+

WO2006131995A1 - Filtre a particules diesel et purificateur utilisant celui-ci - Google Patents

Filtre a particules diesel et purificateur utilisant celui-ci Download PDF

Info

Publication number
WO2006131995A1
WO2006131995A1 PCT/JP2005/014739 JP2005014739W WO2006131995A1 WO 2006131995 A1 WO2006131995 A1 WO 2006131995A1 JP 2005014739 W JP2005014739 W JP 2005014739W WO 2006131995 A1 WO2006131995 A1 WO 2006131995A1
Authority
WO
WIPO (PCT)
Prior art keywords
particulate filter
diesel particulate
heat
nonwoven fabric
oxide catalyst
Prior art date
Application number
PCT/JP2005/014739
Other languages
English (en)
Japanese (ja)
Inventor
Masahiko Matsumoto
Original Assignee
Tosco Co., Ltd.
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tosco Co., Ltd. filed Critical Tosco Co., Ltd.
Publication of WO2006131995A1 publication Critical patent/WO2006131995A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B01D39/14—Other self-supporting filtering material ; Other filtering material
    • B01D39/20—Other self-supporting filtering material ; Other filtering material of inorganic material, e.g. asbestos paper, metallic filtering material of non-woven wires
    • B01D39/2068—Other inorganic materials, e.g. ceramics
    • B01D39/2082—Other inorganic materials, e.g. ceramics the material being filamentary or fibrous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/92—Chemical or biological purification of waste gases of engine exhaust gases
    • B01D53/94—Chemical or biological purification of waste gases of engine exhaust gases by catalytic processes
    • B01D53/944—Simultaneously removing carbon monoxide, hydrocarbons or carbon making use of oxidation catalysts
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2239/00—Aspects relating to filtering material for liquid or gaseous fluids
    • B01D2239/02—Types of fibres, filaments or particles, self-supporting or supported materials
    • B01D2239/0241—Types of fibres, filaments or particles, self-supporting or supported materials comprising electrically conductive fibres or particles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/40—Mixed oxides
    • B01D2255/402—Perovskites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts

Definitions

  • the present invention relates to a diesel particulate filter that enables simultaneous and complete removal of particulate matter (PM) and nitrogen oxides (NOx) contained in exhaust gas discharged from a diesel engine car. And a purification apparatus using the same.
  • Diesel engines are widely used mainly in trucks in Japan because of their excellent fuel economy and durability. Especially in Europe, excellent fuel economy and global warming gas CO emissions
  • PM particulate matter
  • NOx nitrogen oxides
  • a method for removing these particulate matter (PM) and nitrogen oxide (NOx) a method of providing a diesel particulate filter (DPF) on the exhaust gas side of a diesel engine is known.
  • DPF diesel particulate filter
  • a filter that has been used for a long time a filter using a nonwoven fabric of silicon carbide-based inorganic fibers can be cited. This filter collects PM contained in exhaust gas with a non-woven fabric and heats it to a high temperature (approximately 600 ° C) to convert the components of PM, carbon (C) and hydrocarbons (HC), into CO.
  • a diesel particulate filter carrying a perovskite-type compound having a nitrogen oxide NOx reducing action on the surface of fibers contained in such a nonwoven fabric (See Patent Document 2).
  • Patent Document 2 where the powerful perovskite type compound lacks the ability to remove PM, PM is removed by heating and heat treatment in an oxidizing atmosphere, regardless of the catalyst.
  • a so-called ceramic method is used in which component oxides and carbonates are mixed and fired.
  • the perovskite type spinel type composite oxidation catalyst manufactured by the alkoxide method or the simple nitrate dipping method has a small specific surface area (about 0.5m 2 Zg), and the exhaust gas and the catalyst have sufficient contact. Not done. Further, this composite oxidation catalyst is supported so as to cover a support such as a non-woven fabric and does not have a particle structure. Therefore, in such a diesel particulate filter, PM (carbon) is converted to CO and NOx is completely converted to nitrogen.
  • Patent Document 1 Japanese Patent Laid-Open No. 7-11933
  • Patent Document 2 JP 2002-301320 A
  • Patent Document 3 Japanese Patent Laid-Open No. 2003-239722
  • the first object of the present invention is to sufficiently remove particulate matter (PM), especially NO, which causes air pollution and dust pollution that are emitted from diesel engine exhaust gas power.
  • PM particulate matter
  • SPM small suspended particulate matter
  • NOx nitrogen oxides
  • a second object of the present invention is to provide a diesel particulate filter comprising a nonwoven fabric made of heat resistant fibers and a particulate composite oxide catalyst supported on the surface of the heat resistant fibers.
  • the third object of the present invention is to capture and remove particulate matter (PM), particularly suspended particulate matter (SPM) having a small particle diameter, on the surface of the nonwoven fabric, and to remove nitrogenous acid.
  • the object is to provide a compact and high-performance diesel particulate filter and a purification device for diesel engine exhaust gas, which can reduce and remove substances (NOx) at the same time, detoxify diesel engine exhaust gas with high efficiency.
  • a fourth object of the present invention is to provide a method for producing a diesel particulate filter comprising a non-woven fabric made of heat-resistant fibers and a composite oxide catalyst supported on the surface of the heat-resistant fibers.
  • the present inventors have supported the surface of a non-woven fabric made of a specific heat-resistant fiber with particles of a mouth-bushite complex oxide catalyst having a specific particle size. It was found that the diesel particulate filter showed good simultaneous removal performance of particulate matter (PM) and nitrogen oxides (NOx).
  • PM particulate matter
  • NOx nitrogen oxides
  • a diesel particulate filter comprising a nonwoven fabric composed of heat-resistant fibers and a perovskite-type composite oxide catalyst supported on the surface of the heat-resistant fibers, wherein the composite oxide catalyst is 0.1 to : It relates to a diesel particulate filter characterized by being particles having an average particle size of LOOnm.
  • the above-mentioned mouthbskite-type composite oxide catalyst has the formula (I):
  • A, B and C may be the same or different from each other.
  • the diesel particulate filter according to 1 above represented by:
  • the perovskite-type composite oxide catalyst is La K CoO, La Sr CoO or La
  • the nonwoven fabric thickness 0.1. 3 to: L0mm, and the force of density 0. 05 ⁇ : having L OgZcm 3, relates to a diesel particulate filter according to any force 1 above 1-4.
  • the present invention relates to a purifier for exhaust gas discharged.
  • a non-woven fabric comprising heat-resistant conductive fibers and particles of a perovskite-type composite oxide catalyst having an average particle diameter of 0.1 to 1 OOnm supported on the surface of the heat-resistant conductive fibers.
  • a diesel particulate filter manufacturing method comprising:
  • the diesel particulate filter of the present invention comprises a nonwoven fabric composed of heat-resistant fibers, And a mouth bumskite complex oxide catalyst supported on the surface of the heat resistant fiber.
  • a nonwoven fabric composed of heat-resistant fibers
  • a mouth bumskite complex oxide catalyst supported on the surface of the heat resistant fiber.
  • the nonwoven fabric of the present invention also has heat resistant fiber strength.
  • the heat-resistant fiber of the present invention is a fiber having a heat resistance of 800 ° C or higher, preferably 1000 ° C or higher.
  • the heat-resistant fiber of the present invention is preferably a heat-resistant conductive fiber in order to adhere the velovskite complex oxide catalyst particles by electrophoresis.
  • the heat-resistant conductive fiber of the present invention preferably has an electric resistance of, for example, 1.4 ⁇ ′cm or less, preferably 0.1 ⁇ ′cm or less.
  • the heat resistant fiber of the present invention is alkali resistant in order to support an alkali metal oxide containing K or the like.
  • the degree of alkali resistance is appropriately determined by measuring the tensile strength of a fiber that has been immersed in a 2.0% NaCl aqueous solution and then heat-treated in air at 1000 ° C. for 2 hours to reduce the strength. .
  • the heat-resistant fiber of the present invention is suitably an inorganic or organic fiber.
  • the inorganic fibers include silicon fibers mainly composed of silicon, silicon carbide fibers, and alumina fibers. More preferably, the silicon carbide fiber may contain components such as Ti, Zr and / or A1 in order to improve alkali resistance. These components are suitably contained in an amount of 0.1 to 2% by mass based on the entire fiber.
  • Such fibers include silicon carbide fibers, two-calon fibers (Si—O—C composition ratio 57.2: 32.7: 10, manufactured by Nippon Carbon Co., Ltd.), Tyranno Fiber (registered trademark) heat-resistant Darade ZM ( Si—C—O—Zr composition ratio 56: 34: 9: 1), Tyranno Fiber (registered trademark) heat-resistant grade S (Si-OC-Ti composition ratio 50: 30: 18: 2) Tyranno fiber (registered trademark) heat resistant Grade SA (Si-OC-Al composition ratio 67: 31: 1: 2) (Tyranno fiber (registered trademark) is all manufactured by Ube Industries, Ltd.) is preferable.
  • organic fiber carbon fiber is mentioned, for example.
  • the heat-resistant fiber of the present invention may be a combination of two or more of these fibers.
  • the average diameter of the heat-resistant fiber of the present invention is, for example, 3 to 20 ⁇ m, preferably 9 to 14 ⁇ m. If the diameter is 3 ⁇ m or more, it is preferable because the fibers themselves scatter and do not release gas-generating substances into the atmosphere.
  • the fiber length of the heat-resistant fiber of the present invention is, for example, 10 to: LOOmm, preferably 3
  • the tensile strength of the heat resistant fiber of the present invention is, for example, 1 to 5 GPa, preferably 2 to 4 GPa as measured by JIS K-7023.
  • the nonwoven fabric of the present invention is obtained by converting the above heat-resistant fiber into a nonwoven fabric by a known method, for example, a spunbond method, or JP-A 2000-199160 "Method and apparatus for producing inorganic short fiber felt". It can be.
  • the thickness of the nonwoven fabric of the present invention is, for example, 0.3 to LOmm, preferably 0.5 to 5 mm, more preferably 1 to 3 mm.
  • the basis weight of the nonwoven fabric of the present invention is, for example, 50 to: LOOOgZm 2 , preferably 100 to 500 g, more preferably 150 to 400 gZm 2 .
  • the strength density of the nonwoven fabric of the present invention is, for example, 0.05-: L Og / cm 3 , preferably 0.1-0.8 gZcm 3 , more preferably 0.2-0.6 gZcm 3 . Is appropriate. If the force density is 0.2 gZcm 3 or more, the PM collection performance can be sufficiently maintained, and if it is 1. OgZcm 3 or less, the exhaust gas using the diesel particulate filter of the present invention is used. This is preferable because the exhaust gas pressure of the water purification apparatus can be kept low.
  • the perovskite complex oxide is represented by a basic composition ABO,
  • A contains a metal ion having a large ion radius, such as a rare earth metal or an alkaline earth metal
  • B contains a transition metal ion.
  • the perovskite complex oxide catalyst of the present invention contains at least two elements selected from K, Ni, Sr, Co, La, Cu, V, Mn, Fe, Cs, Ba, Ce, Li and Pd.
  • the velovskite complex oxide catalyst of the present invention has the following formula (I):
  • A, B and C may be the same or different from each other.
  • a preferred perovskite type complex oxide catalyst of the present invention contains at least two elements selected from La, K, Co, Sr and Mn.
  • A is La
  • B is selected from K
  • Sr Li or Cs
  • C is selected from Co or Mn
  • Q 0. 1 to 0.3
  • p + q 1, and r is 1.
  • More preferred perovskite complex oxide catalysts of the present invention are La K CoO, La Sr
  • the perovskite complex oxide catalyst of the present invention is a particle having an average particle diameter of 0.1 to: L00 nm, preferably 0.5 to 50 nm, more preferably 1 to 20 nm.
  • L00 nm average particle diameter of 0.1 to: L00 nm, preferably 0.5 to 50 nm, more preferably 1 to 20 nm.
  • catalyst particles of about m When using catalyst particles of about m, it is necessary to sinter at 1000 ° C for 2 hours, but when using a catalyst with a small particle size as in the present invention, 400-800 If it is sintered at about ° C for 2 hours, it can be supported with sufficient strength.
  • the heat-resistant fiber surface can be completely and uniformly coated with a small amount of support.
  • the contact between the catalyst and the heat-resistant fiber surface can be kept stronger.
  • the specific surface area of the perovskite-type composite oxide catalyst of the present invention measured by the BET method is 10 m 2 m 2 / g or more, more preferably 30 m 2 / g or more, and still more preferably 50 m 2 / g. As described above, for example, 50-: L00m 2 / g is appropriate.
  • the perovskite type composite of the present invention The specific surface area of the acid oxide catalyst is measured by the BET method according to JIS R1626.
  • the diesel particulate filter of the present invention comprises a nonwoven fabric composed of the above-mentioned heat-resistant fiber, preferably a heat-resistant conductive fiber, and particles of the above-mentioned belobskite complex oxide catalyst supported on the fiber surface of this nonwoven fabric. .
  • the particles of the velovskite type complex oxide catalyst are contained in an amount of, for example, 0.120% by mass, preferably 0.55% by mass, with respect to the mass of the nonwoven fabric made of heat-resistant fibers.
  • the particles of the perovskite complex oxide catalyst are uniformly supported on the surface of the heat-resistant fiber of the nonwoven fabric without gaps. It is preferable that the surface of the non-woven heat-resistant fiber is substantially coated with particles of the perovskite complex oxide catalyst.
  • the layer of the particles of the open-bumskite complex oxide catalyst supported on the heat-resistant fiber surface is at least one layer, more preferably two or more layers.
  • the particle size of the particles of the velovskite complex oxide catalyst of the present invention supported on the heat-resistant fiber surface is the same as that before the support, for example, 0.1 to: LOOnm, preferably 0.5 50 nm More preferably, l is 20 nm.
  • the layer thickness of the particles of the perovskite complex oxide catalyst of the present invention is, for example, 0.1 1 00, preferably 50 nm, more preferably 20 50 nm.
  • the diesel particulate filter of the present invention is produced by preparing a perovskite-type composite oxide catalyst having a specific particle size, and supporting this bottom-bskite-type composite oxide catalyst on the surface of a heat resistant fiber of a nonwoven fabric. Is done.
  • the velovskite type complex oxide catalyst of the present invention may be produced by any known method, but is suitably produced by the ethylene glycol method shown below. Specifically, first, K ⁇ Ni ⁇ Sr ⁇ Co, La ⁇ Cu ⁇ V, Mn, Fe ⁇ Cs ⁇ Ba ⁇ Ce ⁇ Li ⁇ Pd and other formulas (I): Salts of elements constituting A, B and C of ABCO, preferably Nitrates,
  • P qr 3 Prepare sulfate or hydrochloride.
  • the salt is weighed and dissolved in a solvent such as alkylene glycol, such as ethylene glycol, propylene glycol, or preferably ethylene glycol, at room temperature so that the salt concentration is 1M.
  • a solvent such as alkylene glycol, such as ethylene glycol, propylene glycol, or preferably ethylene glycol, at room temperature so that the salt concentration is 1M.
  • a solvent such as alkylene glycol, such as ethylene glycol, propylene glycol, or preferably ethylene glycol
  • the obtained solution is transferred to a baking container, and it is 0.1 to 10 per minute from normal temperature under normal pressure. C, preferably at a rate of 0.5 to 5 ° C per minute and heated to 100 to 200 ° C, preferably 200 ° C, to completely remove the solvent. Thereafter, the temperature is further increased to 400 ° C to 800 ° C, preferably 600 ° C at a rate of 5 to 30 ° C per minute, preferably 10 to 20 ° C per minute. While maintaining, for example, the residue is calcined for 1 to 10 hours, preferably about 5 hours, to fix the perovskite structure of the catalyst.
  • oxygen or air is introduced into the firing container at a flow rate of 0.5 liter Z minutes or more, preferably 1 liter Z minutes or more. Do it while sending.
  • the obtained fired product is cooled to room temperature and then pulverized to obtain particles of a perovskite complex oxide catalyst having a target particle size.
  • the pulverization is performed using a mortar, for example, if it is 50 g of catalyst particles, 20 minutes, and crushing for a total of 1 to 6 hours, preferably about 4 hours.
  • the diesel particulate filter of the present invention can be manufactured, for example, according to the following steps.
  • the particles of the perovskite complex oxide catalyst of the present invention are suspended in an alcoholic aqueous solution.
  • the alcoholic aqueous solution contains alcohol and water which are liquid at room temperature (25 ° C).
  • the alcohol include alcohols having 1 to 3 carbon atoms such as methanol, ethanol, n-propanol, and isopropanol. Ethanol is preferable.
  • Alcohol is contained, for example, 85 to 99%, preferably 92 to 97%, based on the total volume of the alcoholic aqueous solution.
  • ion-exchanged water can be used as the water.
  • water is contained, for example, in an amount of 1 to 15%, preferably 3 to 8%, based on the total volume of the alcoholic aqueous solution.
  • the alcoholic aqueous solution may contain a ionic surfactant that dissolves in alcohol as a dispersant.
  • the dispersant may be contained in an amount of 0.2 to 0.6% by mass, preferably 0.4 to 0.5% by mass, based on the mass of the velovskite complex oxide catalyst of the present invention.
  • the suspension suitably contains, for example, 5 to 50 g, preferably 10 to 30 g of the perovskite complex oxide catalyst particles of the present invention in 1 liter of an alcoholic aqueous solution.
  • (2-2-2) A step in which the nonwoven fabric is used as a negative electrode, a potential difference is applied between the positive electrode and the negative electrode in the suspension, and the catalyst particles are adhered on the heat-resistant conductive fiber surface of the nonwoven fabric of the present invention.
  • a potential difference is applied to the suspension, and the catalyst particles of the present invention are adhered to the surface of the heat-resistant conductive fibers of the nonwoven fabric of the present invention using so-called electrophoresis.
  • particles of the perovskite complex oxide catalyst of the present invention are dispersed. Around these particles, hydrogen ions separated by hydraulic force are attached and are positively charged in the suspension. Therefore, by applying a potential difference between the positive electrode and the negative electrode in the suspension using the nonwoven fabric as the negative electrode, the positively charged catalyst particles gather on the surface of the heat-resistant fiber of the nonwoven fabric, which is the negative electrode, and adhere by electrostatic energy.
  • the positive electrode for example, a carbon electrode or CZC (carbon composite) can be used.
  • a non-woven fabric of the present invention preferably a metal mesh sandwiching the non-woven fabric of the present invention, for example, a stainless steel mesh (pore diameter 0.5 to 5 mm, preferably 1 to 3 mm, opening 5 to 50 mm, preferably 10 ⁇ 30mm).
  • a potential difference is applied between the positive electrode and the negative electrode.
  • the potential difference is, for example, voltage: 50 to 200V, preferably ⁇ 100 to 150V, current: 100 to 2000 mA, preferably 200 to 1000 mA, more preferably 200 to 800 mA, 5 to 30 minutes, preferably 5 Give ⁇ 20 minutes.
  • the nonwoven fabric of the present invention in which the catalyst particles adhere to the surface of the heat-resistant conductive fiber is taken out of the suspension after the electrophoresis. Thereafter, the aqueous alcoholic solution is naturally dried at room temperature, for example, for 1 to 10 hours, preferably for about 5 hours, and the suspension is also removed. Further, the nonwoven fabric is sintered to carry the catalyst particles on the surface of the heat-resistant conductive fiber. Sintering uses, for example, an electric furnace or the like, for example, 400 to 1000 ° C, preferably 600 to 900 ° C, more preferably 800 ° C for 1 to 5 hours, preferably 1.5 to 3 For 2 hours, more preferably 2 hours.
  • the catalyst particles supported on the heat-resistant conductive fiber surface in this way have no change in the size or structure of the particles before and after the support.
  • the diesel particulate filter of the present invention is used in a purification apparatus for diesel engine exhaust gas.
  • a diesel engine exhaust gas purifier is attached to the rear of the diesel engine combustion chamber and in front of the exhaust port for releasing the exhaust gas into the atmosphere.
  • a diesel engine exhaust gas purification apparatus includes the diesel particulate filter of the present invention.
  • the exhaust gas is introduced into the purification device, passes through a diesel particulate filter in the purification device, and then released to the outside of the purification device.
  • particulate matter (PM) and nitrogen oxides (NOx) contained in the exhaust gas are trapped and put into the gaps (holes) of the heat-resistant fibers contained in the diesel particulate filter. accumulate.
  • the deposited particulate matter (PM) and nitrogen oxides (NOx) react on the bottom bskite-type complex oxide catalyst supported on the surface of the heat-resistant fiber and react with carbon C, which is the main component of PM.
  • NOx O undergoes oxidation reaction to become CO, and at the same time NO
  • NOx may be decomposed due to the fact that the reaction formula of the actual reaction is more complicated.
  • the velovskite complex oxide catalyst of the present invention works well. In other words, under excessive NOx, ionic conductivity is improved at high temperatures, the catalytic reduction action is activated, and nitrogen oxides NOx are decomposed well. On the other hand, even under excessive C, the perovskite-type composite oxide catalyst of the present invention can efficiently oxidize C due to the activity of the catalytic reaction between NOx and C, which has high low-temperature activity. Can do.
  • the diesel particulate filter in the purification apparatus for diesel engine exhaust gas of the present invention has one layer or two layers of a non-woven fabric of heat-resistant fiber carrying the velovskite type composite oxide catalyst of the present invention. It may be a laminate of more than one layer.
  • a non-woven fabric of heat-resistant fiber carrying the velovskite type composite oxide catalyst of the present invention may be a laminate of more than one layer.
  • PM particulate matter
  • a three-layer structure provided with the following nonwoven fabric layer is appropriate.
  • the thickness of the nonwoven fabric laminate is, for example, 5 to 50 mm, and preferably 10 to 30 mm. is there.
  • the diesel particulate filter in the diesel engine exhaust gas purification apparatus of the present invention comprises a non-woven fabric made of a heat-resistant fiber carrying the bevelskite-type composite oxide catalyst of the present invention.
  • the laminate may be sandwiched between a sheet of heat-resistant metal plates and the resulting laminate may be bent into a bellows shape.
  • the contact area of the exhaust gas can be increased, pressure loss when particulate matter (PM) remains on the nonwoven fabric can be prevented, and the purification equipment can be made compact. it can.
  • examples of the heat-resistant metal plate include stainless steel (such as SUS301 and SUS304).
  • the thickness of the heat-resistant metal plate is, for example, 1 to 8 mm, preferably 2 to 5 mm.
  • the diesel engine exhaust gas purification device of the present invention is a diesel particulate filter heating device for preventing clogging of the diesel particulate filter due to particulate matter (PM) remaining on the nonwoven fabric. May be included.
  • Heating temperature is below the heat resistant temperature of the heat resistant fiber or catalyst used, for example, when using silicon carbide fiber or when using a perovskite complex oxide catalyst containing Mn as the catalyst, 800 ° C or less, More preferably, the temperature is set to 600 ° C or lower.
  • a microwave irradiation device is preferable. The microwave irradiation device can raise the temperature of the nonwoven fabric in a short time and is easy to control the temperature. When using the microwave irradiation apparatus, it is necessary to use silicon carbide fiber or silicon fiber, which is a microwave absorber, as the heat-resistant fiber of the present invention.
  • catalyst particles are used for X-ray analysis and confirmed to have a perovskite structure with a composition ratio of La Sr CoO.
  • the average particle size of the obtained catalyst particles was about 10 nm as measured with a scanning electron microscope.
  • the specific surface area was measured by the BET method according to JIS R1626 and found to be 50 m 2 / g.
  • a non-woven fabric made of silicon carbide fiber (Tyranno Fiber (registered trademark) heat-resistant grade ZM (Si-CO-Zr composition ratio 56: 34: 9: 1))) (Tosco Ceramic manufactured by Tosco Corporation) Fiber felt) (length x width x thickness: 290 x 210 x I. 57 mm) sandwiched between stainless steel wire meshes with a hole diameter of 2 mm and openings of 20 mm was used.
  • the silicon carbide fiber used has a fiber diameter of 10 / ⁇ ⁇ , a fiber length of 40 mm, a tensile strength of 3.4 GPa (measured in accordance with JIS K-7023), and the nonwoven fabric has a basis weight of 380 g / m 2 and a strength. It has a density of 0.24 g / cm 3 .
  • two carbon plates (length X width X thickness: 300 X 240 X 5 mm) were used as the positive electrode. These positive electrodes were placed above and below the negative electrode so as to be parallel to the negative electrode with an interval of 15 mm.
  • a DC voltage of 100 V and 800 mA was applied to the positive electrode and the negative electrode for 15 minutes, and particles of the velovskite complex oxide catalyst were supported on the silicon carbide fiber. Thereafter, the nonwoven fabric was taken out of the suspension, naturally dried at room temperature for 5 hours, and then sintered at 800 ° C. for 2 hours. Gain On the resulting non-woven silicon carbide fiber, 1.0% by mass of catalyst particles was supported with respect to the total mass of the non-woven fabric and the catalyst particles.
  • the supported catalyst particles are perovskite type complex oxides having a composition of La Sr CoO by X-ray analysis.
  • the particles of the velovskite complex oxide catalyst of the present invention have a multilayer structure, and the thickness of the layer was about 50 nm as measured by a scanning electron microscope.
  • Example 1 and Comparative Example 1 were evaluated for their ability to decompose particulate matter (PM) and nitrogen oxides (NOx).
  • the evaluation was conducted by preparing a test gas simulating the exhaust gas emitted from the diesel engine and passing this test gas to the purification equipment filled with the diesel particulate filter obtained in Example 1 and Comparative Example 1.
  • the gas components that passed through the filter were analyzed by gas chromatography.
  • a test gas a gas having a composition of 5% 0 -0.5% NO-He was used.
  • purification purification
  • the equipment used was a stainless steel SUS304 cylindrical reaction tube with an inner diameter of 15 mm and a height of 300 mm, with an exhaust gas inlet and outlet on the upper and lower surfaces.
  • This reaction tube three diesel particulate filters having a diameter of 15 mm and a thickness of 1.57 mm were stacked and filled, and the exhaust gas was set to pass through the three diesel particulate filters.
  • the diesel particulate filter used was carbon black (Tokai Black # 8500 grade 14nm (particle size 14nm) manufactured by Tokai Carbon Co., Ltd.) in order to reproduce the state where particulate matter (PM) was collected by the filter. , 6% by mass was used with respect to the mass of the diesel particulate filter used.
  • test gas was passed through a purification apparatus at a flow rate of 40 mlZ, and then generated CO, CO, and N N O were analyzed at 15 minute intervals with a gas chromatograph (manufactured by Shimadzu Corporation). Examination
  • test gas temperature (temperature outside the reaction tube) was increased from 200 ° C to 700 ° C at 1 ° C / min.
  • NO nitrogen oxides
  • Example 1 The test result of Example 1 is shown in Graph 1, and the test result of Comparative Example 1 is shown in Graph 2.
  • Example 1 As shown in graphs 1 and 2, the concentration of CO and CO in the test gas was determined in Example 1. Indicates a higher concentration than Comparative Example 1. Further, although not shown in the graph, in Example 1, CO is not generated (Oppm) —in the comparative example, CO is generated in each temperature region (for example, 485. 290 ppm at C, 500. 375ppm for C, 515. 298ppm for C). Therefore, it can be seen that the diesel particulate filter of Example 1 has a high particulate matter (PM) decomposition capacity, and that the treated carbon C becomes completely CO and can be released into the atmosphere.
  • PM particulate matter
  • Example 1 has a higher concentration than that of Comparative Example 1.
  • the temperature at which N and N O start to be generated is 365 ° C in Example 1.
  • Comparative Example 1 is around 410 ° C. Therefore, the diesel particulate filter of Example 1 has a high ability to decompose nitrogen oxides (NOx) and can effectively remove nitrogen oxides (NOx) even when the sample gas is at a relatively low temperature. It can be seen that it can be decomposed.
  • FIG. 1 is a scanning electron micrograph on the surface of silicon carbide fiber of the diesel particulate filter obtained in Example 1.
  • FIG. 2 is a scanning electron micrograph on the surface of silicon carbide fiber of the diesel particulate filter obtained in Comparative Example 1.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Combustion & Propulsion (AREA)
  • Ceramic Engineering (AREA)
  • Biomedical Technology (AREA)
  • Inorganic Chemistry (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Catalysts (AREA)
  • Processes For Solid Components From Exhaust (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)
  • Filtering Materials (AREA)
  • Exhaust Gas After Treatment (AREA)

Abstract

L'invention concerne un filtre à particules diesel capable d'éliminer la matière particulaire (PM) qui est émise par un gaz d'échappement de moteur diesel et constitue une cause de pollution de l'air et de pollution due à la poussière, en particulier avec de la matière particulaire (PM) contenue dans le gaz d'échappement de moteur diesel avec le NOx retiré de manière satisfaisante. Plus particulièrement, le filtre est capable d'éliminer simultanément la matière particulaire en suspension (SPM) de faible diamètre de particule et les oxydes d'azote (NOx). Il est prévu un filtre à particules diesel ayant un tissu non tissé en fibre thermostable et, porté à la surface de la fibre thermostable, un catalyseur d'oxyde de composite de pérovskite, caractérisé en ce que le catalyseur d'oxyde de composite consiste en des particules de 0,1 à 100 nm de diamètre moyen.
PCT/JP2005/014739 2005-06-06 2005-08-11 Filtre a particules diesel et purificateur utilisant celui-ci WO2006131995A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005-165580 2005-06-06
JP2005165580A JP4918230B2 (ja) 2005-06-06 2005-06-06 ディーゼルパーティキュレートフィルタ及びこれを用いた浄化装置

Publications (1)

Publication Number Publication Date
WO2006131995A1 true WO2006131995A1 (fr) 2006-12-14

Family

ID=37498206

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2005/014739 WO2006131995A1 (fr) 2005-06-06 2005-08-11 Filtre a particules diesel et purificateur utilisant celui-ci

Country Status (2)

Country Link
JP (1) JP4918230B2 (fr)
WO (1) WO2006131995A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009154086A (ja) * 2007-12-26 2009-07-16 Honda Motor Co Ltd 排ガス浄化触媒

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007021409A (ja) * 2005-07-19 2007-02-01 Chokoon Zairyo Kenkyusho:Kk ディーゼルパティキュレートフィルターの製造方法
JP2008168228A (ja) * 2007-01-12 2008-07-24 Okayama Univ 未燃カーボンを用いてディーゼルエンジン排ガス中の窒素酸化物を浄化するための触媒と方法
FR2942624B1 (fr) * 2009-03-02 2011-03-18 Rhodia Operations Composition comprenant une perovskite a base de lanthane sur un support en alumine ou en oxyhydroxyde d'aluminium, procede de preparation et utilisation en catalyse
CN102989448A (zh) * 2012-12-18 2013-03-27 天津大学 一种镧锰钙钛矿型脱NOx催化剂的制备方法及应用

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002357120A (ja) * 2001-05-30 2002-12-13 Isuzu Motors Ltd 排気ガス浄化装置
JP2003164760A (ja) * 2001-11-29 2003-06-10 Denso Corp セラミック触媒体
JP2003239722A (ja) * 2002-02-13 2003-08-27 Ube Ind Ltd ディーゼルパティキュレートフィルター
JP2005030279A (ja) * 2003-07-10 2005-02-03 Isuzu Motors Ltd フィルタ

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2002357120A (ja) * 2001-05-30 2002-12-13 Isuzu Motors Ltd 排気ガス浄化装置
JP2003164760A (ja) * 2001-11-29 2003-06-10 Denso Corp セラミック触媒体
JP2003239722A (ja) * 2002-02-13 2003-08-27 Ube Ind Ltd ディーゼルパティキュレートフィルター
JP2005030279A (ja) * 2003-07-10 2005-02-03 Isuzu Motors Ltd フィルタ

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2009154086A (ja) * 2007-12-26 2009-07-16 Honda Motor Co Ltd 排ガス浄化触媒

Also Published As

Publication number Publication date
JP4918230B2 (ja) 2012-04-18
JP2008212759A (ja) 2008-09-18

Similar Documents

Publication Publication Date Title
CN107876043B (zh) 一种用于烟气净化的陶瓷催化滤芯及烟气一体化脱硫脱硝除尘方法
EP1437491B1 (fr) Filtre catalyseur pour la purification de gaz d'échappement
EP1918046B1 (fr) Materiau composite, substrat d'un materiau composite, liquide de dispersion d'un materiau composite, et leurs procedes de fabrication
JP5519181B2 (ja) 内燃機関の排気浄化装置
WO2007010643A1 (fr) Structure en nid d’abeille et appareil nettoyant un gaz d’échapement
WO2006025283A1 (fr) Circuit d’épuration de gaz d’échappement
JP2005296935A (ja) 排ガスフィルタおよびその製造方法、並びに、排ガス処理装置
JP2007209913A (ja) 触媒材およびその製造方法並びにディーゼルパティキュレートフィルタ
US20090263303A1 (en) Purification Device and Method for Purifying a Fluid Stream
EP2221104B1 (fr) Catalyseur de purification
JP2007253144A (ja) ハニカム構造体及び排ガス浄化装置
JP2004330118A (ja) 排ガス浄化用フィルタ
WO2006131995A1 (fr) Filtre a particules diesel et purificateur utilisant celui-ci
CN114867546A (zh) 用于捕获颗粒物的催化剂制品
CN105597517B (zh) 清除烟雾烟味的装置及其应用
JP2003080031A (ja) フィルタ要素及び排ガス浄化用フィルタ
Nie et al. Electricity-driven rapid regeneration of ceramic paper-based soot filters with conductive potassium-supported antimony-doped tin oxide catalyst
CN103861612A (zh) 一种用于柴油机尾气碳烟捕集催化的催化剂
KR20060127863A (ko) 디젤 엔진 배기 가스용 필터 및 장치
JP2009072693A (ja) 多孔質触媒を含むディーゼルパティキュレートフィルタ
JP6627813B2 (ja) 触媒付きパティキュレートフィルタの製造方法
JP6194699B2 (ja) 触媒付パティキュレートフィルタの製造方法
JP2018119467A (ja) 排ガス浄化装置
JP4431528B2 (ja) ディーゼルパティキュレートフィルタの製造方法
JP5880160B2 (ja) 触媒付パティキュレートフィルタ

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
NENP Non-entry into the national phase

Ref country code: DE

WWW Wipo information: withdrawn in national office

Country of ref document: DE

122 Ep: pct application non-entry in european phase

Ref document number: 05770821

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: JP

点击 这是indexloc提供的php浏览器服务，不要输入任何密码和下载