CN103648605B

CN103648605B - Ceramic honeycomb filter and manufacture method thereof

Info

Publication number: CN103648605B
Application number: CN201280026598.0A
Authority: CN
Inventors: 冈崎俊二; 曾我航; 小松顺二
Original assignee: Hitachi Metals Ltd
Current assignee: Proterial Ltd
Priority date: 2011-04-01
Filing date: 2012-03-28
Publication date: 2015-10-21
Anticipated expiration: 2032-03-28
Also published as: WO2012137655A1; JP2014113510A; CN103648605A

Abstract

A kind of ceramic honeycomb filter for removing particulate matter from waste gas comprises multiple ceramic honeycomb, each ceramic honeycomb has a large amount of eyelets separated by porous eyewall, described multiple ceramic honeycomb is in axial direction connected end-to-end, and at least one group of adjacent ceramic honeycomb is connected in the mode be shifted at least partially of eyelet wall; The open area ratio A of 25 eyelets in the five-element five row of arbitrary continuation ₀(=A ₀₂/ A ₀₁) mean value be 0.9 or less, wherein A ₀₁and A ₀₂represent the aperture area perpendicular to each eyelet in the cross section of the axis of exhaust gas upstream side ceramic honeycomb and the aperture area of this eyelet after being narrowed by the upstream side end surfaces of the eyelet wall of the downstream ceramic honeycomb in adjacent ceramic honeycomb respectively; And described downstream ceramic honeycomb all has 15 μm or larger roughness (maximum height Rz) on both eyelet wall end surfaces and eyelet wall inner surface.

Description

Ceramic honeycomb filter and manufacture method thereof

Technical field

The present invention relates to the ceramic honeycomb filter for the clean waste gas got rid of from the internal combustion engine of such as Diesel engine etc. and so on and manufacture method thereof.

Background technology

The waste gas got rid of from the internal combustion engine of such as Diesel engine etc. and so on comprises a large amount of particulate matter (hereinafter referred to as " PM ").Because the PM be discharged in air causes environmental pollution, therefore filter is used for catching PM.As shown in Figure 11 (a) He 11 (b), such as, ceramic honeycomb filter 50 comprises ceramic honeycomb, this ceramic honeycomb comprises a large amount of eyelets separated by porous eyewall 51, alternately be arranged on the connector (upstream side connector 53a and downstream connector 53b) in the eyelet on exhaust gas entrance side end a and waste gas outlet side end b, eyelet 52a and inlet-side end portions obstruction eyelet 52b is blocked by the outlet side end portion alternately arranged, exhaust gas entrance side end a and exhaust gas entrance side end b form checkerboard pattern (such as, see JP2001-269585A).

As shown in by the dotted arrow in Figure 11 (a) and 11 (b), waste gas flows into and blocks eyelet 52a at the outlet side end portion of the inlet-side end portions opening of ceramic honeycomb filter, and blocks eyelet 52b outflow by porous eyewall 51 from adjacent inlet-side end portions.When waste gas passing hole eyewall 51, the PM in waste gas is caught by eyelet wall, thus cleaning exhaust gas.

But, all blocked at two ends owing to catching eyelets all in ceramic honeycomb filter at the PM with the structure described in JP2001-269585A, therefore when cleaning exhaust gas, the pressure loss that the waste gas experience passed through is larger.

When the PM discharged from Diesel engine continues captured, the PM caught gathers in the filter, reduces strainability.Therefore, such as, should hot filtration apparatus be passed through, the PM gathered is burnt, for regeneration.But if the filter with a large amount of PM be captured according to the driving condition of vehicle is reproduced, then a large amount of PM is by burned and produce amount of heat, the eyelet wall of possible molten ceramic alveolate texture.In addition, even if the PM burning of catching, solid ashes may build up and blocking filter.

In order to address these problems, as shown in Figure 12 (a) He 12 (b), JP2004-251137A discloses a kind of ceramic honeycomb filter 60, it comprises alveolate texture, this alveolate texture comprises a large amount of longitudinal directions separated by porous eyewall 61 and penetrates eyelet, only be formed in the connector 63b on an end surfaces side b of eyelet 62a, eyelet 62a is provided with the connector 63b with relatively large aperture area, to reduce the amount being penetrated into the waste gas the eyelet 62b of another end surfaces b from an end surfaces a flowing into and do not have connector, thus avoid the sharply reduction of the capture rate of filter.But, adopt to be provided with and there is relatively large aperture area to guarantee the eyelet 62a of the connector 63b of PM acquisition performance, the effective area being used as the eyelet wall of filter of ceramic honeycomb filter 60 reduces, cause the pressure drop characteristics of difference, thus PM acquisition performance and pressure drop characteristics can not be met simultaneously.

Summary of the invention

The technical problem that invention will solve

Therefore, target of the present invention is to provide a kind of ceramic honeycomb filter suppressing the pressure loss of waste gas while maintaining PM acquisition performance, its opposing fusing corrosion of regeneration period and blocking of ashes, thus avoids the pressure loss to increase.

The technical scheme of technical solution problem

As the result of the creative research of the above-mentioned target of consideration, inventor has been found that, in conventional ceramic honeycomb filter, be formed in outlet and the connector at inlet-side end portions place causes pressure loss increase and the ashes that gather to plugged filter while waste gas process, and the connection of multiple ceramic honeycomb provides the ceramic honeycomb filter with high PM acquisition performance and the loss of low exhaust gas pressure, does not form connector in the end of ceramic honeycomb.Complete the present invention based on this discovery.

Therefore, ceramic honeycomb filter for removing particulate matter from waste gas of the present invention comprises multiple ceramic honeycomb, each ceramic honeycomb has a large amount of eyelets separated by porous eyewall, and described multiple ceramic honeycomb is in axial direction connected end-to-end

At least one group of adjacent ceramic honeycomb is connected in the mode be shifted at least partially of eyelet wall;

The open area ratio A of 25 eyelets in the five-element five row of arbitrary continuation ₀(=A ₀₂/ A ₀₁) mean value be 0.9 or less, wherein A ₀₁and A ₀₂represent the aperture area perpendicular to each eyelet in the cross section of the axis of exhaust gas upstream side ceramic honeycomb respectively, and the aperture area of this eyelet after being narrowed by the upstream side end surfaces of the eyelet wall of the downstream ceramic honeycomb in adjacent ceramic honeycomb; And

Described downstream ceramic honeycomb has 15 μm or larger roughness (maximum height Rz) on eyelet wall end surfaces, and on eyelet wall inner surface, have 15 μm or larger roughness (maximum height Rz).

Preferably, arbitrary continuation the five-element five arrange in 25 eyelets in Δ A _maxmaximum be equal to or greater than 0.1 and be less than 1, wherein each Δ A _maxthe open area ratio (A of any eyelet ₀) and the open area ratio (A of the eyelet adjacent with this any eyelet ₁, A ₂, A ₃, A ₄...) the maximum value of difference.

Preferably, adjacent ceramic honeycomb is connected in the mode of eyelet wall at their thickness direction superior displacement, and displacement width is 0.1-0.5 times of eyelet wall spacing.

Preferably, described adjacent ceramic honeycomb is shifted in a rotational direction using the axis as center around them, the mode of angle in the scope of 35-55 ° between the eyelet wall of a ceramic honeycomb and the eyelet wall of another ceramic honeycomb be connected.

Ceramic honeycomb filter is preferably made up of 2-15 ceramic honeycomb.

Preferably, when watching along the longitudinal direction, eyelet comprises the quadrangular cross section with arched corner, and a pair relative bight has and is greater than another radius of curvature to the radius of curvature in relative bight.

Preferably, described adjacent ceramic honeycomb is connected in the mode that end-to-end gap is 0.01-3mm.

Preferably, multiple described ceramic honeycomb has the aperture efficiency of 75% or less.

Preferably, at least one group of adjacent ceramic honeycomb can have different aperture efficiencies.

Preferably, in the cross section of axis being parallel to each ceramic honeycomb, a () adjacent eyelet wall is parallel, and (b) divides the quantity of ground or the eyelet of opening to be fully 1 ~ 5 in every 300mm length of ceramic honeycomb in peripheral upper surface.

Method for manufacturing ceramic honeycomb filter by axially connecting multiple ceramic honeycomb of the present invention comprises: moldable ceramic material is extruded into honeycomb shape, the moldable ceramic material extruded is cut into predetermined length, the dry extrudate cut off is to form the ceramic honeycomb of multiple drying, arrange the ceramic honeycomb of described drying with eyelet wall in the mode of their end displacement, and sinter the ceramic honeycomb of the drying arranged.

After the sintering, multiple ceramic honeycomb preferably on their peripheral surface on the whole by paint.

Method for manufacturing ceramic honeycomb filter by axially connecting multiple ceramic honeycomb of the present invention comprises: moldable ceramic material is extruded into honeycomb shape, extrudate is cut into predetermined length, the dry extrudate cut off is to form the ceramic honeycomb of multiple drying, arrange the ceramic honeycomb of described drying in the mode of their end displacement with eyelet wall, integrally apply the peripheral surface of the ceramic honeycomb of the drying arranged with coating, and sinter described ceramic honeycomb.

Method for manufacturing ceramic honeycomb filter by axially connecting multiple ceramic honeycomb of the present invention comprises: moldable ceramic material is extruded into honeycomb shape, extrudate is cut into predetermined length, the extrudate that dry and sintering cuts off is to form multiple ceramic honeycomb, arrange described ceramic honeycomb with eyelet wall in the mode of their end displacement, and integrally apply the peripheral surface of the described ceramic honeycomb arranged with coating.

Preferably, multiple described ceramic honeycomb is bonded via the jointing material of periphery of the end surfaces being applied to them.

Preferably, adjacent ceramic honeycomb is connected when eyelet walls displace: any eyelet wall that positioner and the peripheral end portion of on the end surfaces from a ceramic honeycomb extend to another peripheral end portion roughly aligns by (a) by following manner, b a described ceramic honeycomb is moved preset distance by () in the x and/or y direction, or around the axis of a described ceramic honeycomb, it is rotated predetermined angular, and (c) by with the end surfaces for the identical localization method of a described ceramic honeycomb, another ceramic honeycomb being arranged in a described ceramic honeycomb.

Preferably, described positioner is metal and/or nonmetal thread-like member or light.

The beneficial effect of the invention

Because ceramic honeycomb filter of the present invention suppresses the pressure loss in the waste gas passed therethrough, maintain high PM acquisition performance simultaneously, and its opposing at it by the fusing corrosion in the regeneration of burning and the blocking of ashes, therefore it is particularly suitable for clean waste gas of discharging from Diesel engine.

Accompanying drawing explanation

Fig. 1 (a) is the schematic cross sectional views of the example that ceramic honeycomb filter of the present invention is shown.

Fig. 1 (b) is the schematic diagram of the ceramic honeycomb filter of the end surfaces side that Fig. 1 (a) is shown.

Fig. 2 (a) is the exemplary cut away view of the amplification along the line B-B intercepting in Fig. 1 (a).

Fig. 2 (b) is the schematic cross sectional views of the aperture area of the eyelet illustrated in Fig. 2 (a).

Fig. 2 (c) is the schematic cross sectional views of aperture area after being narrowed by the eyelet wall in adjacent alveolate texture of the eyelet illustrated in Fig. 2 (a).

Fig. 3 (a) is the schematic diagram of the example of the five-element five row eyelet of the arbitrary continuation illustrated in the ceramic honeycomb comprising triangle eyelet.

Fig. 3 (b) is the schematic diagram of the example of the five-element five row eyelet of the arbitrary continuation illustrated in the ceramic honeycomb comprising quadrangle eyelet.

Fig. 3 (c) is the schematic diagram of the example of the five-element five row eyelet of the arbitrary continuation illustrated in the ceramic honeycomb comprising hexagon eyelet.

Fig. 4 (a) is the schematic cross sectional views of another example that ceramic honeycomb filter of the present invention is shown.

Fig. 4 (b) is the schematic diagram of the ceramic honeycomb filter of the end surfaces side that Fig. 4 (a) is shown.

Fig. 5 (a) is the exemplary cut away view of the amplification along the line C-C intercepting in Fig. 4 (a).

Fig. 5 (b) is the schematic cross sectional views of the aperture area of the eyelet illustrated in Fig. 5 (a).

Fig. 5 (c) is the schematic cross sectional views of aperture area after being narrowed by the eyelet wall in adjacent alveolate texture of the eyelet illustrated in Fig. 5 (a).

Fig. 6 is the intention of the cross part of the eyelet wall illustrated in ceramic honeycomb.

Fig. 7 is the schematic diagram of the nib for ceramic honeycomb extrusion molding illustrated at base substrate outlet side.

Fig. 8 is the schematic cross sectional views that the ceramic honeycomb filter comprising ceramic honeycomb is shown, the end surfaces periphery of this ceramic honeycomb is provided with chamfering and rounded portions.

Fig. 9 is the schematic cross sectional views of the ceramic honeycomb filter that (in the present invention) example 25 is shown.

Figure 10 (a) schematically shows the sectional view being parallel to axial direction and dividing the example of the eyelet of ground or whole opening in peripheral upper surface.

Figure 10 (b) schematically shows the sectional view being parallel to axial direction and dividing another example of the eyelet of ground or whole opening in peripheral upper surface.

Figure 11 (a) is the front view of the example that conventional ceramic honeycomb filter is shown.

Figure 11 (b) is the sectional view being parallel to axial direction of the example that conventional ceramic honeycomb filter is shown.

Figure 12 (a) is the front view of another example that conventional ceramic honeycomb filter is shown.

Figure 12 (b) is the sectional view being parallel to axial direction of another example that conventional ceramic honeycomb filter is shown.

Figure 13 (a) is the schematic diagram of the aperture area of any eyelet illustrated in the upstream side ceramic honeycomb in ceramic honeycomb filter of the present invention.

Figure 13 (b) is the schematic diagram of the aperture area of the eyelet illustrated in ceramic honeycomb filter of the present invention, and this aperture area is narrowed by the eyelet wall of downstream ceramic honeycomb.

Figure 14 (a) is the schematic cross sectional views of the example that the ceramic honeycomb filter connected with jointing material is shown.

Figure 14 (b) is the schematic diagram of the ceramic honeycomb filter in end surfaces side that Figure 14 (a) is shown.

Figure 14 (c) is the schematic cross sectional views of another example that the ceramic honeycomb filter connected with jointing material is shown.

Figure 14 (d) is the schematic diagram of the ceramic honeycomb filter in end surfaces side that Figure 14 (c) is shown.

Figure 15 (a) is the schematic diagram of the method illustrated for arranging multiple ceramic honeycomb, and the end surfaces of wherein said multiple ceramic honeycomb is at eyelet wall thickness direction superior displacement.

Figure 15 (b) is the schematic diagram of the method illustrated for arranging multiple ceramic honeycomb, and the end surfaces of wherein said multiple ceramic honeycomb is at eyelet wall thickness direction superior displacement.

Figure 15 (c) is the schematic diagram of the method illustrated for arranging multiple ceramic honeycomb, and the end surfaces of wherein said multiple ceramic honeycomb is at eyelet wall thickness direction superior displacement.

Figure 15 (d) is the schematic diagram of the method illustrated for arranging multiple ceramic honeycomb, and the end surfaces of wherein said multiple ceramic honeycomb is at eyelet wall thickness direction superior displacement.

Figure 15 (e) is the schematic diagram of the method illustrated for arranging multiple ceramic honeycomb, and the end surfaces of wherein said multiple ceramic honeycomb is at eyelet wall thickness direction superior displacement.

Figure 16 (a) is the schematic diagram of the method illustrated for arranging multiple ceramic honeycomb, and its perforations wall is shifted in a rotational direction in their end.

Figure 16 (b) is the schematic diagram of the method illustrated for arranging multiple ceramic honeycomb, and its perforations wall is shifted in a rotational direction in their end.

Figure 16 (c) is the schematic diagram of the method illustrated for arranging multiple ceramic honeycomb, and its perforations wall is shifted in a rotational direction in their end.

Figure 16 (d) is the schematic diagram of the method illustrated for arranging multiple ceramic honeycomb, and its perforations wall is shifted in a rotational direction in their end.

Figure 16 (e) is the schematic diagram of the method illustrated for arranging multiple ceramic honeycomb, and its perforations wall is shifted in a rotational direction in their end.

Detailed description of the invention

Below embodiments of the invention will be described, object is not limit the invention to these embodiments.Within the scope of the invention, suitably any amendment and improvement can be carried out based on the knowledge of those skilled in the art to design etc.

[1] ceramic honeycomb filter

(1) embodiment

Fig. 1 (a) and the ceramic honeycomb filter of the present invention 10 shown in 1 (b) comprise two ceramic honeycombs 11,12, each ceramic honeycomb has a large amount of eyelets 2 separated by porous eyewall 1, porous eyewall 1 is axially connected at their end surfaces place, waste gas is caused and flows to ceramic honeycomb 12 from ceramic honeycomb 11, to remove PM from waste gas.These two ceramic honeycombs 11,12 are connected in the mode be shifted at least partially of eyelet wall, the open area ratio A of 25 eyelets that the five-element five of arbitrary continuation are arranged ₀(=A ₀₂/ A ₀₁) mean value A _ave0.9 or less, wherein A01 represents the aperture area of an eyelet in the cross section of the axis of the ceramic honeycomb 11 perpendicular to the upstream side in exhaust gas flow direction, and A02 represents the aperture area of an above-mentioned eyelet after being narrowed by the end surfaces 121 of downstream ceramic honeycomb 21.Downstream ceramic honeycomb 12 comprises the eyelet wall end surfaces with 15 μm or larger roughness (maximum height Rz) and the eyelet wall inner surface with 15 μm or larger roughness (maximum height Rz).Unless otherwise specified herein, axial direction aligns with exhaust gas flow direction (axial direction of eyelet).

Two ceramic honeycombs 11 are being connected in the mode be shifted at least partially of eyelet wall, when 12, outlet side (downstream) opening of the eyelet in upstream side ceramic honeycomb 11 is partly blocked by the eyelet wall 121 of downstream ceramic honeycomb 12, and exhaust flow path connection portion is narrowed.Therefore, the waste gas entering the eyelet of upstream side ceramic honeycomb 11 is by the connecting portion of downstream ceramic honeycomb 12 and eyelet, PM during it in waste gas is caught by the upstream side end surfaces of the eyelet wall 121 of downstream ceramic honeycomb 12, and is caught by the eyelet wall inner surface of downstream ceramic honeycomb due to the pressure reduction between adjacent eyelet.When eyelet wall end surfaces and eyelet wall inner surface have 15 μm or larger roughness (maximum height Rz), the PM in waste gas is caught by eyelet wall end surfaces and eyelet wall inner surface effectively.Because ceramic honeycomb filter 10 comprises the flow path being communicated to outlet side end surfaces from entrance side end surfaces, keep PM acquisition performance simultaneously, therefore when waste gas passes therethrough, the pressure loss can be remained low.

In ceramic honeycomb filter of the present invention, eyelet wall end surfaces and the eyelet wall inner surface of the downstream ceramic honeycomb that the most of PM in waste gas are connected are caught equably, and PM burning is with regeneration filter, and large localized heat can not be produced as conventional blocking type ceramic honeycomb filter, this causes ceramic honeycomb seldom to melt corrosion.And the ashes stayed after burning PM easily flow out ceramic honeycomb filter, cause filter seldom to block.

As shown in Fig. 1 (a), periphery wall 5 is formed in these two ceramic honeycombs 11 when the eyelet walls displace of two ceramic honeycombs 11,12, on 12, to increase the intensity of ceramic honeycomb filter 10.

Perforated openings area ratio A ₀be calculated as follows.Light is made to pass through the ceramic honeycomb filter connected from downstream end surfaces, to obtain the photo of perforated openings from upstream side.When not observing connecting portion well at the end surfaces of ceramic honeycomb filter, the position that the both sides in the direction perpendicular to axial direction of connecting portion are about 10mm from connecting portion is in the axial direction cut off, to obtain the photo of perforated openings.If Fig. 2 (a) is to 2 (c), from the aperture area A being perpendicular to the eyelet the cross section of the axis of upstream side ceramic honeycomb 11 that this photo is determined ₀₁, and the aperture area A of an above-mentioned eyelet after being narrowed by the upstream side end surfaces of the eyelet wall 121 of downstream ceramic honeycomb 21 ₀₂, with the open area ratio A by each eyelet ₀be calculated as (A ₀₂/ A ₀₁).As shown in Fig. 2 (c), by from aperture area A ₀₁in deduct the eyelet wall 121 of downstream ceramic honeycomb 12 upstream side end surfaces be projected in perpendicular to the area on the opening of the eyelet in the cross section of the axis of upstream side ceramic honeycomb 11, determine aperture area A ₀₂.The aperture area A of these eyelets ₀₁and A ₀₂calculating preferably to be undertaken by image analyzer.

Fig. 3 (a) illustrates the example of 25 eyelets in the five-element five row eyelet of arbitrary continuation in the alveolate texture comprising triangle eyelet, quadrangle eyelet and hexagon eyelet respectively to 3 (c).Term " five-element five of arbitrary continuation arrange " refers to five continuous lines of optional five continuous eyelets.When except triangle eyelet, quadrangle eyelet and hexagon eyelet, equally, five lines of five arbitrary eyelets continuously can be selected similarly.

Open area ratio A ₀(=A02/A ₀₁) mean value A _avebe preferably 0.85 or less, be more preferably 0.80 or less.The eyelet wall end surfaces of downstream ceramic honeycomb and the roughness (maximum height Rz) of eyelet wall inner surface preferably 20 μm or larger, more preferably 25 μm or larger.At open area ratio A ₀(=A ₀₂/ A ₀₁) mean value A _aveand the roughness of eyelet wall end surfaces and eyelet wall inner surface is when above-mentioned scope, the improved efficiency of catching the PM in waste gas of eyelet wall end surfaces and eyelet wall inner surface.

As the open area ratio (A of any eyelet ₀) and the open area ratio (A of the eyelet adjacent with this any eyelet ₁, A ₂, A ₃, A ₄...) between the maximum value of difference when being represented by Δ Amax, the maximum of the Δ Amax of 25 eyelets during the five-element five of arbitrary continuation arrange is preferably 0.1 or larger and be less than 1, is more preferably 0.2-0.5.Open area ratio (the A of any eyelet ₀) and the open area ratio (A of the eyelet adjacent with this any eyelet ₁, A ₂, A ₃, A ₄...) between the absolute value of difference larger, the pressure reduction between adjacent eyelet is larger, causes the PM be captured on the eyelet wall inner surface of downstream ceramic honeycomb to increase.In addition, the absolute value of this difference makes too greatly the pressure loss increase.

Such as, in the quadrangle eyelet such as shown in Figure 13 (a), upstream side ceramic honeycomb 11 with there is aperture area A ₀₁the open area ratio of adjacent four eyelets of any eyelet are aperture area A that these four eyelets are narrowed by the upstream side end surfaces of the eyelet wall 121 of downstream ceramic honeycomb 12 ₁₂, A ₂₂, A ₃₂and A ₄₂with the aperture area A of these four eyelets ₁₁, A ₂₁, A ₃₁and A ₄₁ratio, that is, A ₁=(A ₁₂/ A ₁₁), A ₂=(A ₂₂/ A ₂₁), A ₃=(A ₃₂/ A ₃₁), and A ₄=(A ₄₂/ A ₄₁).The open area ratio (A0) of any eyelet and the open area ratio (A of the eyelet adjacent with this any eyelet ₁, A ₂, A ₃, A ₄) between the absolute value of difference be absolute value (A ₀-A ₁), (A ₀-A ₂), (A ₀-A ₃) and (A ₀-A ₄), and the maximum of these values is Δ Amax.About each in 25 eyelets in the five-element five row of arbitrary continuation, determine Δ Amax, and assess the maximum in them.

The open area ratio A of 25 eyelets in arranging as the five-element five of wherein arbitrary continuation ₀(=A ₀₂/ A ₀₁) mean value be 0.9 or less structure, ceramic honeycomb filter of the present invention can have structure A, wherein adjacent ceramic honeycomb 11,12 are connected in the mode be shifted along the thickness direction of eyelet wall 111,121, as, such as, shown in Fig. 2 (a).Displacement width, that is, the distance X between the eyelet wall 111 of the ceramic honeycomb 11 as shown in Fig. 2 (a) and the eyelet wall 121 of ceramic honeycomb 12 or Y, preferably the 0.1-0.5 of eyelet wall spacing doubly.Due to 0.1 times or larger that displacement width is eyelet wall spacing, therefore the PM flowed in the waste gas in the eyelet of upstream side ceramic honeycomb 11 is easily caught by the upstream side end surfaces of the eyelet wall 121 of downstream ceramic honeycomb 12, and between adjacent eyelet, there is large pressure reduction, cause the amount of the PM caught by the eyelet wall inner surface of downstream ceramic honeycomb to increase.In addition, because the ultimate range between eyelet wall is 0.5 times of eyelet wall spacing, the maximum of the width that is therefore shifted is 0.5 times of eyelet wall spacing.

The open area ratio A of 25 eyelets in arranging as the five-element five of wherein arbitrary continuation ₀(=A ₀₂/ A ₀₁) mean value be 0.9 or less structure, ceramic honeycomb filter of the present invention can have structure B, wherein ceramic honeycomb is connected in the mode rotated around their axis, as Fig. 4 (a), shown in 4 (b) He 5 (a)-5 (c).Angle θ between the eyelet wall 111 of a ceramic honeycomb 11 and the eyelet wall 121 of another ceramic honeycomb 12 is preferably in the scope of 35-55 °.

Other may be structure C, structure D and structure D, in structure C, adjacent ceramic honeycomb is connected in the following manner, namely the thickness direction along eyelet wall is shifted with the distance of 0.1-0.5 eyelet wall spacing doubly, and with the rotation of the angle θ in the scope of 35-55 ° between the eyelet wall of a ceramic honeycomb and the eyelet wall of another ceramic honeycomb around the axis of ceramic honeycomb, in structure D, the ceramic honeycomb with different eyelet wall spacing is connected, in structure D, the ceramic honeycomb with different eyelet wall spacing is connected in the mode rotated around the axis of ceramic honeycomb.

In said structure C, angle θ between the eyelet wall of a ceramic honeycomb and the eyelet wall of another ceramic honeycomb is the scope of 35-55 °, and the opposite end surface of adjacent ceramic honeycomb is shifted with the distance of 0.1-0.5 times of eyelet wall spacing.

(2) other embodiment

Although connect two ceramic honeycombs in the above-described embodiments, 3 or more ceramic honeycombs can axially connect to form ceramic honeycomb filter end-to-end.The ceramic honeycomb connecting larger quantity makes downstream ceramic honeycomb have can to catch the eyelet wall end surfaces of the larger quantity of PM, causes the PM acquisition performance improved.But because the ceramic honeycomb connecting larger quantity makes the pressure loss of waste gas higher, therefore, the quantity of the ceramic honeycomb connected is preferably 2 ~ 15, is more preferably 2 ~ 12.

When connection 3 or more ceramic honeycomb, at least one group of adjacent ceramic honeycomb should be connected in the mode of their eyelet walls displace.And in order to improve PM acquisition performance, adjacent eyelet wall is preferably shifted in all connecting portions.The displacement of adjacent ceramic honeycomb does not need in all connecting portions all identical, but can by the method for through-thickness shift holes eyewall, around axis rotating hole eyewall method, combination has the method for the ceramic honeycomb of different eyelet wall spacing or their combination is appropriately carried out.

Ceramic honeycomb filter of the present invention preferably has the quadrangle eyelet cross section with arched corner.Eyelet with arched corner not only has the intensity of improvement at connecting portion, but makes the eyelet wall end surfaces of downstream ceramic honeycomb in connecting portion, have the area of increase, easily to catch PM by eyelet wall end surfaces.And, because flow path narrows in connecting portion, therefore between adjacent eyelet, there is larger pressure reduction, make the PM easily caught by eyelet wall surface in waste gas.As shown in Figure 6, a pair relative bight preferably has and is greater than another radius of curvature R 1, R1 to the radius of curvature R 2, R2 in relative bight.When bight has this radius of curvature, between adjacent eyelet, there is larger pressure reduction, make the PM easily caught by eyelet wall in waste gas, cause good PM acquisition performance.

Adjacent ceramic honeycomb is preferably connected in the mode in the gap between end surfaces with 0.01-3mm.There is predetermined gap in connecting portion, there is large space for gathering the PM on the eyelet wall end surfaces being trapped in downstream ceramic honeycomb, causing the PM acquisition performance improved.And the pressure loss in waste gas streams can be retained as low.When the end surfaces gap of adjacent ceramic honeycomb is more than 3mm, exhaust flow path narrows in connecting portion, causes the pressure reduction between adjacent eyelet large.As a result, the PM in waste gas is not easy to be caught by eyelet wall surface, causes the PM acquisition performance of ceramic honeycomb filter low.Below use description to the method forming this gap.

Each ceramic honeycomb preferably has the aperture efficiency of 75% or less.When aperture efficiency is 75% or less, the pressure loss of the waste gas of flowing can be remained low with high PM acquisition performance.When aperture efficiency is greater than 75%, ceramic honeycomb has low intensity, makes to be difficult to connect multiple ceramic honeycomb.In order to suppress the pressure loss of the waste gas flowed, aperture efficiency is preferably 40% or larger.

In another embodiment of the present invention, the ceramic honeycomb with different openings ratio can be connected to form the ceramic honeycomb filter be made up of multiple ceramic honeycomb.Adopt this structure, exhaust flow path narrows in connecting portion, causes the pressure reduction between adjacent eyelet large.As a result, the pressure loss in waste gas streams can be suppressed while very well catching PM.

As shown in Figure 10 (a) or 10 (b), adjacent eyelet wall 1 is preferably almost parallel in the axial cross section of ceramic honeycomb.Further, in above-mentioned cross section, at the eyelet 2 of peripheral surface 4 upper part ground or whole openings _outthe quantity per unit length (300mm) that is preferably ceramic honeycomb be 1-5.At the eyelet 2 of peripheral surface 4 upper shed _outwhen being 1-5, eyelet wall axially tilts, and the PM in waste gas is easily trapped in the eyelet wall end surfaces of downstream ceramic honeycomb and the whole region of eyelet wall inner surface.Therefore, PM is caught well, suppresses the pressure loss in waste gas streams simultaneously.But, when 6 or larger eyelets 2 _outwhen peripheral surface 4 upper shed, in waste gas streams, there is undesirable high pressure loss.

In order to improve the capture rate on the eyelet wall end surfaces of the downstream ceramic honeycomb of PM in connected ceramic honeycomb and eyelet wall inner surface, ceramic honeycomb preferably has the porosity of 50-80%, the eyelet wall thickness of 0.2-0.5mm, and the eyelet spacing of 1-3mm.More preferably, it has the porosity of 55-70%, the eyelet wall thickness of 0.25-0.45mm, and the eyelet spacing of 1.2-2mm.

[2] manufacture method of ceramic honeycomb filter

(1) first method

Ceramic honeycomb filter of the present invention is made by following step: (a) is by ceramic material and adhesive, lubricant, hole forms material, the mixing such as water and the moldable ceramic material combined to prepare plasticizing, b () extrudes this moldable ceramic material by cellular extrusion molding mould, and the ceramic honeycomb base substrate with predetermined length that drying produces, to obtain dry ceramic honeycomb, c () is approximately perpendicular to the end surface portion of the ceramic honeycomb of the axial direction mill-drying of dry ceramic honeycomb by grinding machine etc., d () arranges the ceramic honeycomb of multiple ground drying in the mode of their end displacement with eyelet wall, and sinter the ceramic honeycomb of the drying of arranging.It can also comprise (e) step with the peripheral surface of the ceramic honeycomb that paint connected and sintered.

A () prepares the step of moldable ceramic material

Ceramic material and adhesive, lubricant, hole form material, water etc. and mix and combine to prepare the moldable ceramic material plastified.Ceramic material is preferably from being formed at least one selected group that the composite of the composite of material, carborundum, silicon and carborundum, silicon nitride, mullite, aluminium oxide, spinelle, carborundum and cordierite, lithium aluminosilicate and aluminium titanates form by cordierite, cordierite.Among them, cordierite forms material is preferred.

The cordierite formation material being combusted into cordierite by sintering has the SiO comprising 42-56% (by mass) ₂, the Al of 30-45% (by mass) ₂o ₃with the ceramic material of the chemical composition of the MgO of 12-16% (by mass).Particularly, it comprises the multiple inorganic material selected from talcum, kaolin, calcined kaolin, aluminium oxide, aluminium hydroxide and silica for the ratio realizing above-mentioned chemical composition.

In order to obtain the ceramic honeycomb on eyelet wall end surfaces and eyelet wall inner surface with 15 μm or larger roughness (maximum height Rz), hole forms the mean particle size that material preferably has 5-70 μm.The use that hole forms material can form micropore on the end surfaces of the ceramic honeycomb of sintering and eyelet wall inner surface, thus increases their surface roughness.Although limiting holes does not form material, as long as it can provide large surface roughness, it can be graphite, resin, foamed resin, foaming resin, ceramic coated resin, cornstarch, flour etc.

B () is molded and drying steps

Extrude moldable ceramic material to form ceramic honeycomb base substrate by cellular extrusion molding mould, it is chopped to predetermined length, subsequently by dryings such as hot-air furnace, heat-treatment furnace, micro-wave ovens, to provide dry ceramic honeycomb.

As shown in Figure 7, extrusion molding mould comprises multiple extrusion molding mould hole 31, each extrusion molding mould hole has the curved surface (rounded portions) with radius of curvature R 1 and R2 in the intersection bight of molded indentation 32, it can be formed comprise the ceramic honeycomb of the quadrangle eyelet with arched corner, wherein the radius of curvature R 1 in a pair relative bight is greater than another radius of curvature R 2 to relative bight, as shown in Figure 6.

The step on (c) abrasive tip surface

The axial direction that each end surface portion of dry ceramic honeycomb is approximately perpendicular to it by grinding machine etc. is polished, to provide the eyelet wall end surfaces with 15 μm or larger roughness (maximum height Rz), preferably, when being formed with holes the ceramic honeycomb that material is made, adopt the grinding machine of about #50 to #270, and adopt coarse granule grinding machine when not using hole to form material.

(d) sintering step

Arrange the ceramic honeycomb of ground drying with eyelet wall in the mode of their end displacement, and sinter the ceramic honeycomb of the drying arranged, to form the ceramic honeycomb filter be connected in the mode of their eyelet walls displace.

(e) coating step

By connect, the peripheral surface of ceramic honeycomb filter that the ceramic honeycomb of sintering is formed by paint, so that the connecting portion of ceramic honeycomb and their resistance to fracture is linked together integratedly.

Coating can be the ceramic material being mixed with adhesive and water.Ceramic material can be the material identical or different with ceramic honeycomb, particularly, can be cordierite, cordierite forms material, carborundum, silicon/silicon carbide composite, silicon nitride, mullite, aluminium oxide, silica, spinelle, carborundum/cordierite composite, lithium aluminosilicate, aluminium titanates etc.

(2) second method

The ceramic honeycomb in first method with multiple dryings of polished end surfaces can be connected in the mode of their eyelet wall end surfaces displacement, their peripheral surface is integrally applied by above-mentioned coating, and is sintered the ceramic honeycomb filter of the eyelet walls displace making them subsequently.When the method, ceramic honeycomb and coating are integrally sintered, to obtain the firmer ceramic honeycomb filter of the high strength connection with ceramic honeycomb.

(3) the third method

Multiple ceramic honeycombs dry are in the second approach sintered to form ceramic honeycomb, this ceramic honeycomb is shifted with their eyelet wall end and is integrally connected by the mode of paint on their peripheral surface, to obtain the ceramic honeycomb filter of their eyelet wall end displacement.The grinding of end surfaces can be carried out after the sintering.

(4) other method

The formation of (i) peripheral chamfer and rounded portions

As shown in Figure 8, multiple ceramic honeycomb 11,12,13,14 can be provided with chamfering 6 or rounded portions 7 on end surfaces periphery.When having the multiple ceramic honeycombs 11 being formed in chamfering 6 on periphery or rounded portions 7,12,13,14 with their eyelet walls displace and when being connected by the mode of paint on peripheral surface, coating on ceramic honeycomb is thick in connecting portion than in peripheral surface, thus strengthens the intensity of connecting portion.Knot chamfering 6 or rounded portions 7 can be formed after drying or sintered ceramic alveolate texture.

(ii) formation of the eyelet of opening on peripheral surface

Such as, the removal of the peripheral surface of the ceramic honeycomb of the drying formed as mentioned above by relying on machining, obtain a kind of ceramic honeycomb, it has at it 1-5 the eyelet dividing ground or whole openings in peripheral upper surface in the length perpendicular to the every 300mm in the cross section of axis, as shown in Figure 10.The peripheral surface of dry ceramic honeycomb is removed by machining, makes its axis from the axis predetermined oblique angle of eyelet 2.The ceramic honeycomb of the drying after processing can be processed further on the two ends of the axis of the ceramic honeycomb perpendicular to drying, to obtain the ceramic honeycomb in the cross section paralleled to the axis with the eyelet dividing ground or whole opening in peripheral upper surface.In order to have 1-5 the eyelet dividing ground or whole opening in peripheral upper surface on the per unit length (300mm) of ceramic honeycomb, process in the mode of the angle between the axis of the ceramic honeycomb in drying and the axis of eyelet 2 with suitable adjustment.Can carry out by the removal of machining to peripheral surface after the ceramic honeycomb that sintering is dry.

Another kind of method length for the manufacture of the every 300mm in its cross section paralleled to the axis being included in the ceramic honeycomb of 1-5 eyelet of peripheral surface upper part ground or whole opening comprises from extrusion shaping machine vertically (on gravity direction) extruded ceramic alveolate texture, and direction and the grade of the active force of the bottom supporting ceramic honeycomb is applied in by adjustment, make the eyelet in ceramic honeycomb leave their axis bending.The ceramic honeycomb with the eyelet leaving axis bending produced is dried, and its outer peripheral portion is removed by machining, so that the ceramic honeycomb of the drying after processing has the axis of the axis predetermined oblique angle relative to eyelet 2.Axis perpendicular to the ceramic honeycomb of this drying provides the ceramic honeycomb of 1-5 the eyelet being included in peripheral surface upper part ground or whole opening in the length of its every 300mm in the cross section paralleled to the axis on two ends to the machining of the ceramic honeycomb of this drying.Can carry out by the removal of machining to peripheral surface after the ceramic honeycomb that sintering is dry.

(iii) jointing material

Multiple ceramic honeycomb can be arranged, wherein their eyelet walls displace via jointing material.The connecting portion of ceramic honeycomb is strengthened in the use of jointing material, makes its resisting breakage.As shown in Figure 14 (a) He 14 (b), jointing material 21 is preferably applied to the periphery of the end surfaces of adjacent ceramic honeycomb 11,12.Jointing material 21 periphery be applied on it of the end surfaces of ceramic honeycomb refer to end surfaces from outermost peripheral to the region of the degree of depth of 5 times of eyelet spacing.Jointing material 21 can be applied to dry ceramic honeycomb or the ceramic honeycomb of sintering.As shown in Figure 14 (c) He 14 (d), jointing material does not need to be applied to whole neighboring area, and can be coated to desired periphery according to adhesive strength.

Jointing material can be and ceramic fibre, the ceramic material of the mixing such as inorganic bond, or and heat-resistant ceramic fiber, ceramic particle, the ceramic material that cement etc. mix either individually or in combination.If needed, organic bond, inorganic bond etc. can be added.Above-mentioned ceramic material can be identical or different with the material of ceramic honeycomb.Particularly, at least one selected the group formed from the composite of the composite being formed material, carborundum, silicon and carborundum by cordierite, cordierite, mullite, aluminium oxide, silica, spinelle, carborundum and cordierite, lithium aluminosilicate and aluminium titanates can be adopted.

As shown in Figure 14 (a)-14 (d), ceramic honeycomb 11,12 is set via jointing material 21, wherein at ceramic honeycomb 11, there is between the end surfaces of 12 gap of 0.01-3mm.The part being applied to the jointing material 21 of end surfaces can eyelet on upstream end surface, thus firmly bonds ceramic honeycomb.

(iv) method for arranging of eyelet walls displace

Explanation is used for the method for arranging multiple ceramic honeycomb with their eyelet wall in the mode of end surfaces superior displacement.The end surfaces of each ceramic honeycomb is cut or be ground to predetermined axial length, can determine this predetermined axial length rightly according to the quantity of the total length of connected ceramic honeycomb filter and ceramic honeycomb.Although be not restrictive, all ceramic honeycombs preferably have identical axial length, the ceramic honeycomb with axially different length can be combinationally used.After drying of ceramic alveolate texture, the machining of its end surfaces can be carried out before or after sintering.

Figure 15 (a) illustrates the binding appts 80 for arranging described multiple ceramic honeycomb in the mode of end surfaces superior displacement with the eyelet wall of multiple ceramic honeycomb to 15 (e) and 16 (a) to 16 (e).Binding appts 80 comprises the workbench 81 it being arranged ceramic honeycomb, and for locating the device of the ceramic honeycomb be arranged on workbench 81.Workbench 81 can move on the horizontal level along X and Y-direction, and around the center axis thereof of workbench 81.Positioner can adopt metal and/or non-metal wire parts or light.Metal and/or non-metal wire parts can be steel wire, copper cash, ceramic fibre, nylon (trade mark) fiber, yarn, filament etc., and light can be light beam, laser beam etc.Figure 15 (a) illustrates the example of the binding appts 80 of two laser beam sources 82,83 comprised as positioner to 15 (e) and 16 (a) to 16 (e).By support bar 84,85 two laser beam sources 82,83 supported can move up and down, and can be fixed on any position, and make from laser beam sources 82,83 light flatly launched and optical axis 821,831 vertically intersect.

(A) displacement method on eyelet wall thickness direction

The method being used for arranging multiple ceramic honeycomb in the mode of eyelet wall thickness direction superior displacement with eyelet wall end surfaces is described to 15 (e) referring to Figure 15 (a) in (a1) to (e1).

(a1) at laser beam sources 82, 83 when being fixed on the At The Height of the axial length being substantially equal to the first ceramic honeycomb 11, first ceramic honeycomb 11 is placed on workbench 81 in end surfaces mode below, and be located so that on another end surfaces, any eyelet wall 111-2 extending to another peripheral end portion from a peripheral end portion roughly aligns with the optical axis 821 of the laser beam launched from laser beam sources 82, and roughly align [Figure 15 (a)] perpendicular to the eyelet wall 111-3 of this any eyelet wall 111-2 with the optical axis 831 of the laser beam launched from laser beam sources 83.

(b1) workbench 81 moves [Figure 15 (b)] along X and/or Y-direction (perpendicular to eyelet wall thickness direction) in the scope of 0.1-0.5 times of eyelet wall spacing.

(c1) at laser beam sources 82, when 83 height moving to the axial length being substantially equal to the second ceramic honeycomb 12 further are also fixed, second ceramic honeycomb 12 is placed on the first ceramic honeycomb 12 in end surfaces mode below, and be located so that on another end surfaces, any eyelet wall 111-2 extending to another peripheral end portion from a peripheral end portion roughly aligns with the optical axis 821 of the laser beam launched from laser beam sources 82, and roughly align [Figure 15 (c)] perpendicular to the eyelet wall 111-3 of this any eyelet wall 111-2 with the optical axis 831 of the laser beam launched from laser beam sources 83.

(d1) workbench 81 moves [Figure 15 (d)] along X and/or Y-direction in the scope of 0.1-0.5 times of eyelet wall spacing.

(e1) similarly, when workbench 81 moves, by adopting the positioner of laser beam sources 82,83, the 3rd ceramic honeycomb 13 is positioned on the second ceramic honeycomb 12 [Figure 15 (e)].

When connection 4 or more ceramic honeycomb, can repeat if the operation identical with (c1) and (d1) is to arrange the ceramic honeycomb of desired amt.

(B) by means of the displacement method of the rotation around central axis

The method being used for arranging multiple ceramic honeycomb in the mode that their end is shifted in a rotational direction with eyelet wall is described in following (a2) to (e2) with reference to Figure 16 (a) to 16 (e).

(a2) when laser beam sources 82 is fixed on the At The Height of the axial length being substantially equal to the first ceramic honeycomb 11, first ceramic honeycomb 11 is arranged to workbench 81 coaxial in end surfaces mode below, make on another end surfaces, any eyelet wall 111-2 extending to another peripheral end portion from a peripheral end portion roughly aligns [Figure 16 (a)] with the optical axis 821 of the laser beam launched from laser beam sources 82.

(b2) workbench 81 rotates [Figure 16 (b)] in the angular range of 35-55 °.

(c2) when laser beam sources 82 moves further and is fixed to the height of the axial length being substantially equal to the second ceramic honeycomb 12, second ceramic honeycomb 12 is placed on the first ceramic honeycomb 12 in end surfaces mode below, make on another end surfaces, any eyelet wall 111-2 extending to another peripheral end portion from a peripheral end portion roughly aligns [Figure 16 (c)] with the optical axis 821 of the laser beam launched from laser beam sources 82.

(d2) workbench 81 rotates [Figure 16 (d)] in the angular range of 35-55 °.

(e2) similarly, by comprising the positioner of laser beam sources 82, the 3rd ceramic honeycomb 13 is placed on the second ceramic honeycomb 12 [Figure 16 (e)], and workbench 81 rotates predetermined angular.

When connection 4 or more ceramic honeycomb, can repeat if the operation identical with step (c2) and (d2) is with the ceramic honeycomb of stacking desired amt.

Although adopt in superincumbent explanation and comprise the positioner of laser beam sources, any device that roughly can align with any eyelet wall extending to another peripheral end portion from a peripheral end portion on the end surfaces of ceramic honeycomb can be adopted.Such as, also can be positioned by the such as thread-like member of steel wire, copper cash, ceramic fibre, nylon (trade mark) fiber, yarn, filament etc. and so on and the light except laser beam.

Example

In further detail the present invention is described by by example below, there is not the intention limiting the invention to these examples.

Kaolin powder, talcum powder, silica powder and alumina powder form material powder to form cordierite, and it has the SiO comprising for 51% (by mass) ₂, the Al of 35% (by mass) ₂o ₃, and the chemical composition of the MgO of 14% (by mass).100 parts (by mass) this cordierite forms material powder and 8 parts of (by mass) adhesives (methylcellulose and hydroxypropyl methylcellulose), lubricant, with 7.0 parts of (by mass) the foamed resin bone dry mixing with the mean particle size of 40 μm forming material as hole, and mix with water subsequently, to form plasticity mold pressing ceramic material.

Adopt the extrusion molding mould comprising the bending bight (rounded portions) with radius of curvature R 1=0.05mm and R2=0.02mm as shown in Figure 7 at the cross part of molded indentation, moldable ceramic material is extruded, and is cut into predetermined length.The ceramic honeycomb produced dry 20 minutes by microwave dryer, to obtain the eyelet wall thickness with 0.30mm, 180 eyelet/inches ²perforation density, 71% the ceramic honeycomb of drying of aperture efficiency, the opposing corner areas of its perforations has radius of curvature R 1=0.05mm and R2=0.02mm (see 6).The peripheral surface of the ceramic honeycomb of this drying is machined the axis predetermined oblique angle making its axis relative to eyelet, thus obtains length to be 300mm and external diameter be the ceramic honeycomb A of the drying of 270mm.In the cross section paralleled to the axis, the peripheral surface upper part ground of dry body after processing or the quantity of whole eyelets of opening are 2.

Except changing the machining angle of the thickness of molded indentation in extrusion molding mould and the peripheral surface of spacing and dry body, there is with the mode manufacture identical with the ceramic honeycomb A of drying the ceramic honeycomb B to M of the drying of the structure shown in table 1.The amount that dry ceramic honeycomb E and F is formed with holes material is reduced to the moldable ceramic material of 5.0 parts (by mass) and is formed, and dry ceramic honeycomb M is made into by adopting the extrusion molding mould without rounded portions.

The ceramic honeycomb A to M of these unsintered dryings is sintered 8 days with the maximum temperature of 1410 DEG C in sintering furnace, to obtain ceramic honeycomb A to M.Incidentally, have employed the ceramic honeycomb A to M of the unsintered drying of the length cutting into 150mm, 75mm, 37.5mm and 25mm respectively and ceramic honeycomb A to M of sintering.

Table 1

Table 1 (Continued)

Example 1

Adopt binding appts 80 [see Figure 15 (a) to 15 (e)], the drying of ceramic alveolate texture C of two 150mm length is arranged end-to-end in the mode of their eyelet wall [in each in the X shown in Fig. 2 (a) and Y-direction] displacement 0.3 times of eyelet wall spacing on each eyelet wall thickness direction.Jointing material is not used at relative end surfaces.Arrange two dry ceramic honeycombs are sintered 8 days with the maximum temperature of 1410 DEG C in sintering furnace.The slurry comprising cordierite, adhesive and water is applied to the peripheral surface also drying of the ceramic honeycomb of sintering, to make the ceramic honeycomb filter with the external diameter of 270mm and the length of 300mm.

Example 2

There is the ceramic honeycomb filter of the external diameter of 270mm and the length of 300mm, except two dry bodies are shifted 45 ° with their eyelet wall in a rotational direction around their central axis with such as identical with example mode manufacture.

Example 3

The long drying of ceramic alveolate texture C of binding appts 80, two 150mm is adopted to be arranged end-to-end via the jointing material comprising cordierite formation material, adhesive and water in the mode of their eyelet wall [in each in the X shown in Fig. 2 (a) and Y-direction] displacement 0.1 times of eyelet wall spacing on each eyelet wall thickness direction.Jointing material is that 2 times of the eyelet spacing of the end surfaces of dry ceramic honeycomb C [see Figure 14 (a) and 14 (b)] are thick.Arrange two dry ceramic honeycombs are sintered 8 days with the maximum temperature of 1410 DEG C, to make the ceramic honeycomb filter with the external diameter of 266.7mm and the length of 301mm in sintering furnace.

Example 9

Adopt the binding appts 80 shown in Figure 16 (a)-16 (e), there is the ceramic honeycomb filter of the external diameter of 266.7mm and the length of 301mm, except two dry bodies are shifted 10 ° with their eyelet wall in a rotational direction around their central axis with the mode manufacture identical with example 3.

Example 15

There is the ceramic honeycomb filter of the external diameter of 266.7mm and the length of 301mm, except two dry bodies are with their eyelet wall [in each in the X shown in Fig. 2 (a) and Y-direction] displacement 0.1 times of eyelet wall spacing and arranging around be shifted the in a rotational direction mode of 10 ° of their central axis on each eyelet wall thickness direction with the mode manufacture identical with example 3.

Example 4,10 and 16

To manufacture example 4 with example 3,9 modes identical with 15, each ceramic honeycomb filter with the external diameter of 270mm and the length of 301mm of 10 and 16, except changing as the displacement that illustrates in table 2, and with comprising the peripheral surface (see example 1) of ceramic honeycomb of slurry coating sintering of cordierite, adhesive and water.

Example 5 and 11

Replace except adopting dry ceramic honeycomb D, except dry ceramic honeycomb C, manufacturing each ceramic honeycomb filter with the external diameter of 270mm and the length of 301mm of example 5 and 11 in the mode identical with 10 with example 4.

Example 6

Adopt binding appts 80, the drying of ceramic alveolate texture J that drying of ceramic alveolate texture D and two 75mm of two 75mm length is long forms the jointing material of material, adhesive and water with D in the mode of their adhesive surface [in each in the X shown in Fig. 2 (a) and Y-direction] displacement 0.3 times of eyelet wall spacing on each eyelet wall thickness direction via comprising cordierite, D, the order of J, J is arranged end-to-end.Jointing material is that 2 times of eyelet spacing are thick, and the degree of depth in their eyelet is 3mm.Four that arrange dry ceramic honeycombs are sintered 8 days with the maximum temperature of 1410 DEG C, to make the ceramic honeycomb filter with the external diameter of 270mm and the length of 303mm in sintering furnace.

Example 7

Outside the displacement of adhesive surface in X, Y both direction is changed over eyelet wall spacing 0.4 times, manufacture the ceramic honeycomb filter with the external diameter of 270mm and the length of 303mm in the same manner as in Example 6.

Example 8

Except with the alveolate texture D of drying, D is at X, Y both direction superior displacement 0.1 times of eyelet wall spacing, dry alveolate texture D, J are at the alveolate texture J of X, Y both direction superior displacement 0.3 times of eyelet wall spacing and drying, J is at X, the mode of Y both direction superior displacement 0.1 times of eyelet wall spacing arranges dry alveolate texture D, D, J according to priority, outside J, manufacture the ceramic honeycomb filter with the external diameter of 270mm and the length of 303mm in the same manner as in Example 6.

Example 12 and 13

In each in example 12 and 13, except adopting dry alveolate texture D, D, I, I replace dry alveolate texture D, D, J, J, and change they as outside the displacement that illustrates in table 2, manufacture each two ceramic honeycomb filters with the external diameter of 270mm and the length of 303mm in the same manner as in Example 6.

Example 14

Except with the alveolate texture D of drying, D is shifted 10 °, dry alveolate texture D in a rotational direction, J is shifted the alveolate texture J of 45 ° and drying in a rotational direction, be shifted the in a rotational direction mode of 10 ° of J sequentially arranges alveolate texture D, D, outside J, J, manufacture the ceramic honeycomb filter with the external diameter of 270mm and the length of 303mm in the same manner as in Example 6.

Example 17,21 and 22

The long sintering alveolate texture D of binding appts 80, four 75mm is adopted to be arranged end-to-end via the jointing material comprising cordierite in the mode of two eyelet wall thickness direction (X and Y both direction) superior displacements as shown in Table with their eyelet wall adhesive surface.The thickness of jointing material is 2 times of the eyelet spacing on the end surfaces of each ceramic honeycomb D, and in their eyelet, the degree of depth is 3mm.Comprise silica, adhesive and water slurry body be applied to four be connected after the peripheral surface of ceramic honeycomb D and dried, to make the ceramic honeycomb filter with the external diameter of 270mm and the length of 307.5mm of the ceramic honeycomb filter with the external diameter of 270mm and the length of 303mm of example 17, the ceramic honeycomb filter with the external diameter of 270mm and the length of 301.5mm of example 21 and example 22.

Example 18

Except the sintering alveolate texture D that the sintering alveolate texture E adopting 75mm long replaces 75mm long, manufacture the ceramic honeycomb filter with the external diameter of 270mm and the length of 303mm in the same manner as in Example 17.

Example 19

Except the sintering alveolate texture D that the sintering alveolate texture F adopting 75mm long replaces 75mm long, manufacture the ceramic honeycomb filter with the external diameter of 270mm and the length of 303mm in the same manner as in Example 17.

Example 20

Except the sintering alveolate texture D that the sintering alveolate texture G adopting 75mm long replaces 75mm long, manufacture the ceramic honeycomb filter with the external diameter of 270mm and the length of 303mm in the same manner as in Example 17.

Example 23

Except sequentially connecting the 75mm long sintering alveolate texture B of the long sintering alveolate texture D of replacement four 75mm, outside D, H, J, manufacture the ceramic honeycomb filter with the external diameter of 270mm and the length of 303mm in the same manner as in Example 17.

Example 24

Adopt binding appts 80, the sintering alveolate texture A that 37.5mm is long, B, D, H, I, J, K and L (altogether 8) is arranged with this order via the jointing material comprising cordierite in the upper such mode be shifted as shown in table 2 of two eyelet wall thickness directions (X and Y both direction) end-to-end with their eyelet wall, and each sintering alveolate texture has two 3-mm chamferings on its end surfaces periphery.The thickness of jointing material is 2 times of the eyelet spacing on the end surfaces of each ceramic honeycomb, and the degree of depth is 3mm in their eyelet.Comprise silica, adhesive and water slurry body be applied to connection after sintering alveolate texture A, B, D, H, I, J, the peripheral surface of K and L (altogether 8) is also dried, to make the ceramic honeycomb filter with the external diameter of 270mm and the length of 307mm.

Example 25

Except connecting the sintering alveolate texture A replacing 37.5mm long on two end surfaces peripheries, B, D, H, 12 25mm of I, J, K and L long, outside the sintering alveolate texture D on two end surfaces peripheries with 3-mm chamfering, have the ceramic honeycomb filter of the external diameter of 270mm and the length of 311mm in the same manner as in Example 24, it has the structure shown in Fig. 9.

Example 26

Except adopting that 13 25mm grow, that there is 3-mm chamfering on two end surfaces peripheries sintering alveolate texture D, manufacture the ceramic honeycomb filter with the external diameter of 270mm and the length of 337mm in the same manner as in Example 25.

Example 27

Except each sintering alveolate texture D on two end surfaces peripheries with 12 25mm length of 3-mm chamfering is shifted 45 ° in a rotational direction with their adhesive surface, and the gap between adjacent alveolate texture is 3.0mm, 3.0mm, 3.0mm respectively from upstream side, 3.0mm, 2.0mm, 2.0mm, 2.0mm, 2.0mm, outside 1.0mm, 1.0mm and 1.0mm, manufacture the ceramic honeycomb filter with the external diameter of 270mm and the length of 323mm in the same manner as in Example 25.

Example 28

Adopt binding appts 80, the long sintering alveolate texture D of each six 25mm on two end surfaces peripheries with 3-mm chamfering is connected via the jointing material that the 2.0mm comprising cordierite is thick in be shifted the in a rotational direction mode of 45 ° of their adhesive surface, to form the upstream side component for ceramic honeycomb filter.The thickness of jointing material is 3 times of the eyelet spacing on the end surfaces of each ceramic honeycomb, and is 3mm in the degree of depth of their eyelet.Except becoming except 1.0mm by each gap between adhesive surface, formed the downstream component being used for ceramic honeycomb filter by six alveolate texture D with the method identical with upstream side component.Upstream side component and downstream component are connected via the jointing material that the 3.0mm comprising cordierite is thick along the be shifted mode of 45 ° of direction of rotation with them.The thickness of jointing material is 3 times of the eyelet spacing on the end surfaces of each ceramic honeycomb, and is 3mm in the degree of depth of their eyelet.The slurry comprising silica, adhesive and water is applied to the peripheral surface of the upstream side component after connection and downstream component and dried, to make the ceramic honeycomb filter with the external diameter of 270mm and the length of 318mm.

Comparative example 1

By alternately blocking the eyelet on two end surfaces of the ceramic honeycomb M of sintering with plugging material, manufacture the ceramic honeycomb filter with the structure described in JP2001-269585A, it has the external diameter of 270mm and the length [see Figure 11 (a) and 11 (b)] of 300mm.

Comparative example 2

By only blocking the eyelet of the one-tenth on an end surfaces (waste gas outlet side end surface) of the ceramic honeycomb M of sintering with checkerboard pattern, manufacture the ceramic honeycomb filter with the structure described in JP2004-251137A, it has the external diameter of 270mm and the length [see Figure 12 (a) and 12 (b)] of 300mm.

Comparative example 3

Except the vanishing that will be shifted, manufacture ceramic honeycomb filter in the same manner as in Example 17.

About the ceramic honeycomb filter of example 1-28 and comparative example 1-3, show in table 2 the gap between the displacement of the eyelet wall in connecting portion, adhesive surface, the quantity of alveolate texture, arbitrary continuation the five-element five arrange in the mean value A of open area ratio of 25 eyelets ₀between the maximum value Δ A of difference _maxin maximum, the eyelet adjacent with each eyelet open area ratio (A ₁, A ₂, A ₃, A ₄) and filtration device structure.And, by method described below, in the blocking of PM capture rate, the pressure loss, fusing corrosion resistance and ashes, ceramic honeycomb filter is measured.

The assessment of (a) PM capture rate

The carbon dust with the granular size of 0.042 μm produced with the speed of 3g/h by particulate matter generator in 2 hours with 10Nm ³/ minute air mass flow be supplied to each ceramic honeycomb filter.According to the Mass Calculation PM capture rate of the quality of the carbon dust of being caught by honeycomb filter and the carbon dust of introducing.Assessed by following standard:

Perfect: PM capture rate is 85% or larger.

Fine: PM capture rate is equal to or greater than 70% and is less than 85%.

Good: PM capture rate is equal to or greater than 50% and is less than 70%.

Good: PM capture rate is equal to or greater than 30% and is less than 50%, and

Difference: PM capture rate is less than 30%.

In table 2 assessment result is shown.

The assessment of (b) pressure drop characteristics

When each ceramic honeycomb filter is arranged on testboard, make air with 7.5Nm ³/ minute traffic flow, to measure the pressure reduction as the pressure loss between the entrance side of honeycomb filter and outlet side.By following criterion evaluation initial pressure loss property:

Difference: the pressure loss is greater than 1.0kPa,

It is good: the pressure loss is greater than 0.8kPa and is less than or equal to 1.0kPa,

Good: the pressure loss is greater than 0.6kPa and is less than or equal to 0.8kPa, and

Perfect: the pressure loss is less than or equal to 0.6kPa.

In table 2 assessment result is shown.

The assessment of (c) fusing corrosion resistance

Carbon dust is supplied to ceramic honeycomb filter, until per unit filter volume captures the carbon dust of 6g/L in the mode identical with during measurement PM capture rate.The honeycomb filter of being caught carbon dust by it is connected to external test facility (not shown), and from combustion furnace supply high-temperature combustion gas, thus the temperature of each honeycomb filter is raised with the speed of 1.6 DEG C/sec.When temperature reaches 600 DEG C, the supply of burning gases stops, and carries out oneself's burning of captured carbon dust subsequently, with the carbon dust of being caught by honeycomb filter that burns completely.After being combusted, the existence of the fusing corrosion of the honeycomb filter of cooling is observed by X-ray.When not observing fusing corrosion, repeating the increase of the 2g/L of the amount of carbon dust, until there is fusing corrosion, thus the maximum carbon amounts of catching not melting corrosion being defined as melting corrosion resistance.Corrosion resistance is melted according to the carbon amounts assessment of catching of not melting corrosion by following standard:

It is perfect: the carbon amounts of catching is equal to or greater than 20g,

It is good: the carbon amounts of catching is equal to or greater than 14g and is less than or equal to 18g,

Good: the carbon amounts of catching is equal to or greater than 8g and is less than or equal to 12g, and

Difference: the carbon amounts of catching is equal to or less than 6g.

In table 2 assessment result is shown.

The assessment of (d) plugged filter

Parallel direction is breaking at the honeycomb filter after the assessment of melting resistance vertically, to obtain the photo of its cross section.In 10 any eyelets, determined the area of the part wherein gathering ashes by graphical analysis, using the amount assessing the ashes gathered in each sample as about the relative value of area (100) of part wherein gathering ashes in comparative example 1.By following criterion evaluation ashes to the blocking of filter:

It is perfect: the relative quantity of the ashes gathered is equal to or less than 70,

It is good: the relative quantity of the ashes gathered is greater than 70 and is less than or equal to 80,

Good: the relative quantity of the ashes gathered is greater than 80 and is less than or equal to 90, and

Difference: the relative quantity of the ashes gathered is greater than 90 and is less than or equal to 100.

In table 2 assessment result is shown.

Table 2

Remarks: * 1: the magnifying power of eyelet wall spacing.

Table 2 (Continued)

Numbering	Jointing material	Coating
			Example 1	Nothing	Cordierite
Example 2	Nothing	Cordierite
			Example 3	Cordierite forms material	Nothing
Example 4	Cordierite forms material	Cordierite
			Example 5	Cordierite forms material	Cordierite
Example 6	Cordierite forms material	Cordierite
			Example 7	Cordierite forms material	Cordierite
Example 8	Cordierite forms material	Cordierite
			Example 9	Cordierite forms material	Nothing
Example 10	Cordierite forms material	Cordierite
			Example 11	Cordierite forms material	Cordierite
Example 12	Cordierite forms material	Cordierite
			Example 13	Cordierite forms material	Cordierite
Example 14	Cordierite forms material	Cordierite
			Example 15	Cordierite forms material	Nothing
Example 16	Cordierite forms material	Cordierite
			Example 17	Cordierite	Silica
Example 18	Cordierite	Silica
			Example 19	Cordierite	Silica
Example 20	Cordierite	Silica
			Example 21	Cordierite	Silica
Example 22	Cordierite	Silica
			Example 23	Cordierite	Silica
Example 24	Cordierite	Silica
			Example 25	Cordierite	Silica
Example 26	Cordierite	Silica
			Example 27	Cordierite	Silica

Example 28	Cordierite	Silica
			Comparative example 1	-	-
Comparative example 2	-	-
			Comparative example 3	Cordierite	Silica

Table 2 (Continued)

Remarks: * 2: the mean value of the open area ratio of 25 eyelets in the five-element five row of arbitrary continuation.

Remarks: * 3: the Δ A of the eyelet in the five-element five row of arbitrary continuation _maxmaximum, wherein Δ A _maxthe open area ratio (A of each eyelet ₀) and the open area ratio (A of the eyelet adjacent with this eyelet ₁, A ₂, A ₃and A ₄) between the maximum value of difference.

Table 2 (Continued)

Numbering	PM capture rate	Pressure drop characteristics	Fusing corrosion resistance	Plugged filter
					Example 1	Good	Good	Good	Perfect
Example 2	Good	Good	Good	Perfect
					Example 3	Good	Perfect	Perfect	Perfect
Example 4	Good	Good	Good	Perfect
					Example 5	Good	Good	Perfect	Perfect
Example 6	Very good	Perfect	Good	Good
					Example 7	Good	Perfect	Good	Good
Example 8	Good	Perfect	Good	Good
					Example 9	Good	Perfect	Perfect	Perfect
Example 10	Good	Good	Good	Perfect
					Example 11	Good	Perfect	Perfect	Perfect
Example 12	Very good	Perfect	Good	Good
					Example 13	Good	Perfect	Good	Good
Example 14	Good	Perfect	Good	Good
					Example 15	Good	Perfect	Perfect	Perfect
Example 16	Good	Good	Perfect	Perfect
					Example 17	Very good	Perfect	Good	Good

Example 18	Good	Perfect	Good	Good
					Example 19	Good	Perfect	Good	Good
Example 20	Very good	Good	Good	Good
					Example 21	Very good	Good	Good	Good
Example 22	Good	Perfect	Good	Good
					Example 23	Very good	Perfect	Good	Good
Example 24	Perfect	Good	Good	Good
					Example 25	Perfect	Good	Good	Good
Example 26	Perfect	Good	Good	Good
					Example 27	Perfect	Good	Good	Good
Example 28	Perfect	Good	Good	Good
					Comparative example 1	Perfect	Difference	Difference	Difference
Comparative example 2	Difference	Perfect	Perfect	Perfect
					Comparative example 3	Difference	Perfect	Perfect	Perfect

The test block cut away from another ceramic honeycomb filter manufactured each example and comparative example is measured in the porosity of ceramic honeycomb A to M and the roughness of median pore size and eyelet wall end surfaces and eyelet wall inner surface.

Porosity and median pore size is measured by mercury porosimetry, this mercury porosimetry comprises and is arranged on the measurement eyelet of the Autopore III that can obtain from Micromeritics by the test block cut away from each ceramic honeycomb filter (10mm × 10mm × 10mm), eyelet is measured in assessment, and it is pressurizeed, to determine the relation between the pressure of the mercury be introduced in test block and volume by introducing mercury subsequently.

According to the relation between the relation determination pore size between the pressure of mercury and volume and accumulation voidage.At 0.5psi (0.35 × 10 ^-3kg/mm2) pressure place introduced by mercury, according to the capillary calculation of pressure pore size of the contact angle and 484dyne/cm with 130 °.Adopt the 2.52g/cm of cordierite ³true specific gravity, according to measure total void volume calculate porosity.Median pore size is defined as the pore size at the accumulation voidage place of 50%, and it is determined according to the relation between the pore size measured by mercury porosimetry and accumulation voidage.

The roughness of eyelet wall end surfaces and eyelet wall inner surface is evaluated by their maximum height Rz.Adopt and comprise the surface roughness instrument SURFTEST (can obtain from Mitutoyo company) that its tip has the stylus of the radius of curvature of 5 μm, three some place measured hole eyewall end surfaces in the scope of 2mm in a longitudinal direction and the roughness of eyelet wall inner surface.About eyelet wall end surfaces and eyelet wall inner surface, the maximum height Rz measured according to JIS B0601-2001 is by average.These results are shown in table 3.

Table 3

Remarks: * 1: maximum height Rz.

As shown in table 2, ceramic honeycomb filter of the present invention can suppress the pressure loss in the waste gas passed therethrough, and maintains high PM acquisition performance simultaneously.On the other hand, although the ceramic honeycomb filter of comparative example 1 has good PM capture rate, there is poor pressure drop characteristics.The ceramic honeycomb filter of comparative example 2 and 3 has not enough PM acquisition performance.

Claims

1. a ceramic honeycomb filter, for removing particulate matter from waste gas, this ceramic honeycomb filter comprises multiple ceramic honeycomb, each ceramic honeycomb has a large amount of eyelets separated by porous eyewall, described multiple ceramic honeycomb is in axial direction connected end-to-end

The open area ratio A of 25 eyelets in the five-element five row of arbitrary continuation ₀(=A ₀₂/ A ₀₁) mean value be 0.9 or less, wherein A ₀₁represent the aperture area perpendicular to each eyelet in the cross section of the axis of exhaust gas upstream side ceramic honeycomb, A ₀₂represent the aperture area of this eyelet after being narrowed by the upstream side end surfaces of the eyelet wall of the downstream ceramic honeycomb in adjacent ceramic honeycomb;

Described downstream ceramic honeycomb has 15 μm or larger roughness Rz on eyelet wall end surfaces, and has 15 μm or larger roughness Rz on eyelet wall inner surface; And wherein

In the cross section of axis being parallel to each ceramic honeycomb, a () adjacent eyelet wall is parallel and axially tilts, and (b) divides the quantity of ground or the eyelet of opening to be fully 1 ~ 5 in every 300mm length of ceramic honeycomb in peripheral upper surface.

2. ceramic honeycomb filter according to claim 1, wherein Δ A _maxmaximum be equal to or greater than 0.1 and be less than 1, Δ A _maxthe open area ratio (A of any eyelet in 25 eyelets in the five-element five row of arbitrary continuation ₀) and the open area ratio (A of the eyelet adjacent with described any eyelet ₁, A ₂, A ₃, A ₄...) between the maximum value of difference.

3. ceramic honeycomb filter according to claim 1, wherein said adjacent ceramic honeycomb is doubly connected to the mode of eyelet wall spacing with their eyelet wall through-thickness displacement 0.1-0.5.

4. ceramic honeycomb filter according to claim 1, wherein said adjacent ceramic honeycomb is shifted around their central axis in a rotational direction with their eyelet wall, the mode of angle in the scope of 35-55 ° between the eyelet wall of a ceramic honeycomb and the eyelet wall of another ceramic honeycomb is connected.

5. ceramic honeycomb filter according to claim 1, wherein said ceramic honeycomb filter is made up of 2-15 ceramic honeycomb.

6. ceramic honeycomb filter according to claim 1, wherein when watching along the longitudinal direction, each eyelet comprises the quadrangular cross section with arched corner, and a pair relative bight has and is greater than another radius of curvature to the radius of curvature in relative bight.

7. ceramic honeycomb filter according to claim 1, wherein said adjacent ceramic honeycomb is connected in the mode that end-to-end gap is 0.01-3mm.

8. ceramic honeycomb filter according to claim 1, wherein multiple described ceramic honeycomb has the aperture efficiency of 75% or less.

9. ceramic honeycomb filter according to claim 8, wherein at least one group of adjacent ceramic honeycomb has different aperture efficiencies.

10., for the manufacture of a method for ceramic honeycomb filter according to claim 1, comprise the steps:

Moldable ceramic material is extruded with honeycomb shape,

The moldable ceramic material extruded is cut into predetermined length,

The dry extrudate cut off to form the ceramic honeycomb of multiple drying,

Arrange the ceramic honeycomb of described drying in the mode of their end displacement with eyelet wall, and

Sinter the ceramic honeycomb of the drying arranged.

11. methods for the manufacture of ceramic honeycomb filter according to claim 10, the peripheral surface of the described ceramic honeycomb wherein sintered integrally is applied by coating.

12. methods for the manufacture of ceramic honeycomb filter according to claim 10, are wherein coated to the periphery of the end surfaces of described ceramic honeycomb by jointing material, to connect described ceramic honeycomb with described jointing material.

13. 1 kinds of methods for the manufacture of ceramic honeycomb filter according to claim 1, the method comprises the steps:

Moldable ceramic material is extruded with honeycomb shape,

Extrudate is cut into predetermined length,

The dry extrudate cut off to form the ceramic honeycomb of multiple drying,

Arrange the ceramic honeycomb of described drying in the mode of their end displacement with eyelet wall,

The peripheral surface of the ceramic honeycomb of the drying arranged integrally is applied with coating, and

Sinter described ceramic honeycomb.

14. 1 kinds of methods for the manufacture of ceramic honeycomb filter according to claim 1, the method comprises the steps:

Moldable ceramic material is extruded with honeycomb shape,

Extrudate is cut into predetermined length,

Drying also sinters the extrudate of cut-out to form multiple ceramic honeycomb,

Described ceramic honeycomb is arranged in the mode of their end displacement with eyelet wall, and

The peripheral surface of the described ceramic honeycomb arranged integrally is applied with coating.

15. methods for the manufacture of ceramic honeycomb filter according to any one of claim 10-14, wherein connect adjacent ceramic honeycomb by following manner when eyelet walls displace:

A any eyelet wall that positioner and the peripheral end portion of on the end surfaces from a ceramic honeycomb extend to another peripheral end portion roughly aligns by (),

B a described ceramic honeycomb is moved preset distance by () in the x and/or y direction, or around the axis of a described ceramic honeycomb, it is rotated predetermined angular, and

(c) by with the end surfaces for the identical localization method of a described ceramic honeycomb, another ceramic honeycomb being arranged in a described ceramic honeycomb.

16. methods for the manufacture of ceramic honeycomb filter according to claim 15, wherein said positioner is metal and/or nonmetal thread-like member or light.