CN1902384A - Exhaust emission control filter containing particulate matter, exhaust emission control method and device thereof - Google Patents
Exhaust emission control filter containing particulate matter, exhaust emission control method and device thereof Download PDFInfo
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Abstract
本发明涉及一种除去颗粒物质的过滤器，能防止堵塞或灰分阻塞，无需采取专门手段，比如回洗和加热燃烧，其由廉价材料制成；本发明还涉及使用该过滤器的废气排放控制方法和装置。(1)一种含颗粒物质的废气排放控制过滤器，其采用一对支承废气排放控制催化剂的多孔波纹板和多孔平板作为基本单元，并且具有通过将多孔波纹板叠加以使它们的脊线交替地垂直交叉而形成的模制体，而且模制体的与波纹板脊线垂直交叉的一个侧面、或者是垂直交叉侧面的相互邻接的两个面被密封，并且在多孔波纹板之间经由多孔平板分别形成有废气流入通道和废气流出通道。(2)一种过滤器，具有废气排放控制催化剂，该催化剂是一种用于氧化废气中的一氧化氮的氧化催化剂。
The present invention relates to a filter for removing particulate matter, which can prevent clogging or ash blockage without taking special measures such as backwashing and heating combustion, and is made of inexpensive materials; the present invention also relates to an exhaust gas emission control method and device using the filter. (1) An exhaust gas emission control filter containing particulate matter, which uses a pair of porous corrugated plates and a porous flat plate that support an exhaust gas emission control catalyst as a basic unit, and has a molded body formed by stacking the porous corrugated plates so that their ridges alternately cross vertically, and one side of the molded body that crosses the corrugated plate ridges vertically, or two adjacent surfaces of the vertically crossed side surfaces, is sealed, and an exhaust gas inlet channel and an exhaust gas outflow channel are respectively formed between the porous corrugated plates via the porous flat plate. (2) A filter having an exhaust gas emission control catalyst, which is an oxidation catalyst for oxidizing nitrogen monoxide in exhaust gas.
Description
Technical field
The present invention relates to a kind of toxic emission controlled filter device that contains particulate matter, it can be in a kind of mode efficiently, remove particularly particulate matter (PM) contained from the waste gas of diesel emission, and has low ventilation loss, and when ashes and cigarette ash gather, can remove sediments and need not to adopt large-sized equipment; The device that the invention still further relates to the exhaust gas purifying method of a kind of PM of containing and use above-mentioned filter.
Background technique
Diesel engine (DE) is one of the most effective internal-combustion engine, because the carbon dioxide (CO of its each quantitative output power
2) discharge amount reduced and very economical, thereby can use low-quality fuel, such as heavy oil.There is a kind of trend, promptly uses diesel engine continually to prevent global warming.This is because people rethink that the stationary power generation facility of automobile and use diesel engine have high energy efficient and carbon dioxide (CO
2) discharge amount little.
Yet, from these use heavy oil or the diesel engine of light gas oil, giving off a large amount of particulate matter (PM) as its fuel, unburned hydrocarbon mixes with cigarette ash in the particulate matter, and this has become the principal element and the social concern of pollution.Various industries are studied and are developed aspect the PM removing such as diesel engine manufacturer and auto-maker, and make research and invention aspect the filter of PM ability having fabulous removing, thereby design prefilter oxidation catalyst and DP (diesel particulate) filter (DPF), its middle filtrator is manufactured into and is supported with a kind of oxidation catalyst so that the nitrous oxide in the waste gas (NO) is oxidized to nitrogen dioxide (NO
2) and burning cigarette ash, thereby prevent or delay to be stopped up for a long time (for example, non-patent literature 1) by cigarette ash.
In these technology, many technology are wanted by making thin-walled that waste gas makes by the porous ceramics of a few μ m sizes and filtering exhaust.By plate shape or cylindrical filter, the filter (its mesh is alternately silted up) of employing ceramic honeycomb porous molding and the filter that adopts the fine metal wire fabric to make that calcining metal or pottery are obtained, all be known.And, by these filters are had NO is oxidized to NO
2With oxidation and the burning cigarette ash the filter that ability was obtained, its objective is can prevent or limit these filters blocked (for example, patent documentation 1 and 2 and non-patent literature 2).
Non-patent literature 1: Japanese industry Environmental Management Association (Japan EnvironmentalManagement Association for Industry), environmental management (EnvironmentalManagement), the 37th volume, P441-449
Patent documentation 1: Japanese unexamined patent application communique No.1-318715
Patent documentation 2: Japanese unexamined patent application communique No.60-235620
Non-patent literature 2: the academic report collected works of Japanese car IEEE (Society ofAutomotive Engineers of Japan Academic Lecture Publisher) No.22-2
Above-mentioned conventional art has high DP calcination efficiency and premium properties.Yet; these technology are used under the situation that light oil or heavy oil acts as a fuel and these technology are being applied under the situation of the stationary power generation machine that uses DE at waste gas; have following problems: (i) these filters are based on by utilizing pore to remove by filter the basic principle of PM; thereby ventilation loss is big, and weakens the performance of high efficiency DE through regular meeting.(ii) producing because of inappropriate running under the situation of a large amount of cigarette ashes, the many tendencies that obstruction is all arranged of these filters, and the elimination obstruction that finally need take some countermeasures, such as, back scrubbing filter or heating and burning cigarette ash are to prevent obstruction.(iii) the ashes in the fuel are accumulated in the pore of filter and cause stopping up, and this has shortened the working life of filter.Not burned cigarette ash and the NO that consumes (iv) are not set under the situation of denitrification apparatus in the downstream of waste gas
2Be discharged, cause producing tobacco and secondary pollution problems.
Summary of the invention
An object of the present invention is to solve the problems referred to above of conventional art, and provide a kind of filter of removing particulate matter, its material by cheapness is made, and can prevent to be stopped up or seal by ashes and do not need to take special means, such as the heating and the burning of back scrubbing or cigarette ash.Also device that purpose provides a kind of exhaust gas purifying method and uses above-mentioned filter of the present invention.
To achieve these goals, the present patent application claimed invention is as follows.
(1) a kind of exhaust emission control filter that contains particulate matter, it adopts a pair of porous corrugated sheet that is supported with a kind of exhaust gas purifying catalyst and porous flat plate as an elementary cell, and have by the described moulded parts that stack forms to porous corrugated sheet and porous flat plate, so that alternately square crossing of the crestal line of porous corrugated sheet, and, two sides that adjoin each other with the side square crossing of described corrugated sheet crestal line or square crossing side moulded parts are sealed, thereby are formed with waste gas flow channel and flow pass respectively via porous flat plate between described porous corrugated sheet.
(2) according to above-mentioned (1) filter, wherein, described exhaust gas purifying catalyst is a kind of oxidation catalyst, its nitrous oxide in can oxidation gaseous effluent.
(3) according to above-mentioned (1) or the filter of (2), wherein, described oxidation catalyst comprises platinum.
(4) according to above-mentioned (1) to (3) each filter, wherein, described oxidation catalyst comprises titanium oxide.
(5) a kind of exhaust gas purifying method that contains particulate matter, it adopts according to each filter of above-mentioned (1) to (4), comprise: the crestal line of waste gas from passage along corrugated sheet introduced described filter, this passage is formed between the porous corrugated sheet and porous flat plate of molding, cleaned gas flows through porous flat plate and porous corrugated sheet in the permission passage, then along the crestal line of adjacent corrugated sheet from adjacent passage exhausting air, adjacency channel is formed between porous flat plate and the porous corrugated sheet and with the described channel vertical along this corrugated sheet crestal line and intersects.
(6) a kind of waste gas cleaning plant that contains particulate matter, comprise above-mentioned (1) desired filter, one be used for that waste gas is introduced that the device of described waste gas flow channel of filter and one is used for will be from the device of the carrier frequency channel break of the gas of described flow pass discharging.
(7) according to above-mentioned (6) waste gas cleaning plant, wherein, the described device that is used to block gas channel has a kind of structure, this structure have permit gas by or the conversion function passed through of blocking-up gas.
(8) a kind of exhaust emission control filter that contains particulate matter, it has a molding, this molding is provided with a pair of porous corrugated sheet and the porous flat plate as elementary cell, molding is by forming the elementary cell mutual superposition, so that alternately square crossing of the crestal line of porous corrugated sheet, wherein, molding and one of surface square crossing of described corrugated sheet crestal line, or it is sealed with the side of described corrugated sheet crestal line square crossing and two surfaces adjoining each other, between these porous corrugated sheets, to form waste gas flow channel and waste gas flow pass by described porous flat plate, and, on two surfaces of porous corrugated sheet and a surperficial upper support that contacts with this porous corrugated sheet of porous flat plate have can oxidization of nitric oxide oxidation catalyst, form the waste gas flow channel, and, described oxidation catalyst neither is supported on of also not being supported in porous flat plate on two surfaces of porous corrugated sheet and the surface that this porous corrugated sheet contacts, and forms the waste gas flow pass.
(9) according to above-mentioned (8) filter, wherein, described oxidation catalyst comprises platinum.
(10) according to above-mentioned (8) or the filter of (9), wherein, described oxidation catalyst comprises titanium oxide.
(11) a kind of exhaust gas purifying method that contains particulate matter, it adopts according to each filter of above-mentioned (8) to (10), comprise: the crestal line of waste gas from passage along corrugated sheet introduced described filter, this passage is formed between porous corrugated sheet and the porous flat plate and at the molding internal support described oxidation catalyst, crestal line along an adjacent corrugated plate discharges from passage with the gas that is cleaned in the molding, this passage is formed between the porous flat plate and porous corrugated sheet that does not have catalyzer, and intersects with the channel vertical of this corrugated sheet crestal line.
(12) a kind of waste gas cleaning plant that contains particulate matter, it comprises above-mentioned (8) filter that requires, one be used for that waste gas is introduced that the device of described waste gas flow channel of filter and one is used for will be from the device of the carrier frequency channel break of the gas of described flow pass discharging.
(13) according to above-mentioned (12) waste gas cleaning plant, wherein, the described device that is used to block gas channel has a kind of structure, this structure have permit gas by or the conversion function passed through of blocking-up gas.
According to exhaust emission control filter and the exhaust gas purifying method that contains PM of the present invention, can realize having the DPF of catalyzer, it has high-performance and has reduced pressure and falls, and does not have to use the ceramic post sintering filter of the costliness that is used at present.And, because PM can be burned and be removed effectively, even when the amount of oxidation catalyst such as the platinum of costliness is greatly reduced, so cost is considerably reduced.In addition, in the present invention, direction and the sealing configuration thereof of waste gas being introduced exhaust emission control filter are prevented that with activation filter from being stopped up by things such as dusts by design like this effectively.
And, among the exhaust steam passage that will alternately be formed in the molding, only the passage that is introduced on the direction along waste gas is designed to be supported with oxidation catalyst, after PM is removed, NO in the passage in the waste gas is almost not oxidized, thereby makes it possible to prevent NO
2From this device, emit.
Description of drawings
Fig. 1 is a kind of explanatory of exhaust emission control filter, and an example of the present invention is shown;
Fig. 2 is the explanatory of an elementary cell, and it is made up of a porous corrugated sheet and a porous flat plate;
Fig. 3 is the explanatory of the used DPF piece of the present invention;
Fig. 4 is the waste gas flow channel among the present invention and the explanatory of flow pass;
Fig. 5 is used for illustrating the view that gathers at DPF particulate matter of the present invention;
Fig. 6 is used for illustrating the view that gathers at traditional DPF particulate matter;
Fig. 7 is a kind of explanatory of exhaust emission control filter, and another example of the present invention is shown;
Fig. 8 is the explanatory of a reactor, and DPF of the present invention is loaded into wherein;
Fig. 9 is the explanatory of a reactor, and DPF used in the example is loaded into wherein.
Reference character:
1 porous corrugated sheet
2 porous flat plates
3 DPF pieces
4 sealing materials
5 particulate matters
The hole wall of 6 ceramic DPF (cell wall)
7 reactors
8 flanges
9 DPF support accessory
10 valves
Embodiment
According to a kind of exhaust emission control filter that contains particulate matter of the present invention, has a kind of molding, this molding is provided with a pair of porous corrugated sheet and the porous flat plate as an elementary cell, described plate is supported with a kind of exhaust gas purifying catalyst, such as a kind of oxidation catalyst, this catalyzer can be oxidized to NO with the NO in the waste gas
2And molding is by forming the setting so that the crestal line of porous corrugated sheet alternately meets at right angles with described elementary cell stack, wherein, sealed with two sides that adjoin each other of side of the corrugated sheet crestal line square crossing of molding or square crossing side.
Fig. 1 is an explanatory of the filter (DPF) of removing particulate matter, and one embodiment of the present of invention are shown.Fig. 2 is the explanatory of an elementary cell among the present invention, and it is made up of a porous corrugated sheet and a porous flat plate.Fig. 3 is the explanatory of molding, and wherein elementary cell is applied.
In Fig. 1, DPF is provided with molding (being known as DPF here, determines) 3 and a kind of sealing material 4 of a bulk.This DPF piece 3 is constructed like this, and a plurality of elementary cells of being made up of a pair of porous corrugated sheet 1 and porous flat plate 2 (as shown in Figure 2) are applied, the setting so that the crestal line of porous corrugated sheet 1 alternately meets at right angles, as shown in Figure 3.On one of them side of piece 3, be provided with sealing material 4, the crestal line square crossing of the porous corrugated sheet 1 of described side and formation DPF piece 3.Like this, between sealing material 4 and porous corrugated sheet 1, form a waste gas flow channel a (pending gas) and a gas flow pass b (Purge gas) (see figure 4) by porous flat plate 2.
In the present invention, as the material of porous corrugated sheet 1 and porous flat plate 2, such as the nonwoven fabric or the woven fabric that can adopt the ceramic fiber that has used the silica aluminum type, steel fiber plate or pottery are such as the porous sintered body of steinheilite.From obtaining to have the viewpoint of highly porous lightweight DPF, in these materials, thickness is that 0.5 to 0.1mm ceramic nonwoven fabric (plate) is preferential especially the employing.Although the shape to the corrugated sheet of porous corrugated sheet 1 has no particular limits,, under the situation that adopts above-mentioned thickness of slab, the pitch of ripple and highly preferably being designed respectively in the scope of 2-10mm and 1-5mm.As for the shape of the elementary cell of being made up of porous corrugated sheet 1 and porous flat plate 2, two boards preferably bundles mutually by inorganic binder, although they can be superposeed simply.
As for sealing material, material is comprised its sealing configuration has no particular limits, as long as can stoping, it on the surperficial facing surfaces of the crestal line introducing of the corrugated sheet of porous corrugated sheet 1, is forming exhaust gas flow path with the waste gas quilt.Can adopt such means, such as, a kind of method, wherein, want sealed lip-deep flow channel be filled in a kind of inorganic solidified material, a kind of method, wherein flow channel a kind of inorfil pulvilliform sealing material of being applied ointment or plaster under pressure, perhaps a kind of method, wherein flow channel is stopped up by sheet metal.And, can adopt a kind of material to cover the periphery of DPF piece and form integral body with the supporting hole wall of DPF piece, this material is to prepare such as the ceramic binder with high viscosity by soak into a kind of high adhesive glue to inorganic fiber mat, thereby forms the high sealing material of a kind of soundness.
Porous corrugated sheet 1 and porous flat plate 2 are necessary to support a kind of exhaust gas purifying catalyst, especially a kind of oxidation catalyst component, and it in waste gas is introduced the described exhaust steam passage of side, is oxidized to NO with NO contained in the waste gas at least
2As catalytic component, can adopt a kind of known catalyzer, this catalyzer is to make by allowing a kind of common precious metal to be supported on the support with large surface area such as platinum (Pt), such as titanium oxide, aluminium oxide, zirconium oxide or silica.When after the high heavy oil of combustion of sulfur amount, handling waste gas, particularly preferably be and adopt titanium oxide with highly-acidproof energy.
For the DPF of the application of the invention comes purifying exhaust air, pending gas by along the crestal line of corrugated sheet by being formed at DPF piece 3 porous corrugated sheet 1 and the passage between the porous flat plate 2 supply.Particularly, as shown in Figure 4, be formed with a passage a and the passage b along direction B along direction A on DPF, passage a is formed between porous corrugated sheet 1 and the porous flat plate 2, and wherein direction B is perpendicular to direction A.The pending gas of introducing from direction A can only be introduced into passage a (waste gas flow channel), simultaneously, the gas that is introduced into passage a pass on the porous flat plate 2 the hole and along direction B flow channel b (waste gas flow pass), this passage b is formed by porous flat plate 2, another porous corrugated sheet 1 and another porous flat plate 2 adjacent with this porous flat plate 2, because the sealed material 4 of the exit portion of passage a seals.When waste gas passed through porous flat plate 2, PM contained in the gas was removed and is accumulated on the surface of porous flat plate 2 by filtration.Fig. 5 shows the schematic representation of the state of the PM that is gathered.In Fig. 5, the PM (particulate matter) that symbol 5 expressions are gathered.
And when pending gas contacted with porous flat plate 2 with porous corrugated sheet 1, the catalyst oxidation with oxidability that the NO in the pending gas is supported on these plates became NO
2According to following formula (1), the PM that gathers (cigarette ash) passes through NO
2Reaction be oxidized to CO
2, be removed then.Thereby might prevent such trouble, promptly along with the variation of time, the pressure of porous corrugated sheet 1 and porous flat plate 2 falls the PM that increases or gathered and stops up.
In DPF of the present invention, as shown in Figure 5, there is not PM to gather on the surface of the porous corrugated sheet 1 in passage a.Thereby the NO in the gas can effectively contact with the porous corrugated sheet 1 that is positioned at porous flat plate 2 upstreams, and PM is accumulated on the porous flat plate 2, causes NO
2Effective generation.So accumulating in porous flat plate 2 lip-deep PM can be by NO
2Oxidation and removing with effective and efficient manner.Thereby, even the amount at the precious metal of the amount of the catalyzer of porous corrugated sheet 1 and porous flat plate 2 upper supports and the costliness that will be used is reduced, also can carry out the oxidation of PM effectively and always reduce the amount of the cigarette ash of deposition, make the low pressure drop running of DPF become possibility.Should be noted that cigarette ash can not effectively be burnt in formed traditional DPF by the passage that alternately stops up cellular molding, because NO is arranged in the generation of the bottom of accumulated soot
2, as shown in Figure 6.
Shift to passage b by filtering the gas of therefrom removing cigarette ash, this passage b is made up of the porous corrugated sheet 1 and the porous flat plate 2 of supporting NO oxidation catalyst.NO gas among the passage b also is oxidized to NO
2Thereby, when being used to reduce urea or NH
3Middle NO
xDenitrating catalyst when being present in the downstream of passage b, preferentially carry out according to the denitration reaction of following formula (2) with very high speed, even under low temperature condition, the NO in the waste gas
xAlso removed very effectively, improved the denitration ability of system.
In the present invention, the NO in the waste gas is oxidized to NO
2Oxidation catalyst can be supported on all the porous corrugated sheets 1 and porous flat plate 2 that constitute described.Yet catalyzer can only be supported among the passage a that constitutes the waste gas flow channel, particularly on two surfaces of the porous corrugated sheet 1 that constitutes the waste gas flow channel and on the surface that contacts with porous corrugated sheet 1 at porous flat plate 2.
In the previous case, oxidation catalyst is supported on all porous corrugated sheets 1 and the porous flat plate 2, and the NO in the waste gas that PM is therefrom removed is also by oxidation in passage b.Thereby, the NO of the high poison that is produced is not set under the situation of denitrification apparatus in the downstream of filter
2Be discharged in the air, cause producing secondary pollution thus, produce tobacco and similar problem.At this moment, preferably as latter event, only be that the passage a that constitutes the waste gas flow channel is made into to support oxidation catalyst, and the passage b of formation waste gas flow pass is made into not support oxidation catalyst.This structural limitations in passage b NO be oxidized to NO
2Thereby, prevented NO
2The discharge system.
When not supporting oxidation catalyst,, can use support as it is if porous corrugated sheet 1 and porous flat plate 2 have high rigidity in the inside of passage b.Yet, improving under the situation of support intensity, the slurries of titanium oxide, aluminium oxide or zirconic nonactive oxide or colloidal sol can be used as strengthening agent and are supported on two surfaces of porous corrugated sheet 1 on each surface with the porous flat plate 2 that contacts with porous corrugated sheet 1.
Easily introduce and these slurries are pulled out the other way around by the direction A of slurries from Fig. 4 catalytic component, also by the direction B of strengthening agent slurries from Fig. 4 easily introduced and these slurries pulled out the other way around, the surface, inside of passage a just can be made into the supporting catalyst component, and the surface, inside of passage b can be made into to support above-mentioned strengthening agent.At this moment, preferably the surface that slurries are not introduced into passage is wherein protected, such as by to this surface coverage sealing material.And, can adopt a kind of method, wherein when the elementary cell of support was manufactured into as shown in Figure 2, said components was supported, and these components are comprised or is coated on the support, and the elementary cell that is generated is applied then.
Fig. 7 is the explanatory of a kind of DPF, and another example of the present invention is shown.In Fig. 7, DPF and difference shown in Figure 1 are that sealing material 4 is to be set on two adjacent surfaces, and these two surfaces are perpendicular to the side of the corrugated sheet crestal line of DPF piece 3.This structure guarantees that the pending gas that is introduced into this DPF piece 3 can be discharged in one direction, thereby is loaded into that dead-space volume is reduced in the reactor of DPF, thereby makes waste gas cleaning plant compacter.
Fig. 8 is an explanatory, and the various examples of DPF structure when DPF of the present invention is loaded in the reactor are shown.Fig. 8 (A) is an explanatory of this reactor, the DPF that is provided with sealing material 4 on two surfaces of DPF piece 3 packs into wherein, Fig. 8 (B) and 8 (C) are the explanatory of a reactor, this reactor is provided with a valve 10, and this valve will be blocked with the exhaust steam passage on the surperficial relative side of introducing waste gas.In Fig. 8 (B), the combination of two sealed materials 4 in plane and valve 10 seals, and in Fig. 8 (C), only a surface is sealed by valve 10.When valve 10 is provided for sealing, by switch on or off valve 10 control waste gas can by by or be stopped.Thereby because misoperation or engine failure, when passage was surpassed the soot oxidation ability of DPF by cigarette ash (PM) obstruction, valve 10 was unlocked with exhausting air, thereby the cigarette ash that gathers can be discharged from promptly running is returned to its reset condition.
Example
To explain in more detail the present invention by example below, right rather than will limit the present invention with these examples.
Example 1
A kind of stack piece that is made of the thick porous corrugated sheet of 0.2mm and thick porous flat plate of 0.2mm has been soaked into a kind of 15% TiO
2Colloidal sol (making) by Ishihara Sangyo Co., Ltd, described plate is made by the nonwoven fabric of silica aluminum fiber that (the corrugated honeycomb of intersection is made by NICHIAS company, corrugated sheet pitch: 3.3mm, gap between two flat boards: 1.9mm, boundary dimension: 300mm * 300mm * 300mm), stack piece are dried by ventilation and 150 ℃ of dryings.Then, the stack piece is soaked into a kind of dinitro diamino platinum (dinitrodiammineplatinum) solution (Pt concentration: 1.33g/L), dry once more and 600 ℃ of calcinings so that for DPF makes a kind of base material, DPF supports a kind of oxidation catalyst that contains 0.2g/L Pt.
Example 2
The base material that is used to make the DPF with oxidation catalyst is to adopt the mode identical with example 1 to make, and the 1.33g/L of concentration from example 1 that is dinitro diamino platinum becomes 0.32g/L.
Example 3
By solution (Pt concentration: the TiO of suspension 300g 1.7g/L) at a kind of dinitro diamino platinum
2(trade (brand) name: G5 is made surface area: 320m to powder by Millennium Pharmaceuticals limited company
2/ g) prepared a kind of slurries are kept 2 hours so that the Pt component is absorbed into TiO down at 80 ℃
2The surface.(trade (brand) name: Silicasol-OS is made SiO to the silica gel of 1kg by Nissan Chemical Industries (chemical industry) Co., Ltd
2Concentration: 20%) be added in the resulting solution of 1kg, the pH value of solution is regulated by a kind of salpeter solution, to obtain a kind of catalyst slurry that will be supported in the passage a.
Prepare the thick corrugated-crossed shape honeycomb of a kind of 0.2mm, its nonwoven fabric by the silica aluminum fiber is made and (is made corrugated sheet pitch: 3.3mm, the gap between two flat boards: 1.9mm, boundary dimension: 300mm * 300mm * 300mm) by NICHIAS company.Adopt a kind of method, wherein, slurries are introduced a surface by the direction A from Fig. 4, discharge from facing surfaces then, catalytic component only is supported in the internal surface of passage a, ventilated and dry, calcine so that for DPF makes a kind of base material 150 ℃ of dryings and at 600 ℃, DPF supports a kind of oxidation catalyst that contains 0.1g/L Pt.
Example 4
By solution (Pt concentration: the TiO of suspension 300g 1.7g/L) at a kind of dinitro diamino platinum
2(trade (brand) name: G5 is made surface area: 320m to powder by Millennium Pharmaceuticals limited company
2/ g) prepared a kind of slurries are kept 2 hours so that the Pt component is absorbed into TiO down at 80 ℃
2The surface.(the trade (brand) name: Silicasol-OS of the silica gel of 1kg, make by Nissan Chemical Industries (chemical industry) Co., Ltd) be added in the resulting solution of 1kg, the pH value of this solution is regulated by a kind of salpeter solution, to obtain a kind of catalyst slurry that will be supported in the passage a.
In addition, and the silica gel of 1kg (trade (brand) name: Silica sol-OS, made SiO by Nissan ChemicalIndustries (chemical industry) Co., Ltd
2Concentration: 20%) be added into a kind of of 1kg by suspension 300g TiO
2(trade (brand) name: CR50 is made surface area: 3m to powder by Ishihara Sangyo Co., Ltd
2/ g) in the prepared slurries, the pH value of this solution is regulated by a kind of salpeter solution, to obtain a kind of nonactive inorganic oxide slurries that will be supported in the passage b.
Prepare the thick corrugated-crossed shape honeycomb of a kind of 0.2mm, its nonwoven fabric by the silica aluminum fiber is made and (is made corrugated sheet pitch: 3.3mm, the gap between two flat boards: 1.9mm, boundary dimension: 300mm * 300mm * 300mm) by NICHIAS company.Adopt a kind of method, wherein, the above-mentioned slurries that are used for passage a are introduced a surface by the direction A from Fig. 4, and discharge from facing surfaces, and catalytic component only is supported in the internal surface of passage a, is ventilated and dries, 150 ℃ of dryings.Then, adopt a kind of method, wherein, the above-mentioned slurries that are used for passage b are introduced a surface by the direction B from Fig. 4, and from the facing surfaces discharge, described nonactive oxide is supported in the internal surface of passage b, is ventilated and dries, 150 ℃ of dryings, and make a kind of base material 600 ℃ of calcinings so that for the DPF with oxidation catalyst.
Example 5
The base material that is used to make the DPF with oxidation catalyst is to adopt the mode identical with example 4 to make, the catalyst slurry flow channel b that just is used for passage a, rather than inactive ingredients slurries flow channel b is with supporting catalyst, thereby makes passage a and b be supported with a kind of NO-oxidation component.
Comparative example 1
A kind of commercially available DPF (is made by Hitachi Metals (Hitachi Metals) Co., Ltd, honeycomb is counted 100cpsi, 5.66 inch * 6 are inch long) make by cordierite ceramic, it is made by alternately the opening portion of the passage of honeycomb molding being stopped up, this DPF is soaked into a kind of TiO 2 sol and (is made TiO by Ishihara Sangyo Co., Ltd
2Content: 30%), then dry to support the TiO of 60g/L with centrifuge
2The DPF that is soaked into TiO 2 sol is after 150 ℃ of dryings, further by a kind of dinitro diamino platinic acid solution impregnation, thereby based on PDF the Pt that is supported amount is 1.6g/L, drying is then 600 ℃ of temperature lower calcinations 2 hours, to make a kind of DPF with catalyzer.
Comparative example 2
The base material that is used to make the DPF with catalyzer is to adopt the mode identical with comparative example 1 to make, and is that the concentration of dinitro diamino platinum is diluted to 1/8 amount with the platinum that will be supported and reduces to 0.2g/L.
The test example
Each base material that will be used for being manufactured on the DPF with oxidation catalyst that example 1-5 obtains is cut into the cuboid that 150mm is long, 150mm is high and 117mm is wide, its one of them a kind of sealing material in surface.This base material (DPF piece) is filled in the reactor as shown in Figure 9, thereby one of surface that all the other are not sealed is (gas supply side) up.In other words, this DPF piece 3 is fixed on the DPF supporting accessory 9 that is arranged in the reactor 7, thereby this not sealed surface up.And each the DPF piece with catalyzer that is obtained in comparative example 1 and 2 is filled in the columniform reactor, and has sealed the periphery of DPF piece and this reactor.
Each of these reactors is set at the floss hole place of the diesel engine that acts as a fuel with heavy oil, and exhaust gas discharged is allowed to 100m from diesel engine
3The speed of/h is discharged, to detect following project.It the results are shown in the table 1.
(1) existence of cigarette ash during engine start.
(2) situation (dpf temperature: about 300 ℃) of rising falls in pressure when low load operation.
(3) the rising situation (dpf temperature: about 400 ℃) of falling with pressure falls in pressure when 100% specified running.
(4) when 100% specified running in the concentration of the entrance and exit place of DPF particulate matter.
(5) under 100% specified running situation at the outlet port of DPF NO
2Concentration.
Table 1
| The Pt amount (g/L) that is supported | The visual observation of cigarette ash during starting | The rising that pressure falls during low-load | Situation during 100% load | The rate of removing (%) of PM | DPF outlet port NO 2Concentration (ppm) | ||
| (mmH falls in pressure 2O) | Rising in time falls in pressure | ||||||
| Example 1 | 0.2 | Do not have | On a small quantity | 140 | Do not have | 90 or more | - |
| Example 2 | 0.05 | Do not have | On a small quantity | 140 | Do not have | 90 or more | - |
| Example 3 | 0.1 | Do not have | On a small quantity | 140 | Do not have | 90 or more | 40 |
| Example 4 | 0.1 | Do not have | On a small quantity | 150 | Do not have | 90 or more | 30 |
| Example 5 | 0.2 | Do not have | On a small quantity | 140 | Do not have | 90 or more | 80 |
| Comparative example 1 | 1.6 | Do not have | On a small quantity | 160 | Do not have | 90 or more | 220 |
| Comparative example 2 | 0.2 | Do not have | Sharply rise, stop up in 2 hours | 320 | 5 hours internal pressure rising 40mmH 2O | 90 or more | 80 |
The result who is obtained has been shown in the table 1, from the table can find that the DPF with oxidation catalyst according to the present invention can make cigarette ash be burnt effectively, its pressure can be fallen even the amount of catalyst Pt is very little be suppressed to one low-level.
From table 1, can find, compare with the DPF that in comparative example, is obtained, the DPF with oxidation catalyst that obtains in example 1-5 of the present invention can make cigarette ash be burnt more effectively, even the amount of catalyst Pt is very little, but also its pressure can be fallen be suppressed to one low-level.And can know, because this oxidation catalyst is not supported among the passage b (waste gas flow pass), at DPF outlet port NO in example 3 and 4
2Concentration be limited to one low-level, demonstrating these DPF of the present invention is good on environment.In turn, have at DPF under the situation of oxidation catalyst of example 5, at DPF outlet port NO
2Concentration be raised because oxidation catalyst is supported in the whole exhaust steam passage.Yet, in this case, a denitrating catalyst device is set by downstream at DPF, just can prevent that NO2 from discharging system.
On the contrary, increase falls in traditional its pressure of ceramic DPF that is obtained in comparative example 1 and 2, and at the outlet port of each DPF NO
2Concentration also increase.
Industrial applicibility
According to the present invention, particle mass-energy contained in the waste gas that particularly discharges from diesel engine is removed, and has low ventilation loss and high efficient, and when ash content and cigarette ash gather, they can also be removed and but need not to adopt large-sized equipment, this can guarantee to provide a kind of DPF that is conducive to prevent the cheapness of environmental air pollution, thereby DPF of the present invention will produce very large society and economic benefit.
Claims (13)
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003393879 | 2003-11-25 | ||
| JP393879/2003 | 2003-11-25 | ||
| JP2004099149A JP4758071B2 (en) | 2003-11-25 | 2004-03-30 | PM-containing exhaust gas purification filter, exhaust gas purification method, and purification apparatus |
| JP099149/2004 | 2004-03-30 | ||
| PCT/JP2004/017395 WO2005052327A1 (en) | 2003-11-25 | 2004-11-24 | Particulate matter-containing exhaust emission controlling filter, exhaust emission controlling method and device |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1902384A true CN1902384A (en) | 2007-01-24 |
| CN1902384B CN1902384B (en) | 2012-09-05 |
Family
ID=37657562
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2004800393306A Expired - Fee Related CN1902384B (en) | 2003-11-25 | 2004-11-24 | Exhaust emission control filter containing particulate matter, exhaust emission control method and device thereof |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP2008309160A (en) |
| CN (1) | CN1902384B (en) |
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|---|---|---|---|---|
| US4343631A (en) * | 1981-01-30 | 1982-08-10 | Westinghouse Electric Corp. | Hot gas particulate removal |
| WO1989003720A1 (en) * | 1987-10-23 | 1989-05-05 | Massachusetts Institute Of Technology | Methods and devices for gas cleaning |
| JP2954609B2 (en) * | 1989-10-12 | 1999-09-27 | 旭硝子株式会社 | Exhaust black smoke removal device |
| JP3900421B2 (en) * | 2001-11-09 | 2007-04-04 | トヨタ自動車株式会社 | Wall flow type diesel exhaust gas purification filter type catalyst and diesel exhaust gas purification device |
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2004
- 2004-11-24 CN CN2004800393306A patent/CN1902384B/en not_active Expired - Fee Related
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- 2008-07-08 JP JP2008177756A patent/JP2008309160A/en active Pending
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| JP2008309160A (en) | 2008-12-25 |
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