CN101074161B - Aluminum titanate-mullite cellular ceramic and its production - Google Patents
Aluminum titanate-mullite cellular ceramic and its production Download PDFInfo
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- CN101074161B CN101074161B CN2007100214782A CN200710021478A CN101074161B CN 101074161 B CN101074161 B CN 101074161B CN 2007100214782 A CN2007100214782 A CN 2007100214782A CN 200710021478 A CN200710021478 A CN 200710021478A CN 101074161 B CN101074161 B CN 101074161B
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- mullite
- aluminum titanate
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Abstract
An aluminum titanate-mullite cellular ceramic and its production are disclosed. The process is carried out by putting into clay alumina, titanium oxide, ashlar and magnesite-alumina spinel, mixing, wet grinding in ball grinder into powder below 500 meshes, filter pressing, vacuum mud refining to make mud blocks, adding into plastic adhesive with methyl-cellulose and polyvinyl alcohol, extruding, forming, drying and firing at 1450-1600 degree to obtain final product. It's stable, has high melt point, low heat expansion coefficient, excellent chemical-corrosive and thermal shock resistances. Itcan be used in high-temperature heat-storage burning system in industrial furnace, petroleum catalytic cracking and tailed-gas catalytic purifying of automobile industries.
Description
Technical field
The technical field of the invention is silicate material, industrial ceramics field.
Background technology
Early 1990s, NKK Corp (NKK) and Japanese industry stove Co., Ltd. (NFK) have developed jointly a kind of novel thermophore, are called high-efficiency ceramic hold over system HRS (High-cycle Regenerative Combustion System).NKK has carried out test of many times, and the data that record are analyzed.Found that the air themperature that enters burner after preheating is near the exhaust gas emission temperature.Data presentation, air preheating temperature reach 1300 ℃, the interior O of stove
2Content is that 11% o'clock NOx quantity discharged is 40kg/m
3The exploitation of HRS, realized that not only the fume afterheat limit reclaims and the reduction significantly of NOx quantity discharged, and this novel burner causes also and has produced a kind of new combustion technology-High Temperature Air Combustion HTAC (High Temperature AirCombustion).
The theory significance of high-temperature air burning (HTAC) technology has been to widen the understanding scope of people to temperature and oxygen concentration relation, and realized reducing significantly under the hot conditions combustion processes of oxygen concentration technically, solved the contradiction that high-temp combustion and NOx generate.The principal character of this technology is:
1. adopt the high-efficiency heat-accumulating waste-heat recovery device, make high-temperature flue gas and freezing air alternating current through heat storage and carry out heat exchange by switching, thereby the funnel temperature of original thousands of degree is reduced to 200 ℃ even lower level, has reclaimed high-quality waste heat to greatest extent;
2. freezing air can be preheating to more than 1000 ℃, even very near the temperature of combustion zone, has brought up the far different new flame pattern of a kind of and traditional luminous flame, and has obtained good uniform temperature field distribution;
3. by the burning under the tissue hypoxia concentration conditions, further greatly reduce generation and the discharging of NOx.
The height of Regenerative Combustion System temperature benefit and thermo-efficiency directly depends on the performance of heat storage.Heat storage mainly contains three kinds of ceramic honey comb, heat-storing sphere and heat accumulation pipes.The specific surface area of ceramic honey comb is more than 5 times of ball, and the big 4-5 of heat-transfer capability times, gas-flow resistance has only 1/3 of ball, and depth of penetration heating is little.So ceramic honey comb more helps realizing low oxygen combustion than heat-storing sphere, make furnace temperature evenly, heat transfer rate, tapping fast, reduce greatly that oxidation is decreased and the generation of NOx gas, significantly improve the environmental protection and energy saving effect.Adopt the regenerator volume of ceramic honey comb to significantly reduce, can arrange the burner of q.s, satisfy the thermal load needs.And the straight gas channel of ceramic honey comb is compared more difficult obstruction with the labyrinth passage of bead, and self-cleaning is good, is applicable to China's unclean characteristics of burning.
The heat storage material that generally adopts is a cordierite honeycomb ceramic at present, and its typical rerum natura is as follows: hole wall density: 1.6g/cm
3Thermal expansivity: 1.0 * 10
-6/ ℃; Thermal conductivity under the room temperature: 9.2 * 10
-3J/ (cm.s. ℃); Compressive strength: 12.4MPa (being parallel to the duct), 1.7MPa (perpendicular to the duct).But find in actual applications, because the cleanliness of China's fuel is relatively poor, mostly contain various impurity in the metallurgical furnace waste gas, cause when high temperature uses, cordierite honeycomb ceramic can react with the part material in the waste gas, thereby has reduced its work-ing life.In order to improve its high-temperature stability, mullite, Al have been developed again in succession
2O
3, Si
3N
4, ZrO
2Deng ceramic honey comb, chemical stability when having improved the physical strength, use temperature of solid support material and high temperature greatly, but owing to the raising of these material coefficient of thermal expansion coefficients along with intensity increases, the temperature that requires at heat-accumulation combustion sharply changes under the severe environmental conditions of (the chilling temperature difference is more than 800 ℃ in air), still is subjected to bigger influence their work-ing life.
Aluminium titanates be at present known to unique low bulk and high temperature resistant structured material of integrating.Have fine qualities such as high melting-point, low-thermal-expansion, resistance to chemical attack, high-heat resistance shock resistant.Aluminium titanates-mullite material that processing method by " complex phase modification " makes is a kind of novel composite material.It has high temperature (1300～1350 ℃) folding strength and the thermal shock resistance that is much better than mullite material, is suitable under purification atmosphere, working, and be a kind of excellent performance, industrial use refractory materials widely.
Summary of the invention
The purpose of this invention is to provide a kind of aluminum titanate-mullite cellular ceramic and preparation method thereof, this aluminum titanate-mullite cellular ceramic possesses premium propertiess such as high-melting-point, low-thermal-expansion, resistance to chemical attack, high-heat resistance shock resistant, compressive strength height, water-intake rate stable and controllable, has higher work-ing life.
For achieving the above object, the technical solution used in the present invention is:
A kind of aluminum titanate-mullite cellular ceramic, the mass percent of its feed composition:
Clay, wherein aluminum oxide 〉=30% 45～65%
Aluminum oxide 25～39%
Titanium dioxide, wherein titanium oxide 〉=98% 8～18%
Magnesium-aluminium spinel 1～5%
Cristobalite 1～3%
Described aluminum titanate-mullite cellular ceramic is characterized in that, the granularity of described clay＜5 μ m.
Described aluminum titanate-mullite cellular ceramic is characterized in that, the granularity of described aluminum oxide, titanium dioxide, cristobalite, magnesium-aluminium spinel＜500 orders.
A kind of preparation method of aluminum titanate-mullite cellular ceramic is characterized in that comprising the steps:
(1), get the raw materials ready by following mass percent:
Clay, wherein aluminum oxide 〉=30% 45～65%
Aluminum oxide 25～39%
Titanium dioxide, wherein titanium oxide 〉=98% 8～18%
Magnesium-aluminium spinel 1～5%
Cristobalite 1～3%
(2), with the wet-milling of above-mentioned raw materials mixing and water adding, press filtration obtains filter mud again, practices and to rub filter mud, drying;
(3), the bonding agent that adds linolic acid, oleic acid, methylcellulose gum, polyvinyl alcohol composition mixes;
(4), ageing is handled;
(5), practice and to rub filter mud, extrusion moulding, drying is burnt till under 1450～1600 ℃ of temperature, can make aluminum titanate-mullite cellular ceramic.
Described white silk is rubbed filter mud and is adopted the vacuum white silk to rub filter mud.
In the described bonding agent, the weight proportion of linolic acid, oleic acid, methylcellulose gum, polyvinyl alcohol is 1: 0.5-1.5: 0.5-10: 0.5-10.
With raw materials such as clay, aluminum oxide, titanium oxide, cristobalite, magnesium-aluminium spinel in ball milling wet-milling to less than 500 purpose powders, powder behind the ball milling becomes clod after press filtration and vacuum white silk are rubbed filter mud, adding is the bonding agent of main component with methylcellulose gum or polyvinyl alcohol, through the technical process of extrusion moulding, can produce aluminium titanates-mullite Multiphase ceramic honey comb.
The present invention utilizes clay to have preferably plasticity-and cooperates ridgity material such as aluminum oxide, makes the ceramic honey comb that makes have advantages such as intensity height, water-intake rate be stable.Simultaneously, utilize the stable aluminium titanates and the mullite that possess premium propertiess such as high-melting-point, low-thermal-expansion, resistance to chemical attack, high-heat resistance shock resistant to be compounded to form composite diphase material, realize the moulding of porous, thin-walled, slotted hole honeycomb ceramic product according to performance requriements.
Beneficial effect of the present invention, the present invention is because the aluminum titanate-mullite cellular ceramic that adopts technique scheme to make possesses premium propertiess such as high-melting-point, low-thermal-expansion, resistance to chemical attack, high-heat resistance shock resistant, compressive strength height, water-intake rate stable and controllable, use in the area that the fuel cleanliness factor is relatively poor, have higher work-ing life.
Embodiment
Embodiments of the invention see Table 1,
Preparation method of the present invention is,
Batching: raw materials such as clay, aluminum oxide, titanium oxide, cristobalite, magnesium-aluminium spinel are formed by following mass ratio:
Clay (aluminum oxide 〉=30%) 45～65%
Aluminum oxide 25～39%
Titanium dioxide (titanium oxide 〉=98%) 8～18%
Magnesium-aluminium spinel 1～5%
Cristobalite 1～3%
Above-mentioned raw materials is carried out moulding according to the following steps:
Batching → ball milling mixing → filter mud → vacuum white silk is rubbed filter mud → drying → mix → ageing → extrude → dry → burn till
Described ageing is to place 24-48 hour;
(wherein firing temperature is at 1450～1600 ℃)
Be aluminum titanate-mullite cellular ceramic by above step gained.
Table 1
The physicals of aluminum titanate-mullite cellular ceramic honeycomb ceramic sees Table 2, according to the lot of data analysis, in the scope of the present invention's design, the performance index of product fluctuate in certain controlled range, and this index is far above the product that is made by mullite, mullite-cordierite raw material, and the key indexs such as thermal expansivity of product are also comparatively desirable.
Table 2
Claims (5)
1. aluminum titanate-mullite cellular ceramic, the mass percent of its feed composition:
Clay, wherein aluminum oxide 〉=30% 45～65%
Aluminum oxide 25～39%
Titanium dioxide, wherein titanium oxide 〉=98% 8～18%
Magnesium-aluminium spinel 1～5%
Cristobalite 1～3%
。
2. aluminum titanate-mullite cellular ceramic as claimed in claim 1 is characterized in that, the granularity of described clay＜5 μ m.
3. aluminum titanate-mullite cellular ceramic as claimed in claim 1 is characterized in that, the granularity of described aluminum oxide, titanium dioxide, cristobalite, magnesium-aluminium spinel＜500 orders.
4. the preparation method of an aluminum titanate-mullite cellular ceramic is characterized in that comprising the steps:
(1), get the raw materials ready by following mass percent:
Clay, wherein aluminum oxide 〉=30% 45～65%
Aluminum oxide 25～39%
Titanium dioxide, wherein titanium oxide 〉=98% 8～18%
Magnesium-aluminium spinel 1～5%
Cristobalite 1～3%
(2), with the wet-milling of above-mentioned raw materials mixing and water adding, press filtration obtains filter mud again, practices and to rub filter mud, drying;
(3), the bonding agent that adds linolic acid, oleic acid, methylcellulose gum, polyvinyl alcohol composition mixes; In the described bonding agent, the weight proportion of linolic acid, oleic acid, methylcellulose gum, polyvinyl alcohol is 1: 0.5-1.5: 0.5-10: 0.5-10;
(4), ageing is handled;
(5), practice and to rub filter mud, extrusion moulding, drying is burnt till under 1450～1600 ℃ of temperature, can make aluminum titanate-mullite cellular ceramic.
5. the preparation method that ceramic honey comb as claimed in claim 4 adopts is characterized in that, described white silk is rubbed filter mud and adopted the vacuum white silk to rub filter mud.
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| CN101074161B true CN101074161B (en) | 2010-06-02 |
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Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102471173B (en) * | 2009-06-29 | 2014-02-19 | 陶氏环球技术有限责任公司 | Process for producing cemented and skinned acicular mullite honeycomb structures |
| KR101830064B1 (en) * | 2010-04-26 | 2018-02-21 | 다우 글로벌 테크놀로지스 엘엘씨 | Composition for extrusion-molded bodies |
| CN102584313B (en) * | 2011-12-24 | 2013-11-06 | 山东科技大学 | In-situ authigenic mullite whister reinforced aluminum titanate porous ceramic material and preparation method thereof |
| CN102701726A (en) * | 2012-06-19 | 2012-10-03 | 贵州大学 | Cellular heating ceramic containing rare earth oxide and preparation method thereof |
| CN103833338B (en) * | 2014-01-04 | 2015-04-01 | 安徽省含山瓷业股份有限公司 | Nanometer quartz sand domestic ceramic |
| JP6502495B2 (en) * | 2014-11-19 | 2019-04-17 | コーニング インコーポレイテッド | Ceramic powder with controlled size distribution |
| CN105924202B (en) * | 2016-04-28 | 2019-01-04 | 河南省格林沃特环保科技有限公司 | A kind of diesel engine vent gas post-processing technology of preparing of SCR catalyst carrier |
| CN112010537A (en) * | 2020-08-05 | 2020-12-01 | 武汉重远炉窑工程技术服务有限公司 | Refractory material suitable for glass kiln and preparation method thereof |
| CN115417680B (en) * | 2022-08-26 | 2023-07-25 | 郑州荣盛窑炉耐火材料有限公司 | Aluminum titanate-mullite refractory material for high-thermal shock kiln furniture and preparation method thereof |
Citations (4)
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|---|---|---|---|---|
| CN1235133A (en) * | 1998-05-11 | 1999-11-17 | 佟定远 | High strength and heat-resisting ceramics for manufacturing liquid raising pipe of low pressure aluminum casting apparatus |
| JP2004277237A (en) * | 2003-03-17 | 2004-10-07 | National Institute Of Advanced Industrial & Technology | Silicon nitride ceramic having steam corrosion resistant layer at high temperature |
| US6849181B2 (en) * | 2002-07-31 | 2005-02-01 | Corning Incorporated | Mullite-aluminum titanate diesel exhaust filter |
| CN1942228A (en) * | 2004-04-21 | 2007-04-04 | 康宁股份有限公司 | Aluminum titanate ceramic articles and methods of making same |
-
2007
- 2007-04-14 CN CN2007100214782A patent/CN101074161B/en not_active Expired - Fee Related
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1235133A (en) * | 1998-05-11 | 1999-11-17 | 佟定远 | High strength and heat-resisting ceramics for manufacturing liquid raising pipe of low pressure aluminum casting apparatus |
| US6849181B2 (en) * | 2002-07-31 | 2005-02-01 | Corning Incorporated | Mullite-aluminum titanate diesel exhaust filter |
| JP2004277237A (en) * | 2003-03-17 | 2004-10-07 | National Institute Of Advanced Industrial & Technology | Silicon nitride ceramic having steam corrosion resistant layer at high temperature |
| CN1942228A (en) * | 2004-04-21 | 2007-04-04 | 康宁股份有限公司 | Aluminum titanate ceramic articles and methods of making same |
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