.8).
Preferably, the mullite fiber in the membrane active powder material is mullite fiber powder with low length-diameter ratio (length-diameter ratio is 20) or common mullite short fiber (length-diameter ratio is 100);
preferably, the average particle size of the nano particles in the aluminum-silicon sol in the step B is 160nm; the mass ratio of the prepared film active powder is as follows: mullite fiber: activated carbon powder: composite sintering auxiliary agent: aluminum-silicon sol: aluminum fluoride = 1.3:1:0.5: (0.65-1.235): (0.56-2.52).
Preferably, the mass fraction of the binder polyvinyl alcohol in the step A is 8% -12% of the mass of the mullite support powder; and B, the mass fraction of the binder polyvinyl alcohol in the step is 5-10% of the mass of the active powder of the film layer.
Preferably, the pressure in the dry press molding process is 5-8MPa, and the pressing time is 30-60s.
Preferably, the sintering environment of the active powder is a closed or open crucible.
Preferably, the drying and calcining processes are as follows: standing at room temperature for 12-24h, controlling sintering temperature at 1300-1500deg.C, heating and cooling rate at 0.5-3deg.C/min, and maintaining for 1-5h to generate in situ growth reaction.
The mullite whisker-based ceramic fiber membrane prepared by mullite fiber powder with the whisker length of 5-20 mu m has the average pore diameter of 1.2-10 mu m and the bending strength of 12-15 MPa, and is improved by 3-5 times compared with the prior art; and the membrane layer whisker is not broken after vibrating for 30min in an ultrasonic water bath, the membrane layer whisker and the support body are well combined, the stability is high, and the gas permeability of the mullite whisker-based ceramic fiber membrane reaches 69.25-130 m 3 .m -2 h -1 kPa -1 The retention rate of the membrane on different particle sizes can reach 99.9 percent.
The beneficial effects are that:
the invention has the beneficial effects that: the operation method is simple, and the application effect is obvious. The ceramic fiber membrane is prepared from mullite whiskers with excellent physical and chemical properties as raw materials. The mullite whisker-based ceramic fiber membrane prepared by the method has a series of advantages of high temperature resistance, chemical corrosion resistance, high mechanical strength and the like. The staggered whisker formed film layer not only reduces the phenomenon of infiltration, but also increases the contact area with dust-containing air flow in subsequent application, and improves the interception performance of the ceramic fiber film on nano-scale dust particles.
Drawings
Fig. 1 is an SEM image of the whisker growth condition on the surface of the mullite fiber coated with the aluminosilicate sol in example 3.
Fig. 2 is a film layer diagram of the mullite whisker-based ceramic fiber film of example 3.
Fig. 3 is a pore size diagram of the mullite whisker-based ceramic fiber membrane of example 3.
Fig. 4 is a plot of darcy's permeability versus porosity and pore size for the mullite whisker-based ceramic fiber membrane of example 3.
Fig. 5 is an SEM image of the interfacial bond morphology of the membrane layer and the support layer after the mullite whisker-based ceramic fiber membrane in example 3 is subjected to ultrasonic vibration.
FIG. 6 is a graph showing the retention properties of mullite whisker-based ceramic fiber membranes of example 3.
Detailed Description
Example 1
Firstly, placing the agglomerated mullite short fibers (average length is 1000 mu m and length-diameter ratio is 100) into water, stirring and dispersing, filtering off excessive water, and placing the mixture into a baking oven at 120 ℃ for baking to obtain the mullite short fibers with good dispersibility. And mixing the mullite short fibers, the composite sintering aid and the activated carbon powder according to a certain mass ratio to obtain the support powder. Wherein the mullite staple fiber: activated carbon powder: composite sintering aid = 1:1:0.8, continuously adding PVA solution accounting for 8wt% of the total mass of the mullite support powder, grinding uniformly again, and then performing dry pressing molding under 5MP to prepare the mullite support; secondly, uniformly coating the mullite short fibers by using aluminum-silicon sol, putting the mullite short fibers into an oven to dry the moisture of the aluminum-silicon sol, and grinding the mullite short fibers with a composite sintering aid, a pore-forming agent and a binder to prepare film active powder, wherein the film active powder is uniformly ground according to the following mass ratio: mullite staple fiber: activated carbon powder: composite sintering auxiliary agent: aluminum-silicon sol: aluminum fluoride = 1.3:1:0.5:0.65:0.56. adding PVA accounting for 5wt.% of the active powder of the membrane layer, mixing uniformly again, removing agglomerated large particles through a 40-mesh standard sieve to prepare uniform active powder of the membrane layer, uniformly sieving the active powder of the membrane layer to cover the surface of a mullite-based support, staying for 30s under 8MPa for compression molding, standing at room temperature for 12h, setting sintering temperature in a closed crucible at 1300 ℃, controlling the heating and cooling rate at 0.5 ℃/min, and carrying out high temperature under the heat preservation for 1hThe mullite support is grown in situ, the average flexural strength of the prepared mullite support is about 13MPa, the average pore diameter of a membrane layer is 3.6 mu m, the porosity is about 55.8%, and the gas permeability can reach 130 m 3 m -2 h -1 kPa -1 。
Example 2
Firstly, placing the agglomerated mullite fiber powder (average length is 200 mu m and length-diameter ratio is 20) into water, stirring and dispersing, filtering off excessive water, and placing the mixture into a baking oven at 120 ℃ for baking to obtain mullite fiber powder with good dispersibility. And mixing the mullite fiber powder, the composite sintering aid and the activated carbon powder according to a certain mass ratio to obtain the support powder. Wherein the mullite fiber powder: activated carbon powder: composite sintering aid = 1.1:1:0.7, continuously adding PVA solution accounting for 10 weight percent of the total mass of the mullite support powder, grinding uniformly again, and then performing dry pressing molding under 6MP to prepare the mullite support; secondly, uniformly coating mullite fiber powder by using aluminum-silicon sol, putting the mullite fiber powder into an oven to dry the moisture of the aluminum-silicon sol, and grinding the mullite fiber powder with a composite sintering aid, a pore-forming agent and a binder to prepare film active powder, wherein the film active powder is uniformly ground according to the following mass ratio: mullite fiber powder: activated carbon powder: composite sintering auxiliary agent: aluminum-silicon sol: aluminum fluoride = 1.3:1:0.5:0.91:1.12. adding PVA accounting for 8wt.% of the active powder of the membrane layer, mixing uniformly again, removing agglomerated large particles through a 40-mesh standard sieve to prepare uniform active powder of the membrane layer, uniformly sieving and covering the active powder of the membrane layer on the surface of a mullite-based support, standing for 45s under 8MPa pressure for compression molding, standing for 12h at room temperature, setting sintering temperature in an open crucible at 1400 ℃, controlling the heating and cooling rate at 1 ℃/min, and carrying out high-temperature in-situ growth under 2h of heat preservation to prepare the mullite support with average breaking strength of about 15MPa, wherein the average pore diameter of the membrane layer is 4.3 mu m, the porosity is 58%, and the gas permeability can reach 115 m 3 m -2 h -1 kPa -1 。
Example 3
Firstly, placing agglomerated mullite fiber powder (average length is 200 mu m and length-diameter ratio is 20) into water, stirring and dispersingFiltering out excessive water, and drying in a baking oven at 120 ℃ to obtain fiber powder with good dispersibility. And mixing the mullite fiber powder, the composite sintering aid and the activated carbon powder according to a certain mass ratio to obtain the support powder. Wherein the mullite fiber powder: activated carbon powder: composite sintering aid = 1.3:1:0.5, continuously adding PVA solution with 10-wt% of the total mass of the mullite support powder, and performing dry pressing molding under 6MP to prepare the mullite support; secondly, uniformly coating mullite fiber powder by using aluminum-silicon sol, putting the mullite fiber powder into an oven to dry the moisture of the aluminum-silicon sol, and grinding the mullite fiber powder with a composite sintering aid, a pore-forming agent and a binder to prepare film active powder, wherein the film active powder is uniformly ground according to the following mass ratio: mullite fiber powder: activated carbon powder: composite sintering auxiliary agent: aluminum-silicon sol: aluminum fluoride = 1.3:1:0.5:1.105:1.4. adding PVA accounting for 10wt.% of the active powder of the membrane layer, mixing uniformly again, and removing the agglomerated large particles through a 40-mesh standard sieve to prepare uniform active powder of the membrane layer; uniformly screening and covering the active powder of the membrane layer on the surface of a mullite-based support, then staying for 60s under the pressure of 8MPa for compression molding, standing for 24 hours at room temperature, setting the calcining temperature in a closed crucible to 1400 ℃, controlling the heating and cooling rate to 2 ℃/min, and carrying out high-temperature in-situ growth under the condition of heat preservation for 3 hours to prepare the mullite carrier with the average flexural strength of about 15MPa, wherein the average pore diameter of the membrane layer is 2.7 mu m, the porosity is 59%, and the gas permeability can reach 110m 3 ·m -2 h -1 kPa -1 . Table 1 is a comparison of mechanical properties and pore structure properties for ceramic fiber membrane supports prepared using mullite fibers of different aspect ratios. The support body of the ceramic fiber membrane prepared by using the mullite fiber powder has higher flexural strength and more obvious raw material cost advantage. Fig. 1 is an SEM image of the mullite fiber powder uniformly coated with the aluminum-silicon sol in the example, promoting the formation of mullite crystal nuclei, and successfully constructing an asymmetric whisker film layer by growing the whisker on the fiber surface well. FIG. 2 is an SEM image of a mullite whisker-based ceramic fiber film prepared from mullite fiber powder in this example, wherein the film thickness is about 550 μm; FIG. 3 is mullite prepared in this exampleThe pore diameter distribution of the whisker-based ceramic fiber membrane layer is about 2.7 mu m; fig. 4 shows the relationship between darcy permeability, porosity and pore size of the ceramic fiber membranes prepared by this work and other research works, and the work is superior to the average level, which indicates that the prepared ceramic membranes have greater application value in structural performance. FIG. 5 is an SEM image of the combination between the membrane layer and the support layer after the mullite whisker-based ceramic fiber membrane is ultrasonically cleaned in a 40KHz ultrasonic cleaner for 30min, wherein the whisker on the surface of the membrane layer is not broken, and the combination between the membrane layer and the support body is good; FIG. 6 shows the mullite whisker-based ceramic fiber film prepared in this example, showing a retention of 99.9% or more for both kinds of dust of different particle diameters, for dust particle filtration tests of 300nm and 2.5. Mu.m.
Table 1 comparison of the Properties of the ceramic fiber film prepared from mullite fiber powder and mullite staple fiber of example 3
Example 4
Firstly, placing the agglomerated mullite fiber powder (average length is 200 mu m and length-diameter ratio is 20) into water, stirring and dispersing, filtering off excessive water, and placing the mixture into a baking oven at 120 ℃ for baking to obtain the mullite fiber powder with good dispersibility. Then mixing mullite fiber powder, a composite sintering aid and activated carbon powder according to a certain mass ratio to obtain a support powder, wherein the mullite fiber powder is prepared by the following steps: activated carbon powder: composite sintering aid = 1.4:1:0.4. continuously adding PVA solution with the total mass of 12-wt% of the mullite support powder, and performing dry pressing molding under 6MPa to obtain the mullite support; secondly, uniformly coating mullite fiber powder by using aluminum-silicon sol, putting the mullite fiber powder into an oven to dry the moisture of the aluminum-silicon sol, and grinding the mullite fiber powder with a composite sintering aid, a pore-forming agent and a binder to prepare film active powder, wherein the film active powder is uniformly ground according to the following mass ratio: mullite fiber powder: activated carbon powder: composite sintering auxiliary agent: aluminum-silicon sol: aluminum fluoride = 1.3:1:0.5:1.235:2.52. then adding PVA accounting for 10wt.% of the active powder mass of the film layer for mixing againMixing uniformly, and removing the agglomerated large particles through a 40-mesh standard sieve to prepare uniform membrane active powder; uniformly sieving and covering the active powder of the membrane layer on the surface of the mullite-based support, then staying for 60s under the pressure of 5MPa for compression molding, standing for 24 hours at room temperature, setting the calcining temperature in a closed crucible at 1500 ℃, controlling the heating and cooling rates at 3 ℃/min, and carrying out high-temperature in-situ growth under the condition of heat preservation for 5 hours to prepare the whisker carrier with the average pore diameter of 1.8 mu m, the porosity of 59 percent, the average breaking strength of about 14.9MPa and the gas permeability of 69.25m 3 m -2 h -1 ·kPa -1 。
Claims (2)
1. A preparation method of a mullite whisker-based ceramic fiber membrane is characterized by comprising the following steps: the specific operation steps are as follows:
A. grinding mullite fibers with different length-diameter ratios, a composite sintering aid and pore-forming agent activated carbon powder according to a certain proportion to obtain uniform support powder, and extruding a green disc type mullite-based support by a dry pressing molding method under the action of a certain amount of binder; the mullite fibers with different length-diameter ratios are respectively selected as follows: mullite short fibers with the length-diameter ratio of 100 or mullite fiber powder with the length-diameter ratio of 20; the mullite-based support is prepared by mixing the following substances in mass ratio: mullite fiber: activated carbon powder: composite sintering aid= (1-1.4): 1: (0.4-0.8); the composite sintering aid is prepared by compounding kaolin and potassium feldspar according to the mass ratio of 1:2;
B. uniformly mixing aluminum-silicon sol and mullite fibers, putting the mixture into a baking oven for drying, uniformly mixing a composite sintering aid, activated carbon powder and aluminum fluoride to prepare active powder of a film layer, adding a binder with certain mass for uniform mixing, and screening and removing large particles through a 40-mesh standard sieve to obtain uniform active powder of the film layer; the mass ratio of each substance in the prepared film active powder is as follows: mullite fiber: activated carbon powder: composite sintering auxiliary agent: aluminum-silicon sol: aluminum fluoride = 1.3:1:0.5: (0.65-1.235): (0.56-2.52);
C. uniformly spreading the screened and uniform film active powder on a mullite-based support, pressing and forming under a certain pressure, standing at room temperature for 12-24h, drying, sintering at 1300-1500 ℃, and controlling the heating and cooling rate at 0.5-3 ℃/min; the heat preservation time is 1-5h, and the sintering process is carried out in a closed ceramic container to obtain the mullite whisker-based ceramic fiber membrane;
wherein the pressure in the dry pressing forming process is 5-8MPa, and the pressing time is 30-60s.
2. The method for preparing the mullite whisker-based ceramic fiber membrane according to claim 1, which is characterized in that: the binder selected in the step A and the step B is polyvinyl alcohol (PVA) solution, wherein the adding amount in the step A is 8% -12% of the mass of the mullite support powder; the adding amount in the step B is 5-10% of the mass of the active powder of the film layer.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211043180.2A CN115215672B (en) | 2022-08-29 | 2022-08-29 | Preparation method of mullite whisker-based ceramic fiber membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211043180.2A CN115215672B (en) | 2022-08-29 | 2022-08-29 | Preparation method of mullite whisker-based ceramic fiber membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN115215672A CN115215672A (en) | 2022-10-21 |
| CN115215672B true CN115215672B (en) | 2023-08-22 |
Family
ID=83617555
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202211043180.2A Active CN115215672B (en) | 2022-08-29 | 2022-08-29 | Preparation method of mullite whisker-based ceramic fiber membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN115215672B (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104446578A (en) * | 2014-11-11 | 2015-03-25 | 天津大学 | Method for preparing mullite fiber or mullilte whisker high-temperature structural material |
| CN105084878A (en) * | 2015-03-31 | 2015-11-25 | 海南大学 | Preparation method of acicular mullite porous ceramic block material with superhigh amount of porosity |
| CN108264338A (en) * | 2017-01-04 | 2018-07-10 | 齐鲁工业大学 | A kind of high porosity mullite crystal whisker porous ceramic pipe and preparation method |
| CN108440008A (en) * | 2018-05-04 | 2018-08-24 | 南京工业大学 | A kind of high porosity ceramic filtering material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20080095690A1 (en) * | 2006-10-24 | 2008-04-24 | Wei Liu | Nano-sized needle crystal mullite film and method of making |
| WO2009158294A1 (en) * | 2008-06-27 | 2009-12-30 | Dow Global Technologies Inc. | Method for making porous acicular mullite bodies |
-
2022
- 2022-08-29 CN CN202211043180.2A patent/CN115215672B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104446578A (en) * | 2014-11-11 | 2015-03-25 | 天津大学 | Method for preparing mullite fiber or mullilte whisker high-temperature structural material |
| CN105084878A (en) * | 2015-03-31 | 2015-11-25 | 海南大学 | Preparation method of acicular mullite porous ceramic block material with superhigh amount of porosity |
| CN108264338A (en) * | 2017-01-04 | 2018-07-10 | 齐鲁工业大学 | A kind of high porosity mullite crystal whisker porous ceramic pipe and preparation method |
| CN108440008A (en) * | 2018-05-04 | 2018-08-24 | 南京工业大学 | A kind of high porosity ceramic filtering material and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 董雷 ; 陈拥军 ; 骆丽杰 ; 李豪 ; 李天峰 ; .冷冻干燥法制备晶须结构的莫来石多孔陶瓷.陶瓷学报.2016,(03),259-264. * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN115215672A (en) | 2022-10-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108176249B (en) | Preparation method of silicon carbide nanofiber membrane | |
| CN109650935B (en) | Preparation method of porous alumina ceramic membrane with adjustable pore shape | |
| WO2017004776A1 (en) | Porous alumina ceramic ware and preparation method thereof | |
| CN102718494A (en) | Preparation method of composite silicon carbide ceramic filter membrane material | |
| CN109279909B (en) | Preparation method of high-strength boron carbide porous ceramic | |
| CN105236986B (en) | A kind of preparation method and applications of multichannel silicon carbide flat ceramic film support | |
| CN105801122B (en) | A kind of preparation method of graded pore structure silicon carbide-based porous ceramics | |
| CN104072141A (en) | Preparation method of silicon carbide honeycomb ceramics | |
| CN108854589B (en) | Mullite whisker hollow fiber membrane for oil-water separation and preparation method thereof | |
| Qiao et al. | Al-DTPA microfiber assisted formwork construction technology for high-performance SiC membrane preparation | |
| CN113999046B (en) | Preparation method of low-temperature reaction sintered silicon carbide ceramic membrane | |
| CN111285702A (en) | Ceramic fiber filter membrane material and preparation method thereof | |
| CN115215672B (en) | Preparation method of mullite whisker-based ceramic fiber membrane | |
| WO2024078182A1 (en) | Preparation method for ceramic fiber filter pipe with high air permeability | |
| CN112521177B (en) | Low-melting-point porous ceramic material and preparation method thereof | |
| CN108164282B (en) | Attapulgite composite ceramic membrane support and preparation method and application thereof | |
| CN109665810A (en) | A kind of molecular screen membrane supporter and preparation method thereof and molecular screen membrane | |
| WO2023155929A1 (en) | Process for preparing porous support body ceramic by using spheroidizing agent micro powder | |
| CN111620698B (en) | Hierarchical pore ceramic sponge material with low-thermal-conductivity nanofiber framework and preparation method thereof | |
| CN114133270B (en) | Hollow flat plate ceramic filter membrane and preparation method thereof | |
| CN106565258B (en) | A kind of winding preparation method of high porosity porous ceramics pipe | |
| CN110511005A (en) | A kind of preparation method of axis disk rotary ceramic supporting body | |
| CN113318518B (en) | Filter element, preparation method and application thereof | |
| CN114988903A (en) | High-strength low-shrinkage porous ceramic and preparation method thereof | |
| CN114368194A (en) | High-temperature-resistant heat-insulating ceramic composite material and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |