CN1767883A - Honeycomb structure - Google Patents
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- CN1767883A CN1767883A CN 200480008409 CN200480008409A CN1767883A CN 1767883 A CN1767883 A CN 1767883A CN 200480008409 CN200480008409 CN 200480008409 CN 200480008409 A CN200480008409 A CN 200480008409A CN 1767883 A CN1767883 A CN 1767883A
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Abstract
A honeycomb structure (1) has porous partition walls (2) arranged so as to form through-holes (3a, 3b) penetrating in the A-axis direction from one end to the other end of the structure. The structure has cordierite as the main component. When the value of porosity is P (%), the value of compressive strength in the A-axis direction, C (MPa), and the value of opening ratio, A (%), the structure satisfies the relationship of C>=(600e<-0.0014AP>)+0.5. Further, the structure has low pressure-loss, is unlikely to break, and has excellent collecting efficiency.
Description
Technical field
The present invention relates to honeycomb structure, particularly relate to the filter that can be suitable for being used as exhaust gas purification and use, and the honeycomb structure of catalyst carrier.
Background technology
Engine for automobile, particularly the influence of environment is caused very big concern recently from the particulate material of discharges such as Diesel engine and NOx, as the important means of removing this type of harmful substance, carried out being equipped with the multiple research of the utilization of the filter of honeycomb structure in porous matter next door or catalyst carrier etc.
For example, developed as the honeycomb structure of capture from the filter (hereinafter referred to as DPF) of the particulate material (hereinafter referred to as PM) of Diesel engine discharge.The honeycomb structure that DPF uses generally has the porous matter next door that disposes in the mode that form to connect axial a plurality of through holes, and has and seize the structure that next door and adjacent through hole are closed at the end face of opposition side each other on both sides by the arms.Then, flow in the through hole of an end face upper shed, make it pass through the interior next door of honeycomb structure, just can capture, remove the particulate material of discharging in the gas by making discharge gas.
When this honeycomb structure for example is equipped on car body,, and under this state, use usually by Metal Packaging.Therefore, under the low situation of the isobaric intensity of honeycomb structure, damaged situation takes place when using when having encapsulation or under encapsulation state.Therefore, when the encapsulation honeycomb structure, need honeycomb structure to have 1MPa or its above isobaric intensity usually.On the one hand, for example under the situation that honeycomb structure is used as DPF and catalyst carrier etc., the pressure loss of discharging gas becomes problem.That is, cause producing the pressure loss through honeycomb structure and cause Diesel engine and the output decline of explosive motor such as petrol engine and the deterioration of Fuel Consumption owing to discharging gas.To this, can effectively reduce the pressure loss though increase the porosity and the aperture opening ratio of honeycomb structure, increase the intensity decline of the porosity of honeycomb structure and isobaric intensity that aperture opening ratio can cause honeycomb structure usually etc. and be easy to breakage.Therefore, even increase the porosity and aperture opening ratio for reducing the pressure loss etc., also requiring is that isobaric intensity is high and be difficult to damaged honeycomb structure.
In the past, have high capture rate to provide, low pressure loss, and the honeycomb structure of the characteristic of low-thermal-expansion rate be purpose, disclosing with the cordierite is that main component and coefficient of thermal expansion are 3 * 10
-6Or it is following, the porosity is 55～80%, average fine pore is the honeycomb structure (spy opens flat 9-77573 communique) of 25～40 μ m.In addition, to remove the exhaust gas purifying filter of ability be purpose a kind of breakage that prevents filter and melting loss to be provided and to have good particulate, disclose at the porosity be 55～80%, average fine pore is 30～50 μ m, and whole pore volume be that X, diameter 100 μ m or the pore volume more than it are the honeycomb structure and the manufacture method (spy opens the 2002-357114 communique) thereof of Y/X≤0.05 under the situation of Y.But, can not obtain the honeycomb structure that the pressure loss is little and be difficult to breakage.
Summary of the invention
The present invention proposes in light of this situation, even its purpose is to provide the porosity and aperture opening ratio greatly also to be difficult to damaged honeycomb structure and manufacture method thereof.
A first aspect of the present invention, a kind of honeycomb structure is provided, it possesses the porous matter next door that disposes in the mode that penetrates into a plurality of through holes of another end from an end along the formation of A direction of principal axis, cordierite is a principal component, in the value of the porosity is that the value of P (%), the axial compressive strength of A is that the value of C (MPa), aperture opening ratio is under the situation of A (%), satisfies following formula (1)
C 〉=(600e
-0.0014APZ1=0.5, the comparatively ideal Z1=1.0 of being among the)+Z1 (1), the better relation that is become when being Z1=1.5.
In a first aspect of the present invention, comparatively ideal is in a plurality of through holes, the open end of fixed through hole sealed in the end of arbitrary end.And average fine pore is comparatively ideal to be the above discontented 30 μ m of 15 μ m or its, and fine pore to be the pore of 10～40 μ m with the volumetric ratio of whole pores comparatively ideal is 50% or more than it, better is 70% or more than it.In addition, to be the above pore of 70 μ m or its with the volumetric ratio of whole pores comparatively ideal is 10% or below it for fine pore.In addition, to be the above pore of 10 μ m or its with the volumetric ratio of whole pores comparatively ideal is 30% or below it for fine pore, and better is 10% or below it.In addition, the porosity is comparatively ideal is 55% or more than it, better is 60～70%.In addition, the axial thermal coefficient of expansion of B is comparatively ideal is 1.0 * 10
-6/ ℃ or below it, and the thickness in next door is 290～310 μ m, every 25.4mm on the section vertical with the A direction of principal axis
2Via count be 270～330, above-mentioned P (%) and above-mentioned C (MPa) are comparatively ideal to be to satisfy following formula (2)
C 〉=(600e
-0.088PThe relation that is become during Z2=0.5 among the)+Z2 (2), but better be the relation that is become when satisfying Z2=1.0, the relation that is become when it is desirable to satisfy Z2=1.5 especially.
The present invention also provides a kind of manufacture method of honeycomb structure, this method can be made and comprise: forming process, it will contain the mixing and shaping of raw material that cordierite forms raw material, pore-creating material and water, obtain to possess the honeycomb structure in the porous matter next door that disposes in the mode that penetrates into a plurality of through holes of another end from an end along the formation of A direction of principal axis; Ablating work procedure, it is fired above-mentioned formed body, makes the following honeycomb structure of a kind of manufacturing, is that the value of P (%), the axial compressive strength of A is that the value of C (MPa), aperture opening ratio is under the situation of A (%) in the value of the porosity, satisfies following formula (1)
C 〉=(600e
-0.0014APThe honeycomb structure of Z1=0.5, the comparatively ideal Z1=1.0 of being among the)+Z1 (1), the better relation that is become when being Z1=1.5.
The honeycomb structure that a second aspect of the present invention provides a kind of manufacture method of honeycomb structure and utilizes this manufacture method manufacturing, the manufacture method of this honeycomb structure comprises: forming process, it will contain the mixing and shaping of raw material that cordierite forms raw material, pore-creating material and water, obtain to possess the honeycomb structure in the porous matter next door that disposes in the mode that penetrates into a plurality of through holes of another end from an end along the formation of A direction of principal axis; Ablating work procedure, above-mentioned formed body is fired, and above-mentioned cordierite forms raw material and comprises aluminium source raw material, kaolin, talcum and silica, and the average grain diameter of above-mentioned aluminium source raw material is that 1～6 μ m, kaolinic average grain diameter are that the average grain diameter of 1～10 μ m, talcum and silica is 10～60 μ m.In a second aspect of the present invention, comparatively ideal is that the average grain diameter of aluminium source raw material is that 1～4 μ m, kaolinic average grain diameter are that the average grain diameter of 1～6 μ m, talcum and silica is respectively 10～30 μ m, and the average grain diameter of better is aluminium source raw material is that 1～2 μ m, kaolinic average grain diameter are that the average grain diameter of 1～3 μ m, talcum and silica is respectively 10～30 μ m.
In manufacture method of the present invention, comparatively ideal be also comprise with in the above-mentioned through hole fixed through hole in the closing step of a certain end sealing.And above-mentioned pore-creating material is comparatively ideal to be to comprise the resin that foams by heating, and above-mentioned pore-creating material comparatively ideal be to comprise the resin that has foamed, and above-mentioned pore-creating material comparatively ideal be to comprise graphite.
Even the honeycomb structure of the first aspect among the present invention big also difficult damaged honeycomb structure that is the porosity and aperture opening ratio, and can be suitable for use as filter that exhaust gas purifying such as DPF uses, catalyst carrier etc.And the manufacture method of the honeycomb structure by the second aspect among the present invention can make and press down the honeycomb structure of making first aspect aptly.
Description of drawings
Fig. 1 (a) is the stereogram of a mode of signal honeycomb structure of the present invention, and Fig. 1 (b) is the local amplification plan view of the 1b part of Fig. 1 (a).
Fig. 2 is the figure of the relation of the expression axial compressive strength of A and the porosity.
Fig. 3 is the cutaway view of a mode of signal honeycomb structure of the present invention.
The specific embodiment
To describe the honeycomb structure and the manufacture method thereof of a first aspect of the present invention according to concrete embodiment in detail below, and the manufacture method of the honeycomb structure of second aspect and by the honeycomb structure of this manufacture method gained, but the present invention is not limited to following embodiment.Have again, below said section all do not refer to perpendicular to the vertical section of (for example A direction of principal axis among Fig. 1 (a)) of through hole as having to specify.
Shown in Fig. 1 (a), Fig. 1 (b), the honeycomb structure 1 of first aspect is a main component with the cordierite among the present invention, and possesses to form along the A direction of principal axis from an end (end face 42) and penetrate into the porous matter next door 2 that the mode of a plurality of through hole 3a of another end (end face 44) and 3b disposes.
The key character of first aspect is: in the value of the porosity is that the value of P (%), the axial compressive strength of A is that the value of C (MPa), aperture opening ratio is under the situation of A (%), satisfies following formula (1)
C 〉=(600e
-0.0014APZ1=0.5 among the)+Z1 (1), comparatively ideal is Z1=1.0, the better relation that is become when being Z1=1.5.Is in the honeycomb structure of main component originally with the cordierite, owing to improving the porosity and then intensity decline of aperture opening ratio in order to reduce the pressure loss, so relation of P (%) and C (MPa) and A (%), for example the value at A (%) is in the honeycomb structure of 62.8 (%), when the value of P (%) is about 69.5 (%), the value of C (MPa) only for about 1.4 (MPa), when the value of P (%) is about 60.3 (%), the value of C (MPa) only is about 3.5 (MPa).When obtaining these type of data of existing honeycomb structure, aperture opening ratio is about 62.8% P (%) and the curve of approximation of C (MPa), as shown in Figure 2, is following formula (3)
C=600e
-0.088P(3) relation shown in.And the porosity is 33% o'clock, and the curve of approximation of the relation between aperture opening ratio A (%) and the axial compressive strength C of A (MPa) is following formula (4)
C＝600e
-0.0462AP (4)
Shown relation.Therefore, the pass of the P (%) in the existing honeycomb structure and A (%) and C (MPa) is the following formula (5) that merges following formula (3) and (4)
C=600e
-00014AP(5) relation.
The inventor is for improving the contract value of intensity of A axial compression, and the result of research is: be used as the cordierite raw material by the raw material that uses specific average grain diameter, the relation that obtains P (%) and A (%) and C (MPa) satisfies following formula (1)
C≥(600e
-0.0014AP)+Z1 (1)
In the honeycomb structure of the relation that become during Z1=0.5.That is, for example in aperture opening ratio is about 62.8% honeycomb structure, by existing following formula (3)
C＝600e
-0.088P (3)
Shown relation, the value that can find out the C (MPa) that can obtain the same porosity increase to 0.5MPa or the honeycomb structure of the relation changed more than it, can successfully obtain the tectosome of the little and difficult breakage of the pressure loss.That is, the honeycomb structure of first aspect, the relation of same porosity P (%) and C (MPa) in the scope of regional X shown in Figure 2, promptly satisfies following formula (2)
C 〉=(600e
-0.088PZ2=0.5 is the relation that is become among the)+Z2 (2), and when with the formula (4) of aperture opening ratio and the axial compressive strength of A
C=600e
-0.0462APWhen (4) consistent, can successfully be met in following formula (1)
C 〉=(600e
-0.0014APThe honeycomb structure of the relation that is become during Z1=0.5 among the)+Z1 (1).And, can find out A axial compression contract intensity and the proportional substantially relation of isobaric intensity, even and can successfully obtain increasing the porosity and/or aperture opening ratio also can improve isobaric intensity, also difficult damaged honeycomb structure when the encapsulation honeycomb structure for example.In a first aspect of the present invention, though Z1=0.5 in the formula (1) then can be Z1=1.0 if improve isobaric intensity required, and comparatively ideal be enough securities of the breakage can obtain to be used to prevent to encapsulate the time.Have again, Z1=1.5 can be more satisfactoryly in enough securities of keeping the breakage when being used to prevent to encapsulate, realize the high porosityization of honeycomb structure.
In the present invention, the porosity is meant the ratio of the volume of the volume in next door and the pore that these next doors are contained, the A direction of principal axis is meant the length direction of the through hole shown in Fig. 1 (a), and the axial compressive strength of A is meant the compressive strength of Tong Over by measuring according to the method for JASO specification M505～87.Aperture opening ratio is meant the ratio of the total area of through hole 3 and next door 2 on the section of the area of through hole 3 and honeycomb structure 1.
Under the situation of honeycomb structure as filters such as DPF with first aspect, shown in Fig. 1 (a), Fig. 1 (b), decide certain end of the open end of through hole 3a and 3b, it is certain the sealed state in end face 42 and 44, in this case, comparatively ideal be with accompany next door and adjacent through hole 3 between mutually relative square end portion sealing so that end face 42 and 44 is grid-like.Have, in filters such as DPF, though the neither sealing of opening that also can be whole under the situation of paying attention to the pressure loss, comparatively ideal under the situation of paying attention to arresting efficiency is certain end of the whole openings of sealing again.In addition, inferior in the situation that honeycomb structure is used for catalyst, the situation that existence needn't seal is so sealing in the present invention not necessarily.
Be used as under the situation of filters such as DPF at the honeycomb structure with first aspect, average fine pore is comparatively ideal to be more than the 15 μ m and below the 30 μ m.Therefore, can obtain the little and good arresting efficiency of the pressure loss.The inventor is when carrying out the experiment that captures about the PM of average fine pore and arresting efficiency, and discovery can obtain the little and good arresting efficiency of the pressure loss in above-mentioned average fine pore scope.This is that then the pressure loss is excessive because if average fine pore is too small, if PM excessive then that see through the next door becomes too much.Here, capture rate is meant that the PM amount that is captured in the honeycomb structure is with respect to the PM amount that imports in the honeycomb structure.
Have again, fine pore be the volumetric ratio of the pore of 10～40 μ m and whole pore comparatively ideal be 50% or more than it, better is 70% or more than it.If the little pore of fine pore is too much, for example catalyst is stated under the situations such as honeycomb structure, the pore that then is plugged is too much, and cause the increase of the pressure loss, if the big pore of fine pore is too much, the PM that then sees through the next door becomes too much, so arresting efficiency descends.Same reason, fine pore be the volumetric ratio of above pore of 70 μ m or its and whole pore comparatively ideal be 10% or below it.Still same reason, fine pore be the volumetric ratio of 10 μ m or its following pore and whole pore comparatively ideal be 30% or below it, better is 10% or below it.
In the honeycomb structure of first aspect, to make the porosity be 55% or be comparatively ideal more than it according to reasons such as reducing the pressure loss, but from reduce this point of the pressure loss better be that the porosity is 60% or more than it.Particularly in a first aspect of the present invention, even also can obtain on this aspect of sufficient intensity the porosity also preferably 60% or more than it improving the porosity.On the other hand, in the purposes of paying attention to intensity, had better not excessively improve the porosity, comparatively ideal is 70% or below it.
In first aspect, though the thermal coefficient of expansion of the next door of section shown in Figure 3 vertical (B direction of principal axis) is 1.0 * 10
-6/ ℃, but more satisfactory from the viewpoint that suppresses thermal stress and inhibition thermal stress damage due.The thermal coefficient of expansion here is meant the thermal coefficient of expansion in 40～800 ℃.
In the present invention,, cause the disposal ability of processed fluid to descend if next door 2 is blocked up and the increase of the pressure loss, approach then the undercapacity of honeycomb structure if next door 2 is crossed though the thickness in next door has no particular limits.The ideal thickness in next door 2 be 100～1000 μ m, comparatively ideal is 150～750 μ m, better is the scope of 200～500 μ m.
And, though each square inch (6.4516cm on the section of honeycomb structure
2) via count (cell density) have no particular limits, if the intensity of honeycomb structure reaches the effective filtration area deficiency as the filter situation but cell density is too small, the pressure loss of the situation that processed liquid flows through if cell density is excessive becomes excessive.Cell density it is desirable to 50～1000/square inch (7.75～155/cm
2), comparatively ideal is 75～500/square inch (11.6～77.5/cm
2), better is 100～400/square inch (15.5～62.0/cm
2) scope.In addition, though the section shape of through hole (compartment shape) is not particularly limited, the viewpoint from making it is desirable to any in triangle, quadrangle, hexagon and the bellows-shaped.
A concrete ideal style of the honeycomb structure in a first aspect of the present invention is that next door thickness is 290～310 μ m, cell density is 270～330/square inch, and the mode of the relation of axial compressive strength C of A (MPa) and porosity P (%) is: in following formula (2)
C 〉=(600e
-0.088PThe mode that is become during Z2=0.5 among the)+Z2 (2).According to this mode, can obtain high pressure degree, and the breakage can suppress to encapsulate the time.Have, Z2=1.0 is enough securities of the mode that the become breakage can obtain to be used to suppress to encapsulate ideally the time again.Have again, the mode that is become during Z2=1.5 can make ideally the honeycomb structure of the safe enough of realizing keeping the breakage when being used to prevent to encapsulate high porosityization, and the pressure loss is little and the honeycomb structure of difficult fragmentation.
The main component of honeycomb structure of the present invention is a cordierite.That is, cordierite need for the ojosa body weight 50% or more than it, it is desirable to weight 70% or more than it, weight that better is 90% or more than it.And the section shape of honeycomb structure of the present invention is not particularly limited, and except that circle, can get ellipse, Long Circle, avette, triangle roughly, all shapes such as quadrilateral type polygon roughly.
It is desirable to the mounting catalyst in the honeycomb structure of the present invention, for example have the metal of catalytic capability.For example, be used to catalyst that burning beginning temperature is reduced being used under the situation of DPF best mounting.Representative with metal of catalytic capability can be enumerated Pt, Pd, Rh, comparatively ideal be with wherein at least a mounting in honeycomb structure.
Next illustrates the example of manufacture method of the honeycomb structure of a first aspect of the present invention.At first, carry out forming raw material and mixing with the raw material of pore-creating material and water and make base soil, and its press forming is formed the forming process of above-mentioned cellular tectosome comprising cordierite.Then, as required the open end of deciding through hole is used and for example contain cordierite and form raw material, adhesive, and the slurry sealing of water.This has been sealed or untight tectosome drying after, utilize with institute's fixed temperature and fire firing forming process and just can obtaining honeycomb structure of shaping.
Here, cordierite forms the raw material that raw material is meant cordierite or forms cordierite by firing shaping.As for example being meant mixtures such as aluminium derived components, kaolin, talcum, quartz, fused silica, mullite, magnesite such as aluminium oxide and/or aluminium hydroxide, it is desirable to these raw materials are formed by the theory of cordierite crystallization and cooperate by firing the raw material that is shaped and forms cordierite.
Next specifies the manufacture method of the honeycomb structure of second aspect present invention.The manufacturing engineering of second aspect comprises above-mentioned forming process and ablating work procedure.The key character of a second aspect of the present invention is that cordierite forms raw material and comprises aluminium source raw material, kaolin, talcum and silica at least, and to have used the average grain diameter of aluminium source raw material be that 1～6 μ m, kaolinic average grain diameter are that the average grain diameter of 1～10 μ m, talcum and silica is the raw material of 10～60 μ m.
By making raw material is that this composition and the particle diameter that makes each composition are in this scope, in a first aspect of the present invention, can produce the honeycomb structure of the relation that is become when satisfying Z1=0.5 in the formula (1) aptly.That is, can produce the axial compressive strength of the porosity and A is higher levels of honeycomb structure.Have again, by the average grain diameter that makes aluminium source raw material is that 1～4 μ m, kaolinic average grain diameter are that the average grain diameter of 1～6 μ m, talcum and silica is the raw material of 10～30 μ m, can produce the honeycomb structure that satisfies the relation of Z1=1.0 in the formula (1), and by the average grain diameter that makes aluminium source raw material is that 1～2 μ m, kaolinic average grain diameter are that the average grain diameter of 1～3 μ m, talcum and silica is the raw material of 10～30 μ m, can produce the honeycomb structure that satisfies the relation of Z1=1.5 in the formula (1).And the porosity, pore directly distribute and also can be at an easy rate in the ideal range in the first aspect.
Particularly, in the past as aluminium source raw material and kaolin such as aluminium oxide and aluminium hydroxides, usually use has greater particle size, but by make these particle diameters littler and with the talcum of greater particle size and silica combination, for with the identical in the past aperture opening ratio and the porosity, can obtain to have axial compressive strength of higher A and the high honeycomb structure of isobaric intensity than in the past honeycomb structure.
Here, aluminium source raw material is meant aluminium oxide and/or aluminium hydroxide, is only using aluminium oxide or aluminium hydroxide to be used as under the situation of aluminium source raw material, makes particle diameter separately enter above-mentioned scope, and makes both particle diameters enter above-mentioned scope under the situation of both and usefulness.And, by the aluminium source raw material that mixing has two different average grain diameters, also can make its average diameter enter above-mentioned scope and use them.And, for kaolin,, also can make its average diameter enter above-mentioned scope and use them by the kaolin that mixing has two different average grain diameters.In addition, for talcum and silica,, also can make its average diameter enter above-mentioned scope and use them by talcum and the silica that mixing has two different average grain diameters.
As the pore-creating material that uses, for example can enumerate graphite, Foamex, wheat flour, starch, phenolic resins, polymethyl methacrylate, polyethylene or polyethylene terephthalate etc.Wherein, it is desirable to contain Foamex.As the pore-creating material, containing the resin that foams owing to heating gives birth on this aspect of open pore at fecund, from the viewpoint that improves as the performance of filter is desirable, uses by heating and gives birth to open pore and can suppress tectosome and be out of shape on this aspect better at fecund at 100 ℃ or the resin that foams more than it.The viewpoint that contains the breakage in the resin that foamed the next door when preventing to fire is desirable.
Except that above-mentioned raw materials, it is desirable to also add adhesive and/or dispersant.Adhesive can be enumerated: for example, hydroxypropyl cellulose, methylcellulose, hydroxyethylcellulose, carboxymethyl cellulose or polyvinyl alcohol etc., dispersant can be enumerated: glycol, dextrin, fatty acid soaps or polyalcohol etc.
The cooperation ratio of base soil is, for example, weight portion with respect to the main component raw material is 100, the weight portion of pore-creating material is 5～40, the weight portion of decentralized medium is 10～40 and adds the adhesive of 3～5 weight portions, the dispersant of 0.5～2 weight portion as required, can mix and make then.Kneading device, producing device can be enumerated mixing roll and press combined to be used as continuous mixing press etc.
The drying means of tectosome can be enumerated: for example, heated-air drying, microwave drying, dielectric (Lure) drying, drying under reduced pressure, vacuum drying or freeze drying etc.It is desirable to fire forming temperature is 1400～1440 ℃, and fires shaping firing under the condition of environmental gas that the shaping environmental gas is a normal atmospheric.
In a second aspect of the present invention, it is desirable to comprise the sealing work of through hole that sealing is decided.Closing step can by to deciding raw material for example cordierite form and to add water, adhesive etc. in the raw material and become pulpous state, and it is adapted to sealing institute decides the open end of through hole and carry out drying and/or fire shaping and finish.Sealing it is desirable to seize the relative end sealing of next door and adjacent through hole on both sides by the arms so that the honeycomb structure end face is grid-like finishes.And, though closing step so long as after forming process which in stage finish can, need fire under the situation of shaping in sealing, it is desirable to before firing forming process, finish so that finish by once firing to be shaped.
To be described in more detail the present invention according to embodiment below, but the present invention is not limited to these embodiment.
(embodiment 1～11 and comparative example 1～3)
Use aluminium oxide (alum clay), aluminium hydroxide, kaolin, talcum and the fused silica of the average grain diameter shown in the table 1 to be used as cordierite formation raw material, and to wherein adding as the graphite of pore-creating material, the resin that has foamed (Foamex), pass through the resin (for Foamex) that heating is foamed in the cooperation ratio shown in the table 2, add water-soluble cellulose derivative, interfacial agent and water again as adhesive, carry out mixing, stirring and press forming then, to form honeycomb structure.After being dried, seal so that each end face is grid-like by being mixed with the slurry that cordierite forms raw material and adhesive and dispersant, further after the drying, fire with 1425 ℃, obtaining having next door thickness, cell density, the aperture opening ratio shown in the table 3, and compartment is shaped as tetragonal honeycomb structure.
(mensuration of the porosity)
By demand perfection portion's pore volume and calculate the porosity of mercury penetration method.The real density of cordierite is 2.52g/cm
3Average fine pore is the value of the center pore diameter in the volume reference.
The mensuration of intensity (the A axial compression contract)
The axial length of A is 25.4mm, is that the columniform test film of 25.4mm is peeled off from honeycomb structure with the diameter of the direction that meets at right angles with it, and measures the axial compressive strength of A with autoplotter.Force cell is 25kN, and increasing the weight of speed is 0.5mm/min.
(mensuration of thermal coefficient of expansion)
Make the opening vertical (for example A direction of principal axis of Fig. 1 (a)) of honeycomb structure be the A direction of principal axis, vertical (for example B direction of principal axis of Fig. 1 (b)) in the next door on the honeycomb structure section is the B direction of principal axis, and measures the coefficient of linear thermal expansion between on all directions 40～800 ℃.
(table 1)
| Average grain diameter (μ m) | ||||||||
| Alum clay | Aluminium hydroxide | Kaolin | Talcum | Fused silica | Graphite | Expanded material | | |
| Embodiment | ||||||||
| 1 | 4 | 2 | 4 | 25 | 50 | 40 | 50 | |
| | 4 | 2 | 8 | 25 | 25 | 50 | ||
| | 4 | 2 | 4 | 25 | 25 | 20 | 15 | |
| | 4 | 2 | 6 | 25 | 12 | 50 | 15 | |
| Embodiment 5 | 2 | 2 | 6 | 25 | 25 | 50 | 15 | |
| Embodiment 6 | 2 | 2 | 6 | 25 | 25 | 50 | 15 | |
| Embodiment 7 | 2 | 2 | 4 | 12 | 25 | 40 | 15 | |
| Embodiment 8 | 2 | 1 | 2 | 25 | 12 | 40 | ||
| Embodiment 9 | 4 | 2 | 6 | 25 | 25 | 50 | ||
| Embodiment 10 | 4 | 2 | 6 | 25 | 25 | 20 | 50 | |
| Embodiment 11 | 2 | 2 | 10 | 25 | 40 | 40 | ||
| Comparative example 1 | 6 | 2 | 6 | 25 | 25 | 40 | 50 | |
| Comparative example 2 | 4 | 2 | 6 | 25 | 100 | 50 | ||
| Comparative example 3 | 6 | 2 | 10 | 25 | 50 | 50 | ||
(table 2)
| Cooperation ratio (part by weight) | ||||||||
| Alum clay | Aluminium hydroxide | Kaolin | Talcum | Fused silica | Graphite | Expanded material | | |
| Embodiment | ||||||||
| 1 | 14 | 15 | 19 | 40 | 12 | 10 | 1.7 | |
| | 14 | 15 | 19 | 40 | 12 | 2 | ||
| | 14 | 15 | 19 | 40 | 12 | 3.6 | 2 | |
| | 14 | 15 | 19 | 40 | 12 | 1.8 | 2 | |
| Embodiment 5 | 14 | 15 | 19 | 40 | 12 | 1.7 | 2 | |
| Embodiment 6 | 19.5 | 7.8 | 19 | 40 | 12 | 1.8 | 2 | |
| Embodiment 7 | 14 | 15 | 19 | 40 | 12 | 1.8 | 2.5 | |
| Embodiment 8 | 14 | 15 | 19 | 40 | 12 | 2 | ||
| Embodiment 9 | 14 | 15 | 19 | 40 | 12 | 1.5 | ||
| Embodiment 10 | 14 | 15 | 19 | 40 | 12 | 10 | 1.5 | |
| Embodiment 11 | 14 | 15 | 19 | 40 | 12 | 1.7 | ||
| Comparative example 1 | 14 | 15 | 19 | 40 | 12 | 10 | 1.5 | |
| Comparative example 2 | 14 | 15 | 19 | 40 | 12 | 1.6 | ||
| Comparative example 3 | 14 | 15 | 19 | 40 | 12 | 1.7 | ||
(table 3)
| Next door thickness (μ m) | Cell density (individual/square inch) | Aperture opening ratio A (%) | The A axial compression intensity C (MPa) that contracts | Porosity P (%) | Y1 (*1) | Y2 (*2) | Average fine pore (μ m) | Thermal coefficient of expansion A axle ℃ -1 | Thermal coefficient of expansion B axle ℃ -1 | |
| Embodiment 1 | 304 | 300 | 62.8 | 1.8 | 70 | 0.53 | 0.53 | 29 | 0.7 | 1.0 |
| | 304 | 300 | 62.8 | 2.0 | 69 | 0.61 | 0.62 | 22 | 0.8 | 1.0 |
| | 304 | 300 | 62.8 | 2.3 | 68 | 0.78 | 0.79 | 19 | 0.5 | 0.9 |
| | 304 | 300 | 62.8 | 3.5 | 63 | 1.14 | 1.15 | 17 | 0.4 | 0.7 |
| Embodiment 5 | 304 | 300 | 62.8 | 3.4 | 65 | 1.42 | 1.43 | 21 | 0.6 | 0.9 |
| Embodiment 6 | 304 | 300 | 62.8 | 3.0 | 67 | 1.34 | 1.35 | 23 | 0.5 | 0.8 |
| Embodiment 7 | 304 | 300 | 62.8 | 4.5 | 68 | 2.98 | 2.99 | 23 | 0.5 | 0.8 |
| Embodiment 8 | 304 | 300 | 62.8 | 3.2 | 73 | 2.22 | 2.23 | 17 | 0.4 | 0.7 |
| Embodiment 9 | 275 | 275 | 67.3 | 3.5 | 58 | 0.96 | - | 25 | 0.5 | 0.8 |
| Embodiment 10 | 432 | 100 | 68.9 | 2.0 | 65 | 0.86 | - | 27 | 0.6 | 0.9 |
| Embodiment 11 | 275 | 275 | 67.3 | 2.1 | 66 | 0.90 | - | 27 | 0.7 | 1.0 |
| Comparative example 1 | 304 | 300 | 62.8 | 1.8 | 65 | -0.18 | -0.17 | 26 | 0.6 | 1.1 |
| Comparative example 2 | 304 | 300 | 62.8 | 2.0 | 60 | -1.07 | -1.06 | 33 | 0.7 | 1.1 |
| Comparative example 3 | 304 | 300 | 62.8 | 1.6 | 62 | -0.98 | -0.96 | 29 | 0.6 | 1.0 |
(*1)：Y1＝C-(600e
-0.0014AP)
(*2)：Y2＝C-(600e
-0.088P)
The result is displayed in Table 3.Shown the low A axial compression intensity that contracts by the honeycomb structure of the alum clay of the extraneous particle diameter that uses a second aspect of the present invention, 1～3 manufacturing of kaolinic comparative example.On the one hand as can be known: embodiment 1～11 makes according to a second aspect of the invention, even the honeycomb structure porosity of gained and/or aperture opening ratio height have also shown the high A axial compression intensity that contracts, and be honeycomb structure in and difficult breakage little as the situation downforce loss of the filter of DPF etc.And, the honeycomb structure of embodiment 1～11 gained, its average fine pore is that the above 30 μ m of 15 μ m are following, the porosity be 55% or it is above, fine pore is 10～40 μ m pore be 50% or more than it with respect to the volumetric ratio of whole pores, and arresting efficiency is also good under as the situation of the filter of DPF etc.
As mentioned above, even the honeycomb structure of a first aspect of the present invention is the honeycomb structure of the big also difficulty of the porosity and aperture opening ratio breakage, and applicable to exhaust gas purifyings such as DPF filter, catalyst etc.And the manufacture method of the honeycomb structure by a second aspect of the present invention can be made the honeycomb structure of first aspect aptly.Have again, though the present invention is that the center is illustrated with the honeycomb structure that is used for DPF etc. and be closed, but the invention provides have the honeycomb structure of higher-strength under the fixed porosity and the aperture opening ratio, have or not how sealing or purposes all are favourable.
Claims (27)
1. a honeycomb structure possesses the porous matter next door that disposes in the mode that penetrates into a plurality of through holes of another end from an end along the formation of A direction of principal axis, it is characterized in that:
With the cordierite is main component,
In the value of the porosity is that the value of P (%), the axial compressive strength of A is that the value of C (MPa), aperture opening ratio is under the situation of A (%), satisfies following formula (1)
C≥(600e
-0.0014AP)+Z1 (1)
In the relation that become during Z1=0.5.
2. honeycomb structure according to claim 1 is characterized in that:
The relation that is become when satisfying Z1=1.0 in the formula (1).
3. honeycomb structure according to claim 1 is characterized in that:
The relation that is become when satisfying Z1=1.5 in the formula (1).
4. according to each described honeycomb structure in the claim 1～3, it is characterized in that:
In described a plurality of through holes, the open end of fixed through hole be closed in certain end.
5. honeycomb structure according to claim 4 is characterized in that:
Average fine pore is 15 μ m or its above and discontented 30 μ m.
6. according to claim 4 or 5 described honeycomb structures, it is characterized in that:
Fine pore is the pore of 10～40 μ m and whole volumetric ratios of pores is 50% or more than it.
7. honeycomb structure according to claim 6 is characterized in that:
Fine pore is the pore of 10～40 μ m and whole volumetric ratios of pores is 70% or more than it.
8. according to each described honeycomb structure in the claim 4～7, it is characterized in that:
Fine pore is the above pore of 70 μ m or its and whole volumetric ratios of pores is 10% or below it.
9. according to each described honeycomb structure in the claim 4～8, it is characterized in that:
Fine pore is the following pore of 10 μ m or its and whole volumetric ratios of pores is 30% or below it.
10. honeycomb structure according to claim 9 is characterized in that:
Fine pore is the following pore of 10 μ m or its and whole volumetric ratios of pores is 10% or below it.
11., it is characterized in that according to each described honeycomb structure in the claim 1～10:
The porosity is 55% or more than it.
12. honeycomb structure according to claim 11 is characterized in that:
The porosity is 60～70%.
13., it is characterized in that according to each described honeycomb structure in the claim 1～12:
Next door on the section vertical with the A direction of principal axis of honeycomb structure thermal coefficient of expansion longitudinally is 1.0 * 10
-6/ ℃ or below it.
14., it is characterized in that according to each described honeycomb structure in the claim 1～13:
The thickness in next door is 290～310 μ m, per 1 square inch of (6.4516cm on the section vertical with the A direction of principal axis
2) via count be 270～330, above-mentioned P (%) and above-mentioned C (MPa) satisfy following formula (2)
C≥(600e
-0.088P)+Z2 (2)
In the relation that become during Z2=0.5.
15. honeycomb structure according to claim 14 is characterized in that:
The relation that is become when satisfying Z2=1.0 in the formula (2).
16. honeycomb structure according to claim 14 is characterized in that:
The relation that is become when satisfying Z2=1.5 in the formula (2).
17. the manufacture method of a honeycomb structure is characterized in that, comprising:
Forming process will contain the mixing and shaping of raw material that cordierite forms raw material, pore-creating material and water, obtain to possess the honeycomb structure in the porous matter next door that disposes in the mode that penetrates into a plurality of through holes of another end from an end along the formation of A direction of principal axis; Ablating work procedure is fired above-mentioned formed body, and the value that can be manufactured on the porosity is that the value of P (%), the axial compressive strength of A is that the value of C (MPa), aperture opening ratio is under the situation of A (%), satisfies formula (1)
C≥(600e
-0.0014AP)+Z1 (1)
In the honeycomb structure of the relation that become during Z1=0.5.
18. manufacture method according to claim 17 is characterized in that:
The relation that is become when satisfying Z1=1.0 in the formula (1).
19. manufacture method according to claim 17 is characterized in that:
The relation that is become when satisfying Z1=1.5 in the formula (1).
20. the manufacture method of a honeycomb structure is characterized in that, comprising:
Forming process will contain the mixing and shaping of raw material that cordierite forms raw material, pore-creating material and water, obtain to possess the honeycomb structure in the porous matter next door that disposes in the mode that penetrates into a plurality of through holes of another end from an end along the formation of A direction of principal axis; Ablating work procedure is fired above-mentioned formed body,
Described cordierite forms raw material and comprises aluminium source raw material, kaolin, talcum and silica, and the average grain diameter of described aluminium source raw material is that 1～6 μ m, kaolinic average grain diameter are that the average grain diameter of 1～10 μ m, talcum and silica is 10～60 μ m.
21. manufacture method according to claim 20 is characterized in that:
The average grain diameter of aluminium source raw material is that 1～4 μ m, kaolinic average grain diameter are that the average grain diameter of 1～6 μ m, talcum and silica is respectively 10～30 μ m.
22. manufacture method according to claim 20 is characterized in that:
The average grain diameter of aluminium source raw material is that 1～2 μ m, kaolinic average grain diameter are that the average grain diameter of 1～3 μ m, talcum and silica is respectively 10～30 μ m.
23., it is characterized in that according to each described manufacture method in the claim 17～22:
Also comprise with in the through hole fixed through hole in the closing step of its a certain end sealing.
24., it is characterized in that according to each described manufacture method in the claim 17～23:
Described pore-creating material comprises the resin that foams by heating.
25., it is characterized in that according to each described manufacture method in the claim 17～24:
Described pore-creating material comprises the resin that has foamed.
26., it is characterized in that according to each described manufacture method in the claim 17～25:
Described pore-creating material comprises graphite.
27. a honeycomb structure is characterized in that: utilize the described manufacture method manufacturing of claim 20.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003090178 | 2003-03-28 | ||
| JP090178/2003 | 2003-03-28 | ||
| JP025767/2004 | 2004-02-02 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN1767883A true CN1767883A (en) | 2006-05-03 |
Family
ID=36743282
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 200480008409 Pending CN1767883A (en) | 2003-03-28 | 2004-03-04 | Honeycomb structure |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107129318A (en) * | 2016-02-29 | 2017-09-05 | 日本碍子株式会社 | The manufacture method of honeycomb structured body |
| CN108603432A (en) * | 2016-02-19 | 2018-09-28 | 本田技研工业株式会社 | Exhaust gas purification catalytic converter |
| CN111908937A (en) * | 2020-07-08 | 2020-11-10 | 凯龙蓝烽新材料科技有限公司 | Honeycomb ceramic carrier for VOCs purification catalyst and preparation method thereof |
-
2004
- 2004-03-04 CN CN 200480008409 patent/CN1767883A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108603432A (en) * | 2016-02-19 | 2018-09-28 | 本田技研工业株式会社 | Exhaust gas purification catalytic converter |
| CN107129318A (en) * | 2016-02-29 | 2017-09-05 | 日本碍子株式会社 | The manufacture method of honeycomb structured body |
| CN107129318B (en) * | 2016-02-29 | 2021-03-09 | 日本碍子株式会社 | Method for manufacturing honeycomb structure |
| CN111908937A (en) * | 2020-07-08 | 2020-11-10 | 凯龙蓝烽新材料科技有限公司 | Honeycomb ceramic carrier for VOCs purification catalyst and preparation method thereof |
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