CN1791564A - Honeycomb structure - Google Patents
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- CN1791564A CN1791564A CN 200480001795 CN200480001795A CN1791564A CN 1791564 A CN1791564 A CN 1791564A CN 200480001795 CN200480001795 CN 200480001795 CN 200480001795 A CN200480001795 A CN 200480001795A CN 1791564 A CN1791564 A CN 1791564A
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Abstract
A honeycomb structure 10 of the present invention comprises: porous honeycomb units 11 having multiple through-holes, including the first form of an inorganic material (for example, ceramic particles), the second form of an inorganic material (for example, inorganic fibers or ceramic particles having large particle sizes), and an inorganic binder; and sealing material layers 14 jointing the porous honeycomb units 11 at outer surfaces 13 where the through-holes are not open. The cross-sectional area perpendicular to the through-holes is about 5 to about 50 cm<2>. The ratio of the total cross-sectional area of the porous honeycomb units 11 to the cross-sectional area of the honeycomb structure 10 is not less than about 85%. The honeycomb structure 10 reduces thermal stress or vibration applied to each porous honeycomb unit 11 , by the sealing material layers 14 , and allows for amore effective use of surface on which catalyst components are dispersed.
Description
Technical field
The present invention relates to honeycomb structured body.
Background technology
In the past, the honeycomb catalyst that generally is used to purify the waste gas of motor vehicle emission was following manufacturing: the catalyst metal of the material of the high-specific surface area by loading with activated alumina etc. on the surface of the low cordierite honeycomb structure body of integrative-structure and thermal expansivity and platinum etc. is made.And, as lean mixture engine and diesel motor etc., handle alkaline-earth metals such as also having loaded with Ba and be used for as NOx adsorbent in order under the condition of oxygen surplus, to carry out NOx.Yet,, be necessary to increase the contact probability of waste gas and catalyzer precious metal and NOx adsorbent in order to improve purifying property.Therefore, must further add the specific surface area of larger vector, reduce the size of noble metal granule, and make the catalyzer high dispersing.Yet, the amount of loading with of the material of specific surface areas big (high-specific surface area) such as simple increase activated alumina, can cause the increase of alumina layer thickness, or the generation contact probability can't improve or the excessive bad like this situation of the pressure-losses, therefore study (for example, opening flat 10-263416 communique) in properties such as cell configuration, cell density and wall thickness with reference to the spy.On the other hand, as the honeycomb structured body that is formed by the high-specific surface area material, known being and not being organic fiber and inorganic adhesive be extrusion moulding and the honeycomb structured body (for example, opening flat 5-213681 communique with reference to the spy) made together.In addition, also have a kind of known honeycomb structured body a plurality of cellular units to be glued together, its objective is this kind honeycomb structured body maximization (for example, with reference to the DE4341159 communique) by bonding coat.
Yet, have following problem in the above-mentioned conventional art.Owing to thermal ageing produces sintering, the specific surface area of material descends at the big material of specific surface areas such as activated alumina.And, be accompanied by this phenomenon, catalyst metal aggegations such as the platinum of loading with on the material, particle diameter increases, and specific surface area reduces.That is to say to have high-specific surface area, be necessary that the stage increases its specific surface area in the early stage for making after thermal ageing (using) as support of the catalyst.In addition, as above-mentioned,, be necessary to increase the contact probability of waste gas and catalyzer precious metal and NOx adsorbent in order to improve purifying property.Therefore, need further add larger vector specific surface area, reduce the size of catalyst metal particles and make its high dispersing.Open the spy on the surface of the cordierite-based honeycomb structure described in the flat 10-263416 communique, load with catalyst metal such as big material of specific surface areas such as activated alumina and platinum.In order to improve the contact probability with waste gas, though studying aspect cell configuration, cell density and the wall thickness, increased the specific surface area of support of the catalyst, but still enough not big, therefore the dispersion of catalyst metal and insufficient, the exhaust-gas purifying performance deficiency after the thermal ageing.So, in order to remedy this deficiency, in advance by on carrier, loading with a large amount of catalyst metal or the such structure of support of the catalyst self maximization being solved the problems referred to above.But, precious metal such as platinum costs an arm and a leg and resource-constrained.And because the installing space when being installed in honeycomb structured body on the automobile is limited, these two kinds is not suitable method.
Also have, honeycomb structured body in the Te Kaiping 5-213681 communique, it is obtained with inorganic fibre and inorganic adhesive extrusion moulding by the big material of specific surface area, because base material itself is made of the big material of specific surface area, therefore, specific surface area as carrier is also big, fully the high dispersing catalyst metal.Yet in order to keep specific surface area, base materials such as aluminum oxide are sintering fully, so the non-constant of the intensity of base material.In addition, as mentioned before, installing space is very limited when it is used for automobile.Therefore,, take method, but the intensity of base material is just poorer like this with the spaced walls attenuation in order to increase the specific surface area of carrier on the unit volume.In addition, the coefficient of thermal expansion of base materials such as aluminum oxide is very big, and when firing (calcining) and use, the stress influence that is heated is easy to generate the crack.Consider these, when being used for automobile, because external force such as violent thermal stresses that temperature variation produced or bigger vibration are applied thereto when using, therefore traditional honeycomb structured body has following problem, promptly the structure cracky, can not keep honeycomb structured body shape, can't play the effect of support of the catalyst.
In addition, in the automotive catgalyst carrier in the DE4341159 communique, owing to its objective is that the sectional area of disclosed cellular unit is at 200cm with the honeycomb structured body maximization
2More than, be applied thereto by violent thermal stresses that temperature variation produced and bigger vibration, when using in this case, can have above-mentioned such problem, promptly cracky, can not keep as the honeycomb structured body shape, can't play the effect of support of the catalyst.
Summary of the invention
The present invention is based on the shortcoming of above-mentioned prior art, purpose provides and can make the catalyst component high dispersing can improve honeycomb structured body to the intensity of heat shock resistance and vibration again.
Achieve the above object the honeycomb structured body among following structure the present invention for making.
Honeycomb structured body of the present invention has:
The porous honeycomb unit has several communicating poress, comprises the 1st form inorganic materials and the 2nd form inorganic materials at least, and with the vertical sectional area of this communicating pores be 5cm
2～50cm
2
Sealing material layer, two or more described porous honeycombs unit is bonding mutually in the outside that does not have described communicating pores opening.
Because therefore the structure that this honeycomb structured body has adopted several porous honeycomb unit to be bonded together by sealing material layer can increase the intensity to heat shock resistance or vibration.Its reason can be speculated as, though violent temperature variation etc. and in honeycomb structured body formation temperature distribute, but that the temperature head that exists in each porous honeycomb unit also can remain is very little.Perhaps can be speculated as, thermal shocking or vibration may obtain relaxing because of sealing material layer.In addition, even causing that by thermal stresses etc. the porous honeycomb unit produces under the fissured situation, the sealing material layer can prevent that also fracture propagation from arriving whole honeycomb structure, can also play the effect of honeycomb structured body framework, keep the shape of honeycomb structured body, can not lose function as support of the catalyst.About the unitary size of porous honeycomb, if the area in the cross section that intersects vertically with communicating pores (abbreviates sectional area as.Down together.) not enough 5cm
2, because the sectional area of the unitary sealing material layer of bonding several porous honeycombs increases, the specific surface area of therefore loading with catalyzer reduces relatively, the pressure-losses increases relatively; On the other hand, if sectional area surpasses 50cm
2, unitary oversize, can not fully be suppressed at the thermal stresses that produces in each cellular unit.That is to say, unitary sectional area is controlled at 5cm
2～50cm
2Scope in, can guarantee bigger specific surface area, can contain the pressure-losses again, keep that enough the intensity of thermal stress resistance is had very high weather resistance.Therefore, can this honeycomb structured body of practical application.Utilize this honeycomb structured body, can the high dispersing catalyst component, can improve intensity again to heat shock resistance and vibration.When honeycomb structured body comprised different several porous honeycomb unit of sectional area, so-called here sectional area was meant and constitutes the most basic unitary sectional area of porous honeycomb of honeycomb structured body, then is meant the unitary maximum secting area of porous honeycomb usually.In addition, the ratio that the preferred unitary total sectional area of porous honeycomb accounts for the sectional area of honeycomb structured body is not less than 85%, more preferably is not less than 90%.During this ratio less than 85%, because the sectional area of sealing material layer strengthens and the unitary total sectional area of porous honeycomb reduces, the specific surface area of therefore loading with catalyzer reduces and also increasing relatively of the pressure-losses relatively.On the other hand, this ratio is not less than at 90% o'clock, can further reduce the pressure-losses.
In addition, honeycomb structured body of the present invention has:
The porous honeycomb unit has several communicating poress, comprises the 1st form inorganic materials and the 2nd form inorganic materials at least, is not more than 50cm with the intersect vertically sectional area of face of this communicating pores
2
Sealing material layer, two or more described porous honeycombs unit is bonding in the outside that does not have described communicating pores opening;
And the ratio that the unitary total sectional area of described porous honeycomb accounts for the sectional area of honeycomb structured body is not less than 85%.
Because therefore the structure that this honeycomb structured body has adopted several porous honeycomb unit to be bonded together by sealing material layer can increase the intensity to heat shock resistance or vibration.Its reason can be speculated as, and formation temperature distributes in honeycomb structured body even violent temperature variation etc. make, and the temperature head that exists in each porous honeycomb unit can be retained as very little.Perhaps can be speculated as, thermal shocking or vibration can obtain relaxing because of sealing material layer.In addition, even causing under the fissured situation in porous honeycomb unit by thermal stresses etc., the sealing material layer can prevent that also fracture propagation from arriving whole honeycomb structure, can also play the effect of honeycomb structured body framework, keep the shape of honeycomb structured body, can not lose function as support of the catalyst.If the unitary sectional area of porous honeycomb surpasses 50cm
2, unitary oversize, can not fully be suppressed at the thermal stresses that produces in each cellular unit.And this moment, the shock absorption from sealing material layer opposing thermal stresses and vibration reduced, and therefore preferably sectional area is not more than 50cm
2In addition, the ratio that the unitary total sectional area of porous honeycomb accounts for the sectional area of honeycomb structured body is lower than at 85% o'clock, the sectional area of the material beyond the porous honeycomb unit increases, the specific surface area of loading with catalyzer reduces relatively, the pressure-losses increases relatively simultaneously, so ratio preferably is not less than 85%, more preferably be not less than 90%.Therefore, utilize this honeycomb structured body, energy high dispersing catalyst component can also improve the intensity to heat shock resistance and vibration.When honeycomb structured body comprised different several porous honeycomb unit of sectional area, so-called here sectional area was meant and constitutes the most basic unitary sectional area of porous honeycomb of honeycomb structured body, then is meant the unitary maximum secting area of porous honeycomb usually.
In honeycomb structured body of the present invention, can also have the coated material layer, cover the unitary periphery that does not have the communicating pores opening of the two or more porous honeycombs that combine by sealing material layer.This structure can protect periphery to improve honeycomb structured body intensity.
Shape for the bonding unitary honeycomb structured body of porous honeycomb does not have particular restriction, can be arbitrary shape, arbitrary dimension.For example, can be right cylinder, prism or oval cylinder.
In the honeycomb structured body of the present invention, the 2nd form inorganic materials also can have the effect as the unitary strengthening material of porous honeycomb.So, improved the unitary intensity of porous honeycomb by the 2nd form inorganic materials.
In the honeycomb structured body of the present invention, the 1st form inorganic materials is the inorganic materials with regulation long-width ratio (long limit/minor face), and the inorganic materials of the 2nd form can be the inorganic materials with long-width ratio bigger than described regulation long-width ratio.So, by using the inorganic materials of the 2nd bigger form of long-width ratio, improved the unitary intensity of porous honeycomb.Herein, the long-width ratio of the 2nd form inorganic materials is preferred between 2～1000, between 5～800 for more preferably, between 10～500 for most preferably.If the long-width ratio of the inorganic materials of the 2nd form is lower than 2, can reduce the contribution that improves honeycomb structured body intensity; If surpass 1000, cause the obstruction of inorganic materials during moulding easily, formability meeting variation for forming mould, and when carrying out moulding with methods such as extrusion mouldings, inorganic materials can fracture, cause length uneven, can reduce thus the contribution that improves honeycomb structured body intensity.Here, if the long-width ratio of the 2nd form inorganic materials is unbalanced, can get its mean value.
In the honeycomb structured body of the present invention, the inorganic materials of the 1st form is a ceramic particle, and the inorganic materials of the 2nd form can be an inorganic fibre.Like this, increase specific surface area, improve the unitary intensity of porous honeycomb by inorganic fibre by ceramic particle.
In honeycomb structured body of the present invention, the inorganic materials of the 1st form is the ceramic particle with regulation particle diameter, and the inorganic materials of the 2nd form can be the ceramic particle with particle diameter bigger than described regulation particle diameter.Like this, by using the big ceramic particle of particle diameter, improved the unitary intensity of porous honeycomb.At this moment, the particle diameter of the inorganic materials of the 2nd form more than 5 times or 5 times is preferred at described regulation particle diameter, 10 times～30 times of described regulation particle diameter for more preferably.And the ceramic particle diameter of the inorganic materials of the 2nd form is preferably 10 μ m～60 μ m, more preferably 20 μ m～50 μ m.If be lower than 10 μ m, just can not fully improve the intensity of honeycomb structured body; If surpass 60 μ m, cause the obstruction of particle during moulding easily for forming mould, formability can variation.Here, when the particle diameter of the inorganic materials of the particle diameter of the inorganic materials of the 1st form or the 2nd form is inconsistent, can get its mean value.And, the ceramic particle of the inorganic materials of the 2nd form, can select and the diverse material of the ceramic particle of described the 1st form inorganic materials, also can select the identical but material of shape (as particle diameter etc.) difference or rerum natura difference (as crystallization shape difference or melting temperature (Tm) difference) of ceramic particle kind with described the 1st form inorganic materials.In addition, when using ceramic particle as the inorganic materials of the 2nd form, owing to can improve the intensity of honeycomb structured body by the size that changes particle diameter, its long-width ratio also can be identical with the inorganic materials of the 1st form.
In the honeycomb structured body of the present invention, when using ceramic particle, there is not particular restriction for ceramic particle contained in the honeycomb structured body as the inorganic materials of the 1st form or the 2nd form.For example, can be from silicon carbide, silicon nitride, aluminum oxide, silicon oxide, zirconium white, titanium oxide, cerium oxide and mullite, select a kind of or be no less than two kinds of particles, wherein preferred aluminum oxide.
In the honeycomb structured body of the present invention, when using inorganic fibre, there is not particular restriction for inorganic fibre contained in the honeycomb structured body as the inorganic materials of the 1st form or the 2nd form.For example, can be from aluminum oxide, silicon oxide fibre, silicon carbide fiber, silica-alumina fiber, glass fibre and potassium titanate fiber, select a kind of or be no less than two kinds of inorganic fibres.
The amount of the 1st contained form inorganic materials (ceramic particle etc.) in the honeycomb structured body is preferably 30 weight %～97 weight %, more preferably 30 weight %～90 weight %, further preferred 40 weight %～80 weight %, most preferably 50 weight %～75 weight %.If the amount of the 1st form inorganic materials is lower than 30 weight %, reduce relatively owing to help to increase the amount of the 1st form inorganic materials of specific surface area, the specific surface area of honeycomb structured body is less, just can not the high dispersing catalyst component when loading with catalyst component; If surpass 90 weight %, reduce relatively owing to help to improve the amount of the 2nd form inorganic materials (inorganic fibre etc.) of intensity, the intensity of honeycomb structured body reduces.
The amount of the 2nd contained form inorganic materials (inorganic fibre etc.) in the honeycomb structured body is preferably 3 weight %～70 weight %, 3 weight %～50 weight % more preferably, and more preferably 5 weight %～40 weight % most preferably are 8 weight %～30 weight %.If the amount of the 2nd form inorganic materials is lower than 3 weight %, the intensity of honeycomb structured body reduces; If surpass 50 weight %, reduce relatively owing to help to increase the amount of the 1st form inorganic materials (ceramic particle etc.) of specific surface area, the specific surface area of honeycomb structured body is less, just can not the high dispersing catalyst component when loading with catalyst component.
In the honeycomb structured body of the present invention, can also comprise inorganic adhesive in the porous honeycomb unit.So, even turn down the unitary firing temperature of porous honeycomb, honeycomb structured body also can access enough intensity.Do not have special restriction for the inorganic adhesive that comprises in the honeycomb structured body, for example, can exemplify and be inorganic sol or clay class tackiness agent.Wherein, inorganic sol can be a kind of of selection from alumina sol, silica sol, titanium oxide sol and water glass etc. or be no less than two kinds of inorganic sols.Clay class tackiness agent can be a kind of of selection from potter's clay, kaolin, polynite, multichained construction type clay (sepiolite, attapulgite) etc. or be no less than two kinds of clay class tackiness agents.As solids component contained in the honeycomb structured body, the amount of contained inorganic adhesive in the honeycomb structured body preferably is less than and equals 50 weight %, more preferably 5 weight %～50 weight %, further preferred 10 weight %～40 weight %, most preferably 15 weight %～35 weight %.If the content of inorganic adhesive surpasses then formability variation of 50 weight %.
Do not have particular restriction for the unitary shape of porous honeycomb, between the porous honeycomb unit easily adherent be shaped as preferably, (abbreviate the cross section as with the intersect vertically cross section of face of communicating pores.Down together.) can be square, rectangle, hexagon or fan-shaped.As the unitary example of porous honeycomb, having provided the cross section in Fig. 1 (a) is the synoptic diagram of foursquare rectangular parallelepiped porous honeycomb unit 11.In the porous honeycomb unit 11, existing a lot of inboard communicating poress 12 that lead to from the front side have the outside 13 of communicating pores 12 or not.Do not have special restriction for the wall thickness between each communicating pores 12, it is preferably 0.05mm～0.35mm, and more preferably 0.10mm～0.30mm most preferably is 0.15mm～0.25mm.If wall thickness is lower than 0.05mm, the unitary intensity of porous honeycomb reduces; If surpass 0.35mm, owing to the contact surface area with waste gas diminishes, gas can not fully enter into the depths, is difficult for contacting with waste gas owing to load with in the catalyzer of pars intramuralis, thereby reduces catalyst performance.In addition, the communicating pores quantity of per unit sectional area is preferably 15.5～186/cm
2(100～1200cpsi), more preferably 46.5～170.5/cm
2(300～1100cpsi), most preferably be 62.0～155/cm
2(400～1000cpsi).If communicating pores quantity is less than 15.5/cm
2, then diminish with the contacted spaced walls area of the waste gas of inside, porous honeycomb unit; If communicating pores quantity surpasses 186/cm
2, then the pressure-losses increases, and it is difficult that the unitary making of porous honeycomb becomes.
Shape for the communicating pores that forms in the porous honeycomb unit does not have particular restriction, and the cross section can roughly triangular in shape or hexagon.So, can not increase the pressure-losses or not reduce the purifying property of waste gas, improve the unitary intensity of porous honeycomb, thereby improve the intensity (for example isobaric intensity etc.) of honeycomb structured body.When being trilateral with the cross section of the communicating pores 12 of porous honeycomb unit 11 is example, is illustrated in the different porous honeycomb unit of communicating pores 12 of the section triangle that forms on the above-below direction in Fig. 2 (a); Expression makes the trilateral fixed point of four communicating poress 12 with trilobal(cross)section form the cellular unit of four distressed structures relatively among Fig. 2 (b); The cellular unit that expression is formed by the communicating pores 12 with hexagonal cross-section in Fig. 2 (c).Can in porous honeycomb unit 11, form communicating pores 12 like this.
The unitary sectional area of porous honeycomb that constitutes honeycomb structured body is preferably dimensioned to be 5cm
2～50cm
2, 6cm more preferably
2～40cm
2, most preferably be 8cm
2～30cm
2If sectional area is at 5cm
2～50cm
2Scope between, then can adjust sealing material layer shared ratio in honeycomb structured body.Thus, both can keep the specific surface area of unit volume in the honeycomb structured body significantly, can also the high dispersing catalyst component.Even the external force that has applied thermal shocking or vibration etc. also can be kept the shape of honeycomb structured body.In addition, owing to the pressure-losses can diminish, so preferred cross-sections is long-pending more than or equal to 5cm
2And, can be by the specific surface area of following formula (1) calculating per unit volume.
Next, describe with the manufacture method of an example described honeycomb structured body of the present invention.At first, use the inorganic materials of inorganic materials with described the 1st form, the 2nd form and inorganic adhesive to carry out extrusion moulding, make the formed body of cellular unit as the raw material slurry of main component.Can also cooperate formability in the raw material slurry, suitably to add organic binder bond, dispersion agent and shaping assistant.Do not have particular restriction for organic binder bond, for example, can be from methylcellulose gum, carboxymethyl cellulose, Natvosol, polyoxyethylene glycol, phenol resins and Resins, epoxy, select a kind of or be no less than two kinds of organic binder bonds.When being 100 weight parts with the weight summation of the inorganic materials of the inorganic materials of the 1st form, the 2nd form and inorganic adhesive, the combined amount of organic binder bond preferably be 1～10 weight part.Not having particular restriction for dispersion agent, for example can be, water, organic solvent (benzene etc.) and alcohol (methyl alcohol etc.).Not having particular restriction for shaping assistant, for example can be, ethylene glycol, dextrin, fatty acid soaps and polyalcohols.
Do not have particular restriction for the raw material slurry, preferably mix and rub up.For example can mix with stirrer and pulverizer etc., also available kneader etc. rubs up fully.Forming method for the raw material slurry does not have particular restriction, for example, preferably makes the method for communicating pores shape by extrusion moulding.
Afterwards, preferably the formed body of making is carried out drying.Not having particular restriction for being used for the exsiccant drying machine, can be microwave dryer, hot air dryer, dielectric heat drying machine, drying under reduced pressure machine, Vacuumdrier and freeze drier.And, preferably the formed body of making is carried out degreasing.Condition for degreasing does not have particular restriction, can suitably select according to contained organic kind and content in the formed body, is preferably about 400 ℃ 2 hours.In addition, preferably the formed body of making is fired.There is not particular restriction for the condition of firing, preferred 600 ℃～1200 ℃, more preferably 600 ℃～1000 ℃.Its reason is, if firing temperature is lower than 600 ℃, then sintering can not take place for ceramic particle etc., and the intensity of honeycomb structured body reduces; If surpass 1200 ℃, then the sintering of ceramic particle is excessive, and the specific surface area of unit volume reduces, fully the catalyst component loaded with of high dispersing.Just can obtain having the porous honeycomb unit of a plurality of communicating poress through these operations.
Next, the sealing slurry that forms sealing material layer is coated on the Manufactured porous honeycomb unit, bonding successively each porous honeycomb unit carries out drying afterwards and makes it firm, has just made the cellular unit adherend of specified dimension.There is not particular restriction for sealing material.For example, can use the mixture of mixture, inorganic adhesive and inorganic fibre of inorganic adhesive and ceramic particle or mixture of inorganic adhesive and ceramic particle and inorganic fibre etc.And, in these sealing materials, also can add organic binder bond.There is not particular restriction for organic binder bond.Can be from polyvinyl alcohol, methylcellulose gum, ethyl cellulose and carboxymethyl cellulose etc., select a kind of or be no less than two kinds of organic binder bonds.
Preferred 0.5mm～the 2mm of thickness of the unitary sealing material layer of bonding porous honeycomb.This is because when the not enough 0.5mm of the thickness of sealing material layer, might not reach enough bond strengths.And because sealing material layer can not be as support of the catalyst, if thickness surpasses 2mm, the specific surface area of the unit volume of honeycomb structured body reduces, high dispersing fully just when loading with catalyst component.Also have, if thickness surpasses 2mm, the pressure-losses can increase.In addition, can suitably select the unitary quantity of bonding porous honeycomb according to the size of the honeycomb structured body that uses as honeycomb catalyst.And, can also carry out suitable cutting and grinding to the adherend that forms with the bonding porous honeycomb of sealing material layer unit according to shape, the size of honeycomb structured body.
Can not have the periphery (side) of communicating pores opening to smear coated material at honeycomb structured body, make its dry solidification form coating.So, can protect periphery and improve the intensity of honeycomb structured body.Do not have particular restriction for coated material, both can form yet by forming with the sealing material identical materials by different with it materials.And the blending ratio of each material both can be identical with sealing material in the coated material, also can be different with it.Thickness for coating does not have particular restriction, preferred 0.1mm～2mm.If the not enough 0.1mm of thickness then can not protect periphery, and can not increase the intensity of honeycomb structured body; If thickness surpasses 2mm, then the specific surface area of the unit volume of honeycomb structured body reduces, and just can not make it high dispersing fully when loading with catalyst component.
With (if coating is used in plan, then for after forming coating) behind bonding several porous honeycomb unit of sealing material, preferably they are calcined.This is because when containing organic binder bond in sealing material or coated material, do degreasing like this and remove organic binder bond.Can suitably select the incinerating condition according to contained organic kind and content, be preferably about 700 ℃ 2 hours.When using the honeycomb structured body that makes after calcining, the d/d situation of polluting with regard to not having organic binder bond burning residual in honeycomb structured body of waste gas takes place.As an example of honeycomb structured body, in Fig. 1 (b), provided the synoptic diagram of honeycomb structured body 10.Bonding several cross sections of this cylindrical structural body are foursquare rectangular parallelepiped porous honeycomb unit 11.So form honeycomb structured body 10: with sealing material layer 14 bonding porous honeycomb unit 11, cut into right cylinder after, do not have the periphery (side) of the honeycomb structured body 10 of communicating pores 12 openings again with coated material 16 coverings.In addition, the cross section of porous honeycomb unit 11 is made as fan-shaped or square, is made into the honeycomb structured body of the shape (being right cylinder among Fig. 1 (b)) of defined, the operation that then can omit cutting and grind again.
Purposes for the honeycomb structured body that makes does not have particular restriction, is preferred for purifying the support of the catalyst of automobile exhaust gas.And, when being used as the support of the catalyst of purifying waste gas from diesel engine, use diesel particulate filter (DPF) sometimes simultaneously.This strainer has the ceramic honeycomb structure of silicon carbide etc., has the function by particulate matter (PM) in the burning purification filtering waste gas.In this case, honeycomb structured body of the present invention is also passable in the front side of DPF, also can at rear side.When being arranged on the front side, when honeycomb structured body of the present invention occurred being attended by the reaction of heating, the heat of generation reached the DPF of rear side, the intensification in the time of can promoting to regenerate DPF.On the other hand, when being arranged on rear side, because the PM in the waste gas passes through the through hole in the honeycomb structured body of the present invention again after DPF filters, so be difficult for stopping up, also have, the gaseous constituent that is produced by incomplete combustion during for burning PM in DPF can use honeycomb structured body of the present invention to handle.In addition, this honeycomb structured body both can be applied in purposes that is recorded in the described technical background etc., the purposes in the time of can also being applied to not load with catalyst component (for example, the sorbent material of adsorbed gas composition or liquid component).
And, also can in the honeycomb structured body of making, load with catalyst component, make it become honeycomb catalyst.Not having particular restriction for catalyst component, can be precious metal, alkali metal compound, alkaline earth metal compound, oxide compound etc.Precious metal can be select from platinum, palladium, rhodium a kind of or be no less than two kinds metal; Alkali metal compound can be select from for example potassium, sodium etc. a kind of or be no less than two kinds compound; Alkaline earth metal compound can exemplify and be barium compound etc.; Oxide compound can exemplify and be uhligite (La
0.75K
0.25MnO
3Deng) and CeO
2Deng.Purposes for the honeycomb catalyst of making does not have particular restriction, for example can be as purifying so-called three-way catalyst or the NOx adsorptive catalyst that automobile exhaust gas is used.In addition, do not have particular restriction, both can after making honeycomb structured body, load with, can load with yet in the ceramic particle stage of raw material for loading with of catalyst component.The method of loading with to catalyst component does not have particular restriction, for example can wait by the impregnation method and carry out.
Description of drawings
Fig. 1 is the synoptic diagram of porous honeycomb of the present invention unit 11 and honeycomb structured body 10.
Fig. 2 is the explanatory view of the communicating pores 12 of formation in porous honeycomb of the present invention unit 11.
Fig. 3 is scanning electronic microscope (SEM) photo of the interval wall of porous honeycomb of the present invention unit 11.
Fig. 4 is the table of having concluded the manufacturing conditions of experimental example 1～29.
Fig. 5 is the table of having concluded the manufacturing conditions of experimental example 1, experimental example 30～43.
Fig. 6 is the table of having concluded the manufacturing conditions of experimental example 44～51.
The explanatory view of the experimental example of Fig. 7 is bonding a plurality of porous honeycombs unit 11.
The explanatory view of the experimental example of Fig. 8 is bonding a plurality of porous honeycombs unit 11.
Fig. 9 is the explanatory view of vibrating device 20.
Figure 10 is the explanatory view of pressure-losses determinator 40.
Figure 11 is the table of having concluded the measurement result of experimental example 1～29 and experimental example 44～47.
Figure 12 is the figure that concerns between the expression sectional area of cellular unit and the weight decrement and the pressure-losses.
Figure 13 is the figure that concerns between expression cellar area ratio and the weight decrement and the pressure-losses.
Figure 14 is the table of having concluded the measurement result of experimental example 1, experimental example 30～34.
Figure 15 is the figure that concerns between the long-width ratio of expression silica-alumina fiber and the weight decrement.
Figure 16 is the table of having concluded the measurement result of experimental example 35～43.
Figure 17 is the figure that concerns between the particle diameter of αYang Hualv and the weight decrement.
Figure 18 is the table of having concluded the measurement result of experimental example 48 to 51.
Embodiment
Next, with experimental example the specific embodiment of the present invention is described.
Describe as experimental example with under various conditions example below, but the invention is not restricted to these experimental examples.
[experimental example 1]
At first, the gamma-alumina particle (median size 2 μ m) of 40 weight %, the silica-alumina fiber of 10 weight % (average fiber footpath 10 μ m, the long 100 μ m of average fiber, long-width ratio are 10) and the silica sol (solids concn is 30 weight %) of 50 weight % are mixed mutually, the mixture of relative 100 weight part gained, add organic binder bond methylcellulose gum and the small amount of plasticizer and the lubricant of 6 weight parts, mix afterwards, mediate and obtain mixed component.Next, use extrusion shaping machine that this mixed component is carried out extrusion moulding, thereby obtain thick formed body.
Then, with microwave dryer and the thick formed body of hot air dryer thorough drying, keep carrying out in 2 hours degreasing at 400 ℃.Keep firing in 2 hours at 800 ℃ more afterwards, just obtain porous honeycomb unit 11.This porous honeycomb unit is prism-shaped, and (34.3mm * 34.3mm * 150mm), honeycomb hole (cell) density is 93/cm
2(600cpsi), wall thickness is 0.2mm, and honeycomb hole is shaped as tetragon (square).Fig. 3 has represented scanning electronic microscope (SEM) photo of the wall of this porous honeycomb unit 11.As can be seen, in this porous honeycomb unit 11, the silica-alumina fiber is arranged along the direction of extruding the raw material slurry.
Next, the gamma-alumina particle (median size 2 μ m) of 29 weight %, the silica-alumina fiber of 7 weight % (average fiber footpath 10 μ m, the long 100 μ m of average fiber) and the silica sol (solids concn is 30 weight %) of 34 weight %, the carboxymethyl cellulose of 5 weight % and the water of 25 weight % are mixed, make and have stable on heating sealing slurry.With the bonding porous honeycomb of sealing slurry unit 11.Fig. 7 (a) has represented (to become the front from the one side that communicating pores is arranged.Down together.) the observed bonding adherend of several porous honeycomb unit 11.Smear the thick sealing slurry of 1mm on the outside 13 of described porous honeycomb unit 11, bonding several porous honeycomb unit 11 also make its fixing this adherend that just becomes.After so making adherend, cut this adherend with diamond cutter, be the front and roughly be point-symmetric right cylinder, smear described sealing slurry in the rounded outer surface that does not have communicating pores and make coating, making its thickness is 0.5mm.Afterwards, carry out drying, keep sealing material layer and coating being carried out degreasing in 2 hours at 700 ℃ again, just obtain the honeycomb structured body 10 of cylindric (diameter 143.8mm φ * high 150mm) at 120 ℃.Ceramic particle composition, cell configuration, unit sectional area, the cellar area ratio of having summed up this honeycomb structured body 10 in the table of Fig. 4 (refer to that the unitary total sectional area of porous honeycomb accounts for the ratio of the sectional area of honeycomb structured body.Down together.), the sealing material layer area ratio (refers to that the total sectional area of sealing material layer and coating accounts for the ratio of the sectional area of honeycomb structured body.Down together.) wait every numerical value.
In the table of this Fig. 4 also conclusive table content about aftermentioned experimental example 2～29 is shown.In all samples that in the table of Fig. 4, provides, the inorganic materials of its 2nd form is silica-alumina fiber (average fiber footpath 10 μ m, the long 100 μ m of average fiber, long-width ratio are 10), and inorganic adhesive is silica sol (solids concn is 30 weight %).And the table among Fig. 5 has been summed up every numerical value such as inorganic materials (kind, diameter, length, long-width ratio, particle diameter), cell configuration and unit sectional area of the 2nd form in the aftermentioned experimental example 30～43.In all samples that shows in the table of Fig. 5, the inorganic materials of its 1st form is the gamma-alumina particle, and inorganic adhesive is silica sol (solids concn is 30 weight %), and the cellar area ratio is 93.5%, and the sealing material layer area ratio is 6.5%.Also have, the table among Fig. 6 has been summed up every numerical value such as firing temperature of thickness, cellar area ratio, sealing material layer area ratio and porous honeycomb unit 11 of kind, unit sectional area, the sealing material layer of the inorganic adhesive in the honeycomb structured body 10 in the aftermentioned experimental example 44～51.In all examples that in the table of Fig. 6, provide, the inorganic materials of its 1st form is gamma-alumina particle (median size 2 μ m), and the inorganic materials of the 2nd form is silica-alumina fiber (average fiber footpath 10 μ m, the long 100 μ m of average fiber, long-width ratio are 10).
[experimental example 2～7]
Except the porous ceramics unit design being become shown in Fig. 4 table the shape, use the mode identical to make honeycomb structured body 10 with experimental example 1.Fig. 7 (b), (c), (d) represent the shape of adherend in the experimental example 2,3,4 respectively, and Fig. 8 (a) and (b), (c) represent the shape of adherend in the experimental example 5,6,7 respectively.Because the honeycomb structured body 10 in the experimental example 7 is one-body molded, therefore do not carry out operation bonding and cutting.
[experimental example 8～14]
Except titan oxide particles (median size 2 μ m) is become shown in Fig. 4 table the shape as the ceramic particle of the 1st form inorganic materials and with the porous ceramics unit design, use the mode identical to make porous honeycomb unit 11 with experimental example 1.Then, except with the ceramic particle of titan oxide particles (median size 2 μ m) as sealing material layer and coating, use the mode identical to make honeycomb structured body 10 with experimental example 1.In addition, the shape of adherend is identical with Fig. 7 (a)～(d) respectively in the experimental example 8～11, and the shape of adherend is identical with Fig. 8 (a)～(c) respectively in the experimental example 12～14.And the honeycomb structured body 10 in the experimental example 14 is formed in one.
[experimental example 15～21]
Become shown in Fig. 4 table the shape except the ceramic particle of making the 1st form inorganic materials with silicon oxide particle (median size 2 μ m) and with the porous ceramics unit design, use the mode identical to make porous honeycomb unit 11 with experimental example 1.Then, except doing the ceramic particle of sealing material layer and coating, use the mode identical to make honeycomb structured body 10 with experimental example 1 with silicon oxide particle (median size 2 μ m).In addition, the shape of adherend is identical with Fig. 7 (a)～(d) respectively in the experimental example 15～18, and the shape of adherend is identical with Fig. 8 (a)～(c) respectively in the experimental example 19～21.And the honeycomb structured body 10 in the experimental example 21 is formed in one.
[experimental example 22～28]
Become shown in Fig. 4 table the shape except the ceramic particle of making the 1st form inorganic materials with zirconia particles (median size 2 μ m) and with the porous ceramics unit design, use the mode identical to make porous honeycomb unit 11 with experimental example 1.Then, except doing the ceramic particle of sealing material layer and coating, use the mode identical to make honeycomb structured body 10 with experimental example 1 with zirconia particles (median size 2 μ m).In addition, the shape of adherend is identical with Fig. 7 (a)～(d) respectively in the experimental example 22～25, and the shape of adherend is identical with Fig. 8 (a)～(c) respectively in the experimental example 26～28.And the honeycomb structured body 10 in the experimental example 28 is formed in one.
[experimental example 29]
Cylindric (diameter 143.8mm φ * high 150mm) cordierite honeycomb structure body 10 with sale on the market is an experimental example 29, is formed with the alumina layer of loading with layer as catalyzer in its communicating pores inside.And honeycomb hole is shaped as hexagon, and density is 62/cm
2(400cpsi), wall thickness is 0.18mm.In addition, the shape of the honeycomb structured body of seeing from the front is identical with Fig. 8 (c).
[experimental example 30～34]
Except with the silica-alumina fiber of shape shown in Fig. 5 table as the inorganic materials of the 2nd form, use the mode identical to make porous honeycomb unit 11 with experimental example 1.Then, except silica-alumina fiber that will be identical silica-alumina fiber, use the mode identical to make honeycomb structured body 10 with experimental example 1 as sealing material layer and coating with the porous ceramics unit.In addition, the shape of adherend is identical with Fig. 7 (a) in the experimental example 30～34.
[experimental example 35]
As shown in Figure 5, except as the gamma-alumina particle (median size 2 μ m) of the 1st and the 2nd form inorganic materials, use the mode identical to make porous honeycomb unit 11 with experimental example 1.Then, except the ceramic particle with the 1st and the 2nd form inorganic materials of sealing material layer and coating all is designed to the gamma-alumina particle (median size 2 μ m), use the mode identical to make honeycomb structured body 10 with experimental example 1.In addition, the shape of adherend is identical with Fig. 7 (a) in the experimental example 35.
[experimental example 36～43]
Except with alpha alumina particles shown in Fig. 5 table as the 2nd form inorganic materials, use the mode identical to make porous honeycomb unit 11 with experimental example 1.Then, except using the 2nd form inorganic materials of the alpha alumina particles identical, use the mode identical to make honeycomb structured body 10 with experimental example 1 as sealing material layer and coating with the porous ceramics unit.In addition, the shape of adherend is identical with Fig. 7 (a) in the experimental example 36～43.
[experimental example 44～47]
As shown in the table of Fig. 6, except changing unitary sectional area of porous ceramics and the unitary sealing material layer thickness of bonding porous ceramics, use the mode identical to make honeycomb structured body 10 with experimental example 1.In addition, the shape of adherend is identical with Fig. 7 (a) in the experimental example 44～45, and the shape of adherend is identical with Fig. 7 (c) in the experimental example 46～47.
[experimental example 48]
As shown in the table of Fig. 6, except with alumina sol (solids concn is 30 weight %) as the inorganic adhesive design porous ceramics unit, use the mode identical to make honeycomb structured body 10 with experimental example 1.
[experimental example 49～50]
As shown in the table of Fig. 6, except with sepiolite or attapulgite as the inorganic adhesive design porous ceramics unit, use the mode identical to make honeycomb structured body 10 with experimental example 1.Specifically be exactly, the water of the gamma-alumina particle (median size 2 μ m) of 40 weight %, the silica-alumina fiber of 10 weight % (average fiber footpath 10 μ m, the long 100 μ m of average fiber, long-width ratio are 10), 15 weight % inorganic adhesives and 35 weight % is mixed, with experimental example 1 same organic binder bond, softening agent and the lubricant of adding, carry out moulding and sintering, just obtain porous honeycomb unit 11.Then, use sealing slurry bonding several this porous honeycomb unit 11 identical, cut this adherend then, form coating 16, just obtain the honeycomb structured body 10 of cylindric (diameter 143.8mm φ * high 150mm) with experimental example 1.
[experimental example 51]
As shown in the table of Fig. 6,, use the mode identical to make honeycomb structured body 10 with experimental example 1 except not mixing the inorganic adhesive when the design porous ceramics unit.Specifically be exactly, the gamma-alumina particle (median size 2 μ m) of 50 weight %, the silica-alumina fiber of 15 weight % (average fiber footpath 10 μ m, the long 100 μ m of average fiber, long-width ratio are 10) and the water of 35 weight % are mixed, carry out moulding with experimental example 1 same organic binder bond, softening agent and the lubricant of adding, fire this formed body at 1000 ℃, just obtain porous honeycomb unit 11.Then, use sealing slurry bonding several this porous honeycomb unit 11 identical, and cut this adherend, form coating 16, just obtain the honeycomb structured body 10 of cylindric (diameter 143.8mm φ * high 150mm) with experimental example 1.
[specific area measuring]
S (m
2/ L)=(A/100) * B * C ... formula (1)
[experiment repeatedly of thermal shocking and vibration]
The honeycomb structured body of experimental example 1～51 has been carried out the experiment repeatedly of thermal shocking and vibration.Thermal shock test is following carries out, the thermal insulator aluminum oxide pad that will constitute by sapphire whisker (Mitsubishi Chemical's system polycrystalline mullite, 46.5cm * 15cm, thick 6mm) is trapped among the periphery of honeycomb structured body, the metal shell 21 back inputs of packing into are set 600 ℃ baking oven for, heat and from baking oven, take out after 10 minutes, be quickly cooled to room temperature.Then the honeycomb structured body of putting under this metal shell state is carried out vibration test.Fig. 9 (a) expression vibration test front elevation of vibrating device 20, the side elevational view of Fig. 9 (b) expression vibrating device 20.With the metal shell 21 that honeycomb structured body is housed be installed in operator's console 22 above, fixing and tighten fixing metal shell 21 with the setting tool 23 that slightly is the U font with screw 24.So metal shell 21, operator's console 22 can vibrate under the state that becomes one with setting tool 23.The condition of carrying out vibration test is: frequency 160Hz, and acceleration 30G, amplitude 0.58mm, 10 hours hold-times, room temperature, direction of vibration is Z-direction (up and down).10 alternate repetitions carry out this thermal shock test and vibration test separately, and the weight Ti before the determination test after the weight T0 of honeycomb structured body and the test obtains weight decrement G with following formula (2).
G (weight %)=100 * (T0-Ti)/T0 ... formula (2)
[pressure-losses mensuration]
Honeycomb structured body in the experimental example 1～51 has been carried out pressure-losses mensuration.Figure 10 has represented pressure-losses determinator 40.Measuring method is as follows, will enclose the good honeycomb structured body metal shell of packing into the aluminum oxide pad, and this metal shell is connected on the vapor pipe of co-rail diesel machine of 2L, at the upstream and downstream side setting pressure meter of honeycomb structured body.And, condition determination is set at, engine revolution 1500rpm, moment of torsion 50Nm, the running beginning was measured pressure difference after 5 minutes.
[experimental result]
Table among Figure 11 has been concluded every numerical value such as the weight decrement G of specific surface area S, thermal shocking and vibration repetition test of ceramic particle composition in experimental example 1～29 and the experimental example 44～47, unit sectional area, cellar area ratio, the unitary specific surface area of porous honeycomb, honeycomb structured body and the pressure-losses; Figure 12 represented when be transverse axis with the unitary sectional area of porous honeycomb, coordinate diagram when being the longitudinal axis with the weight decrement G of the thermal shocking measured and vibration repetition test and the pressure-losses; Figure 13 represented when be transverse axis with the cellar area ratio, coordinate diagram when being the longitudinal axis with thermal shocking and the vibration weight decrement G of repetition test and the pressure-losses.Can understand clearly that from the represented experimental example 1～29 of Figure 11 and Figure 12 and the measurement result of experimental example 44～47 if be main component with ceramic particle, inorganic fibre and inorganic adhesive, and the sectional area of porous honeycomb unit 11 is at 5cm
2～50cm
2Scope in, honeycomb structured body just has the bigger serface of unit volume and fully to the intensity of heat shock resistance and vibration.And, as shown in figure 13, can understand, as if being main component, if the sectional area of porous honeycomb unit 11 is at 50cm with ceramic particle, inorganic fibre and inorganic adhesive
2Or lower scope, and the cellar area ratio just can strengthen the specific surface area of the unit volume of honeycomb structured body 85% or when above, obtains fully the intensity of heat shock resistance and vibration is reduced the pressure-losses.Particularly account for 90% or when above, the reduction highly significant of the pressure-losses when the cellar area ratio.
Next, about the experimental example 1,30～34 of the long-width ratio that changed inorganic fibre, the table of Figure 14 has been concluded every numerical value such as the weight decrement G of specific surface area S, thermal shocking and vibration repetition test of specific surface area, honeycomb structured body of diameter, length, long-width ratio, the porous honeycomb unit 11 of silica-alumina fiber and the pressure-losses; Figure 15 represented when the long-width ratio with the silica-alumina fiber be transverse axis, with the coordinate diagram of weight decrement G when being the longitudinal axis of thermal shocking and vibration repetition test.According to this result as can be seen, when in the scope of long-width ratio 2～1000 of inorganic fibre, the honeycomb structure physical efficiency obtains fully the intensity to heat shock resistance and vibration.
In addition, about the experimental example 35～43 of the particle diameter of the ceramic particle that changed the 2nd form inorganic materials, Figure 16 has concluded every numerical value such as the weight decrement G of specific surface area S, thermal shocking and vibration repetition test of specific surface area, honeycomb structured body of shape, the porous honeycomb unit 11 of particle diameter, the porous honeycomb unit 11 of the αYang Hualv of the 2nd form inorganic materials and the pressure-losses; Figure 17 has represented when the particle diameter with the αYang Hualv of the 2nd form inorganic materials is a transverse axis, coordinate diagram when being the longitudinal axis with the weight decrement G of thermal shocking and vibration repetition test.According to this result as can be seen, when the particle diameter of the ceramic particle of the 2nd form inorganic materials was in the scope of 10 μ m～60 μ m, the honeycomb structure physical efficiency obtained fully the intensity to heat shock resistance and vibration.And, when the particle diameter of the ceramic particle of the 2nd form inorganic materials the ceramic particle of the 1st form inorganic materials more than 5 times or 5 times the time, the honeycomb structure physical efficiency obtains fully the intensity to heat shock resistance and vibration.
Next, about the experimental example 51 that the kind that has changed inorganic adhesive is made the experimental example 48～50 of porous honeycomb unit 11 and do not mixed the porous honeycomb unit 11 that inorganic adhesive makes, Figure 18 has concluded every numerical value such as the weight decrement G of specific surface area S, thermal shocking and vibration repetition test of the kind of inorganic adhesive, the sintering temperature of porous honeycomb unit 11, unitary area ratio, the unitary specific surface area of porous honeycomb, honeycomb structured body and the pressure-losses.According to this result as can be seen, when not mixing organic binder bond, under comparatively high temps, fire and to obtain enough intensity.And when being mixed with inorganic adhesive,, also can obtain enough intensity even fire in lower temperature.And, when promptly using alumina sol or clay class tackiness agent, can strengthen the specific surface area of the honeycomb structured body 10 of unit volume as inorganic adhesive, obtain abundant intensity to heat shock resistance and vibration.
[honeycomb catalyst]
Honeycomb structured body in the experimental example 1～43 10 is immersed platinum nitrate solutions, and the platinum weight of regulating the honeycomb structured body 10 that makes unit volume is 2g/L, honeycomb structured body is kept 1 hour at 600 ℃ after loading with catalyst component, just obtains honeycomb catalyst.
Industrial utilizability
The present invention can be used as catalyst carrier, adsorbed gas composition or the liquid that purifying vehicle waste gas is used The adsorbent of body composition etc. is used.
Claims (18)
1. honeycomb structured body, it is that described honeycomb structured body comprises at inner honeycomb structured body that can flow-through fluid:
The porous honeycomb unit, it has a plurality of communicating poress, comprises the 1st form inorganic materials and the 2nd form inorganic materials at least, and with sectional area that this communicating pores intersects vertically be 5cm
2～50cm
2With
Sealing material layer, two or more described porous honeycombs unit is bonding in the outside that does not have described communicating pores opening.
2. honeycomb structured body, it is inner honeycomb structured body that can flow-through fluid, described honeycomb structured body comprises:
The porous honeycomb unit, it has a plurality of communicating poress, comprises the 1st form inorganic materials and the 2nd form inorganic materials at least, and is not more than 50cm with the intersect vertically sectional area of face of this communicating pores
2
Sealing material layer, two or more described porous honeycombs unit is bonding in the outside that does not have described communicating pores opening;
The ratio that the unitary total sectional area of wherein said porous honeycomb accounts for the sectional area of honeycomb structured body is not less than 85%.
3. honeycomb structured body as claimed in claim 1 is characterized in that, the unitary total sectional area of described porous honeycomb accounts for the ratio of sectional area of described honeycomb structured body for being not less than 85%.
4. honeycomb structured body as claimed in claim 1 or 2 is characterized in that, the ratio that the unitary total sectional area of described porous honeycomb accounts for the sectional area of described honeycomb structured body is not less than 90%.
5. as any described honeycomb structured body in the claim 1～4, it is characterized in that also possessing coating, cover the unitary periphery that does not have described communicating pores opening of two or more porous honeycombs that is bonded together with described sealing material layer.
6. as any described honeycomb structured body in the claim 1～5, it is characterized in that described the 2nd form inorganic materials has the effect of the unitary strengthening material of described porous honeycomb.
7. as any described honeycomb structured body in the claim 1～6, it is characterized in that described the 1st form inorganic materials is the inorganic materials with long-width ratio of regulation; Described the 2nd form inorganic materials is the inorganic materials with long-width ratio bigger than described regulation long-width ratio.
8. the honeycomb structured body described in claim 7 is characterized in that, the long-width ratio of described the 2nd form inorganic materials is 2～1000.
9. as any described honeycomb structured body in the claim 1～8, it is characterized in that described the 1st form inorganic materials is a ceramic particle, described the 2nd form inorganic materials is an inorganic fibre.
10. as any described honeycomb structured body in the claim 1～6, it is characterized in that described the 1st form inorganic materials is the ceramic particle with regulation particle diameter, described the 2nd form inorganic materials is the ceramic particle with particle diameter bigger than described regulation particle diameter.
11. the honeycomb structured body described in claim 10 is characterized in that, described the 2nd form inorganic materials has the particle diameter of described regulation particle diameter more than 5 times or 5 times.
12., it is characterized in that described ceramic particle is to be selected from a kind of in the group of being made up of aluminum oxide, silicon oxide, zirconium white, titanium oxide, cerium oxide and mullite or to be no less than two kinds particle as any described honeycomb structured body in the claim 9～11.
13. the honeycomb structured body described in claim 9 is characterized in that, described inorganic fibre is to be selected from a kind of in the group of being made up of aluminum oxide, silicon oxide, silicon carbide, silica-alumina, glass and potassium titanate or to be no less than two kinds inorganic fibre.
14., it is characterized in that as any described honeycomb structured body in the claim 1～13, also contain inorganic adhesive,
Wherein said inorganic adhesive is to be selected from a kind of in the group of being made up of alumina sol, silica sol, titanium oxide sol, water glass, sepiolite and attapulgite or to be no less than two kinds inorganic adhesive.
15. as any described honeycomb structured body in the claim 1～14, it is characterized in that, loaded with catalyst component.
16. the honeycomb structured body described in claim 15 is characterized in that, described catalyst component contains and is selected from a kind of in the group of being made up of precious metal, alkali metal compound, alkaline earth metal compound and oxide compound or is no less than two kinds composition.
17., it is characterized in that it is used for the waste gas of purifying vehicle as any described honeycomb structured body in the claim 1～16.
18., it is characterized in that the cross section of described communicating pores is roughly trilateral or hexagon as any described honeycomb structured body in the claim 1～17.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8110275B2 (en) | 2007-03-30 | 2012-02-07 | Ibiden Co., Ltd. | Mixed particles and honeycomb structure for gas conversion apparatus |
| CN102413919A (en) * | 2009-04-30 | 2012-04-11 | 康宁股份有限公司 | Minireactor array |
| CN101543699B (en) * | 2008-03-27 | 2012-09-05 | 揖斐电株式会社 | Honeycomb structure |
| CN102847560A (en) * | 2012-09-17 | 2013-01-02 | 李少荣 | Production method of oversize specification honeycomb ceramic carrier |
| CN105402010A (en) * | 2015-10-22 | 2016-03-16 | 苏州莲池环保科技发展有限公司 | Formula and manufacturing method of acid and alkali resistant automobile three-way catalytic converter |
| CN107266117A (en) * | 2016-03-31 | 2017-10-20 | 日本碍子株式会社 | The manufacture method of honeycomb structured body and honeycomb structured body |
| CN107715573A (en) * | 2017-11-29 | 2018-02-23 | 成都创客之家科技有限公司 | A kind of rock crushing plant's deduster |
| CN108821795A (en) * | 2012-02-24 | 2018-11-16 | 康宁股份有限公司 | Honeycomb body structure including the cement skin compositions with crystalline inorganic fibrous material |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH05213681A (en) * | 1992-01-31 | 1993-08-24 | Kawata Mfg Co Ltd | Fiber reinforced honeycomb ceramic body and its production |
| JPH0812460A (en) * | 1994-06-22 | 1996-01-16 | Osamu Yamamoto | Honeycomb ceramic structure |
| JP2001096116A (en) * | 1999-09-29 | 2001-04-10 | Ibiden Co Ltd | Ceramic filter aggregate and honeycomb filter |
| JP3965007B2 (en) * | 1999-09-29 | 2007-08-22 | イビデン株式会社 | Porous silicon carbide sintered body, honeycomb filter, ceramic filter assembly |
-
2004
- 2004-12-10 CN CNB2004800017952A patent/CN100460360C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8110275B2 (en) | 2007-03-30 | 2012-02-07 | Ibiden Co., Ltd. | Mixed particles and honeycomb structure for gas conversion apparatus |
| CN101543699B (en) * | 2008-03-27 | 2012-09-05 | 揖斐电株式会社 | Honeycomb structure |
| CN102413919A (en) * | 2009-04-30 | 2012-04-11 | 康宁股份有限公司 | Minireactor array |
| CN108821795A (en) * | 2012-02-24 | 2018-11-16 | 康宁股份有限公司 | Honeycomb body structure including the cement skin compositions with crystalline inorganic fibrous material |
| CN102847560A (en) * | 2012-09-17 | 2013-01-02 | 李少荣 | Production method of oversize specification honeycomb ceramic carrier |
| CN105402010A (en) * | 2015-10-22 | 2016-03-16 | 苏州莲池环保科技发展有限公司 | Formula and manufacturing method of acid and alkali resistant automobile three-way catalytic converter |
| CN107266117A (en) * | 2016-03-31 | 2017-10-20 | 日本碍子株式会社 | The manufacture method of honeycomb structured body and honeycomb structured body |
| CN107266117B (en) * | 2016-03-31 | 2021-03-09 | 日本碍子株式会社 | Honeycomb structure and method for manufacturing honeycomb structure |
| CN107715573A (en) * | 2017-11-29 | 2018-02-23 | 成都创客之家科技有限公司 | A kind of rock crushing plant's deduster |
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