CN1812945A - Honeycomb carrier for exhaust gas clarification catalyst and method for production thereof - Google Patents
Honeycomb carrier for exhaust gas clarification catalyst and method for production thereof Download PDFInfo
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- CN1812945A CN1812945A CNA2004800183312A CN200480018331A CN1812945A CN 1812945 A CN1812945 A CN 1812945A CN A2004800183312 A CNA2004800183312 A CN A2004800183312A CN 200480018331 A CN200480018331 A CN 200480018331A CN 1812945 A CN1812945 A CN 1812945A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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Abstract
The present invention provides a honeycomb carrier used for supporting a cleaning catalyst for cleaning an exhaust gas or the like, especially an NO<SB>x</SB>-containing exhaust gas of a car, excellent in heat resistance, thermal shock resistance, mechanical strength and thermal decomposition resistance, having large corrosion resistance against the catalyst and stably usable over a long period of time, and its manufacturing method. The material of the honeycomb carrier for the exhaust gas cleaning catalyst comprises an aluminum magnesium titanate sintered body obtained by baking a molded body formed from the following raw material mixture at 1,000-1,700[deg.]C. The raw material mixture contains 100 pts. mass of a mixture, which contains an Mg-containing compound, an Al-containing compound and a Ti-containing compound in the same metal component ratio as the metal component ratio in aluminum magnesium titanate represented by the composition formula: Mg<SB>x</SB>Al<SB>2(1+x)</SB>TiO<SB>5</SB>(0<x<1) in terms of oxides, and 1-10 pts. mass of alkali feldspar represented by the composition formula: (Na<SB>y</SB>K<SB>1-y</SB>)AlSi<SB>3</SB>O<SB>8</SB>(0<=y<=1).
Description
Technical field
The present invention relates to carrying is used for purifying various waste gas, especially waste gas and contains NO
xThe carrier and the manufacture method thereof of catalyzer of automobile exhaust gas.
Background technology
In the refining plant of various combustion exhaust, be so-called thermotolerance and resistance to sudden heating especially for the desired main characteristic of honeycomb support of carrying catalyzer used in the purification device for automobile exhaust gas that is widely used now.This is to cause rapid heat release because of the catalytic oxidation owing to unburned hydro carbons in the waste gas and carbon monoxide, thereby can form the high temperature more than 850 ℃, therefore needs high heat resistance.In addition, resistance to sudden heating is can bear the thermal stresses that causes because the temperature that so rapid heating produces rises and unlikely chipping and destructive character in honeycomb.Resistance to sudden heating is, thermal expansivity is more little, and its durable temperature head is big more.
In order to satisfy the such thermotolerance and the requirement of resistance to sudden heating, as the material of honeycomb support, proposed various stupaliths in the past, but only used cordierite material.Use the major cause of cordierite material to be that trichroite has 1400 ℃ high heat resistance, thermal expansivity also is very little in pottery simultaneously, and resistance to sudden heating is strong.
Yet though as the material of honeycomb support, cordierite material has very good properties on thermotolerance and resistance to sudden heating, but then, from problem of environment, is badly in need of the oxynitride (NO that removes as purifying to contain
x) the support of the catalyst of waste gas, have great difficult point.That is, as the NO that removes in the waste gas
xCatalyzer, usually use the catalyzer that contains basic metal and alkaline-earth metal composition, but at this moment, the part of basic metal and alkaline-earth metal at high temperature is penetrated in the trichroite as carrier, cause the deterioration of trichroite with the trichroite reaction, cause the damage of catalyzer simultaneously, therefore cause the NO in the waste gas
xRemove ability drop.In order to prevent this situation, proposed with silicon-dioxide (SiO
2) method etc. of lining catalyst surface, but need additional operation, cost is risen.
On the other hand, from the raising and the problem of environment of fuel cost, become automobile main flow in recent years combustion system, inject fuel directly into in-engine mode and make in the fuel dilution incendiary mode, remove the NO in the waste gas
xBecome than hydro carbons and the prior problem of carbon monoxide.Therefore, wish to have the material of the material of alternative trichroite as the honeycomb support of the cleaning catalyst of carrying waste gas.
Material except that trichroite enumerated potteries such as silicon carbide, silicon nitride, mullite, aluminium titanates, lithium aluminium silicate in No. 01/037971 communique of WO, but these all is not enough to become the material of above-mentioned honeycomb support.That is, thermal expansivity such as silicon carbide, mullite are big, poor thermal shock resistance.In addition, thermotolerance such as silicon nitride, lithium aluminium silicate aspect performance is not enough.
In addition, aluminium titanates surpass also have satisfactory stability under 1700 ℃ the high temperature, minimum thermal expansivity and good resistance to sudden heating.But on the other hand, the anisotropy of crystalline structure is strong, so crystal boundary is easy to generate the dislocation that thermal stresses causes, thereby there is a little shortcoming of physical strength, thereby be difficult to make wall thickness, honeycomb that hole density is big, in addition, be difficult to use as being equipped on exhaust gas purification catalyst carrier automobile etc., that at high temperature bear the load of mechanical vibration.In addition, these aluminium titanates etc. have the decomposition region usually in 800～1280 ℃ temperature range, and existence can't continue the problem of use for a long time in comprising the zone of such temperature range.
The announcement of invention
The invention provides honeycomb support and manufacture method thereof, described honeycomb support is to be used for carrying to purify especially that waste gas contains NO
xThe carrier of catalyzer of automobile exhaust gas, thermotolerance, resistance to sudden heating, physical strength and heat resistanceheat resistant decomposability are good, and to containing the catalyst tolerates corrodibility height of alkaline components, even life-time service can deterioration yet, weather resistance is good.
The inventor is conceived to aluminum magnesium titanate and aluminium titanates in order to solve above-mentioned problem, conscientiously obtains following new discovery after the research.Promptly, discovery is to the mixture that contains the titanium-containing compound, aluminum contained compound and the magnesium-containing compound that form aluminum magnesium titanate to scale, perhaps to containing the titanium-containing compound that forms aluminium titanates and the mixture of aluminum contained compound to scale, add specific alkali feldspar to scale, contain the oxide compound of spinel structure of Mg or MgO or change into the magnesium-containing compound of MgO by sintering, the sintered compact utmost point that the mixture sintering of gained is obtained is suitable as the carrier that is used to carry the catalyzer that purifies automobile exhaust gas.
Therefore, find the honeycomb support that constitutes by above-mentioned sintered compact of the present invention, not only keep resistance to sudden heating based on high heat resistance and low heat expansion property, and it is different with in the past method for producing aluminum magnesium titanate sintered product or al titanate sintering body, have high mechanical strength, heat resistanceheat resistant decomposability, even this sintered compact is used as removal NO at the catalyzer that will contain basic metal and alkaline-earth metal composition simultaneously
xCatalyzer the time, can be as trichroite in the past yet deterioration, can be for a long time, stably use.
Described the present invention is based on above-mentioned new discovery and finishes, and has following main contents.
(1) honeycomb carrier for exhaust gas clarification catalyst, described carrier is the honeycomb support that is used to carry the catalyzer of purifying exhaust air, it is characterized in that, the method for producing aluminum magnesium titanate sintered product of the material of this honeycomb support for mixture is obtained at 1000～1700 ℃ of following sintering, described mixture contain the amount that is converted into oxide compound be 100 mass parts with chemical formula: Mg
xAl
2 (1-x)Ti
(1+x)O
5Mg, Al in (in the formula, 0＜x＜1) represented aluminum magnesium titanate and the metal ingredient of Ti contain the mixture of magnesium-containing compound, aluminum contained compound and titanium-containing compound and 1～10 mass parts chemical formula than same metal ingredient ratio: (Na
yK
1-y) AlSi
3O
8(0≤y≤1) represented alkali feldspar.
(2) honeycomb carrier for exhaust gas clarification catalyst, described carrier is the honeycomb support that is used to carry the catalyzer of purifying exhaust air, it is characterized in that, the al titanate sintering body of the material of this honeycomb support for raw mix is obtained at 1250～1700 ℃ of following sintering, described mixture contains 100 mass parts with TiO
2/ Al
2O
3=40～60/60～40 mol ratio contains TiO
2And Al
2O
3Mixture (being called the X composition), and 1～10 mass parts chemical formula: (Na
yK
1-y) AlSi
3O
8(0≤y≤1) represented alkali feldspar, contain Mg spinel structure oxide compound or MgO or change into the magnesium-containing compound (being called the Y composition) of MgO by sintering.
(3) above-mentioned (2) described Y composition is a chemical formula: (Na
yK
1-y) AlSi
3O
8(0≤y≤1) represented alkali feldspar, contain Mg spinel structure oxide compound and/or MgO or change into the mixture of the magnesium-containing compound of MgO by sintering.
(4) each described honeycomb support in above-mentioned (1)～(3), honeycomb support has wall thickness, 15～124 holes/cm of 0.05～0.6mm
2Hole density, and the void content in next door is 20～50%, thermal expansivity is 3.0 * 10
-6K
-1Below.
(5) each described honeycomb support in above-mentioned (1)～(4), described catalyzer contain the NO that is useful in the removal waste gas
xBasic metal and alkaline-earth metal composition.
(6) each described honeycomb support in above-mentioned (1)～(5), waste gas is the waste gas that injects fuel directly into in-engine mode or make the automobile of fuel dilution incendiary mode.
(7) manufacture method of honeycomb carrier for exhaust gas clarification catalyst, it is characterized in that, the preparation raw mix, adding in this raw mix helps binder mixing, carrying out plasticization makes it can extrusion molding, after extrusion molding is honeycomb, at 1000～1700 ℃ of following sintering, described raw mix contain the amount that is converted into oxide compound be 100 mass parts with chemical formula: Mg
xAl
2 (1-x)Ti
(1+x)O
5Mg, Al in (in the formula, 0＜x＜1) represented aluminum magnesium titanate and the metal ingredient of Ti contain the mixture of magnesium-containing compound, aluminum contained compound and titanium-containing compound and 1～10 mass parts chemical formula than same metal ingredient ratio: (Na
yK
1-y) AlSi
3O
8(0≤y≤1) represented alkali feldspar.
(8) manufacture method of honeycomb carrier for exhaust gas clarification catalyst, it is characterized in that, the preparation raw mix, adding in this raw mix helps binder mixing, carrying out plasticization makes it can extrusion molding, after extrusion molding was honeycomb, at 1250～1700 ℃ of following sintering, described raw mix contained 100 mass parts with TiO
2/ Al
2O
3=40～60/60～40 mol ratio contains TiO
2And Al
2O
3Mixture (being called the X composition), and 1～10 mass parts chemical formula: (Na
yK
1-y) AlSi
3O
8(0≤y≤1) represented alkali feldspar, contain Mg spinel structure oxide compound or MgO or change into the magnesium-containing compound (being called the Y composition) of MgO by sintering.
(9) manufacture method of above-mentioned (7) or (8) described honeycomb carrier for exhaust gas clarification catalyst, the median size of each composition that described raw mix is contained is below 10 μ m.
(10) purifying method of waste gas, described method is to make waste gas contact the purifying method of the honeycomb support of the catalyzer that carries purifying exhaust air, it is characterized in that, the method for producing aluminum magnesium titanate sintered product of the material of this honeycomb support for mixture is obtained at 1000～1700 ℃ of following sintering, described mixture contain the amount that is converted into oxide compound be 100 mass parts with chemical formula: Mg
xAl
2 (1-x)Ti
(1+x)O
5Mg, Al in (in the formula, 0＜x＜1) represented aluminum magnesium titanate and the metal ingredient of Ti contain the mixture of magnesium-containing compound, aluminum contained compound and titanium-containing compound and 1～10 mass parts chemical formula than same metal ingredient ratio: (Na
yK
1-y)AlSi
3O
8(0≤y≤1) represented alkali feldspar.
(11) purifying method of waste gas, described method is to make waste gas contact the purifying method of the honeycomb support of the catalyzer that carries purifying exhaust air, it is characterized in that, the al titanate sintering body of the material of this honeycomb support for raw mix is obtained at 1250～1700 ℃ of following sintering, described mixture contains 100 mass parts with TiO
2/ Al
2O
3=40～60/60～40 mol ratio contains TiO
2And Al
2O
3Mixture (being called the X composition), and 1～10 mass parts chemical formula: (Na
yK
1-y) AlSi
3O
8(0≤y≤1) represented alkali feldspar, contain Mg spinel structure oxide compound or MgO or change into the magnesium-containing compound (being called the Y composition) of MgO by sintering.
The effect of invention
Honeycomb support of the present invention, not only keep resistance to sudden heating based on high heat resistance and low heat expansion property, and different with in the past method for producing aluminum magnesium titanate sintered product or al titanate sintering body, have high mechanical strength and heat resistanceheat resistant decomposability, good for the erosion resistance of catalyzer in addition.Therefore, can be used as and be used for carrying purification and contain NO from any waste gas, especially waste gas of Combustion Source of fixed body and moving body
xThe carrier of catalyzer of automobile exhaust gas.
Honeycomb support of the present invention as mentioned above, not only keeps the resistance to sudden heating based on high heat resistance and low heat expansion property, and has high mechanical strength and heat resistanceheat resistant decomposability, contains NO as purifying in addition
xThe carrier of the catalyzer that contains alkali metal component of waste gas the time reason that can deterioration and unclear.But, infer it is respectively when honeycomb support of the present invention constitutes because following reason when being made of method for producing aluminum magnesium titanate sintered product and by the al titanate sintering body.
(A) honeycomb support of the present invention is when being made of method for producing aluminum magnesium titanate sintered product, the crystallization of aluminum magnesium titanate that forms its basic structure is owing to exist alkali feldspar in its generative process, generate under alkali feldspar is the state of liquid phase thus, so form fine and close crystallization, physical strength improves.In addition, solid solution is in the aluminum magnesium titanate lattice when forming aluminum magnesium titanate by sintering for the contained Si composition of alkali feldspar, and the solid solution form of Si at this moment has the solid solution that exists with the 6 coordinations solid solution inner and that exist with 4 coordinations in the crystal grain top layer these 2 kinds in crystal grain.This is also confirmed with the result that 6 coordinations and 2 kinds of states of 4 coordinations exist by the Si that measures by NMR (nucleus magnetic resonance) in the aluminum magnesium titanate crystallization that observes.
That is, solid solution exists with 6 coordinations in the Si of aluminum magnesium titanate crystal grain inside, is 4 valencys, forms a pair ofly with the Mg of same 6 coordinate divalents, and both are 6 valencys altogether, replace the Al (6 valencys altogether) of 26 adjacent coordinate 3 valencys.Yes for its reason in order to keep the balance of electric charge, also can describe from the ionic radius aspect.Promptly because Si
4+And Mg
2+Ionic radius be respectively 0.54 and 0.86 , both average ion radiuses are 0.70 , approximate Al
3+Ionic radius 0.68 , form with Si
4+And Mg
2+To on energy, replacing Al
3+Solid solution condition.Therefore, think that the good heat resistanceheat resistant decomposability of discovery is because like this by while Si and Mg, aluminum magnesium titanate at high temperature also can suppress the ion diffusion between each positively charged ion, forms stable crystalline structure.
On the other hand, solid solution, and exists with 4 coordinations not with 6 coordinations in the Si on aluminum magnesium titanate crystal grain top layer.Possible this is because the Si on surface is because other positively charged ion that matches of shared Sauerstoffatom is few, thereby formation and 4 more stable coordinations of Sauerstoffatom bonding state.May form the crystalline state of solid solution that be similar to like this in the Si on crystal grain top layer lining aluminum magnesium titanate, even thereby honeycomb support of the present invention is as the carrier that contains alkali-metal catalyzer, for alkaline components at high temperature the corrosion of carrier is also had good anti-corrosion, possess the characteristic that life-time service can deterioration yet.
When (B) honeycomb support of the present invention is made of the al titanate sintering body, by in the mixture that forms aluminium titanates, adding alkali feldspar, be present near the alkali feldspar that becomes liquid phase the temperature that aluminium titanates generates thus, therefore the formation reaction of aluminium titanates is carried out under liquid phase, form fine and close crystallization, physical strength improves.And, the contained Si composition solid solution of alkali feldspar in the lattice of aluminium titanates, displacement Al.Because Si is littler than Al ionic radius, thus with combine of on every side Sauerstoffatom apart from shortening, the value of lattice parameter is littler than pure aluminium titanates.May be therefore, crystalline structure stabilization in the sintered compact that obtains shows very high thermostability, and the heat resistanceheat resistant decomposability significantly improves.
In addition, when in forming the mixture of aluminium titanates, adding the oxide compound of the spinel structure that contains Mg or MgO or changing into the magnesium-containing compound of MgO by sintering, can obtain fine and close sintered compact, can form with pure aluminium titanates and compare sintered compact with very high physical strength.
In addition, when in forming the mixture of aluminium titanates, adding the oxide compound of alkali feldspar and spinel structure and/or MgO simultaneously or changing into the magnesium-containing compound of MgO by sintering, the Si that alkali feldspar is contained and the oxide compound of spinel structure and MgO or change into the contained Mg of magnesium-containing compound of MgO, the position of main displacement Al in aluminium titanates by sintering.When these elements are added separately, originally on the position of the Al of 3 valencys and maintenance charge balance, can be replaced as the element of divalent (Mg) or 4 valencys (Si), sintered compact is in order to keep charge balance, discharge Sauerstoffatom and produce the oxygen room to the outside when adding Mg, thereby keep charge balance, when adding Si, because Si is 4 valencys, so obtain charge balance by Ti 3 valencys that are reduced into of original 4 valencys.
Can infer on the other hand, because Mg lacks 1 than the Al electric charge, Si Duos 1 than the Al electric charge, thereby by oxide compound and MgO that adds alkali feldspar and spinel structure simultaneously or the magnesium-containing compound that changes into MgO by sintering, can obtain charge balance, thus solid solution under the situation that can not have to influence at sintered compact formation element to other.
Especially at this moment, to add the oxide compound and the MgO of alkali feldspar and spinel structure near the ratio that waits mole number or to change into by sintering under the situation of magnesium-containing compound of MgO, compare with the situation of independent interpolation, additive can more stably exist.Owing to these reasons, both synergies, form with the situation of adding separately mutually specific tenacity significantly improve the low heat expansion property that not only harmless aluminium titanates had originally but also have high mechanical strength, the sintered compact that while heat resistanceheat resistant decomposability has also improved.
In addition, the catalyzer that contains alkaline components is had the reason of good anti-corrosion, do following supposition for honeycomb support of the present invention.At first, under the situation of the honeycomb support that constitutes by the aluminium titanates that obtains from the raw mix sintering that contains alkali feldspar, the contained potassium composition of the alkali feldspar crystallizing system outer (being present in crystal boundary) of aluminium titanates Already in when generating aluminium titanates.Therefore, even carrying contains the catalyzer of alkaline components, alkaline components contact honeycomb support, but because potassium for the osmotic pressure step-down of honeycomb support, produces the result who prevents potassium intrusion carrier.
On the other hand, from the oxide compound or the MgO of the spinel structure that contains Mg or change into by sintering under the situation of the aluminium titanates that the raw mix sintering of the magnesium-containing compound of MgO obtains, be owing to contain Mg as alkaline element (alkaline-earth metal a kind of) composition, the acidity of al titanate sintering body descends, so the alkaline components in the catalyzer is alkali (alkali-metal a kind of), its reactive result who descends.
In addition, contain alkali feldspar simultaneously and contain Mg spinel structure oxide compound or MgO or change into by sintering under the situation of the aluminium titanates that the raw mix sintering of the magnesium-containing compound of MgO obtains, because above-mentioned mechanism acts synergistically simultaneously, so produce to the very excellent erosion resistance of alkaline components.
The simple declaration of accompanying drawing
Fig. 1: expression about the survival rate α of the aluminum magnesium titanate of each sintered compact of embodiments of the invention 1-1 and comparative example 1-1 over time.
Fig. 2: expression about the survival rate β of the aluminium titanates of each sintered compact of embodiments of the invention 2-1, embodiment 2-2 and comparative example 2-1 over time.
The best mode that carries out an invention
Among the present invention, the material of above-mentioned honeycomb structured catalyst configurations carrier uses following (A) method for producing aluminum magnesium titanate sintered product or (B) al titanate sintering body.
(A): method for producing aluminum magnesium titanate sintered product
Described sintered compact is the method for producing aluminum magnesium titanate sintered product that raw mix is obtained at 1000～1700 ℃ of following sintering, described raw mix contain the amount that is converted into oxide compound be 100 mass parts with chemical formula: Mg
xAl
2 (1-x)Ti
(1+x)O
5Mg, Al in (in the formula, 0＜x＜1) represented aluminum magnesium titanate and the metal ingredient of Ti contain the mixture of magnesium-containing compound, aluminum contained compound and titanium-containing compound and 1～10 mass parts chemical formula than same metal ingredient ratio: (Na
yK
1-y)AlSi
3O
8(0≤y≤1) represented alkali feldspar.
Above-mentioned magnesium-containing compound, aluminum contained compound and titanium-containing compound as raw material uses so long as can synthesize the composition of aluminum magnesium titanate by sintering, are not particularly limited.Magnesium-containing compound, aluminum contained compound and titanium-containing compound can not be different respectively compounds, can be the compounds that contains two or more metal ingredients.These starting compounds are suitably selected to get final product from the compound of the raw material that is used as various potteries such as alumina-ceramic, titanium dioxide ceramic, magnesia ceramics, alumina titanate ceramics, magnesium titanate ceramics, spinel ceramics, aluminum magnesium titanate pottery usually.The object lesson of such compound can exemplify Al
2O
3, TiO
2, oxide compound such as MgO, MgAl
2O
4, Al
2TiO
5, MgTi
2O
5, each spinel structure body etc. of containing Mg and Ti contains the composite oxides of metal ingredient more than 2 kinds, contains the compound (carbonate, nitrate, vitriol etc.) of the metal ingredient more than a kind or 2 kinds that is selected from Al, Ti and Mg.
The blending ratio of magnesium-containing compound, aluminum contained compound and titanium-containing compound is to make the ratio of the contained metal ingredient of these compounds be and above-mentioned chemical formula: Mg
xAl
2 (1-x)Ti
(1+x)O
5Mg, Al in (in the formula, 0＜x＜1) represented aluminum magnesium titanate and the metal ingredient of Ti better are same ratios than same ratio.By using with above-mentioned each compound of such mixed, can obtain having with as the aluminum magnesium titanate of metal ingredient in the mixture of raw material than identical metal ingredient ratio.
Obtain honeycomb support of the present invention, need in the above-mentioned mixture that contains magnesium-containing compound, aluminum contained compound and titanium-containing compound, add alkali feldspar as additive.Alkali feldspar is the sintering aid of aluminum magnesium titanate, also has simultaneously the effect of adding the Si composition in aluminum magnesium titanate concurrently, with chemical formula: (Na
yK
1-y)AlSi
3O
8Expression.In the formula, y satisfies 0≤y≤1, better is 0.1≤y≤1, and good especially is 0.15≤y≤0.85.Alkali feldspar fusing point with the y value in this scope is low, and is effective especially to the sintering that promotes aluminum magnesium titanate.
The usage quantity of alkali feldspar is converted into each compound magnesium-containing compound, aluminum contained compound and the titanium-containing compound as raw material that oxide compound amounts to 100 mass parts relatively, is about 1～10 mass parts, better is about 3～5 mass parts.After the total amount that raw mix is converted into oxide compound here is meant and is used for removing contained moisture of raw mix and organic heat treated, carry out under the situation of presintering the quality after the presintering, before the formal sintering again.
In the mixture that contains magnesium-containing compound, aluminum contained compound and titanium-containing compound, added in the raw mix of alkali feldspar, can add the character that other sintering aids improve the sintered compact that obtains as required.Other sintering aid can exemplify for example SiO
2, ZrO
2, Fe
2O
3, CaO, Y
2O
3Deng.
Above-mentioned raw materials mixture thorough mixing, pulverizing.The mixing of raw mix, pulverizing are not particularly limited, and can be undertaken by known method.Can use for example ball mill, medium stirrer etc.The degree of grinding of raw mix is not particularly limited, and median size better is below 10 μ m, and good especially is 1～5 μ m.Raw mix is so long as in the scope that does not form secondary particle, and particle diameter is the smaller the better.
Better be in raw mix, to add to help binder.Help binder can use tackiness agent, pore-forming material, releasing agent, defoamer and the known auxiliary agents such as coagulating agent that looses.Tackiness agent better is polyvinyl alcohol, Microcrystalline Wax latex, methylcellulose gum, carboxymethyl cellulose etc.Pore-forming material better is gac, coke, polyvinyl resin, starch, graphite etc.Releasing agent better is a stearic acid latex etc., and defoamer better is n-Octanol, octyl phenoxyethanol etc., and loosing and coagulating agent better is diethylamine, triethylamine etc.
Help the usage quantity of binder to be not particularly limited, in the present invention, relatively each compound is converted into magnesium-containing compound, aluminum contained compound and the titanium-containing compound as raw material that oxide compound amounts to 100 mass parts, all converting with solids component better is respectively in following scope.Promptly, tackiness agent better is to use about 0.2～0.6 mass parts, and pore-forming material better is to use about 20～50 mass parts, and releasing agent better is to use about 0.2～0.7 mass parts, defoamer better is to use about 0.5～1.5 mass parts, and loosing with fixed attention, agent better is to use about 0.5～1.5 mass parts.
Add the above-mentioned raw mix that helps binder mix, mixing, will carry out plasticization and make its mixture after can extrusion molding form honeycomb by extrusion molding.The method of extrusion molding can be used known method, and the cross-sectional shape in the hole of honeycomb can be any in circle, ellipse, tetragon, the trilateral.In addition, the configuration of honeycomb can be round shape, polygon tubular.The honeycomb that shaping obtains better is to carry out drying, then 1000～1700 ℃, better be 1250～1450 ℃ of following sintering.Agglomerating atmosphere is not particularly limited, and better is the oxygen-containing atmospheres such as air that adopt usually.Sintering time proceed to sintering fully till, adopt usually about 1～20 hour.
Heat-up rate and cooling rate when carrying out above-mentioned sintering also are not particularly limited, and suitably set the condition that does not occur crack etc. on the sintered compact that obtains is got final product.For example better being, helping binder in order fully to remove moisture contained in the raw mix, tackiness agent etc., is not to heat up sharp, but gently heats up.In addition, before being heated to above-mentioned sintering temperature, better be in the temperature range about 500～1000 ℃ as required, by demulcent intensification carrying out presintering in about 10～30 hours, thereby can when aluminum magnesium titanate forms, alleviate the intravital thermal stresses of sintering, can suppress fissured generation in the sintered compact.
The sintered compact that obtains like this is with chemical formula: Mg
xAl
2 (1-x)Ti
(1+x)O
5(in the formula, 0＜x＜1) represented aluminum magnesium titanate is a basal component, and the contained Si composition of alkali feldspar is solid-solubilized in the lattice of aluminum magnesium titanate.Such sintered compact as mentioned above, becomes and has high heat resistance and resistance to sudden heating, and by making the crystalline structure stabilization, has the sintered compact of excellent mechanical intensity and heat resistanceheat resistant decomposability.
(B) al titanate sintering body
Described sintered compact is the al titanate sintering body that raw mix is obtained at 1250～1700 ℃ of following sintering, and described raw mix contains 100 mass parts with TiO
2/ Al
2O
3=40～60/60～40 mol ratio contains TiO
2And Al
2O
3The X composition, and 1～10 mass parts Y composition.
The TiO of above-mentioned formation aluminium titanates
2And Al
2O
3Not necessarily to all be pure TiO
2And Al
2O
3,, be not particularly limited so long as can generate the composition of aluminium titanates by sintering.They suitably select to use from the compound of the raw material that is used as various potteries such as alumina-ceramic, titanium dioxide ceramic, alumina titanate ceramics usually.Also can use and for example contain Al, Ti as the composite oxides of metal ingredient, carbonate, nitrate, vitriol etc.
TiO
2And Al
2O
3With TiO
2/ Al
2O
3=40～60/60～40 mol ratio is used, and better is to use with 45～50/55～50.Especially in above-mentioned scope, by with Al
2O
3/ TiO
2Mol ratio be set in more than 1, can avoid the eutectic point of sintered compact.Al among the present invention
2O
3And TiO
2Use as mixture, also be collectively referred to as the X composition among the present invention.
In the honeycomb support of the present invention, need add the Y composition as additive to above-mentioned X composition.A kind of as the Y composition, alkali feldspar uses chemical formula: (Na
yK
1-y)AlSi
3O
8Represented feldspar.In the formula, y satisfies 0≤y≤1, better is 0.1≤y≤1, and good especially is 0.15≤y≤0.85.Alkali feldspar fusing point with the y value in this scope is low, and is effective especially to the sintering that promotes aluminium titanates.
As other Y composition, the oxide compound that contains the spinel structure of Mg can use for example MgAl
2O
4, MgTi
2O
4The oxide compound of such spinel structure can be a natural mineral, also can use to contain MgO and Al
2O
3Material, contain MgO and TiO
2Material or the spinel oxides that obtains of this material of sintering.In addition, can also mix that different types of oxide compound with spinel structure uses more than 2 kinds.In addition, as the precursor of MgO,, can exemplify for example MgCO so long as can form can using of MgO by sintering
3, Mg (NO
3)
2, MgSO
4Or their mixture etc.
The usage ratio of above-mentioned X composition and Y composition is very important, corresponding 100 mass parts X compositions, and the Y composition is 1～10 mass parts.This be X composition and Y composition respectively by the ratio of oxide compound, when using the raw material except that oxide compound, be converted into the value of oxide compound.Corresponding 100 mass parts X compositions, when the Y composition was less than 1 mass parts, the additive effect of Y composition did not reach the degree of the characteristic that can improve sintered compact.On the contrary, when surpassing 10 mass parts,,, too much remaining component of adding is present in the sintered compact so becoming independent oxide compound owing to substantially exceeding Si or Mg element to aluminium titanates crystalline solid solution limit, causing the especially result of thermal expansivity increase, is unfavorable.Corresponding 100 mass parts X compositions, the Y composition is special ideal in 3～7 mass parts.
Among the present invention, above-mentioned Y composition better is to use chemical formula simultaneously: (Na
yK
1-y) AlSi
3O
8Represented alkali feldspar and contain oxide compound and/or MgO or its precursor of the spinel structure of Mg uses their mixture.When using this mixture, can realize the significantly raising of above-mentioned function.Above-mentioned alkali feldspar and contain the oxide compound of spinel structure of Mg and/or the mixture of MgO or its precursor in, the former/latter's mass ratio better is 20～60/80～40, good especially is 35～45/65～55.In above-mentioned scope, serve as etc. that mole ground exists with the ratio of Si/Mg, not under the situation in this scope, be difficult to bring into play Si and Mg and be solidly soluted into synergy in the aluminium titanates simultaneously, be unfavorable.
Among the present invention, except above-mentioned X composition and Y composition, can use other sintering aids to improve the character of the sintered compact that obtains as required.Other sintering aid can exemplify for example SiO
2, ZrO
2, Fe
2O
3, CaO, Y
2O
3Deng.
Above-mentioned raw mix thorough mixing, the pulverizing that contains X composition and Y composition.The mixing of raw mix, pulverizing are not particularly limited, and can be undertaken by known method.Can use for example ball mill, medium stirrer etc.The degree of grinding of raw mix is not particularly limited, and median size better is below 30 μ m, and good especially is 8～15 μ m.Wherein, so long as in the scope that does not form secondary particle, particle diameter is the smaller the better.
Help the usage quantity of binder to be not particularly limited, in the present invention, corresponding to X composition, the Y composition (being converted into oxide compound) as the raw material that amount to 100 mass parts, all converting with solids component better is respectively in following scope.Promptly, tackiness agent better is to use about 0.2～0.6 mass parts, and pore-forming material better is to use about 20～50 mass parts, and releasing agent better is to use about 0.2～0.7 mass parts, defoamer better is to use about 0.5～1.5 mass parts, and loosing with fixed attention, agent better is to use about 0.5～1.5 mass parts.
Add the above-mentioned raw mix that helps binder mix, mixing, will carry out plasticization and make its mixture after can extrusion molding form honeycomb by extrusion molding.The method of extrusion molding can be used known method, and the cross-sectional shape in the hole of honeycomb can be any in circle, ellipse, tetragon, the trilateral.In addition, the configuration of honeycomb can be round shape, polygon tubular.The honeycomb that shaping obtains better is to carry out drying, then 1250～1700 ℃, better be 1300～1450 ℃ of following sintering.Agglomerating atmosphere is not particularly limited, and better is the oxygen-containing atmospheres such as air that adopt usually.Sintering time proceed to sintering fully till, adopt usually about 1～20 hour.
Heat-up rate and cooling rate when carrying out above-mentioned sintering also are not particularly limited, and suitably set the condition that does not occur crack etc. on the sintered compact that obtains is got final product.For example better being, helping binder in order fully to remove moisture contained in the raw mix, tackiness agent etc., is not to heat up sharp, but gently heats up.In addition, before being heated to above-mentioned sintering temperature, better be in the temperature range about 500～1000 ℃ as required, by demulcent intensification carrying out presintering in about 10～30 hours, thereby can when aluminum magnesium titanate forms, alleviate the intravital thermal stresses of sintering, can suppress fissured generation in the sintered compact.
In the sintered compact that obtains like this, with the aluminium titanates that forms by the X composition as basal component, as the Y composition, the Si composition that alkali feldspar is contained, and the Mg composition solid solution of magnesium-containing compound that derives from oxide compound, the MgO of the spinel structure that contains Mg or change into MgO by sintering is in the lattice of aluminium titanates.Such sintered compact as mentioned above, becomes and has high mechanical strength and low thermal coefficient of expansion concurrently, and by making the crystalline structure stabilization, has the sintered compact of good heat resistanceheat resistant decomposability.
By above-mentioned (A) method for producing aluminum magnesium titanate sintered product or (B) honeycomb that constitutes of al titanate sintering body have wall thickness and be for example 15～124 holes/cm for for example 0.05～0.6mm, hole density
2Cellular structure.And the void content in next door is for example 20～50%, and thermal expansivity is for example 3.0 * 10
-6K
-1Below.This honeycomb can suppress the pyrolysis of aluminum magnesium titanate or aluminium titanates, thereby can stably use under the high temperature from about room temperature to 1600 ℃.
Above-mentioned honeycomb can contain hydro carbons, carbon monoxide, NO with acting on to purify
x, SO
xEtc. the various waste gas of objectionable constituent, especially contain NO in the waste gas
xThe support of the catalyst of automobile exhaust gas.Particularly, honeycomb support of the present invention at high temperature has stability to alkali, so for contain higher concentration NO in waste gas
x, to inject fuel directly into in-engine mode or make the automobile exhaust gas of fuel dilution incendiary mode be effective.
The kind of the catalyzer that carrier carried can use in the past the removal hydro carbons and the known various catalyzer such as so-called three-way catalyst of carbon monoxide, the present invention is useful on the NO that removes in the waste gas to containing
xThe basic metal or the catalyzer of alkaline-earth metal composition effective especially.To containing in basic metal or the alkaline-earth metal to removing NO
xThe catalyzer of effective potassium, barium, particularly potassium, carrier of the present invention are effective.
The method that honeycomb of the present invention carries above-mentioned catalyzer adopts known method.During bearing catalyst,, can be situated between as required with the big material of specific surface, for example aluminum oxide or silicon-dioxide in order to improve load-carry duty.That is, can on honeycomb support, carry aluminum oxide or silicon-dioxide, again bearing catalyst on the aluminum oxide of this carrying or silicon-dioxide.The honeycomb that has carried catalyzer uses suitable maintenance material, better is to be equipped in the tank body to use.
Embodiment
Below, according to embodiment the present invention is specifically described, but the present invention is not limited to these explanations certainly.
Embodiment 1-1
The mixture that periclasite (periclase) the type magnesium oxide that is existed as natural mineral by 26.7 quality % (20 moles of %) easy-sintering alpha-type aluminum oxide, 62.8 quality % (60 moles of %) anatase-type titanium oxide and 10.5 quality % (20 moles of %) corresponding to 100 mass parts constitutes adds 4 mass parts (Na
0.6K
0.4) AlSi
3O
8Represented alkali feldspar, 0.25 mass parts as the polyvinyl alcohol of tackiness agent, diethylamine that 1 mass parts is coagulated agent as loosing, 0.5 mass parts as the polypropylene glycol of defoamer and 35 mass parts as the gac below the particle diameter 30 μ m of pore-forming material, after mixing 3 hours with ball mill, dry more than 12 hours under 120 ℃ with drying machine, obtain raw material powder.
The raw material powder that obtains is crushed to about median size 5 μ m,, obtains having wall thickness 0.1mm, density 93 holes, hole/cm with vacuum extrusion shaper (Miyazaki ironworker corporate system) extrusion molding
2The diameter of quadrilateral hole cross-sectional shape: the columnar honeycomb of 129mm, length: 150mm.After this honeycomb drying, in 1400 ℃ of sintering 4 hours in atmosphere.Then, by putting the cold sintered compact that obtains.
Comparative example 1-1
Operate except not using the alkali feldspar identically, obtain the sintered compact of the honeycomb shape that constitutes by method for producing aluminum magnesium titanate sintered product with embodiment 1-1.
Comparative example 1-2
Use cordierite powder (2MgO2Al
2O
35SiO
2) as the material of honeycomb support, by of known method operation, make and the identical shaped honeycomb of embodiment 1-1 then.
[about the testing of characteristic of honeycomb formed bodies]
To the honeycomb formed bodies of the above embodiments 1-1 and comparative example 1-1,1-2 measure void content (%), from the thermal expansivity (* 10 of room temperature to 800 ℃
-6K
-1), drop into the heat shock resistance temperature that method obtains in the water (℃), softening temperature (℃) and compressive strength (MPa), its result is as showing shown in the 1-1.Void content, thermal expansivity, heat shock resistance temperature, softening temperature, compressive strength are measured according to the method for JISR1634, JISR1618, JISR1648, JISR2209, JISR1608 respectively.When measuring compressive strength, from each honeycomb formed bodies cut the longitudinal and transverse hole count in a cross section all be 5, length direction is the square tube shape test sample of 15mm, it is 3 directions of direction (diagonal) that 45 degree tilt from (A) length direction (axial), (B) vertical direction (tangential), (C) and major axis measures.
Table 1-1
| Void content (%) | Thermal expansivity (* 10 -6K -1) | The heat shock resistance temperature (℃) | Softening temperature (℃) | Compressive strength (MPa) | |||
| (A) | (B) | (C) | |||||
| Embodiment 1-1 | 34 | 1.0 | 850 | 1580 | ＞14 | ＞3 | ＞2 |
| Comparative example 1-1 | 35 | 0.2 | 860 | 1600 | ＞9 | ＞1.5 | ＞0.8 |
| Comparative example 1-2 | 35 | 0.6 | 650 | 1320 | ＞10 | ＞1.3 | ＞0.2 |
[test of heat resistanceheat resistant decomposability]
Cutting from the honeycomb support of embodiment 1-1 all is the test film of vertical 10mm * horizontal 10mm * long 10mm, is placed in 1100 ℃ the high-temperature atmosphere, carries out the heat resistanceheat resistant decomposability over time by the survival rate α (%) that investigates aluminum magnesium titanate and tests.
The collection of illustrative plates that the survival rate of aluminum magnesium titanate is measured (XRD) from X-ray diffraction is tried to achieve by the following method.
Produce MgAl during at first, owing to the aluminum magnesium titanate thermolysis
2O
4(spinel) and TiO
2(rutile), the integrated intensity (I of the diffraction peak of (110) face of usefulness rutile
TiO2 (110)) and the integrated intensity (I of the diffraction peak of (023) face of aluminum magnesium titanate
MAT (023)) try to achieve the strength ratio R of aluminum magnesium titanate by following formula to rutile.
R＝I
MAT(023)/(I
MAT(023)+I
TiO2(110))
In addition, the sintered compact before the thermal treatment of carrying out under 1100 ℃ is also used the same method try to achieve the strength ratio R of aluminum magnesium titanate rutile
0Then, R and the R that tries to achieve with aforesaid method
0Try to achieve the survival rate α (%) of aluminum magnesium titanate by following formula.
α＝(R/R
0)×100
About the survival rate α (%) of the aluminum magnesium titanate of each sintered compact of embodiment 1-1 and comparative example 1-1 over time shown in the chart of Fig. 1.As shown in Figure 1, the sintered compact of embodiment 1-1 is compared with the sintered compact of comparative example 1-1, and the survival rate α of aluminum magnesium titanate is higher through still keeping for a long time, and the heat resistanceheat resistant decomposability is good.
[alkaline resistance test of honeycomb]
Remove automobile exhaust gas NO in order to investigate honeycomb for conduct
xThe erosion resistance of potassic catalyzer of catalyzer, carried out following test.The use temperature of the honeycomb support of automobile exhaust gas is in the scope of room temperature to 850 ℃, in addition, the potassium concn of potassic catalyzer is not very high, but in this test, carry out being placed on temperature for a long time and keeping accelerated test under the severe condition in 900 ℃ the stove with being immersed in test film dry again behind the saltpetre aqueous solution of concentration 1 mol.
[test method]
Cutting the cross section respectively from the honeycomb of embodiment 1-1 and comparative example 1-2 is the square of length of side 30mm, the test film of long 50mm, with this test film in the saltpetre aqueous solution of concentration 1 mol under room temperature dipping 1 hour.Then, this test film is following dry 1 hour at 70 ℃.Dried honeycomb is inserted in the tube furnace of internal diameter 5cm, long 42cm, in this tube furnace, fed the air that contains 10% moisture, under following condition, keep the specified time simultaneously with 25cc/ minute.Then, the honeycomb that takes out from tube furnace is carried out XRD determining, investigate the alteration of honeycomb material.The air that contains 10% moisture that feeds in tube furnace prepares by the tank that is controlled at 60 ℃ by making air.The result of test is shown in table 1-2.
Conservation condition
Temperature in the stove: 900 ℃, the intensification of stove, cooling rate: 100 ℃/hour
Hold-time: 50 hours, 100 hours, 150 hours, 200 hours
Table 1-2
| Hold-time | ||||
| 50 hours | 100 hours | 150 hours | 200 hours | |
| The honeycomb of embodiment 1-1 | Do not change | Do not change | Do not change | Do not change |
| The honeycomb of comparative example 1-2 | Do not change | Near 2 θ=28 °, find KAlSiO 4The peak | At KAlSiO 4The place, peak find to increase | At KAlSiO 4The place, peak find to increase |
By the result who shows 1-2 as can be known, the honeycomb of embodiment 1-1 is compared with the honeycomb of comparative example 1-2, has the stronger erosion resistance to potassium.
Embodiment 2-1
By the mixture that 56.1 quality % (50 moles of %) easy-sintering alpha-type aluminum oxide and 43.9 quality % (50 moles of %) anatase-type titanium oxide constitute, add 4 mass parts (Na corresponding to 100 mass parts
0.6K
0.4) AlSi
3O
8Represented alkali feldspar as additive, 0.25 mass parts as the polyvinyl alcohol of tackiness agent, diethylamine that 1 mass parts is coagulated agent as loosing, 0.5 mass parts as the polypropylene glycol of defoamer and 35 mass parts gac as particle diameter 50～80 μ m of pore-forming material, after mixing 3 hours with ball mill, dry more than 12 hours under 120 ℃ with drying machine, obtain raw material powder.
The raw material powder that obtains is crushed to about median size 5 μ m,, obtains having wall thickness 0.1mm, density 93 holes, hole/cm with vacuum extrusion shaper (Miyazaki ironworker corporate system) extrusion molding
2The diameter of quadrilateral hole cross-sectional shape: the columnar honeycomb of 129mm, length: 150mm.After this honeycomb drying, in 1400 ℃ of sintering 4 hours in atmosphere.Then, by putting the cold sintered compact that obtains.
Comparative example 2-1
Operate except not using the alkali feldspar identically, obtain the sintered compact of the honeycomb shape that constitutes by the al titanate sintering body with embodiment 2-1.
Comparative example 2-2
Use cordierite powder (2MgO2Al
2O
35SiO
2), by of known method operation, make and the identical shaped honeycomb of embodiment 2-1 then.
Embodiment 2-2
By the mixture that 56.1 quality % (50 moles of %) easy-sintering alpha-type aluminum oxide and 43.9 quality % (50 moles of %) anatase-type titanium oxide constitute, add 4 mass parts (Na corresponding to 100 mass parts
0.6K
0.4) AlSi
3O
8Represented alkali feldspar and 6 mass parts chemical formula: MgAl
2O
4Represented spinel compound as additive, 0.25 mass parts as the polyvinyl alcohol of tackiness agent, diethylamine that 1 mass parts is coagulated agent as loosing, 0.5 mass parts as the polypropylene glycol of defoamer and 35 mass parts gac as particle diameter 50～80 μ m of pore-forming material, after mixing 3 hours with ball mill, dry more than 12 hours under 120 ℃ with drying machine, obtain raw material powder.
The raw material powder that use obtains, by similarly pulverize with embodiment 2-1, be shaped, drying and sintering obtain honeycomb support.
Embodiment 2-3
By the mixture that 56.1 quality % (50 moles of %) easy-sintering alpha-type aluminum oxide and 43.9 quality % (50 moles of %) anatase-type titanium oxide constitute, add 6 mass parts chemical formula: MgAl corresponding to 100 mass parts
2O
4Represented spinel compound as additive, 0.25 mass parts as the polyvinyl alcohol of tackiness agent, diethylamine that 1 mass parts is coagulated agent as loosing, 0.5 mass parts as the polypropylene glycol of defoamer and 35 mass parts gac as particle diameter 50～80 μ m of pore-forming material, after mixing 3 hours with ball mill, dry more than 12 hours under 120 ℃ with drying machine, obtain raw material powder.
The raw material powder that use obtains, by similarly pulverize with embodiment 2-1, be shaped, drying and sintering obtain honeycomb support.
[about the testing of characteristic of honeycomb formed bodies]
To the honeycomb formed bodies of the above embodiments 2-1,2-2,2-3 and comparative example 2-1,2-2 measure void content (%), from the thermal expansivity (* 10 of room temperature to 800 ℃
-6K
-1), drop into the heat shock resistance temperature that method obtains in the water (℃), softening temperature (℃) and compressive strength (MPa), its result is as showing shown in the 2-1.Void content, thermal expansivity, heat shock resistance temperature, softening temperature, compressive strength are measured according to the method for JISR1634, JISR1618, JISR1648, JISR2209, JISR1608 respectively.When measuring compressive strength, from each honeycomb formed bodies cut the longitudinal and transverse hole count in a cross section all be 5, length direction is the square tube shape test sample of 15mm, it is 3 directions of direction (diagonal) that 45 degree tilt from (A) length direction (axial), (B) vertical direction (tangential), (C) and major axis measures.
Table 2-1
| Void content (%) | Thermal expansivity (* 10 -6K -1) | The heat shock resistance temperature (℃) | Softening temperature (℃) | Compressive strength (MPa) | |||
| (A) | (B) | (C) | |||||
| Embodiment 2-1 | 34 | 1.2 | 950 | 1670 | ＞5.0 | ＞2.5 | ＞1.2 |
| Embodiment 2-2 | 35 | 1.5 | 880 | 1620 | ＞8.3 | ＞5.1 | ＞1.0 |
| Embodiment 2-3 | 32 | 0.9 | 1220 | 1680 | ＞4.3 | ＞2.3 | ＞1.0 |
| Comparative example 2-1 | 30 | 0.8 | 980 | 1680 | ＞0.4 | ＞0.1 | ＞0.1 |
| Comparative example 2-2 | 35 | 0.6 | 650 | 1320 | ＞10 | ＞1.3 | ＞0.2 |
By table 2-1 as can be known, the honeycomb support of embodiment 2-1,2-2,2-3 all keeps reality is used enough compressive strengths.Comparative example 2-1 intensity is low, not enough for the reality use, and the softening temperature of comparative example 2-2 is low, poor heat resistance.
[test of heat resistanceheat resistant decomposability]
Cutting from the honeycomb support of embodiment 2-1,2-2 and comparative example 2-1 all is the test film of vertical 10mm * horizontal 10mm * long 10mm, be placed in 1000 ℃ the high-temperature atmosphere, carry out the test of heat resistanceheat resistant decomposability over time by the survival rate β (%) that investigates aluminium titanates.
The collection of illustrative plates that the survival rate of aluminium titanates is measured (XRD) from X-ray diffraction is tried to achieve by the following method.
Produce Al during at first, owing to the aluminium titanates thermolysis
2O
3(corundum) and TiO
2(rutile), the integrated intensity (I of the diffraction peak of (110) face of usefulness rutile
TiO2 (110)) and the integrated intensity (I of the diffraction peak of (023) face of aluminium titanates
AT (023)) try to achieve the strength ratio r of aluminium titanates by following formula to rutile.
r＝I
AT(023)/(I
AT(023)+I
TiO2(110))
In addition, the sintered compact before the thermal treatment of carrying out under 1000 ℃ is also used the same method try to achieve the strength ratio r of aluminium titanates rutile
0Then, r and the r that tries to achieve with aforesaid method
0Try to achieve the survival rate β (%) of aluminium titanates by following formula.
β＝(r/r
0)×100
About the survival rate β (%) of the aluminium titanates of each sintered compact of embodiment 2-1,2-2 and comparative example 2-1 over time shown in the chart of Fig. 2.As shown in Figure 2, the sintered compact of embodiment 2-1,2-2 is compared with comparative example 2-1, and survival rate is higher through still keeping for a long time, and the heat resistanceheat resistant decomposability is good.In addition, the survival rate through the embodiment 2-1 after 100 hours of Fig. 2 reduces slightly, but the sintered compact of embodiment 2-2 is still kept higher survival rate, and the heat resistanceheat resistant decomposability is better than embodiment 2-1.
[alkaline resistance test of honeycomb]
Remove automobile exhaust gas NO in order to investigate honeycomb for conduct
xThe erosion resistance of potassic catalyzer of catalyzer, carried out following test.The use temperature of the honeycomb support of automobile exhaust gas is in the scope of room temperature to 850 ℃, in addition, the potassium concn of potassic catalyzer is not very high, but in this test, carry out being placed on temperature for a long time and keeping accelerated test under the severe condition in 900 ℃ the stove with being immersed in test film dry again behind the saltpetre aqueous solution of concentration 1 mol.
[test method]
Cutting the cross section respectively from the honeycomb of embodiment 2-1, embodiment 2-2 and comparative example 2-2 is the square of length of side 30mm, the test film of long 50mm, with this test film in the saltpetre aqueous solution of concentration 1 mol under room temperature dipping 1 hour.Then, this test film is following dry 1 hour at 70 ℃.Dried honeycomb is inserted in the tube furnace of internal diameter 5cm, long 42cm, in this tube furnace, fed the air that contains 10% moisture, under following condition, keep the specified time simultaneously with 25cc/ minute.Then, the honeycomb that takes out from tube furnace is carried out XRD determining, investigate the alteration of honeycomb material.The air that contains 10% moisture that feeds in tube furnace prepares by the tank that is controlled at 60 ℃ by making air.The result of test is shown in table 2-2.
Conservation condition
Temperature in the stove: 900 ℃, the intensification of stove, cooling rate: 100 ℃/hour
Hold-time: 50 hours, 100 hours, 150 hours, 200 hours
Table 2-2
| Honeycomb | Hold-time | |||
| 50 hours | 100 hours | 150 hours | 200 hours | |
| Embodiment 2-1 | Do not change | Do not change | Do not change | Do not change |
| Embodiment 2-2 | Do not change | Do not change | Do not change | Do not change |
| Comparative example 2-2 | Do not change | Near 2 θ=28 °, find KAlSiO 4The peak | At KAlSiO 4The place, peak find to increase | At KAlSiO 4The place, peak find to increase |
By the result who shows 2-2 as can be known, the honeycomb of embodiment 2-1, embodiment 2-2 is all good to the erosion resistance of alkali.
Claims (11)
1. honeycomb carrier for exhaust gas clarification catalyst, described carrier is the honeycomb support that is used to carry the catalyzer of purifying exhaust air, it is characterized in that, the method for producing aluminum magnesium titanate sintered product of the material of this honeycomb support for mixture is obtained at 1000～1700 ℃ of following sintering, described mixture contain the amount that is converted into oxide compound be 100 mass parts with chemical formula: Mg
xAl
2 (1-x)Ti
(1+x)O
5The metal ingredient of Mg in the represented aluminum magnesium titanate, Al and Ti contains the mixture of magnesium-containing compound, aluminum contained compound and titanium-containing compound and 1～10 mass parts chemical formula than same metal ingredient ratio: (Na
yK
1-y) AlSi
3O
8Represented alkali feldspar, in the formula, 0＜x＜1,0≤y≤1.
2. honeycomb carrier for exhaust gas clarification catalyst, described carrier is the honeycomb support that is used to carry the catalyzer of purifying exhaust air, it is characterized in that, the al titanate sintering body of the material of this honeycomb support for raw mix is obtained at 1250～1700 ℃ of following sintering, described mixture contain 100 mass parts be called the X composition with TiO
2/ Al
2O
3=40～60/60～40 mol ratio contains TiO
2And Al
2O
3Mixture, and 1～10 mass parts is called the chemical formula of Y composition: (Na
yK
1-y) AlSi
3O
8Represented alkali feldspar, the oxide compound of spinel structure that contains Mg or MgO or change into the magnesium-containing compound of MgO by sintering, in the formula, 0≤y≤1.
3. honeycomb carrier for exhaust gas clarification catalyst as claimed in claim 2, its feature are that also the Y composition is a chemical formula: (Na
yK
1-y) AlSi
3O
8Represented alkali feldspar, the oxide compound of spinel structure that contains Mg and/or MgO or change into the mixture of the magnesium-containing compound of MgO by sintering, in the formula, 0≤y≤1.
4. as each the described honeycomb carrier for exhaust gas clarification catalyst in the claim 1～3, its feature is that also honeycomb support has wall thickness, 15～124 holes/cm of 0.05～0.6mm
2Hole density, and the void content in next door is 20～50%, thermal expansivity is 3.0 * 10
-6K
-1Below.
5. as each the described honeycomb carrier for exhaust gas clarification catalyst in the claim 1～4, its feature is that also described catalyzer contains the NO that is useful in the removal waste gas
xBasic metal and alkaline-earth metal composition.
6. as each the described honeycomb carrier for exhaust gas clarification catalyst in the claim 1～5, its feature is that also waste gas is the waste gas that injects fuel directly into in-engine mode or make the automobile of fuel dilution incendiary mode.
7. the manufacture method of honeycomb carrier for exhaust gas clarification catalyst, it is characterized in that, the preparation raw mix, adding in this raw mix helps binder mixing, carrying out plasticization makes it can extrusion molding, after extrusion molding is honeycomb, at 1000～1700 ℃ of following sintering, described raw mix contain the amount that is converted into oxide compound be 100 mass parts with chemical formula: Mg
xAl
2 (1-x)Ti
(1+x)O
5The metal ingredient of Mg in the represented aluminum magnesium titanate, Al and Ti contains the mixture of magnesium-containing compound, aluminum contained compound and titanium-containing compound and 1～10 mass parts chemical formula than same metal ingredient ratio: (Na
yK
1-y) AlSi
3O
8Represented alkali feldspar, in the formula, 0＜x＜1,0≤y≤1.
8. the manufacture method of honeycomb carrier for exhaust gas clarification catalyst, it is characterized in that, the preparation raw mix, adding in this raw mix helps binder mixing, carrying out plasticization makes it can extrusion molding, after extrusion molding is honeycomb, at 1250～1700 ℃ of following sintering, described raw mix contain 100 mass parts be called the X composition with TiO
2/ Al
2O
3=40～60/60～40 mol ratio contains TiO
2And Al
2O
3Mixture, and 1～10 mass parts is called the chemical formula of Y composition: (Na
yK
1-y) AlSi
3O
8Represented alkali feldspar, the oxide compound of spinel structure that contains Mg or MgO or change into the magnesium-containing compound of MgO by sintering, in the formula, 0≤y≤1.
9. as the manufacture method of claim 7 or 8 described honeycomb carrier for exhaust gas clarification catalyst, its feature is that also the median size of each composition that described raw mix is contained is below 10 μ m.
10. the purifying method of waste gas, described method is to make waste gas contact the purifying method of the honeycomb support of the catalyzer that carries purifying exhaust air, it is characterized in that, the method for producing aluminum magnesium titanate sintered product of the material of this honeycomb support for mixture is obtained at 1000～1700 ℃ of following sintering, described mixture contain the amount that is converted into oxide compound be 100 mass parts with chemical formula: Mg
xAl
2 (1-x)Ti
(1+x)O
5The metal ingredient of Mg in the represented aluminum magnesium titanate, Al and Ti contains the mixture of magnesium-containing compound, aluminum contained compound and titanium-containing compound and 1～10 mass parts chemical formula than same metal ingredient ratio: (Na
yK
1-y) AlSi
3O
8Represented alkali feldspar, in the formula, 0＜x＜1,0≤y≤1.
11. the purifying method of waste gas, described method is to make waste gas contact the purifying method of the honeycomb support of the catalyzer that carries purifying exhaust air, it is characterized in that, the al titanate sintering body of the material of this honeycomb support for mixture is obtained at 1250～1700 ℃ of following sintering, described mixture contain 100 mass parts be called the X composition with TiO
2/ Al
2O
3=40～60/60～40 mol ratio contains TiO
2And Al
2O
3Mixture, and 1～10 mass parts is called the chemical formula of Y composition: (Na
yK
1-y) AlSi
3O
8Represented alkali feldspar, the oxide compound of spinel structure that contains Mg or MgO or change into the magnesium-containing compound of MgO by sintering, in the formula, 0≤y≤1.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003203271A JP4609831B2 (en) | 2003-07-29 | 2003-07-29 | Honeycomb carrier for exhaust gas purification catalyst and manufacturing method thereof |
| JP203271/2003 | 2003-07-29 | ||
| JP321537/2003 | 2003-09-12 |
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| CN2007100971354A Division CN101091925B (en) | 2003-07-29 | 2004-07-29 | Honeycomb carrier for exhaust gas clarification catalyst and method for production thereof |
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| CN100400464C CN100400464C (en) | 2008-07-09 |
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| CN (1) | CN100400464C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102143925A (en) * | 2008-09-04 | 2011-08-03 | 住友化学株式会社 | Aluminum titanate ceramic manufacturing method |
| CN103566920A (en) * | 2012-08-01 | 2014-02-12 | 通用电气公司 | Substance and exhaust device and method using same |
| CN105924202A (en) * | 2016-04-28 | 2016-09-07 | 河南省格林沃特净化器股份有限公司 | Preparation technology of SCR catalyst carrier for diesel engine tail gas post-treatment |
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| JPH0654477A (en) * | 1992-07-28 | 1994-02-25 | Sanyo Electric Co Ltd | Bearing device of motor |
| FR2933398B1 (en) * | 2008-07-04 | 2011-02-18 | Saint Gobain Ct Recherches | OXIDE-FILLED GRAINS COMPRISING AL, TI AND MG AND CERAMIC PRODUCTS COMPRISING SUCH GRAINS |
| JP5368081B2 (en) * | 2008-12-25 | 2013-12-18 | 住友化学株式会社 | Method for producing aluminum titanate-based fired body |
| WO2012070386A1 (en) * | 2010-11-24 | 2012-05-31 | 住友化学株式会社 | Honeycomb filter |
| JP2014018768A (en) * | 2012-07-20 | 2014-02-03 | Sumitomo Chemical Co Ltd | Exhaust gas purifying system |
| WO2015182773A1 (en) * | 2014-05-30 | 2015-12-03 | 住友化学株式会社 | Honeycomb filter intermediate, honeycomb filter, and processes for producing said intermediate and said filter |
| WO2018198999A1 (en) * | 2017-04-26 | 2018-11-01 | 大塚化学株式会社 | Honeycomb structure and exhaust gas purification device |
| CN114515570A (en) * | 2022-01-30 | 2022-05-20 | 华南理工大学 | Catalyst for ethyl acetate oxidation molding and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS605545B2 (en) * | 1980-03-19 | 1985-02-12 | 日本碍子株式会社 | Low expansion ceramics and their manufacturing method |
| JPS573767A (en) * | 1980-06-04 | 1982-01-09 | Nippon Toki Kk | High temperature-stable high strength aluminium titanate sintered body |
| DE3772061D1 (en) * | 1986-01-28 | 1991-09-19 | Matsushita Electric Ind Co Ltd | METHOD FOR PRODUCING CERAMIC BODIES WITH HEAT SHOCK RESISTANCE. |
| JP2828986B2 (en) * | 1988-03-31 | 1998-11-25 | 株式会社東芝 | Ceramic sintered body |
| JPH02311361A (en) * | 1989-05-27 | 1990-12-26 | Toyota Motor Corp | Production of aluminum titanate sintered compact stable at high temperature |
| JPH08290963A (en) * | 1995-04-21 | 1996-11-05 | Matsushita Electric Ind Co Ltd | Material having low thermal expansion and discharge gas filter using the same |
| JPH0929024A (en) * | 1995-07-21 | 1997-02-04 | Matsushita Electric Ind Co Ltd | Exhaust gas filter |
| JP4267743B2 (en) * | 1999-03-26 | 2009-05-27 | 株式会社オハラ | Polishing method of glass ceramic substrate for information storage medium |
| DE60139569D1 (en) * | 2000-11-06 | 2009-09-24 | Corning Inc | CATALYST FOR CLEANING EXHAUST GASES |
| JP3600933B2 (en) * | 2000-11-08 | 2004-12-15 | オーセラ株式会社 | Method for producing aluminum titanate-based sintered body |
| CN1816379B (en) * | 2003-07-11 | 2010-11-24 | 王世来股份有限公司 | Honeycomb filter for clarifying exhaust gas and method for manufacture thereof |
| ATE430616T1 (en) * | 2003-08-22 | 2009-05-15 | Ohcera Co Ltd | HONEYCOMB FILTER FOR PURIFYING EXHAUST GAS AND METHOD FOR PRODUCING IT |
-
2003
- 2003-07-29 JP JP2003203271A patent/JP4609831B2/en not_active Expired - Fee Related
-
2004
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102143925A (en) * | 2008-09-04 | 2011-08-03 | 住友化学株式会社 | Aluminum titanate ceramic manufacturing method |
| CN103566920A (en) * | 2012-08-01 | 2014-02-12 | 通用电气公司 | Substance and exhaust device and method using same |
| CN103566920B (en) * | 2012-08-01 | 2016-05-25 | 通用电气公司 | Material and the exhaust apparatus and the method that use it |
| US9586193B2 (en) | 2012-08-01 | 2017-03-07 | General Electric Company | Material and exhaust gas system and method for using the same |
| CN105924202A (en) * | 2016-04-28 | 2016-09-07 | 河南省格林沃特净化器股份有限公司 | Preparation technology of SCR catalyst carrier for diesel engine tail gas post-treatment |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2005046667A (en) | 2005-02-24 |
| CN100400464C (en) | 2008-07-09 |
| JP4609831B2 (en) | 2011-01-12 |
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