CN107269347A - Plugged Honeycomb Structure - Google Patents
Plugged Honeycomb Structure Download PDFInfo
- Publication number
- CN107269347A CN107269347A CN201710198393.5A CN201710198393A CN107269347A CN 107269347 A CN107269347 A CN 107269347A CN 201710198393 A CN201710198393 A CN 201710198393A CN 107269347 A CN107269347 A CN 107269347A
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- China
- Prior art keywords
- cell
- intersection point
- next door
- circle
- inflow
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
- F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
- F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
- F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
- F01N3/0222—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being monolithic, e.g. honeycombs
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
- B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
- B01D46/2418—Honeycomb filters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D46/00—Filters or filtering processes specially modified for separating dispersed particles from gases or vapours
- B01D46/24—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies
- B01D46/2403—Particle separators, e.g. dust precipitators, using rigid hollow filter bodies characterised by the physical shape or structure of the filtering element
- B01D46/2418—Honeycomb filters
- B01D46/2425—Honeycomb filters characterized by parameters related to the physical properties of the honeycomb structure material
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
- B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
- B01D53/9404—Removing only nitrogen compounds
- B01D53/9409—Nitrogen oxides
- B01D53/9413—Processes characterised by a specific catalyst
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/01—Engine exhaust gases
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2330/00—Structure of catalyst support or particle filter
- F01N2330/02—Metallic plates or honeycombs, e.g. superposed or rolled-up corrugated or otherwise deformed sheet metal
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
- F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL COMBUSTION ENGINES
- F01N2570/00—Exhaust treating apparatus eliminating, absorbing or adsorbing specific elements or compounds
- F01N2570/14—Nitrogen oxides
Abstract
The present invention provides a kind of plugged honeycomb structure, and it can suppress the reduction, the increase of the pressure loss, the reduction of ash content capacity of aperture area to greatest extent, while mechanical strength and resistance to sudden heating can be improved.The plugged honeycomb structure is in the section vertical with the bearing of trend of cell (2) of honeycomb-structure portion, cell (2a) is flowed into arrange in the way of surrounding outflow cell (2b), also, the quantity for flowing into cell (2a) is more than the quantity of outflow cell (2b)；With multiple intersection point portions (4) for dividing adjacent inflow cell (2a) mutual next door (1), for total amount of more than the 60% intersection point portion (4) of intersection point portion (4), the diameter of a circle (D of inscribe in intersection point portion (4)1) with dividing adjacent inflow cell (2a) and flowing out the diameter of a circle (D of inscribe in the next door (1) of cell (2b)0) between relation meet
Description
Technical field
The present invention relates to the plugged honeycomb structure for wall flow pattern waste gas filter.In more detail, it is related to and is suitable for
The toxic gas such as contained particle-like substance and/or purification nitrogen oxides in removing the waste gas discharged from engines such as car engines
Plugged honeycomb structure.
Background technology
In various industries, power source is used as using internal combustion engine.On the other hand, in internal combustion engine burning fuel when institute
In the waste gas of discharge, in addition to the toxic gases such as nitrogen oxides, also by particle-like substances such as coal smoke ash, ashes (below, sometimes referred to as
For " PM ") it is discharged into air.Particularly, it is worldwide increasingly tight to removing the PM discharged from diesel motor regulation
Lattice, it is net using the wall flow pattern gas with honeycomb as the filter (following, sometimes referred to as " DPF ") for removing PM
Change filter.
The structure of the DPF is as follows：The multiple cells for being formed into fluid flowing path are divided by the next door of Porous, by right
Cell alternately sealing of hole so that the next door of the Porous plays the effect for the filter for removing PM.
Specifically, in the honeycomb structured body used in the past, the waste gas containing PM is made to be flowed from the inflow side end face of the DPF
Enter, PM is trapped by using the next door of Porous to be filtered, then, the waste gas after purification is arranged from outflow side end face
Go out.But, there are the following problems：Along with the inflow of waste gas, accumulated on PM next doors, block the inflow cell of waste gas.If
Occur such cell to block, the problem of pressure loss that will produce DPF increased dramatically.
Therefore, blocked to suppress such cell, the filter area and aperture opening ratio for improving inflow cell are important.But
It is, in the case where inflow cell has different sectional areas, cross sectional shape from outflow cell, to form the thickness in the next door of cell
The part that next door intersects to each other is local sometimes thinning, causes weakened.Accordingly, there exist following problem：By by heap
When PM of the product in DPF is flared off to be regenerated, thermal stress can concentrate on the part in the intersection point portion in thinning next door, from
And crack.
The problem of in order to solve such, it is proposed that wall flow pattern DPF (patent document 1), it is by improving inflow cell
While filter area and aperture opening ratio, the opening diameter for flowing out cell is kept as greatly, during so as to by initial stage and PM accumulations
The pressure loss suppress low, and resistance to sudden heating is high.
In addition, having recorded the R portions by setting substantially arc-shaped in the intersection point portion in all thinning next doors in patent document 1
To prevent the technology of crackle generation.In addition, it is also proposed that arrange the R portions of substantially arc-shaped in the corner portion relative with cell
To prevent the intersection point portion of next door from producing the technology (patent document 2) of cracking.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2014-200741 publications
Patent document 2：Japanese Unexamined Patent Publication 2003-269131 publications
The content of the invention
Invent problem to be solved
But, such as like that, the intersection point portion in the next door of the summit aggregation of 4 inflow cells is the conventional DPF shown in Fig. 5
Stress is easy to the structure concentrated.Therefore, the DPF is being used for the exhaust of car engine as wall flow pattern gas purification filter
During system, in the traveling of automobile, in addition to vibration, sometimes because PM burn (for example, coal soot combustion) caused by urgency
Heating and chilling but produce thermal stress.Moreover, in the case where producing such thermal stress, there is what is cracked in DPF
The problem of possibility further improves such.
The schematic diagram of conventional DPF representative crackle is shown in Fig. 6.Connection flows into the mutual crackle in summit of cell,
It is generally acknowledged that small to the disturbance degree of coal smoke ash leakage.But, if the crack growth, when reaching outflow cell, it is possible to meeting
Occurs the leakage of coal smoke ash, it is therefore desirable to prevent the generation of such thing.Fig. 5 is to schematically show conventional haplotype sealing of hole honeybee
The plan of the inflow side end face of nest structure.Fig. 6 is the enlarged drawing of Fig. 5 conventional plugged honeycomb structure, is schematic
Represent the figure of representative crackle.
As the method for preventing the crackle, as disclosed in patent document 2, for example as, the increasing of cell is carried out in the past
By force.But, when enhanced portion being set in the intersection point portion in whole next doors like that in the past, although can solve the problem that the problem of crackle is produced,
But because the aperture area of cell diminishes, thus there is pressure loss increase, the accumulation capacity (ash content capacity) of ash content (Ash) subtracts
Few such the problem of.In addition, in conventional DPF, due to thermal capacity increase, thus there is light off characteristics (Light-off
Performance such shortcoming) is deteriorated.It should be noted that, light off characteristics refer to the purification of the catalyst supported in DPF
The temperature characterisitic that can be presented.
The present invention be in view of such problems of the prior art and complete.The present invention provides a kind of sealing of hole honeycomb
Structure, it can suppress the reduction, the increase of the pressure loss, the reduction of ash content capacity of aperture area to greatest extent, simultaneously
Improve mechanical strength and resistance to sudden heating.
Method for solving problem
According to the present invention, there is provided plugged honeycomb structure as follows.
[1] a kind of plugged honeycomb structure, possesses：
Honeycomb-structure portion, it has the next door of Porous, and the next door, which divides to be formed from inflow side end face, extends to outflow
Side end face and multiple cells as fluid flowing path,
Inflow side sealing of hole portion, it is disposed in the opening portion of the predetermined inflow cell in the outflow side end face, and
Outflow side sealing of hole portion, it is disposed in the opening portion of the remaining outflow cell in the inflow side end face,
It is described to flow into cell to surround in the section vertical with the bearing of trend of the cell of the honeycomb-structure portion
The mode of the outflow cell is arranged, also, the quantity for flowing into cell is more than the quantity of the outflow cell,
With multiple intersection point portions for dividing the adjacent mutual next door of inflow cell,
For total amount of more than the 60% intersection point portion in the intersection point portion, the circle of inscribe is straight in the intersection point portion
Footpath D1With the diameter of a circle D of the inscribe in the next door of the adjacent inflow cell of division and the outflow cell0Between relation
Following formula (1) is met,
Formula (1)：
[2] plugged honeycomb structure as described described in [1],
For the total amount of intersection point portion, the diameter of a circle D of inscribe in the intersection point portion1With dividing adjacent
The diameter of a circle D of inscribe in the next door for flowing into cell and the outflow cell0Between relation meet the formula (1).
[3] plugged honeycomb structure as described described in [1] or [2], it is described inflow cell in inscribe and with the stream
Enter the tangent diameter of a circle D in the next door of the intersection point portion side of cell2For 0.20~0.80mm.
[4] plugged honeycomb structure as described described in any one of [1]~[3], is only dividing the adjacent inflow
The intersection point portion in the mutual next door of cell, the diameter of a circle D of inscribe in the intersection point portion1With dividing the adjacent ostium
The diameter of a circle D of inscribe in the next door of lattice and the outflow cell0Between relation meet above-mentioned formula (1).
Invention effect
The corner in the intersection point portion in the next door that the plugged honeycomb structure of the present invention is only assembled on the summit of multiple inflow cells,
It is selectively provided with enhanced portion.Thereby, it is possible to suppress the reduction of aperture area, the increasing of the pressure loss, ash to greatest extent
The reduction of partial volume amount and the deterioration of light off characteristics, while improving DPF mechanical strength and resistance to sudden heating.
Brief description of the drawings
Fig. 1 is the stereogram of the plugged honeycomb structure of embodiments of the present invention.
Fig. 2 is the plan of a part for the inflow side end face for schematically showing the plugged honeycomb structure shown in Fig. 1.
Fig. 3 is the sectional view along Fig. 2 A-A ' lines.
Fig. 4 is schematically shown Fig. 2 plan flowed into when side end face is amplified.
Fig. 5 is the plan for the inflow side end face for schematically showing conventional haplotype plugged honeycomb structure.
Fig. 6 is the enlarged drawing of Fig. 5 conventional plugged honeycomb structure, is the figure for schematically showing representative crackle.
Fig. 7 is the enlarged drawing of Fig. 5 conventional plugged honeycomb structure, is to illustrate the figure in the circle of intersection point portion inscribe.
Symbol description
1：Next door, 2：Cell, 2a：Flow into cell, 2b：Flow out cell, 3：Sealing of hole portion, 3a：Inflow side sealing of hole portion, 3b：Stream
Go out side seal hole portion, 4：Intersection point portion, 6a：Flow into side end face, 6b：Flow out side end face, 7：Cellular unit, 8：Bonding layer, 9：Honeycomb knot
Structure portion, 11：Periphery wall, 100：Plugged honeycomb structure, C：Crackle, D0、D1：Diameter of a circle.
Embodiment
Hereinafter, embodiments of the present invention are illustrated.But, the invention is not restricted to following embodiment.Therefore,
It should be understood that without departing from the spirit and scope of the present invention, the common knowledge based on those skilled in the art can be to following
Embodiment is subject to suitably change, improvement etc..
Fig. 1~Fig. 4 is the figure for the plugged honeycomb structure for schematically showing embodiments of the present invention.Here, this implementation
The plugged honeycomb structure 100 of mode both can be the haplotype honeycomb structured body that multiple cellular units are bonded with each other,
Can also be by the integrally formed one-piece type honeycomb structured body in next door and periphery wall.Fig. 1 is embodiments of the present invention
The stereogram of plugged honeycomb structure.Fig. 2 is the one of the inflow side end face for schematically showing the plugged honeycomb structure shown in Fig. 1
Partial plan.Fig. 3 is the sectional view along Fig. 2 A-A ' lines.Fig. 4 is schematically shown Fig. 2 inflow side end face 6a
Plan during amplification.
The plugged honeycomb structure 100 of present embodiment has honeycomb-structure portion 9, inflow side sealing of hole portion 3a and outflow side seal
Hole portion 3b.Honeycomb-structure portion 9 is made up of multiple cellular units 7.Multiple cellular units 7, which each have to divide, to be formed from inflow side
Face 6a extends to the next door 1 of outflow side end face 6b and the Porous of multiple cells 2a, 2b as fluid flowing path.In multiple honeycombs
The side of unit 7 each other, is equipped with bonding layer 8, by engaging multiple cellular units 7 by the bonding layer 8, so that
Form honeycomb-structure portion 9.In the periphery of honeycomb-structure portion 9 in the way of the conjugant engaged around multiple cellular units 7
It is equipped with periphery wall 11.
Inflow side sealing of hole portion 3a is disposed in the opening portion of the predetermined inflow cell 2a in outflow side end face 6b.Flow out side seal
Hole portion 3b is disposed in the remaining outflow cell 2b flowed into the 6a of side end face opening portion.
In plugged honeycomb structure 100, in the section vertical with the bearing of trend of cell 2 of honeycomb-structure portion 9, flow into
Cell 2a is arranged in the way of surrounding outflow cell 2b.In addition, plugged honeycomb structure 100 is configured to, cell 2a number is flowed into
Measure more than the quantity for flowing out cell 2b.Plugged honeycomb structure 100 have it is multiple divide adjacent inflow cell 2a it is mutual every
The intersection point portion 4 of wall 1.Moreover, in plugged honeycomb structure 100, the friendship for dividing the adjacent mutual next doors 1 of inflow cell 2a
Total amount of more than the 60% of point portion 4, with following composition.First, in above-mentioned intersection point portion 4 inscribe diameter of a circle D1
With the diameter of a circle D of the inscribe in the adjacent inflow cell 2a of division and outflow cell 2b next door 10Between relation meet with
Following formula (1).Here, " the intersection point portion 4 " for dividing the adjacent mutual next doors 1 of inflow cell 2a refers to " only divide adjacent inflow
The intersection point portion 4 " that the mutual next doors 1 of cell 2a intersect.That is, " the intersection point portion in the adjacent mutual next doors 1 of inflow cell 2a is divided
4 " refer to the portion that the next door 1 extended using the intersection point as basic point the inflow cell 2a mutual next door 1 adjacent by only dividing is constituted
Position.Hereinafter, unless stated otherwise, only claim " during intersection point portion 4 ", to refer to " divide the friendship in the adjacent mutual next doors 1 of inflow cell 2a
Point portion 4 ".
Formula (1)：
Here, present embodiment is illustrated in reference picture 4.Cell 2a is flowed into the way of surrounding outflow cell 2b
Arranging refers to, for example, the state for being equipped with multiple inflow cell 2a around cell 2b in the way of surrounding it is flowed out at one.
It should be noted that, the cell 2 arranged for the most peripheral of the inflow side end face 6a in plugged honeycomb structure 100 flows into cell
2a is not arranged in the way of surrounding outflow cell 2b sometimes.In addition, in each cellular unit 7, for matching somebody with somebody in most peripheral
If cell 2, flow into cell 2a and also do not arranged sometimes in the way of surrounding and flowing out cell 2b.Here, in Fig. 4, cell shape
Shape is surrounded by the outflow cell 2b of quadrangle by the cell shape pentagonal inflow cell 2a smaller than outflow cell 2b.Need
It is bright, outflow cell 2b cell shape and flow into cell 2a cell shape and be not particularly limited, as long as can with
Flow into cell 2a and surround the shape that outflow cell 2b mode is arranged.For example, being used as cell shape, it may be considered that four sides
The polygons such as shape, pentagon, hexagon, but it is not limited to these.In addition, it is big to flow into cell 2a for 1 outflow cell 2b and 1
Small (in other words, the sectional area of cell), can be the same or different.Here, " cell shape " refers in honeycomb-structure portion
The section vertical with the bearing of trend of cell in cell shape.
In addition, the so-called intersection point portion 4 for dividing adjacent mutual next doors 1 of inflow cell 2a, refer to surround tap hole
The intersection point portion 4 in the next door 1 that multiple inflow cell 2a that lattice 2b mode is arranged are divided each other.It should be noted that, such as Fig. 1 and Fig. 2
Shown, in the vicinity of the periphery wall of plugged honeycomb structure 100, flow into cell 2a shape turns into the shape of partial collapse sometimes
Shape.Turn into the inflow cell 2a of the shape of partial collapse for such cell shape, also serve as one and flow into cell 2a to count
Number.
Then, in intersection point portion 4 inscribe diameter of a circle D1, as shown in figure 4, referring to inscribe in the intersection point portion 4 of next door 1
Diameter of a circle.It should be noted that, " circle of inscribe in intersection point portion 4 " refers to, the intersection point portion 4 of next door 1, and towards intersection point portion
Plurality in 4 inflow cell 2a flows into the tangent inscribed circles of cell 2a.Moreover, for " in intersection point portion 4 circle of inscribe
Diameter D1", when there is multiple inscribed circles tangent with more than half inflow cell 2a, it is set to the straight of the maximum inscribed circle of its diameter
Footpath.
In addition, dividing adjacent inflow cell 2a and the diameter of a circle D of inscribe in the next door 1 for flowing out cell 2b0, such as scheme
Shown in 4, refer to the straight of in the next door 1 beyond the intersection point portion in the next door for flowing into cell 2a and outflow cell 2b the is divided circle of inscribe
Footpath.In other words, refer to and inflow cell 2a relative to each other and outflow cell the 2b part in addition to corner are circumscribed
Diameter of a circle.Hereinafter, sometimes by " circle of inscribe is straight in the next door 1 for dividing adjacent inflow cell 2a and outflow cell 2b
Footpath D0" it is referred to as " the diameter of a circle D of inscribe in next door 10”.Divide adjacent inflows cell 2a and flow out cell 2b every
The diameter of a circle D of inscribe in wall 10It can obtain as follows.First, in the inflow side end face 6a of plugged honeycomb structure 100, with
Machine selection divides 5 positions in adjacent inflow cell 2a and outflow cell 2b next door 1.Also, at selected 5
Next door 1, draws inscribed circle in hypothetical manner, obtains these inscribe diameter of a circles.It regard the average value of inscribe diameter of a circle at 5 as circle
Diameter D0。
Here, in formula (1)Illustrate.In formula (1)Represent as shown in Figure 7 not arrange
In the conventional plugged honeycomb structure of enhanced portion, the circle of inscribe in the intersection point portion 4 for flowing into the mutual next doors 1 of cell 2a is divided
Diameter value.Fig. 7 is the enlarged drawing of Fig. 5 conventional plugged honeycomb structure, is the circle progress to the inscribe in intersection point portion
The figure of explanation.The plugged honeycomb structure 100 of present embodiment has following feature, i.e. dividing adjacent inflow cell 2a
The diameter of a circle D of inscribe in the intersection point portion 4 in mutual next door 11More than the conventional plugged honeycomb structure for not arranging enhanced portion
" diameter of a circle of inscribe in the intersection point portion of same location ".
When using the entire quantity in intersection point portion 4 as 100%, the quantity in intersection point portion 4 of the condition of the formula (1) is met at least
For 60%, more preferably 100%.If the quantity for meeting the intersection point portion 4 of above-mentioned condition is less than 60%, resistance to sudden heating can show
Write and decline.
If in above-mentioned formula (1)Value be less than 1.20, then can not obtain sufficient heat shock resistance
Property.If in addition, in above-mentioned formula (1)Value more than 1.80, then the pressure loss can increase, light off characteristics
It can deteriorate, ash content capacity can be reduced.
In addition, only in the intersection point portion 4 for dividing the adjacent mutual next doors 1 of inflow cell 2a, the inscribe in intersection point portion 4
Diameter of a circle (D1) with dividing adjacent inflows cell 2a and flowing out the diameter of a circle (D of inscribe in cell 2b next door 10) it
Between relation meet formula (1).This is different from the conventional art that whole intersection point portions of next door arrange enhanced portion, such as Fig. 1~Fig. 4 institutes
Show, it is meant that：Only arrange enhanced portion in the intersection point portion 4 for dividing the adjacent mutual next doors 1 of inflow cell 2a in the present invention.Make
Method to make such enhanced portion, can enumerate the metal for example changed by known method during extrusion molding
The method of the shape of mould.Further, it is also possible to by making slurry flow into predetermined inflow cell 2a predetermined corner, so that logical
Cross and form the corner with R to make above-mentioned enhanced portion.It should be noted that, " having enhanced portion " refers to, divides adjacent inflow
The intersection point portion 4 in the mutual next doors 1 of cell 2a meets the relation of the formula (1).In addition, above-mentioned " is only dividing adjacent inflow
In the intersection point portion 4 in the mutual next doors 1 of cell 2a, the diameter of a circle (D of inscribe in intersection point portion 41) with dividing adjacent inflow
Diameter of a circle (the D of inscribe in cell 2a and outflow cell 2b next door 10) between relation meet formula (1) " refer to, for except
Other intersection point portions outside this, can be unsatisfactory for the relation of formula (1).Here, it is so-called be unsatisfactory for above-mentioned formula (1) relation be
Refer to, for example, may be at as conventional artRelation,Value might be less that
1.20.It is to be noted, however, that above-mentioned formula (1) is no to include manufacturing tolerance.
In addition, in cell 2a is flowed into inscribe and the circle tangent with the next door 1 of the inflow cell 2a side of intersection point portion 4 it is straight
Footpath D2Preferably 0.20~0.80mm.Here, flow into cell 2a in inscribe and with the inflow cell 2a side of intersection point portion 4 every
The tangent diameter of a circle D of wall 12As shown in Figure 4.As shown in figure 4, a diameter of D2Circle be present in inflow cell 2a, also, be
The tangent circle with the next door 1 in intersection point portion 4.Such diameter of a circle is exactly above-mentioned " diameter D2”.Here, if diameter D2It is less than
0.20mm, then can not obtain sufficient resistance to sudden heating sometimes.
For the plugged honeycomb structure 100 of present embodiment, the structure for constituting and having honeycomb-structure portion 9 can be listed below
Body is used as a suitable example.For flowing into cell 2a, geometrical surface GSA is preferably 10~30cm2/cm3, more preferably
12~18cm2/cm3.Here, it is above-mentioned " geometrical surface GSA " refer to by flow into cell 2a whole internal surface areas (S) divided by
Value (S/V) obtained by whole volumes (V) of honeycomb-structure portion 9.In general, the filter area of filter is bigger, then more energy
The ulking thickness of PM next doors is reduced, therefore, by being defined to above-mentioned geometrical surface GSA number range, will can be sealed
The pressure loss of porous honeycomb structure body suppresses low.Therefore, if the geometrical surface GSA for flowing into cell 2a is less than 10cm2/
cm3, then the pressure loss can be caused to increase when PM accumulates, thus it is not preferred.In addition, if greater than 30cm2/cm3, then the pressure at initial stage
Power loss can increase, thus not preferred.
In the plugged honeycomb structure 100 of present embodiment, the cell section aperture opening ratio for flowing into cell 2a is preferably 20~
70%, more preferably 25~65%.If the cell section aperture opening ratio for flowing into cell 2a is less than 20%, the pressure loss at initial stage
Increase, thus it is not preferred.In addition, if greater than 70%, then filtration flow-rate accelerates, PM arresting efficiency declines, and then next door 1
Intensity is not enough, thus not preferred.Here, " the cell section aperture opening ratio for flowing into cell 2a " refers to, in honeycomb-structure portion 9 with
Ratio as described below in the vertical section of heart direction of principal axis.That is, refer to " summation for flowing into cell 2a sectional area " relative to
" the gross section product for forming the next door 1 of honeycomb-structure portion 9 " and " whole cell 2 (whole inflow cell 2a and outflow cells
Total ratio of the summation of sectional area 2b) ".
In the plugged honeycomb structure 100 of present embodiment, multiple cells 2 (flowing into cell 2a, outflow cell 2b) it is each
From hydraulic diameter be preferably 0.5~2.5mm, more preferably 0.8~2.2mm.If the respective hydraulic diameter of multiple cells
Less than 0.5mm, then the pressure loss at initial stage can increase, thus not preferred.In addition, if greater than 2.5mm, then waste gas and next door 1
Contact area reduce, purification efficiency declines, thus not preferred.Here, the respective hydraulic diameter of multiple cells is based on each
The sectional area and girth of cell 2, the value calculated by 4 × (sectional area)/(girth).The sectional area of cell 2 refers in honeybee
The area of the cell shape (in other words, cross sectional shape) occurred in the section vertical with central axis direction of nest structural portion 9.Hole
The girth of lattice refers to the length (length in other words, surrounding the blockade line in the section) around the cross sectional shape of the cell.
In view of the pressure loss at initial stage, PM accumulation when the pressure loss and arresting efficiency between balance (trade off),
In the plugged honeycomb structure 100 of present embodiment, the composition that can be listed below is used as suitable example.It is preferred that meet simultaneously：
The geometrical surface GSA for flowing into cell 2a is 10~30cm2/cm3, the cell section aperture opening ratio for flowing into cell 2a is 20~70%
And the respective hydraulic diameter of multiple cells 2 is 0.5~2.5mm.In addition, more preferably meet simultaneously：Flow into the several of cell 2a
What surface area GSA is 12~18cm2/cm3, the cell section aperture opening ratio for flowing into cell 2a is 25~65% and multiple cells 2
Respective hydraulic diameter is 0.8~2.2mm.
, can be with catalyst-loaded on next door 1 in the plugged honeycomb structure 100 of present embodiment.Supported on next door 1
Catalyst refers to, on the inwall of the pore formed in the surface of next door 1 and next door 1, coats catalyst.It is used as catalyst
Species, can enumerate SCR catalyst (zeolite, titanium dioxide, vanadium), containing at least two kinds of noble metals in Pt, Ph, Pd and oxidation
At least one kind of three-way catalyst in aluminium, cerium oxide, zirconium oxide etc.., can be by from direct injection by supporting such catalyst
The Non-toxic such as contained NOx, CO, CH in the waste gas of the discharges such as gasoline engine, diesel engine, meanwhile, it is capable to utilize the effect of catalyst
The PM on the surface of accumulation next door 1 is set easily to be flared off.
For catalyst-loaded method on the plugged honeycomb structure 100 of present embodiment, it is not particularly limited, can
In the method generally implemented using those skilled in the art.Specifically, it can enumerate and be applied by the way that catalyst pulp is entered into water-filling
(Wash coat), and be dried, the method burnt till etc..
Manufacture method to the plugged honeycomb structure 100 of present embodiment is not particularly limited, for example can be by such as
Lower method is manufactured.In the material selected as the material powder of honeycomb-structure portion 9 from foregoing suitable material, addition
Adhesive, further addition surfactant and water, make the base soil of plasticity.As material powder, for example, it can use carbon
SiClx powder.As adhesive, such as can use methylcellulose and hydroxy propyloxy group methylcellulose.By by the base
Native extrusion molding, obtains the formed body of the next door 1 with predetermined cross-sectional shape and the honeycomb-structure portion 9 of cell 2.It is passed through into example
It is dried such as microwave and hot blast.Then, come by using the material same with material used in manufacture honeycomb-structure portion 9
Sealing of hole is carried out, so as to arrange sealing of hole portion 3 (inflow side sealing of hole portion 3a, outflow side sealing of hole portion 3b), a step of going forward side by side is dried.So
Afterwards, degreasing is heated in such as nitrogen atmosphere, is then burnt till in the inert atmospheres such as argon gas, so as to obtain this reality
Apply the plugged honeycomb structure 100 of mode.Firing temperature and firing atmosphere are according to the different and different of raw material, people in the art
Member can select optimal firing temperature and firing atmosphere for selected material.
In present embodiment, it is not particularly limited for constituting the next door of honeycomb-structure portion 9 and the material of periphery wall, but from
The viewpoints such as intensity, heat resistance, durability consider that main component is preferably various ceramics, metal of oxide or non-oxidized substance etc..
As ceramics, cordierite, mullite, aluminum oxide, spinelle, carborundum, silicon nitride and aluminium titanates etc. can be enumerated.As metal,
Fe-Cr-Al systems metal and metal silicide etc. can be enumerated.Preferably use the one kind or two or more conduct selected from these materials
Main component.From the viewpoint of high intensity, high-fire resistance, particularly preferably from by aluminum oxide, mullite, aluminium titanates, cordierite,
Carborundum and silicon nitride composition group in select 1 or two or more as main component.Here, " main component is used as " to refer to
Constitute at least more than the 50 mass %, more preferably preferably more than 70 mass %, more than 80 mass % of honeycomb-structure portion 9.
Material for sealing of hole portion 3 (inflow side sealing of hole portion 3a and outflow side sealing of hole portion 3b) it is not also specifically limited, it is preferred that
For the identical material of honeycomb-structure portion 9.
For the thickness in next door 1, more preferably preferably 100~410 μm, 150~360 μm.If thinner than 100 μm,
The intensity of monolith substrate declines sometimes.If than 410 μ m-thicks, performance is trapped sometimes to be declined, and the pressure loss can increase.This
Outside, in the waste gas that processing is discharged from diesel engine, due to relatively more from the PM amounts in the waste gas that diesel engine is discharged, thus generally have
Reduce the tendency of (the reduction cell density) of cell number.Therefore, in order to be better balanced intensity and trapping performance, the thickness in next door 1
Spend for preferably 150~360 μm.The thickness in next door is that the method in the section of the direction of principal axis by using microscopic monolith substrate is surveyed
Surely the value obtained.
Embodiment
(embodiment 1)
The mass parts of silicon carbide powder 80 and the mass parts of Si powder 20 are mixed, mixed-powder is obtained.In the mixed powder
Adhesive, pore-creating material and water are added in end, shaping raw material is obtained.Then, shaping raw material is kneaded, makes columned base
Soil.
Then, using predetermined extrusion molding mould by the native extrusion molding of base, obtain pentagonal inflow cell and be centered around
The honeycomb formed article of shape around the outflow cell of square.Make 16 honeycomb formed articles.
Then, honeycomb formed article is dried with microwave dryer, and then made with air drier after it is completely dried,
The both ends of the surface of honeycomb formed article are cut off, preliminary dimension is adjusted to.Then, to cover the whole area in inflow side end face of honeycomb formed article
The mode in domain attaches film, and perforated portion is set in the position being consistent with the cell opening portion as outflow cell of film.Then,
The end for having attached film side of honeycomb formed article is immersed in the sealing material of the pulp-like containing ceramic raw material, so that
Sealing material is filled into and flowed into the outflow cell in side end face.And then, for outflow side end face, similarly operate, in stream
Enter and sealing material is filled in cell.
Then, for honeycomb hirudo leech, by carrying out degreasing in 400 DEG C of heating, 5 hours Calais, and then, in argon gas atmosphere
Under, burnt till by heating 2 hours at 1450 DEG C, obtain honeycomb sintered body.The global shape of honeycomb sintered body is four ribs
Column.
Then, 16 honeycomb sintered bodies of gained are adjacent in mutual side mode relative to each other, in the shape
Under state, engaged by engagement material, make honeycomb conjugant.Honeycomb conjugant is with longitudinal arrangement 4, transverse direction in its end face
Arrangement 4, the mode of 16 honeycomb sintered bodies of total arrangement are engaged to make.
Then, the peripheral part of honeycomb conjugant is processed by being ground, made honeycomb conjugant with cell extension
The shape in the vertical section in direction turns into circle.Then, pottery is contained in the most peripheral coating of the honeycomb conjugant through grinding
The periphery coating material of porcelain raw material.
So make the plugged honeycomb structure of embodiment 1.Resulting plugged honeycomb structure is and central axis
A diameter of 143.8mm in section, the length of central axis direction be 152.4mm cylindrical shape.The thickness in next door is 0.3mm, hole
Lattice density is 208 cells/cm2。
Next door thickness (mm), a (mm), b (mm), cell density (cell/cm is displayed in Table 12).Here, a (mm) refers to
With the length of the symbol a scopes represented in Fig. 4.That is, a (mm) refers to the distance between 2 next doors 1 of configured in parallel, it is described every
It is relative with flowing out cell 2b and clipping 1 outflow cell 2b that wall divides inflow cell 2a.In addition, b (mm) refers in Fig. 4 with symbol
The length for the scope that number b is represented.That is, b (mm) refers to the distance between 2 next doors 1 of configured in parallel, and the next door, which is divided, to be flowed into
Cell 2a is relative with flowing out cell 2b and clipping 1 inflow cell 2a.In a (mm) and b (mm), between 2 next doors 1 away from
From be respectively 2 next doors 1 lighting from the centre of the thickness direction in each next door 1 each other with a distance from.
" the diameter of a circle D of inflow cell and inscribe in the next door for flowing out cell is being divided in addition, being displayed in Table 10
(mm) ", " in the intersection point portion for flowing into cell mutual next door the is divided diameter of a circle D of inscribe1(mm) " and "
Value ".In addition, " ratio for meeting the intersection point portion of formula (1) " has been displayed in Table 1.Here, " ratio in the intersection point portion of formula (1) is met
Rate " refers to, in the intersection point portion for dividing the adjacent mutual next door of inflow cell, meets
Relation intersection point portion number ratio.
" in cell is flowed into inscribe and the diameter of a circle D tangent with the next door of intersection point portion side in addition, be displayed in Table 12
(mm)”。
Hereinafter, in the present embodiment, sometimes by " circle of inscribe is straight in the next door for flowing into cell and outflow cell is divided
Footpath D0(mm) " it is referred to as " inscribe diameter of a circle D0(mm)”.In addition, sometimes " the intersection point portion in the mutual next door of inflow cell will be being divided
The diameter of a circle D of middle inscribe1(mm) " it is referred to as " inscribe diameter of a circle D1(mm)”.And then, sometimes will " flow into cell in inscribe and
The tangent diameter of a circle D with the next door of intersection point portion side2(mm) " it is referred to as " inscribe diameter of a circle D2(mm)”。
Table 1
Table 2
(embodiment 2~12)
Change " inscribe diameter of a circle D as shown in table 1 or table 20(mm) ", " inscribe diameter of a circle D1(mm) ", " inscribe
Diameter of a circle D2(mm) plugged honeycomb structure of embodiment 2~12 " and " ratio for meeting the intersection point portion of formula (1) ", is made.
(comparative example 1~4)
Change " inscribe diameter of a circle D as shown in table 1 or table 20(mm) ", " inscribe diameter of a circle D1(mm) ", " inscribe
Diameter of a circle D2(mm) " and " ratio for meeting the intersection point portion of formula (1) ", the plugged honeycomb structure of comparison example 1~4.
For the plugged honeycomb structure of comparative example 1, except dividing the intersection point in the adjacent mutual next door of inflow cell
In portionIn addition, plugged honeycomb structure is made similarly to Example 1.That is, the sealing of hole honeycomb knot of comparative example 1
Structure body "Value " be 1.00.
For embodiment 1~12 and the plugged honeycomb structure of comparative example 1~4, " heat-resisting punching is carried out as follows
Hitting property ", " light off characteristics ", " entrance opening rate " and while accumulating " PM the pressure loss " evaluation.As a result it is shown in Tables 1 and 2.
[resistance to sudden heating]
Resistance to sudden heating is evaluated by heating plus shaking experiment.Specifically, the MAFTEC (business manufactured with Resins Corporation of Mitsubishi
The name of an article) hold the scope that the distance outflow side end face of made plugged honeycomb structure is 130mm.To so holding outflow side
The plugged honeycomb structure of end face is while apply vibration frequency 100Hz, acceleration 30G vibration, while making by propane burner
The air of heating flows through, and carries out the experiment of 100 hours.Heat plus the condition for the heated air in testing that shakes is：Flow
2Nm3/ min, 150~800 DEG C of temperature (1 circulation is 20 minutes).After heating plus experiment of shaking, visually confirm in sealing of hole honeycomb knot
Whether the next door of structure body produces breakage.When not confirming breakage in the next door of plugged honeycomb structure, it is evaluated as " good ", confirms
During to little damage, "available" is evaluated as, when confirming serious damage, be evaluated as " can not ".As a result it is shown in Tables 1 and 2.
[light off characteristics (time (second) for reaching 200 DEG C)]
The evaluation of light off characteristics is carried out as follows：Using plugged honeycomb structure as DPF, make 400 DEG C of burning gases stream
Enter in the DPF, metering DPF outflow side end reaches 200 DEG C of time.Specifically, first, in resulting sealing of hole honeycomb
The periphery winding of structure is pressed into the tinning of SUS409 stainless steel as the ceramics non-heat expandable pad processed for keeping material
With in tank body, obtaining tinning structure.And then, in the outflow side end of tinning structure, K-type armoured thermocouple is set.Then,
By the burning of diesel fuel, 400 DEG C of burning gases are flowed into, monitor the temperature of the thermocouple set in advance, determine it and reach
To the time (second) at 200 DEG C.It should be noted that, as diesel fuel, use light diesel fuel.During light off characteristics are evaluated, to compare
The time (second) for reaching 200 DEG C of the plugged honeycomb structure of example 1, as benchmark (Base), is carried out as follows evaluation.Relative to base
Standard, when the time (second) for reaching 200 DEG C is less than+0.5 second, is designated as " good ".Relative to benchmark, 200 DEG C of time (second) is reached
More than+0.5 second and for less than+1 second when, be designated as "available".Relative to benchmark, when reaching that 200 DEG C of time (second) exceedes+1 second, note
For " can not ".
[entrance opening rate]
The inflow cell flowed into side end face is determined relative to the area shared by the area of section of plugged honeycomb structure
Ratio (%).The entrance opening rate (%) of plugged honeycomb structure is used as using the ratio (%) of the area.Entrance opening rate is commented
In valency, the entrance opening rate (%) using the plugged honeycomb structure of comparative example 1 is carried out as follows evaluation as benchmark (Base).Phase
For benchmark, when entrance opening rate (%) is below+1%, it is designated as " good ".Relative to benchmark, entrance opening rate (%) is more than 1%
And during for below+2%, it is designated as "available".Relative to benchmark, when entrance opening rate (%) exceedes+2%, be designated as " can not ".
[pressure loss when PM accumulates]
The burning gases containing coal smoke ash is flowed into plugged honeycomb structure, make coal soot build-up in plugged honeycomb structure
In, the pressure differential of inflow side and outflow side during based on the grey accumulating amount of coal smoke for 4g/L determines the PM heaps of plugged honeycomb structure
Pressure loss during product.Specifically, first, light diesel fuel is burnt under anaerobic condition, coal smoke ash is generated so as to generate
Burning gases.Moreover, for the grey generating capacity 10g/h of coal smoke, flow 2.4Nm3/ min, 200 DEG C of temperature burning gases, addition are dilute
Release air to be adjusted, so as to make the burning gases containing coal smoke ash for evaluating pressure loss during PM accumulations.Make
The burning gases for containing coal smoke ash flow into plugged honeycomb structure, and the grey accumulating amount of the coal smoke in plugged honeycomb structure reaches
At 4g/L time point, the inflow side of the plugged honeycomb structure and the pressure of outflow side are determined, sealing of hole honeybee is used as using the pressure differential
The pressure loss value during PM accumulations of nest structure.In the evaluation of the pressure loss when PM accumulates, with the sealing of hole honeybee of comparative example 1
The pressure loss value of nest structure is carried out as follows evaluation as benchmark (Base).Relative to benchmark, the increase of pressure loss value is
When below+4%, it is designated as " good ".Relative to benchmark, pressure loss value increase above+4% and for below+8% when, be designated as
"available".Relative to benchmark, when increasing above+8% of pressure loss value, be designated as " can not ".
(result)
As shown in Table 1 and Table 2, the plugged honeycomb structure of embodiment 1~12 " resistance to sudden heating ", " light off characteristics ",
All it is evaluation result more than "available" in whole evaluations of " entrance opening rate " and " pressure loss when PM accumulates ".Particularly,
The evaluation result of plugged honeycomb structure based on embodiment 1~12 and comparative example 1 is understood, if " inscribe diameter of a circle D1
(mm) " it is more than " inscribe diameter of a circle D0(mm) "Times, then the resistance to sudden heating of plugged honeycomb structure is improved.In addition, such as
Comparative example 2 and 3 is such,Value for beyond 1.20~1.80 when, in " light off characteristics ", " entrance opening rate "
In evaluation, as " can not " result.Thus, it can be known that working asValue be set to 1.20~1.80 in the range of when,
" resistance to sudden heating ", " light off characteristics ", " entrance opening rate " and while accumulating " PM the pressure loss " it is whole evaluate relative to than
All it is improved compared with example 1.
Furthermore, it was found that the ratio in the intersection point portion for meeting formula (1), with the decline of the ratio, plugged honeycomb structure
Resistance to sudden heating decline, when less than 60%, resistance to sudden heating declines to a great extent.
It is further known that, if " inscribe diameter of a circle D2(mm) " it is 0.20~0.80mm, then " light off characteristics ", " entrance
The evaluation of aperture opening ratio " and " pressure loss when PM accumulates " is good, if it exceeds 0.80mm, then each evaluation can all decline.
Utilization possibility in industry
The plugged honeycomb structure of the present invention may be used as filter for exhaust gas decontamination.Further, it is also possible to as in this hair
Catalyst-loaded catalyst carrier on the next door of bright plugged honeycomb structure.
Claims (4)
1. a kind of plugged honeycomb structure, possesses：
Honeycomb-structure portion, it has the next door of Porous, and the next door, which divides to be formed from inflow side end face, extends to outflow side
Face and multiple cells as fluid flowing path,
Inflow side sealing of hole portion, it is disposed in the opening portion of the predetermined inflow cell in the outflow side end face, and
Outflow side sealing of hole portion, it is disposed in the opening portion of the remaining outflow cell in the inflow side end face,
In the section vertical with the bearing of trend of the cell of the honeycomb-structure portion, the inflow cell is described to surround
The mode of outflow cell is arranged, also, the quantity for flowing into cell is more than the quantity of the outflow cell,
With multiple intersection point portions for dividing the adjacent mutual next door of inflow cell,
For total amount of more than the 60% intersection point portion in the intersection point portion, the diameter of a circle D of inscribe in the intersection point portion1
With the diameter of a circle D of the inscribe in the next door of the adjacent inflow cell of division and the outflow cell0Between relation expire
Foot formula (1),
Formula (1)：
2. plugged honeycomb structure as described in claim 1,
For the total amount of intersection point portion, the diameter of a circle D of inscribe in the intersection point portion1With divide it is adjacent described in
Flow into the diameter of a circle D of inscribe in the next door of cell and the outflow cell0Between relation meet the formula (1).
3. the plugged honeycomb structure as described in claim 1 or 2,
Inscribe and the diameter of a circle D tangent with the next door of the intersection point portion side of the inflow cell in the inflow cell2For
0.20~0.80mm.
4. such as plugged honeycomb structure according to any one of claims 1 to 3,
Only dividing the intersection point portion in the adjacent mutual next door of inflow cell, the diameter of a circle of inscribe in the intersection point portion
D1With the diameter of a circle D of the inscribe in the next door of the adjacent inflow cell of division and the outflow cell0Between relation expire
The foot formula (1).
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| JP2017062752A JP6802102B2 (en) | 2016-03-30 | 2017-03-28 | Sealed honeycomb structure |
| JP2017-062752 | 2017-03-28 |
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| CN110307060A (en) * | 2018-03-27 | 2019-10-08 | 日本碍子株式会社 | Honeycomb structure |
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| US10814266B2 (en) * | 2017-11-24 | 2020-10-27 | Ngk Insulators, Ltd. | Honeycomb filter |
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| JP2014200741A (en) * | 2013-04-04 | 2014-10-27 | 日本碍子株式会社 | Wall flow type exhaust gas purification filter |
| CN104185496A (en) * | 2012-04-05 | 2014-12-03 | 住友化学株式会社 | Honeycomb structure |
| WO2016013513A1 (en) * | 2014-07-23 | 2016-01-28 | イビデン株式会社 | Honeycomb filter |
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| US5607586A (en) * | 1994-06-08 | 1997-03-04 | T.A.M.I. Industries | Multichannel inorganic element for filtering a fluid |
| JP2003269131A (en) * | 2002-03-13 | 2003-09-25 | Hitachi Metals Ltd | Ceramic honeycomb structure |
| CN1646204A (en) * | 2002-04-09 | 2005-07-27 | 揖斐电株式会社 | Honeycomb filter for clarification of exhaust gas |
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| CN110307060B (en) * | 2018-03-27 | 2022-06-03 | 日本碍子株式会社 | Honeycomb structure |
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| JP6802102B2 (en) | 2020-12-16 |
| CN107269347B (en) | 2020-09-11 |
| JP2017185484A (en) | 2017-10-12 |
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