WO2009137110A1 - Traitement de l'échappement d'un moteur à combustion interne en utilisant des matériaux en fibres de céramique immobilisées - Google Patents

Traitement de l'échappement d'un moteur à combustion interne en utilisant des matériaux en fibres de céramique immobilisées Download PDF

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WO2009137110A1
WO2009137110A1 PCT/US2009/002898 US2009002898W WO2009137110A1 WO 2009137110 A1 WO2009137110 A1 WO 2009137110A1 US 2009002898 W US2009002898 W US 2009002898W WO 2009137110 A1 WO2009137110 A1 WO 2009137110A1
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ceramic
internal combustion
treatment
combustion engines
exhaust emissions
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Gary Lee Carson
John Murray Finley
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    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/033—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices
    • F01N3/035—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters in combination with other devices with catalytic reactors
    • 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
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/86—Catalytic processes
    • B01D53/88—Handling or mounting catalysts
    • 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
    • B01D53/9445—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC]
    • B01D53/9454—Simultaneously removing carbon monoxide, hydrocarbons or nitrogen oxides making use of three-way catalysts [TWC] or four-way-catalysts [FWC] characterised by a specific device
    • 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
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/02—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust
    • F01N3/021—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters
    • F01N3/022—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous
    • F01N3/0226—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for cooling, or for removing solid constituents of, exhaust by means of filters characterised by specially adapted filtering structure, e.g. honeycomb, mesh or fibrous the structure being fibrous
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N3/00—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust
    • F01N3/08—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous
    • F01N3/10—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust
    • F01N3/24—Exhaust or silencing apparatus having means for purifying, rendering innocuous, or otherwise treating exhaust for rendering innocuous by thermal or catalytic conversion of noxious components of exhaust characterised by constructional aspects of converting apparatus
    • F01N3/28—Construction of catalytic reactors
    • F01N3/2803—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support
    • F01N3/2835—Construction of catalytic reactors characterised by structure, by material or by manufacturing of catalyst support fibrous
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/206—Rare earth metals
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/207—Transition metals
    • B01D2255/20707—Titanium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/20—Metals or compounds thereof
    • B01D2255/209—Other metals
    • B01D2255/2092—Aluminium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2255/00—Catalysts
    • B01D2255/40—Mixed oxides
    • B01D2255/407—Zr-Ce mixed oxides
    • 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
    • B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional [3D] monoliths
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01N—GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR MACHINES OR ENGINES IN GENERAL; GAS-FLOW SILENCERS OR EXHAUST APPARATUS FOR INTERNAL-COMBUSTION ENGINES
    • F01N2330/00—Structure of catalyst support or particle filter
    • F01N2330/10—Fibrous material, e.g. mineral or metallic wool
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02T—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO TRANSPORTATION
    • Y02T10/00—Road transport of goods or passengers
    • Y02T10/10—Internal combustion engine [ICE] based vehicles
    • Y02T10/12—Improving ICE efficiencies

Definitions

  • the invention described herein relates to catalytic systems for the treatment of gaseous and particulate components from internal combustion engine exhaust to destroy nitrogen oxides (NO x ) , sulfur oxides (So x ) and carbon monoxide (CO) gaseous components and the capture and oxidation of soot particles and other hydrocarbon (HC) constituents, methane and non-methane hydrocarbon materials.
  • NO x nitrogen oxides
  • So x sulfur oxides
  • CO carbon monoxide
  • Heterogeneous catalyst materials and mediums thereof are commonly used in the post-treatment of effluent gases from combustion processes. These catalyst materials convert toxic combustion by-products including gaseous and particulate pollutants into less-toxic substances.
  • catalytic devices have been constructed from ceramic substrates or stainless steel foils in the shape of a solid monolithic structure, for example a "honeycomb" structure. For the past two decades, these materials have been optimized for use in the automotive and large engine (including diesel engines) market sectors.
  • conventional catalytic devices have not been extensively developed to include nor have they been readily accessible for small engine applications due to technical limitations, size issues, weight constraints, and additional performance requirements dictated by these engine types.
  • Multi- layered wash coatings are used to promote separate, different catalytic reactions within the wash coat.
  • the top layer may catalyze CO and hydrocarbons in the presence of oxygen, while a bottom layer - with respect to gas flow - may be designed for NO x reduction which is favorable in the absence of oxygen.
  • a significant limitation of current catalytic mediums is that at high operational temperatures, i.e. greater than approximately 1,110 0 F (600 0 C), the catalyst particles within the "wash coat" tend to agglomerate into larger particles therein decreasing the available catalyst surface area available for pollutant conversion.
  • An additional change that decreases catalytic performance is a decrease in porosity of the wash-coat structure which limits gas and contaminant flow to the catalyst materials and possible degradation of the support structure - mainly a concern for cordierite materials that have a fusion temperature around at 1,500 0 F (820 0 C) .
  • the principal feature of the present invention is the use of immobilized ceramic fibers such as ceramic nanofibers and/or ceramic microfibers, with and without embedded metal catalyst particles, or catalytic coatings for use in the treatment of gaseous exhaust from internal combustion engines.
  • gaseous exhausts include those emitted from non-road and on-road, spark-ignition 2-cycle and 4-cycle engines, non-spark ignition engines, and handheld (HH) and non-handheld (NHH) engines.
  • the present invention there is an arrangement integrating either self-supported or secondary supported, ceramic, metallic, or composite media utilizing ceramic nanofibers, ceramic microfibers, or a combination of ceramic nanofibers and microfibers, with and without embedded catalyst materials, or catalytic coatings that can be incorporated into a new catalyst/filter muffler combinations or retrofitted into existing, conventional internal combustion engine designs for the removal of hydrocarbon (HC) materials, particulate material (PM) , nitrogen oxides (NO x ) , sulfur oxides (SO x ) , and carbon monoxide (CO) from engine exhaust sources.
  • hydrocarbon hydrocarbon
  • PM particulate material
  • NO x nitrogen oxides
  • SO x sulfur oxides
  • CO carbon monoxide
  • a further embodiment of the present invention is a system utilizing ceramic nanofiber/microfiber composites, metallic forms and supports, extruded and formed ceramic materials, or a combination of materials for particulate material (PM) removal and/or oxidation, for the capture, or removal, or catalytic destruction of particulate material
  • PM particulate material
  • Another feature of the present invention is catalyzed ceramic nanofibers, utilizing a blend of ceramic nanofibers having dispersed metallic catalytic materials partially exposed and/or embedded within a ceramic nanofiber structure covering from 1% to 90% of the ceramic nanofiber external and internal surface area, immobilized on ceramic, metallic, or ceramic/metallic composite structures with various configurations including, but not limited to, extruded materials, fibrous materials, and foil/plate-like material structures.
  • ceramic nanofibers and/or ceramic microfibers with and without catalytic materials can be immobilized by attachment to an inert support structure with or without intermediate conditioning layers and immobilized by attachment and entrainment within a porous or non-porous, fibrous structure.
  • the support structure can be either permeable of non-permeable depending on the application.
  • FIG. IA and FIG. IB illustrate two distinct composite structures.
  • the structure shown in Fig. IA is produced by integrating ceramic nanofibers including the utilization of a ceramic fiber coating placed on the surface of an inert support structure produced from ceramic, metallic or a combination of ceramic/metallic materials, whereas the structure shown in ' FIG. IB includes the formation of a ceramic nanofiber/microfiber matrix. Both structures provide a mechanism of ceramic fiber immobilization.
  • the ceramic fiber material can be catalyzed with various catalyst substances.
  • FIG. 2A and FIG. 2B illustrate two application strategies of ceramic nanofiber/microfiber composite materials for PM and HC removal/oxidation at one level and a single layer of catalyzed ceramic nanofiber/microfiber composites with mixed catalyst composite material at a second level as shown in FIG. 2A and multiple individual catalyst layers of catalyzed ceramic nanofiber/microfiber composite materials used in sequence as shown in FIG. 2B to enhance oxidation of HC, reduction of NO x and SO x , and destruction of CO.
  • FIG. 3A and FIG. 3B illustrate two possible configurations for immobilizing ceramic nanofibers and ceramic microfibers, alone or in combination, on a non- permeable or permeable support structure constructed from ceramic, metallic, or a combination of ceramic/metallic composite materials. Gas flows over the non-permeable coated support structure in FIG.3A while gas can flow through the permeable support structure in FIG. 3B.
  • FIG. 4A and FIG. 4B illustrate rigid support structures for the immobilization of ceramic nanofibers and ceramic microfibers.
  • Rigid support structures can include innovative ceramic structures that provide unique channel geometries to traditional extruded, monolithic ceramic, metallic, or a combination of ceramic/metallic materials with multiple channel configurations including square, round, hexagonal, and trapezoidal openings.
  • Exposed surfaces within the support structure can be coated with ceramic nanofibers, ceramic microfibers and ceramic nanofiber/microfiber combinations and multiple layers for particulate removal and chemical reactions, primarily catalytic reactions involving gaseous constituents.
  • FIG. 5 illustrates a fibrous support structure for the immobilization of ceramic nanofbers wherein different mass ratios of ceramic nanofibers and ceramic microfibers can be utilized to enhance particulate removal performance or catalytic performance.
  • FIG. 6 illustrates a catalyst delivery system using ceramic nanofiber/microfiber composite material for PM and HC removal/oxidation and a mixed catalyzed ceramic nanofiber/microfiber composite for oxidation of HC, reduction of NO x and SO x , and destruction of CO.
  • FIG. 7 illustrates another catalyst delivery system using ceramic nanofiber/microfiber composite material for PM and HC removal/oxidation and a mixed catalyzed ceramic nanofiber/microfiber composite for oxidation of HC, reduction of NO x and SO x , and destruction of CO.
  • ceramic nanofibers, ceramic microfibers, or a combination of ceramic nanofibers and microfibers, with or without embedded catalyst particles, or catalyst coatings are immobilized on permeable or non-permeable ceramic, metallic, or ceramic metallic composite structures for use in the treatment of gaseous exhaust emissions from internal combustion engines defined to include non-road and on-road, spark-ignition 2-cycle and 4-cycle engines, non-spark ignition engines, and handheld (HH) and non-handheld (NHH) engines .
  • a ceramic nanofiber and/or ceramic microfiber matrix 2 is formed on a permeable or non- permeable layer support structure 4, of ceramic, metallic, or ceramic/ metallic composite material whereas, in FIG. IB, a permeable ceramic nanofiber/microfiber matrix 6, is formed.
  • FIG. 2A and FIG. 2B two different application strategies can be employed.
  • the direction of gas flow emissions is indicated by the arrow 7 in the support structure of FIG. 2A.
  • a ceramic nanofiber/microfiber composite matrix is employed for the removal of particulate materials (PM) and hydrocarbon (HC) removal/oxidation and in the second level 10 of support structure of FIG. 2A a single layer of catalyzed ceramic nanofiber/microfiber composite matrix with multiple catalysts is employed to enhance oxidation of HC, reduction of NO x and SO x , and destruction of CO.
  • multiple individual catalyst layers, 12.14. and 16 are employed as a substitute for the single layer in the second level 10 to enhance oxidation of HC, reduction of NO x and SO x , and destruction of CO.
  • FIG. 3A and FIG. 3B illustrate two configurations for immobilizing ceramic nanofibers and ceramic microfibers 18, alone or in combination, on a non-permeable support structure 20 or a permeable support structure 22, each constructed from ceramic, metallic, or a combination of ceramic/metallic composite materials.
  • a non-permeable support structure 20 or a permeable support structure 22 each constructed from ceramic, metallic, or a combination of ceramic/metallic composite materials.
  • Gas emissions flow over the non-permeable coated support structure 20
  • gas emissions can flow through the permeable support structure 22.
  • Ceramic nanofibers, ceramic microfibers, and * various combinations of ceramic nanofibers with ceramic microfibers in a composite matrix can be applied either directly to the support structure or by the use of an intermediate layer to enhance bonding between the support structure and the fibrous materials.
  • Inert structures are desirably used that promote and allow the flow of gases and particulates through a series of channels or voids in which ceramic nanofibers, ceramic microfibers, or a combination of ceramic nanofibers/microfibers with or without embedded catalyst materials, or catalyst coatings can be immobilized.
  • Specific examples of inert, rigid structures comprised of ceramic, metallic, or ceramic/metallic composite materials include multi-channel support structures in single or multiple layers (corrugated configurations) as shown in FIG. 4A with exhaust gas flow direction indicated by the arrows 25, and traditional "honeycomb" monolithic configurations structures of various sizes as illustrated in FIG. 4B with the direction of exhaust gas flow indicated by the arrows 29.
  • FIG.5 A specific example of a random oriented fibrous support structure 24 utilizing ceramic microfibers 26 as a ceramic nanofiber 28 support matrix is illustrated in FIG.5.
  • FIGS 1, 2, 3, 4, and 5 of the present application relate to various methods of utilizing ceramic nanofiber/microfiber structures and coatings, and illustrate support configurations for immobilizing ceramic fibrous materials.
  • Inert support structures can be made out of various materials.
  • Ceramic materials include all metal oxide structures, desirably from aluminum oxide (Al 2 O 3 ) , ceria oxide (CeO 2 ) , ceria/zirconia oxide (Ce/ZrO 2 ) , tin oxide (SnO 2 ) , titanium oxide (TiO 2 ) , and zinc oxide (ZnO 2 ) , and preferably from high-temperature, thermally stable structural polymorphs of aluminum oxide, ceria oxide, zirconia oxide, and mixed ceria/zirconia oxide materials.
  • Metallic support structures can include various grades of stainless steel or carbon steel. Coatings on the stainless steel or carbon steel support structures can include, but are not limited to, ceramic and or/intermediate conditioning layers.
  • Ceramic nanofibers and ceramic microfibers have a metal oxide or mixed metal oxide composition, desirably aluminum oxide (Al 2 O 3 ) , ceria oxide (CeO 2 ) , ceria/zirconia oxide (Ce/ZrO 2 ) , tin oxide (SnO 2 ) , titanium oxide (TiO 2 ) , and zinc oxide (ZnO 2 ) materials, and preferably high-temperature, thermally stable structural polymorphs of aluminum oxide, ceria oxide, zirconia oxide, and mixed ceria/zirconia oxide materials.
  • Catalyst materials include metals from the noble group and also known metals with catalytic properties. Specific examples of catalyst materials incorporated include platinum (Pt), palladium (Pd), rhodium (Rh), and other noble metals.
  • the amount of ceramic nanofibers and ceramic microfibers coated and/or attached to a ceramic, metallic, or ceramic/metallic composite support structure will vary depending on the application and the anticipated conditions during use.
  • the average surface coating will utilize 0.1 to 150 g/m 2 , desirably from 0.5 to 60 g/m 2 , and preferably from 1 to 30 g/m 2 of the mass of ceramic nanofibers, ceramic microfibers, or a combination of ceramic nanofibers/microfibers with or without catalyst particles, or catalyst coating per surface area of support structure where fibers are applied.
  • the ceramic nanofibers described throughout this application can be produced by any suitable method, however, electrospinning methods have been found to be preferable.
  • Examples of catalyzed ceramic nanofibers utilizing aluminum oxide (AI 2 O 3 ) as a ceramic immobilizing structure for various single metal catalyst materials include, palladium (Pd); platinum (Pt), rhodium (Rh), and cerium (Ce) .
  • Each ceramic nanofiber contains nano-size particles of elemental catalysts within and on the surface of each nanofiber where catalyst particles are partially embedded within the nanofiber, therein immobilizing the catalyst particles.
  • the nanofibers have an average diameter of 1 to 500 nm, desirably from about 5 to about 25 to about 250 nanometers, and preferably from about 50 to 100 nanometers while the catalyst particles have an average size of 0.1 to 1,000 nanometers, desirably from about 0.5 to 20, and preferably from about 1 to 15 nanometers
  • TABLE 1 relates to a list of ceramic materials that can be utilized as nanofibers and microfibers within composite materials and a list of the possible catalyst/reactive materials integrated into ceramic nanofibers/microfiber composites supported by permeable or non-permeable rigid or fibrous structures.
  • Ceramic nanofiber materials listed in TABLE 1 can be integrated into various porous composite mediums with varying amounts of nanfibers to dictate the surface area of catalyst or catalysts within the medium, bulk porosity, and particulate removal efficiencies.
  • Composite mediums generally will be made with a combination of ceramic nanfibers and microfibers into a surface coating on a rigid inert support structure or into a woven or non-woven mat and the like to provide suitable reinforcement and support of the composite medium.
  • the composite mediums can either be supported internally or externally by the use of ceramic or metal screens, meshes, perforated tubes and plates, and the like.
  • Additional microfiber materials may include metal fibers or glass fibers.
  • Ceramic nanofibers and catalyzed ceramic nanofibers may either be at the top or bottom regions of the composite medium, or randomly dispersed throughout.
  • the present invention employs the use of a self- contained catalytic device that incorporates ceramic nanofibers and ceramic microfibers alone or in combination, with or without catalyst materials, support structures, inlet/outlet gas ports, passive secondary air injection system, and external housing used either before of after existing emission control components for internal combustion engine exhaust sources.
  • the ceramic nanofiber/microfiber materials can be immobilized within the self-contained device by a variety of methods including the use of ceramic and non-ceramic materials, fibrous structures, amorphous ceramic structures, extruded materials, formed ceramic support structures, metallic forms, or combinations of ceramic and metallic materials.
  • Ceramic and metallic composite materials act as filter and catalyst mediums for the removal and destruction of hydrocarbons (HC), particulate material (PM), nitrogen oxides (NO x ) , sulfur oxides (SO x ) , and carbon monoxide (CO) .
  • a secondary air injection system is optional and may be used to enhance and improve oxidative reactions such as HC and CO destruction/conversion reactions. Both direct and passive air, oxygen, and other oxidant compounds injection technologies can be used.
  • the emission control device and composite materials of the present invention are desirably made by incorporating ceramic nanofiber/microfiber materials along with catalyzed ceramic nanofiber/microfiber materials into either a self-contained, stand alone unit; incorporated into an emission control/muffler combination; or used as a media for advanced emission control systems.
  • Ceramic nanofibers, ceramic microfibers, a combination of ceramic nanofibers/microfibers, with or without catalyst particles, or catalyst coatings can be arranged to target specific reactants or particulate materials by using single or multiple fiber layers, with separate, distinct catalyst and ceramic materials within each layer, and/or with multiple catalyst and ceramic materials with each layer as illustrated in FIG. 2. These fibrous layers can be applied to rigid or fibrous, permeable or non-permeable support structures.
  • Non- catalyzed ceramic nanofiber/microfiber composite materials are generally placed upstream of catalyzed ceramic nanofiber/microfiber composite materials to remove, or capture, or destroy particulate material (PM) and hydrocarbon materials (HC) to limit catalyst deactivation due to surface coverage and catalyst blockage by particulates, coalescence, and adsorption of organic and inorganic materials, and poisoning by undesirable gaseous components.
  • the ceramic nanofiber without embedded catalyst materials may serve as the primary catalyst/reactive material.
  • Catalyzed ceramic nanofiber/microfiber composite materials are generally placed downstream of non-catalyzed ceramic nanofiber/microfiber composite materials to facilitate the destruction/conversion of gaseous constituents within the exhaust stream including but not limited to oxides of nitrogen and sulfur (NO x and SO x ) , hydrocarbon materials
  • HC carbon monoxide
  • CO carbon monoxide
  • One or more catalyst materials can be incorporated into ceramic nanfibers resulting in either a multi-functional medium that can be integrated into processes where different reactions can occur simultaneously or in a single medium that can facilitate single reactions.
  • Multi-functional and single-functional composite mediums can be placed at different locations within pollution control systems to separate desired reactions dependent on temperature, contaminant concentration, reaction rates, etc.
  • Ceramic composite materials described within the present invention are desirably included into a self- contained device, or into catalyst/muffler combination, or immobilized onto a rigid support structure by either sintering the ceramic composite medium to a support media or vacuum molding onto an external support structure.
  • the ceramic nanfober/microfiber can be attached to an external support structure or can be placed within a larger, advanced emission control device.
  • FIG. 6 shows one example of a self-contained catalyst delivery system using perforated tube structures 35 coated with ceramic nanofiber/microfiber materials with and without catalyst materials.
  • the catalyst delivery system uses ceramic nanofiber/microfiber composite material for PM and HC removal/oxidation and a mixed catalyzed ceramic nanofiber/microfiber composite for oxidation of HC, reduction of NO x and SO x , and destruction of CO.
  • the delivery system includes a gas inlet 50 and a gas outlet 51, two end-plates 30 with appropriate connections, an outer containment shell 32, surrounded by insulation 33, with an internal spacer 34 used for proper internal component alignment 34, and an internal support structure for the ceramic nanofiber/microfiber media 35 and catalyzed ceramic nanofiber/microfiber composite media 36 and integrating the option of passive secondary air injection system or systems before or within the catalytic chamber 37.
  • FIG.7 shows a Front view A and a Rear view B of a self-contained device with an interchangeable ceramic nanofiber/microfiber cartridge, or multiple interchangeable cartridges that can be directly mounted to an existing exhaust muffler or emission control device.
  • This delivery system includes two separable plates 41 and 42 with appropriate mounting connections with an exhaust inlet 43 and a treated exhaust exit 44, with internal spacing and compartments where preformed cartridges containing ceramic nanofiber/microfiber composite materials 45 with, or without, catalyst materials can be placed.
  • Catalyst loading ratios will vary depending on the application and operating conditions with mass loadings of 1 to 150 g/ft 3 , desirably 5 to 50 g/ft 3 , and preferably from about 5 to 35 g/ft 3 of composite ceramic nanofiber/microfiber material.
  • the type of catalyst combinations incorporated into the final composite materials include platinum (Pt), palladium (Pd), and rhodium (Rh) either singly or in the following combinations; Pd: Pt, Pd: Rh, Pt: Rh, or Pd: Pt: Rh ( tri-metallic platinum group metal, PGM) .
  • the ratios of platinum, palladium, and rhodium in the various described combinations above are dependent on the specific application environment and can be controlled and tailored during the formulation stage of composite media production.
  • Secondary air injection systems using passive injection technologies may be used to enhance, promote HC and CO destruction/conversion reactions within the entire catalytic chamber or within specific regions within a catalytic emission control device.
  • Passive secondary air injection systems may include but are not limited to Venturis, ejectors, pulse-air injection, check valves, etc., and the like.
  • the invention described herein namely the use of immobilized ceramic fibers such as ceramic nanofibers and/or ceramic microfibers, with and without embedded metal catalyst particles, or catalytic coatings, provides a significant technological advance to catalytic systems for the treatment of gaseous and particulate components from internal combustion engine exhaust to destroy nitrogen oxides (NO x ) , sulfur oxides (So x ) and carbon monoxide (CO) gaseous components and the capture and oxidation of soot particles and other hydrocarbon (HC) constituents, methane and non-methane hydrocarbon materials [0046] Multiple types of ceramic fibers, either catalyzed or non-catalyzed can be integrated into a medium to react with specific gaseous components.
  • NO x nitrogen oxides
  • So x sulfur oxides
  • CO carbon monoxide
  • Catalyzed or non-catalyzed fibers can be applied in multiple, distinct layers with different compositions to sequentially react with specific gaseous components.
  • Ceramic nanofibers provide a significant increase in fiber surface area compared to other fiber types therein increasing the surface area to volume ratios compared to other mediums.
  • the use of ceramic nanofibers also increases the thermal stability of attached and/or embedded catalyst particles within the ceramic nanofiber matrix since small catalyst particles present on and/or within a ceramic nanofiber matrix do not readily coalesce (merge) into larger catalyst particles at high application temperatures catalytic performance at high temperatures is maintained. With the enhanced thermal stability and the use of small catalyst nanoparticles significant cost savings as compared to existing technologies are realized.
  • the use of ceramic fibers (nano- and micro-) within a catalytic medium and/or conduit immobilized by various support structures, both fibrous and rigid, also enhance fluid flow to the catalyst surfaces therein increasing overall catalyst use efficiencies.

Landscapes

  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Combustion & Propulsion (AREA)
  • Mechanical Engineering (AREA)
  • General Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biomedical Technology (AREA)
  • Analytical Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Toxicology (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Exhaust Gas After Treatment (AREA)
  • Exhaust Gas Treatment By Means Of Catalyst (AREA)

Abstract

La présente invention concerne des nanofibres de céramique immobilisées, des microfibres de céramique, ou une combinaison de nanofibres et de microfibres de céramique avec et sans particules de catalyseur intégrées, ou des revêtements de catalyseurs sur des structures supports rigides ou fibreuses, perméables ou imperméables, fabriquées à partir de composites céramiques, métalliques, ou métallo-céramiques destinées à la destruction d'oxydes d'azote (NOx), d'oxydes de soufre (SOx), et de composants gazeux à base de monoxyde de carbone (CO) et la capture et l'oxydation de particules de suies et autres constituants hydrocarbonés (HC), des matériaux hydrocarbonés à base de méthane et sans méthane, provenant de sources d'échappement de moteurs à combustion interne comprenant les moteurs à 2 temps et 4 temps en service hors route et sur la route, à allumage par étincelles, sans allumage par étincelles, et portatifs (HH) et non portatifs (NHH).
PCT/US2009/002898 2008-05-09 2009-05-11 Traitement de l'échappement d'un moteur à combustion interne en utilisant des matériaux en fibres de céramique immobilisées Ceased WO2009137110A1 (fr)

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US61/127,015 2008-05-09

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Cited By (7)

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EP2554254A4 (fr) * 2010-03-31 2015-06-24 Kwangju Inst Sci & Tech Procédé de fabrication d'un catalyseur mixte contenant un nanofil d'oxyde métallique, et électrode et pile à combustible renfermant un catalyseur mixte fabriqué par ledit procédé
CN106999923A (zh) * 2014-11-20 2017-08-01 花王株式会社 催化剂纤维结构的制备方法
WO2019020705A1 (fr) * 2017-07-27 2019-01-31 Haldor Topsøe A/S Réacteur catalytique comprenant un support de particules de catalyseur fibreux
CN113272056A (zh) * 2019-01-21 2021-08-17 日本碍子株式会社 多孔质陶瓷结构体
US11154816B2 (en) 2019-05-30 2021-10-26 Toyota Motor Engineering & Manufacturing North America, Inc. Palladium oxide supported on spinels for NOx storage
CN116673020A (zh) * 2023-05-19 2023-09-01 华南理工大学 双功能大孔锰铈氧化物纤维同步捕获和催化燃烧碳烟颗粒物的应用
US11987914B2 (en) 2018-04-04 2024-05-21 Unifrax I Llc Activated porous fibers and products including same

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP2554254A4 (fr) * 2010-03-31 2015-06-24 Kwangju Inst Sci & Tech Procédé de fabrication d'un catalyseur mixte contenant un nanofil d'oxyde métallique, et électrode et pile à combustible renfermant un catalyseur mixte fabriqué par ledit procédé
CN106999923A (zh) * 2014-11-20 2017-08-01 花王株式会社 催化剂纤维结构的制备方法
US10682637B2 (en) 2014-11-20 2020-06-16 Kao Corporation Method for producing catalyst fibrous structure
WO2019020705A1 (fr) * 2017-07-27 2019-01-31 Haldor Topsøe A/S Réacteur catalytique comprenant un support de particules de catalyseur fibreux
US11987914B2 (en) 2018-04-04 2024-05-21 Unifrax I Llc Activated porous fibers and products including same
CN113272056A (zh) * 2019-01-21 2021-08-17 日本碍子株式会社 多孔质陶瓷结构体
CN113272056B (zh) * 2019-01-21 2023-10-31 日本碍子株式会社 多孔质陶瓷结构体
US11154816B2 (en) 2019-05-30 2021-10-26 Toyota Motor Engineering & Manufacturing North America, Inc. Palladium oxide supported on spinels for NOx storage
CN116673020A (zh) * 2023-05-19 2023-09-01 华南理工大学 双功能大孔锰铈氧化物纤维同步捕获和催化燃烧碳烟颗粒物的应用

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