CN109369157A - One kind having netted hole wall alumina porous ceramic and preparation method thereof - Google Patents

One kind having netted hole wall alumina porous ceramic and preparation method thereof Download PDF

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CN109369157A
CN109369157A CN201811343820.5A CN201811343820A CN109369157A CN 109369157 A CN109369157 A CN 109369157A CN 201811343820 A CN201811343820 A CN 201811343820A CN 109369157 A CN109369157 A CN 109369157A
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ceramic
hole wall
carbon
slurry
netted hole
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杨金龙
刘静静
霍文龙
干科
张在娟
任博
王亚利
闫姝
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Tsinghua University
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Tsinghua University
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    • 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
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    • 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
    • C04B38/0615—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 the burned-out substance being a monolitic element having approximately the same dimensions as the final article, e.g. a porous polyurethane sheet or a prepreg obtained by bonding together resin particles
    • C04B38/062—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 the burned-out substance being a monolitic element having approximately the same dimensions as the final article, e.g. a porous polyurethane sheet or a prepreg obtained by bonding together resin particles the burned-out substance being formed in situ, e.g. by polymerisation of a prepolymer composition containing ceramic powder
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    • C04B2235/42—Non metallic elements added as constituents or additives, e.g. sulfur, phosphor, selenium or tellurium
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    • 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
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    • C04B2235/48—Organic compounds becoming part of a ceramic after heat treatment, e.g. carbonising phenol resins
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Abstract

The invention discloses a kind of netted hole wall alumina porous ceramics and preparation method thereof.It the described method comprises the following steps: nanometer carbon surface being first subjected to organic polymer graft modification processing, obtain the modified Nano carbon that grafting rate is 0.1~100wt%；Modified Nano carbon is mixed to the ceramic slurry for obtaining that solid concentration is 40~80wt% with alumina powder, polyether polyol, isocyanates and silicone oil foam stabilizer；Then the foaming agent of 0.1~0.5wt% and the catalyst of 0.01~1.0wt% are added into slurry, it adjusts slurry NCO/-OH (R), mechanical stirring foaming, 6~50h of dumping under the conditions of 400~800 DEG C, it is then sintered at 1400~1600 DEG C to get netted hole wall alumina porous ceramic.The present invention has the characteristics that simple process and environmental-friendly, prepared netted hole wall alumina porous ceramic has the characteristic that pore structure is controllable, stomata connectivity is high, intensity is high, filter effect is excellent and regeneration rate is high, ceramic membrane can be replaced to have wide application prospect in filtering high-temperature flue gas field.

Description

One kind having netted hole wall alumina porous ceramic and preparation method thereof
Technical field
The invention belongs to filtering high-temperature flue gas technical fields, and in particular to a kind of filtering high-temperature flue gas is aoxidized with netted hole wall Aluminium porous ceramics and preparation method thereof.
Background technique
In recent years, with the height that the high speed development of China's coal-fired industry, the industry such as electric power, building materials, metallurgy and chemical industry generate Warm dusty gas, has seriously polluted the environment, and not only seriously threatens the health of the mankind, but also causes a large amount of thermal loss, resistance Hinder the sustainable development of China's industry.Therefore, the filtration, purification of high-temperature flue gas is particularly important.
Since porosity height and high-temperature behavior are excellent, ceramic membrane is widely used in the purification of high-temperature dusty gas.Though having Graded pore structure, but the stomata connectivity of ceramic membrane poor (easily blocking), filter efficiency are poor that (smoke particle still can be by more Hole film layer is gone directly inside supporter simultaneously in the accumulation of connection micropore neck) and easy peeling (interfacial bonding property between film layer and supporter Difference, and thermal expansion coefficient mismatches, and is also easy to produce peeling damage under heat stress), therefore its application range is subject to certain restrictions.Phase Than in ceramic membrane, alumina porous ceramic has superior performance, if high porosity, the high and antiacid alkali of intensity peel off, in height Warm smoke filtration field has great application prospect.
Currently, the preparation method of alumina porous ceramic mainly has burnout substances addition method, Organic Foam Material dipping and freezing Seasoning etc., but prepared porous ceramics exists the disadvantages of porosity is low, pore structure is uncontrollable and stomata connectivity is poor.Such as Patent " high-strength, highly resistance thermal stability Al2O3The preparation method of porous ceramics " (CN1629102A) is disclosed using charcoal powder as pore-creating The method that agent prepares alumina porous ceramic, but the porous ceramics porosity prepared is only 41%, and product average pore size is only 5 μm, cause its filter efficiency lower.Patent " a kind of filtering high-temperature flue gas orientation perforation porous ceramics and preparation method thereof " (CN104402411A) it discloses and is passed through using freeze-drying preparation aperture along the orientation that open end to closed end changes in gradient Logical alumina porous ceramic.The major defect of this method is embodied in: (1) micropore exists only in closed end, the big ruler with open end Very little duct is only that simple superposition forms graded pore structure, causes the connectivity of material bad, and material regeneration is poor；(2) should Method is formed using freeze-drying, complex process, higher cost and pore structure is uncontrollable.
Summary of the invention
The present invention is directed to overcome prior art defect, it is therefore an objective to provide a kind of controllable pore structure, simple process and at low cost Netted hole wall alumina porous ceramic preparation method, with this method prepare netted hole wall alumina porous ceramic pore structure Controllably, stomata connectivity is good, filter efficiency is high and application prospect is good.
To achieve the above object, the present invention is as follows using technical solution.
A kind of netted hole wall alumina porous ceramic preparation method, comprising the following steps:
1) nanometer carbon surface is subjected to organic polymer graft modification processing, obtaining grafting rate is changing for 0.1~100wt% Property nano-sized carbon；
2) by modified Nano described in alumina powder, polyether polyol, isocyanates, silicone oil foam stabilizer and step 1) Carbon mechanical stirring mixes 3~30min, and the ceramic slurry that solid concentration is 40~80wt% is prepared；
3) ceramic slurry described in step 2) is adjusted into R (NCO/-OH) value, 0.1~0.5wt% of the slurry total amount is added Foaming agent and 0.01~1.0wt% catalyst, obtain mixed slurry；
4) by mixed slurry described in step 3) under the conditions of 500~2000rpm of stirring rate 2~10min of mechanical stirring It foams, obtains ceramic green；
5) ceramic green described in step 4) is placed in draft glue discharging furnace, under the conditions of 400~800 DEG C carry out dumping 6~ 50h keeps the temperature 2~5h under the conditions of 1400~1600 DEG C finally to get netted hole wall alumina porous ceramic.
Further, the technique of the macromolecular grafted modification of nanometer carbon surface is as follows: by organic polymer in volumetric concentration For 20~45min of ultrasonic disperse in 95% acetone soln, organic polymer solution is obtained；Then nano-sized carbon is added to organic It in Polymer Solution, reacts, filters at 60~90 DEG C, solid drying is broken up to get macromolecule modified nano-sized carbon；Wherein, Organic macromolecule dosage is 2~40wt% of macromolecule and nano-sized carbon total amount, and nano-sized carbon dosage is that macromolecule and nano-sized carbon are total 60~98wt% of amount.
Preferably, nano-sized carbon described in step 1) be it is a kind of in nanometer carbon black, graphite or charing starch and its more than；It is described Its end group of organic polymer be-OH ,-NCO orOne of.
Further, ceramic slurry described in step 2) contain 40~80wt% of aluminium oxide, 9~20wt% of polyether polyol, 10~20wt% of isocyanates, 0.5~5wt% of silicone oil foam stabilizer, 0.5~15wt% of modified Nano carbon；The alumina particle ≤45μm。
Preferably, polyether polyol is polyfunctionality polyether polyol；Its molecular weight is 500~3000g/mol, and viscosity is 200~500mPas；The isocyanates is polymethylene multi-phenenyl isocyanate, methyl diphenylene diisocyanate, toluene One of diisocyanate；Its -5~30wt% of NCO content；The silicone oil foam stabilizer is Si-C key hydrolysis silicone oil, viscosity For 200~400mPas.
Further, R value described in step 3) is 0.8~1.2；The foaming agent is deionized water；The catalyst is tin One of class catalyst (stannous octoate, dibutyl tin dilaurate), amines catalyst (triethanolamine, triethylamine) and its with On.
The netted hole wall alumina porous ceramic of above method preparation, the porosity are 50~85%, air permeability 15.4 ~50 × 10-12m2, compression strength is 2.0~12.6MPa.
Due to the adoption of the above technical scheme, compared with prior art, the present invention having following good effect:
(1) novelty of the present invention be embodied in nano-sized carbon surface bond-OH ,-NCO orHigh reaction activity Group is effectively improved its interfacial bonding property with high molecular polymer, it can be achieved that nano-sized carbon polymolecularity.
(2) present invention innovatively using modified Nano carbon surface bonding-OH ,-NCO orHeight reaction Active group and urethane raw crosslink polymerization reaction, and constructing for netted hole wall is realized inside porous ceramics.
(3) polyurethane foam method composite Nano carbon of the present invention is modified, by regulation urethane raw ratio and Modified Nano carbon can realize netted hole wall structure controllable precise, and be not necessarily to subsequent processing (drying of such as product), simple process, week Phase is short, and reaction can be completed in a few minutes under the action of catalyst.
(4) present invention is using deionized water as foaming agent, and source is wide, cheap and energy conservation and environmental protection, has very big Industrialization prospect.
(5) netted hole wall alumina porous ceramic blank strength prepared by the present invention is high, can satisfy production and processing demand, Industrialized production for netted hole wall porous ceramics provides the foundation.
(6) it is 50~85% that the present invention, which prepares the netted hole wall alumina porous ceramic porosity, and air permeability is 15.4~50 ×10-12m2, compression strength is 2.0~12.6MPa, and alternative ceramic membrane can be applied to the filtering of high-temperature flue gas, is had good Application prospect.
Detailed description of the invention
Fig. 1 is the infared spectrum of the modified nano carbon black of different polyether polyol additional amounts of the invention.
Fig. 2 is the SEM figure of netted hole wall alumina porous ceramic prepared by the present invention.
Specific embodiment
The present invention provides a kind of netted hole wall alumina porous ceramic and preparation method thereof, is to be with common alumina powder Raw material makes it participate in polyurethane foam cross-linking reaction in the netted hole wall of porous ceramics Internal architecture by nano-sized carbon graft modification, And by being sintered the netted hole wall alumina porous ceramic of final preparation structure uniformly, controllable.With reference to the accompanying drawings and examples The present invention is described in more detail.
It is first that raw material Unify legislation according to the present invention is as follows to avoid repeating, it repeats no more in embodiment:
Its end group of the macromolecule be-OH ,-NCO orOne of.
Alumina particle≤45 μm.
The polyether polyol molecular weight is 500~3000g/mol, and viscosity is 200~500mPas.
The isocyanates -5~30wt% of NCO content, viscosity≤250mPas.
The silicone oil foam stabilizer viscosity is 200~400mPas.
The foaming agent is deionized water.
The catalyst be tin catalyst (stannous octoate, dibutyl tin dilaurate), amines catalyst (triethanolamine, Triethylamine) one of and its more than.
Embodiment 1
1) nanometer carbon surface is subjected to polyether polyol graft modification processing, the infared spectrum of modified nanometer carbon black is such as Shown in Fig. 1.From figure 1 it appears that-C-O-C- is detected in modified nanometer carbon black, show polyether polyol by Successfully it is grafted to nanometer carbon black surface.By the measurement to grafting front and back nanometer carbon black quality, the grafting rate of nanometer carbon black is obtained For 10wt%；
2) by modified Nano described in alumina powder, polyether polyol, isocyanates, silicone oil foam stabilizer and step 1) Carbon mechanical stirring mixes 6min, and the ceramic slurry that solid concentration is 50wt% is prepared；
3) ceramic slurry described in step 2) is adjusted into R value to 1.1, be added slurry total amount 0.1wt% deionized water and 0.2wt% stannous octoate obtains mixed slurry；
4) by mixed slurry described in step 3), mechanical stirring 3min foams under the conditions of stirring rate 500rpm, obtains To ceramic green；
5) ceramic green described in step 4) is placed in draft glue discharging furnace, dumping 6h is carried out under the conditions of 400 DEG C, is finally existed 2h is kept the temperature under the conditions of 1400 DEG C to get netted hole wall alumina porous ceramic.
The prepared porous zirconia reinforced alumina ceramic porosity is 80.7%, and air permeability is 42.8 × 10-12m2, Compression strength is 4.2MPa.
Embodiment 2
1) charing starch surface is subjected to organic polymer graft modification processing, obtains the Modified Activated Carbon that grafting rate is 20wt% Change starch；
2) it is carbonized modified described in alumina powder, polyether polyol, isocyanates, silicone oil foam stabilizer and step 1) Starch processing machinery is stirred 10min, and the ceramic slurry that solid concentration is 60wt% is prepared；
3) ceramic slurry described in step 2) is adjusted into R value to 1.2, be added slurry total amount 0.2wt% deionized water and 0.5wt% dibutyl tin dilaurate obtains mixed slurry；
4) by mixed slurry described in step 3), mechanical stirring 5min foams under the conditions of stirring rate 1000rpm, Obtain ceramic green；
5) ceramic green described in step 4) is placed in draft glue discharging furnace, dumping 10h is carried out under the conditions of 600 DEG C, is finally existed 3h is kept the temperature under the conditions of 1500 DEG C to get netted hole wall alumina porous ceramic.
The prepared porous zirconia reinforced alumina ceramic porosity is 75.8%, and air permeability is 37.4 × 10-12m2, Compression strength is 6.5MPa.
Embodiment 3
1) graphite surface is subjected to organic polymer graft modification processing, obtains the modified graphite that grafting rate is 30wt%；
2) by modified graphite described in alumina powder, polyether polyol, isocyanates, silicone oil foam stabilizer and step 1) Mechanical stirring mixes 15min, and the ceramic slurry that solid concentration is 70wt% is prepared；
3) ceramic slurry described in step 2) is adjusted into R value to 1.2, be added slurry total amount 0.3wt% deionized water and 0.5wt% triethanolamine obtains mixed slurry；
4) by mixed slurry described in step 3) under the conditions of stirring rate 1500rpm mechanical stirring 10min, obtain ceramics Green compact；
5) ceramic green described in step 4) is placed in draft glue discharging furnace, dumping 15h is carried out under the conditions of 700 DEG C, is finally existed 4h is kept the temperature under the conditions of 1550 DEG C to get netted hole wall alumina porous ceramic.
The prepared porous zirconia reinforced alumina ceramic porosity is 71.8%, and air permeability is 30.2 × 10-12m2, Compression strength is 8.2MPa.
Embodiment 4
1) nano carbon black surface is subjected to organic polymer graft modification processing, obtains the modification that grafting rate is 50wt% and receives Rice carbon black；
2) by modified Nano described in alumina powder, polyether polyol, isocyanates, silicone oil foam stabilizer and step 1) Carbon mechanical stirring mixes 15min, and the ceramic slurry that solid concentration is 70wt% is prepared；
3) ceramic slurry described in step 2) is adjusted into R value to 1.0, be added slurry total amount 0.5wt% deionized water and 1.0wt% triethylamine obtains mixed slurry；
4) by mixed slurry described in step 3), mechanical stirring 10min foams under the conditions of stirring rate 2000rpm, Obtain ceramic green；
5) ceramic green described in step 4) is placed in draft glue discharging furnace, dumping 30h is carried out under the conditions of 800 DEG C, is finally existed 4h is kept the temperature under the conditions of 1600 DEG C to get netted hole wall alumina porous ceramic.
The prepared porous zirconia reinforced alumina ceramic porosity is 62.8%, and air permeability is 25.2 × 10-12m2, Compression strength is 12.6MPa.
Present embodiment has following good effect and outstanding feature compared with prior art:
(1) present invention it is innovative in nano-sized carbon surface bond-OH ,-NCO orHigh reaction activity base Group is effectively improved its interfacial bonding property with high molecular polymer, it can be achieved that nano-sized carbon polymolecularity.
(2) present invention innovate using modified Nano carbon surface bonding-OH ,-NCO orHeight reaction Active group and urethane raw crosslink polymerization reaction, and constructing for netted hole wall is realized inside porous ceramics.
(3) polyurethane foam method composite Nano carbon of the present invention is modified, by regulation urethane raw ratio and Modified Nano carbon can realize netted hole wall structure controllable precise, and be not necessarily to subsequent processing (drying of such as product), simple process, week Phase is short, and reaction can be completed in a few minutes under the action of catalyst.
(4) present invention is using deionized water as foaming agent, and source is wide, cheap and energy conservation and environmental protection, has very big Industrialization prospect.
(5) netted hole wall alumina porous ceramic blank strength prepared by the present invention is high, can satisfy production and processing demand, Industrialized production for netted hole wall porous ceramics provides the foundation.
(6) it is 50~85% that the present invention, which prepares the netted hole wall alumina porous ceramic porosity, and air permeability is 15.4~50 ×10-12m2, compression strength is 2.0~12.6MPa, and alternative ceramic membrane can be applied to the filtering of high-temperature flue gas, is had good Application prospect.
Therefore, the present invention has the characteristics that controllable pore structure, simple process and netted hole wall oxidation at low cost, prepared Aluminium porous ceramic structure is controllable, stomata connectivity is good, filter efficiency is high and application prospect is good.
Technical solution of the present invention is described in detail in above-described embodiment.It is apparent that the present invention is not limited being retouched The embodiment stated.Based on the embodiments of the present invention, those skilled in the art can also make a variety of variations accordingly, but appoint What is equal with the present invention or similar variation shall fall within the protection scope of the present invention.

Claims (7)

1. a kind of netted hole wall alumina porous ceramic preparation method, which comprises the following steps:
1) nanometer carbon surface is subjected to organic polymer graft modification processing, obtains the modification that grafting rate is 0.1~100wt% and receives Rice carbon；
2) gained modified Nano carbon in alumina powder, polyether polyol, isocyanates, silicone oil foam stabilizer and step 1) is mechanical It is stirred 3~30min, obtains the ceramic slurry of 40~80wt% of solid concentration；
3) ceramic slurry obtained by step 2) is adjusted into R (NCO/-OH) value, the foaming of 0.1~0.5wt% of the slurry total amount is added The catalyst of agent and 0.01~1.0wt%, obtains mixed slurry；
4) mixed slurry 2~10min of mechanical stirring under the conditions of 500~2000rpm of stirring rate obtained by step 3) is sent out Bubble, obtains ceramic green；
5) ceramic green obtained by step 4) is placed in draft glue discharging furnace, 6~50h of dumping is carried out under the conditions of 400~800 DEG C, finally 2~5h is kept the temperature under the conditions of 1400~1600 DEG C to get netted hole wall alumina porous ceramic.
2. according to the method for claim 1, which is characterized in that the macromolecular grafted modification process of nanometer carbon surface It is as follows:
(1) it is 20~45min of ultrasonic disperse in 95% acetone soln in volumetric concentration by organic polymer, obtains organic high score Sub- solution；
(2) nano-sized carbon is added in organic polymer solution obtained by step (1), is reacted at 60~90 DEG C；
(3) it filters, solid drying is broken up to get macromolecular grafted modified Nano carbon；
Wherein, organic macromolecule dosage be macromolecule and nano-sized carbon total amount 2~40wt%, nano-sized carbon dosage be macromolecule and 60~98wt% of nano-sized carbon total amount.
3. according to the method for claim 1, which is characterized in that nano-sized carbon described in step 1) be nanometer carbon black, graphite or Carbonize one of starch and more than one mixture；The organic macromolecule end group be-OH ,-NCO orOne of.
4. according to the method for claim 1, which is characterized in that ceramic slurry described in step 2) contain aluminium oxide 40~ 80wt%, 9~20wt% of polyether polyol, 10~20wt% of isocyanates, 0.5~5wt% of silicone oil foam stabilizer, modified Nano carbon 0.5~15wt%；Alumina particle≤45 μm；
The polyether polyol is polyfunctionality polyether polyol；Its molecular weight be 500~3000g/mol, viscosity be 200~ 500mPa·s；The isocyanates is that polymethylene multi-phenenyl isocyanate, methyl diphenylene diisocyanate, toluene two are different One of cyanate；Its -5~30wt% of NCO content；The silicone oil foam stabilizer is Si-C key hydrolysis silicone oil, viscosity 200 ~400mPas.
5. according to the method for claim 1, which is characterized in that R value described in step 3) is 0.8~1.2；The foaming agent For deionized water；The catalyst is tin catalyst or amines catalyst.
6. according to the method for claim 5, which is characterized in that the tin catalyst is stannous octoate and/or two laurels Sour two fourth tin；The amines catalyst is triethanolamine and/or triethylamine.
7. netted hole wall alumina porous ceramic prepared by any one method according to claim 1~6, which is characterized in that its The porosity is 50~85%, and air permeability is 15.4~50 × 10-12m2, compression strength is 2.0~12.6MPa.
CN201811343820.5A 2018-11-13 2018-11-13 One kind having netted hole wall alumina porous ceramic and preparation method thereof Pending CN109369157A (en)

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Cited By (7)

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CN109942314A (en) * 2019-03-12 2019-06-28 昆明理工大学 A method of porous alumina ceramic is prepared using polyurethane
CN111018494A (en) * 2019-12-20 2020-04-17 中国建筑材料科学研究总院有限公司 Nano-pore heat insulation material and preparation method thereof
CN113121258A (en) * 2021-03-17 2021-07-16 宜兴摩根热陶瓷有限公司 High-strength high-porosity porous ceramic and preparation method thereof
CN114106559A (en) * 2021-11-11 2022-03-01 华东理工大学 Preparation method of high-thermal-conductivity high-insulation silicone rubber composite material
CN114669743A (en) * 2022-03-18 2022-06-28 辽宁石油化工大学 Boron carbide reinforced foamed aluminum composite material and preparation method thereof
CN114763309A (en) * 2021-01-15 2022-07-19 中国科学院过程工程研究所 Heating element with net-shaped hole wall and preparation method and application thereof
CN115448706A (en) * 2021-06-09 2022-12-09 中国科学院过程工程研究所 Diatomite-based heating element and preparation method and application thereof

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Cited By (9)

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Publication number Priority date Publication date Assignee Title
CN109942314A (en) * 2019-03-12 2019-06-28 昆明理工大学 A method of porous alumina ceramic is prepared using polyurethane
CN111018494A (en) * 2019-12-20 2020-04-17 中国建筑材料科学研究总院有限公司 Nano-pore heat insulation material and preparation method thereof
CN114763309A (en) * 2021-01-15 2022-07-19 中国科学院过程工程研究所 Heating element with net-shaped hole wall and preparation method and application thereof
CN113121258A (en) * 2021-03-17 2021-07-16 宜兴摩根热陶瓷有限公司 High-strength high-porosity porous ceramic and preparation method thereof
CN115448706A (en) * 2021-06-09 2022-12-09 中国科学院过程工程研究所 Diatomite-based heating element and preparation method and application thereof
CN115448706B (en) * 2021-06-09 2023-08-15 中国科学院过程工程研究所 Diatomite-based heating element and preparation method and application thereof
CN114106559A (en) * 2021-11-11 2022-03-01 华东理工大学 Preparation method of high-thermal-conductivity high-insulation silicone rubber composite material
CN114669743A (en) * 2022-03-18 2022-06-28 辽宁石油化工大学 Boron carbide reinforced foamed aluminum composite material and preparation method thereof
CN114669743B (en) * 2022-03-18 2023-12-05 辽宁石油化工大学 Boron carbide reinforced foam aluminum composite material and preparation method thereof

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Application publication date: 20190222