The present invention relates generally to a device for catalyzing the conversion of pollutant gasses into non-pollutant gasses, and more particularly, to a catalytic converter device for quick installation or replacement on a vehicle or other like exhaust system.
Exhaust systems perform several functions for a modern engine. For example, the exhaust system is expected to manage heat, reduce pollutants, control noise, and sometimes filter particulate matter from exhaust emissions. Generally, these individual functions are performed by separate and distinct components. Take, for example, the exhaust system of a typical small gasoline engine. The small engine exhaust system may use a set of heat exchangers or external baffles to capture and dissipate heat. A separate muffler may be coupled to the exhaust outlet to control noise, while a catalytic converter assembly may be placed in the exhaust fluid path to reduce the concentration of non-particulate pollutants. Although particulates may not generally be a concern in the small gasoline engine, some applications may benefit from the use of a separate particulate filter. Due to space limitations, costs, and engine performance issues, it is not always possible to include separate devices to perform all the desired functions, thereby resulting in an exhaust system that is undesirably hot, polluting, or noisy.
Known exhaust systems are often supplied with catalytic devices to support non-particulate emission control. Due to the physical size, mass and reactivity requirements for these devices, their placement options are quite limited. Each device that must be placed adds additional design time, cost, and weight and also consumes valuable and limited space in the product. As emission requirements tighten, it is likely that more catalytic effect will be required, as well as further particulate control. In other engines, it has not always been possible to find a safe and effective placement location for catalytic devices. These engines, such as small internal combustion engines (ICE), are often found in on-road vehicles, off-road vehicles, motorcycles, lawn equipment, construction and mining equipment, small utility engines, and the like. Unfortunately, these small engines have not been able to fully benefit from catalytic technologies. Additionally, other pollution sources and/or areas where catalytic conversion of pollutant gasses could be beneficial include environmental cleanup, ozone reduction, industrial processes, gas compression, power generation, fuel cells, and the like. In many applications, there is a need for a flexible, yet highly effective method to catalyze and remove the harmful emissions. The ability to reduce noise pollution, as well as prevent injuries or harm due to excess heat generation is also desirable.
In both gasoline and (especially) diesel engines, a major pollutant is particulate matter (such as soot). Soot particles are small, usually ranging from an effective diameter of 10 nm to about 1 micron and above. While there are general EPA guidelines regarding overall particulate matter concentrations that may be emitted, there are also strict regulations regarding soot emissions from engines. Diesel engines produce significantly more soot than do gasoline engines, but with certain emission control systems included in the diesel exhaust system, the particulate matter pollution arising from gasoline engines may now be the same or worse. Additionally, older automobiles (also known as gross-emitters) have considerably higher particulate and non-particulate emission levels. In some applications where particulate emissions need to be controlled, diesel particulate filters, either catalyzed or uncatalyzed, in combination with other emission control technologies (such as a diesel oxidation catalyst) have been found to be effective.
Known catalytic systems do not effectively operate until a threshold operational temperature is reached. During this “light-off” period, substantial particulate and non-particulate pollution is emitted into the atmosphere. Accordingly, it is often desirable to place a catalytic device close to the engine manifold, where exhaust gasses are hottest. In this way, the catalyst may more quickly reach its operational temperature. However, design or safety constraints may limit placement of the catalytic converter to a position spaced away from the manifold. Since these catalytic converters are spaced away from the manifold, light off time is increased, and additional pollutants are exhausted to the atmosphere.
Certain catalytic devices, such as the typical honeycomb catalytic converters developed for the automobile industry, cause significant back-pressure, occupy large volumes to reach high conversion at large spatial velocities, and add significant weight to the vehicle. Unfortunately, other catalytic or filtering solutions are heretofore unable to withstand the harsh operating environments that are associated with these applications (i.e., vibration, shock, acceleration, temperature, thermal shock, acid or alkaline chemical environments, etc. . . . ).
Many engines are in current operation with non-working, limited, or no catalytic converters. For example, many older cars have no converter at all, and those manufactured just a few years ago were required to meet exhaust standards much less stringent than current standards. Also, many vehicles have failing or under-performing emission systems. Some states have emission testing to identify these vehicles, and require that the vehicle emission system be repaired. However, most states have limits as to how much a vehicle owner must spend to repair the emission system, and if the repair would exceed this amount, the owner is not required to make the repair. Since emission system repair is quite expensive, many vehicles are allowed to continue exceeding pollution standards because no cost-effective repair solution is available. Similarly, school busses, trucks, and other diesel vehicles currently do not have any filters installed on them and there is thus the need for retrofit installation to meet current and projected regulations, reduce and reverse environments damage, and protect human life and livelihood.
Air pollution standards, particularly vehicle exhaust gasses, are coming under increased pressure from governments and environmental organizations. The consequence of continued emissions is well recognized, with additional regulations being added and existing regulations more aggressively enforced. However, reduced emissions and more stringent emission regulations may have a short-term negative impact on the overall economy, as additional monies must be spent to meet higher standards. Indeed, governments have been relatively slow to adapt tighter regulations, citing competitive and economic consequences. Accordingly, a more cost effective and efficient catalytic device may ease the transition to a cleaner world, without substantial detrimental economic effects. In particular, it would desirable to provide a cost effective catalytic device that is capable of easy installation on vehicles, small engines, and in industrial exhaust stacks.
Briefly, the present invention provides a simple catalytic device that is easily installed into vehicles, small engines, industrial exhaust stacks and other locations where catalytic conversion of exhaust gasses and/or filtration of particulates is required. The simple catalytic device has a refractive and stable backbone structure that withstands expected mechanical forces. In one example, the backbone is a highly gas-permeable mesh or screen. A substantially fibrous nonwoven refractory material is disposed on the backbone, with a catalytic material coating applied to the fibrous material. In one example only the solid structural components of the backbone are covered with a fibrous refractory layer. In another example, the entire backbone structure, including the gaps between the solid portions, is fully enclosed within the fibrous layer. The catalytic device is constructed to be installable in an exhaust path, where it provides a catalytic conversion for non-particulate matter.
In a more specific example, the exhaust fluid treatment device is constructed as a catalytic screen. The catalytic screen includes a fluid permeable backbone member defining a plurality of apertures that supports a substantially fibrous porous nonwoven refractory material portion disposed thereon. A catalyst material portion is adhered to the substantially fibrous porous nonwoven refractory material portion. The screen may be operationally connected in an exhaust path extending from an exhaust gas source, such as an engine, to the atmosphere to capture particulate matter and/or catalyze the conversion of pollutants in the exhaust gas into non-pollutants.
In another specific example, the exhaust gas treatment system for removing is constructed to include a conduit portion connecting an exhaust gas filter portion to an exhaust gas source. The conduit portion may be part of a pre-existing or in-service vehicle, such as an exhaust pipe of an automobile, and may have a slot or the like formed thereinto for receiving the exhaust gas filter portion. The exhaust gas filter includes a housing portion with a gas permeable backbone portion operationally connected thereto. A substantially fibrous nonwoven refractory material portion disposed on the backbone portion. The system may be operationally connected to an exhaust gas source, such as an engine, to capture particulate matter and/or catalyze the conversion of pollutants in the exhaust gas into non-pollutants. Exhaust gasses thus pass through the filter as they travel toward the atmosphere.
In another specific example, more suited to applications where particulate trapping is desirable, the refractory screening device is constructed as a wall-flow honeycomb diesel particulate filter, a wall-flow tube, or a doughnut-shaped wall-flow diesel particulate filter, wherein the walls of the substrate through which the affluent flows contain an internal backbone structure composed of rigid, structural material (such as wire mesh).
Advantageously, the catalytic device provides a simplified and cost effective means for reducing dangerous exhaust gases. For example, the catalytic device may be attached to a small engine, either as the sole catalytic device or to assist existing devices. In another example, the catalytic device may be coupled into an existing vehicle exhaust system, thereby enabling a cost-effective way to reduce emissions for existing vehicles. Also, the catalytic device may be constructed as a replacement part. This is particularly useful in an application, such as with 2-cycle engines, where the catalytic effect of original equipment diminishes over time due to expelled oil. Further, industrial and residential applications may also benefit from a simple catalytic device. Stoves, heaters, furnaces, evaporators, and other exhausting devices may be provided with cost effective and enhanced emission control. The catalytic device may be disposable or readily serviceable to remove debris resulting from oil, fuel, soot, or ash deposition. The catalytic device may be used as a retrofit device on equipment using diesel engines, such as mining equipment, trucks, power generators, backup generators, marine engines, agricultural engines, automobiles, and the like.
The catalytic device may be incorporated in series, parallel, or on within other emission control or catalytic conversion and/or filtration equipment, such as catalytic converters, mufflers, diesel oxidation catalysts, catalyzed exhaust tubes, catalytic combustors, incinerators, and the like.
These and other features of the present invention will become apparent from a reading of the following description, and may be realized by means of the instrumentalities and combinations particularly pointed out in the appended claims.
The drawings constitute a part of this specification and include exemplary embodiments of the invention, which may be embodied in various forms. It is to be understood that in some instances various aspects of the invention may be shown exaggerated or enlarged to facilitate an understanding of the invention.
Detailed descriptions of examples of the invention are provided herein. It is to be understood, however, that the present invention may be exemplified in various forms. Therefore, the specific details disclosed herein are not to be interpreted as limiting, but rather as a representative basis for teaching one skilled in the art how to employ the present invention in virtually any detailed system, structure, or manner.
The drawing figures herein illustrate and refer to an exhaust system pathway that is specifically described as a component of an internal combustion engine exhaust system. However, it should be appreciated that exhaust pathway may be used on other types of exhaust systems. For example, the exhaust system may be for the petrochemical, biomedical, chemical processing, painting shops, laundromat, industrial exhaust, generation plant, or commercial kitchen applications.
Generally, a catalytic converting device consists of a host or a structural substrate support, and a catalyst that coats the support. A catalytic device contains the appropriate type and mass of support and catalyst so that it can fulfill a precise catalytic function. For example, it may perform a conversion function, such as the conversion of gases into other gaseous products, liquids into other liquids, liquids into gaseous products, solids into liquids, solids into gaseous products or any combination of these specific conversions. Generally, the conversion reaction or reactions are deliberate and well-defined in the context of a particular application, e.g. simultaneous conversion of NOx, HC, CO, conversion of methyl tertiary butyl ether (MTBE) to CO2 and steam, soot to CO2 and steam, and the like.
Referring now to
Generally, catalytic screen 10 includes a structural housing portion 12 to which a backbone support structure 14 is connected. A substantially fibrous, typically nonwoven refractory material 16 is disposed on the backbone 14. The backbone 14 may be a screen, mesh, perforated sheet, wire construct, or the like that is permeable to the flow of gas therethrough. Typically, the backbone 14 is formed from a structural refractory material, such as steel, a highly densified ceramic, or a cer-met composite material; while the backbone 14 itself is gas permeable, its constituent material may be impervious and substantially non-porous. A catalytic material 18 is disposed on at least some of the fibrous material 16 layer. The catalyst material 18 may be added during the formation of the fibrous layer 16, such as at the slurry or green body stage, or may be applied later at the finished body stage. Typically, the fibrous material 16 is disposed on backbone portion 14 so as to leave relatively large exhaust apertures or channels 21, although the fibrous material 16 may be sufficiently thick so as to leave small channels 21, or even substantially no channels 21. It will be appreciated that overall catalytic conversion efficiency and backpressure may be adjusted according to the density of support structure 14, the porosity and thickness of fibrous material 16 attached thereto, the degree of coverage of the fibrous material 16 over the support structure 14, and the type and amount of catalytic material 18 coated to the fibrous layer 16. Likewise, the characteristic porosity and/or pore dimensions of the material 16 may be adjusted to optimize the reaction of particular species with particular reactive agents/catalysts 18.
The housing 12 is typically ring shaped, more typically with a generally circular cross-section, and still more typically is sized for insertion into a generally circular cross-sectioned pipe so as to substantially intersect the flow of exhaust gasses therethrough. Of course, the housing may have any regular or irregular shape convenient for positioning in the flow of an exhaust gas such that the flow is substantially intersected and forced through the area defined by the housing and filled by the support structure 14.
The housing 12 may be made of a structural material, such as aluminum, steel, or the like, and may further include a pair of couplers 22 such that the housing 12 may be inserted as a joint between two sections of conduit 24 that make up a part of the exhaust pathway from the engine to the atmosphere 26. The couplers 22 are typically threaded with matable threading formed on the ends of the pipe sections 24, such that the pipe sections 24 may be threadedly connected to the housing 12 via the couplers 22. Alternately, the housing 12 may be welded into place in the exhaust path, may be snapped into place, may be held in place by an interference fit/by frictional forces, or by any convenient attachment technique or mechanism. More typically, the housing 12 and screen 10 are disposable, i.e., easily removed and replaced.
The backbone or support structure 14 is a gas permeable structure that offers little resistance to the flow of fluids therethrough so as to cause minimal backpressure when inserted into the gas flow of an exhaust system. The backbone 14 may have the form of a screen, a mesh, a donut, a honeycomb, a perforated surface, a plurality of interconnected, criss-crossed wires, a perforated tube, single or multiple ‘hole’ or ‘gap’ distributions, or the like and may be made from any convenient structural material, typically metal or metal alloy, but may also include coated metals, metal fibers or whiskers, cements, structural ceramics (such as cordierite, silicon carbide, mullite, zirconia, alumina or the like, typically prepared from powdered precursors), densified substantially fibrous ceramic materials, cermets, or the like. For lower temperature applications, plastics and the like may be suitable backbone 14 materials.
The substantially fibrous porous nonwoven refractory material 16 is typically adhered substantially uniformly to the backbone 14. Typically, the substantially fibrous porous nonwoven refractory material 16 is coated onto to the backbone 14 with sufficient thickness such that there remain gaps or exhaust gas channels 21 between adjacent coated portions of the backbone 14. (See
The substantially fibrous porous nonwoven refractory material 16 coating the backbone structure 16 is typically made of a matrix of tangled (non-woven) refractory fibers. The fibers are typically chopped to a relatively short length and more typically have diameter to length aspect rations of between about 1:3 to about 1:500. Typical fiber diameters range from about 1.5 to about 15 microns and greater. Typical fiber lengths range from several microns to about 1-2 centimeters or longer, more typically exceed at least about 6 microns, and still more typically may range from about 1 to about 3 centimeters in length. Shorter lengths are typically more convenient for certain ceramic formation processes, such as extrusion. More typically, a bimodal or multimodal distribution of fiber aspect rations is used to enhance the strength of the substantially fibrous porous nonwoven refractory material layer portion 16. For example, the aspect ratios may peak at about 1:10 and about 1:90.
The substantially fibrous porous nonwoven refractory material 16 is typically a refractory material, is more typically a metal oxide, metal carbide and/or metal nitride composition, and is still more typically made of one or more of the following materials: mullite, alumina, silica, alumina-silica, mixtures of alumina and silica, alumina enhanced thermal barrier (“AETB”) material (made from aluminoborosilicate fibers, silica fibers, and alumina fibers), OCTB or HTP material (made from alumina fibers, silica fibers, and boron nitride), fibrous refractory ceramic insulation (FRCI) material (mostly silica fibers), zirconia, aluminum titanate, titania, yttrium aluminum garnet (YAG), aluminoborosilicate, alumina-zirconia, alumina-silica-zirconia, silicon carbide, silicon nitride, mixtures of the same, and the like. For example, AETB is an attractive material for fibers since AETB has a high melting point, low heat conductance, low coefficient of thermal expansion, the ability to withstand thermal and vibrational shock, good chemical resistance to corrosion and weakening, low density, and very high porosity and permeability. Alternately, the substantially fibrous porous nonwoven refractory material 16 comprises ceramic fibers having toughened unipiece fibrous insulation (TUFI) and/or reaction cured glass (RCG) coatings, TEOS coatings, alumina-silica sol-gel coatings, cotronics coatings and other strengthening and/or thermally stabilizing and/or mechanically stabilizing coatings. The refractory fibers may be amorphous, vitreous, partially crystalline, crystalline or polycrystalline. Further, the substantially fibrous porous nonwoven refractory material 16 may include an opacifier for improving its thermal insulation properties, especially its insulation from the radiant transfer of heat.
Example substantially fibrous porous nonwoven refractory material 16 compositions include: (1) 70% silica fibers—28% alumina fibers—2% boron nitride; (2) 80% mullite fibers—20% bentonite clay; (3) 90% mullite fibers—10% kaolinite; (4) 100% aluminoborosilicate fibers (such as a homogenous mixture of 62% alumina—24% silica—14% boria); (5) AETB composition; (6) 90% aluminosilicate fibers—10% silica fibers (all compositions are expressed in weight percents); (7) 90% alumina fibers—10% clay; (8) 80% alumina fibers—20% colloidal silica. The compositions may be present as combinations of individual fibers (i.e., the ‘mullite’ of composition (2) may be present as alumina and silica fibers in a ration of four silica fibers for every alumina fiber) or as homogeneous fibers (i.e., composition 1 may be homogenous fibers of an aluminoborosilicate composition). Additionally, alumina, silica, zirconia, titania or the like may be added as sols, such as via dispersion, infiltration, dipping, or like techniques, to further densify the fibrous refractory material 16. The sol will convert to one or more stable ceramic material compositions (as a function of its composition) upon firing and will provide additional strength and structural support to the fibrous material 16 and may also act as a site for catalyst deposition. Alternately, the sol may contain clays that include silica, alumina, zirconia or the like. Clay-based binders such as bentonite, attapulgite, playgoprsite, montmorillonite, pyrophylite, kaolinite and the like may also be used in the forming process, added as dry mix or in a binder solution.
In one embodiment, the screen 10 includes a substantially fibrous porous nonwoven refractory matrix 16 is formed between a pair of backbone members 14. (See
Further, the substantially fibrous porous nonwoven refractory matrix 16 may be formed on one or more backbone members in discrete layers 46 (see
The fibers form a substantially fibrous porous nonwoven refractory matrix 16 and are typically sintered or otherwise bonded together at their intersections. The substantially fibrous porous nonwoven refractory material 16 is typically at least about 60% porous, is more typically at least about 80% porous, and is still more typically at least about 90% porous. Alternately, the substantially fibrous porous nonwoven refractory material 16 may be coated onto the backbone 14 with a porosity gradient, such that the substantially fibrous porous nonwoven refractory material layer 16 is more porous (or less porous) adjacent the backbone 14 and less porous (or more porous) away from the backbone 14 (i.e., adjacent the exhaust pathway from the engine to the atmosphere 26). Likewise, the substantially fibrous porous nonwoven refractory material layer 16 may have a uniform and typically low density or, alternately, may have a density gradient such that it is denser adjacent the respective pathway component(s) 21 and less dense away from the respective pathway component(s) 21. This may be accomplished by varying the density and porosity of a single fibrous porous nonwoven refractory material layer 16 composition, or, alternately, by forming a fibrous porous nonwoven refractory material layer 16 from a plurality of sublayers, wherein each sublayer is characterized by fibers of different size, aspect ratio and/or density.
Typically, the substantially fibrous porous nonwoven refractory material 16 is selected such that its coefficient of thermal expansion (CTE) is similar to that of the backbone 14 to which it is to be connected. This CTE matching is desirable but not critical, since the substantially fibrous porous nonwoven refractory material 16 is fibrous and typically highly porous, such that there is some ‘give’ built into the material 16. In other words, compressive forces will first cause the material 16 to deform and not crack or fail.
The fibrous porous nonwoven refractory material layer 16 may be formed through a variety of means. For example, the substantially fibrous porous nonwoven refractory material layer 16 may be disposed upon the backbone 14 through such ceramic processing techniques as coating, spraying, dipping, injection molding, compression, cementation, sol-gel application, lamination, solid or liquid phase sintering, vacuum forming, or the like. Alternately, the substantially fibrous porous nonwoven refractory material 16 may be applied on a flat metal backbone 14, which is then perforated and either utilized as a substantially flat planar screen 10 or, alternately, rolled into a cylinder or donut shape for insertion into a pipe section 24. Still alternately, the fibrous layer 16 may be formed onto a backbone 14 made of like, but substantially densified, fibrous material.
Likewise, the substantially porous nonwoven refractory fibrous portion 16 may be formed to varying degrees of thickness. For example, the fibrous portion 16 may be formed as a thick, porous membrane and attached in situ to the backbone portion 14. Alternately, the fibrous portion 16 may be applied with sufficient thickness onto the backbone 14 so as to have more significant particulate capturing capability.
The fibrous porous nonwoven refractory material layer 16 typically includes a catalyst material 18 at least partially coated thereon, typically coating at least portions of the individual fibers. The catalyst material 18 is typically chosen from the noble metals, such as platinum, palladium, and rhodium (either alone or as alloys or combinations), and oxides thereof, but may also be selected from chromium, nickel, rhenium, ruthenium, silver, osmium, iridium, vanadium, gold, binary oxides of palladium and rate earth metals/oxides (such as Sm4PdO7, Nd4PdO7, Pr4PdO7 and/or La4 PdO7), certain perovskite-structured compositions, and the like. The catalyst 18 is typically a material that lowers the potential barrier for a pollutant to nonpollutant reaction (i.e., helping the reaction to occur faster and/or at lower temperatures). Since different catalysts 18 require different threshold temperatures to begin to function, the fibrous porous nonwoven refractory material layer 16 may include more than one catalyst material 18 coated thereupon (either in discrete regions or intermixed with one and other). For example, the fibrous porous nonwoven refractory material layer 16 may include a first catalyst material 18 that begins to function at a first, relatively low temperature and a second catalyst material 18 that activates at a second, higher temperature. The second material 18 may be added because it is cheaper, more chemically and/or thermally stable, has a higher top end temperature for catalyst function, and/or is a more efficient catalyst 18.
Typically, a washcoat layer, such as alumina, ceria, zirconia, titania or the like, is provided between the fibers and the catalyst material 18 to promote adhesion and to improve catalyst efficiency. Both the layer 16 thickness and degree of catalyst 18 coating on the fibers may be increased and/or decreased to tailor the temperature (i.e., the degree of thermal insulation provided) and catalytic activity (catalyst 18 is expensive, and thus it is desirable to not use more than is necessary for a given exhaust gas environment) of the exhaust system. The system 10 allows catalytic benefits coincident with temperature management to increase vehicle safety (such as by lowering exhaust system outer temperature), shorten light-off time, utilize otherwise wasted heat, and the like while simultaneously decreasing pollution emissions. The system 10 may be used in tandem with conventional and pre-existing pollution control methodology, or may be used alone to address pollution emissions from heretofore uncontrolled sources, such as lawn mowers. Since the screen 10 typically includes open exhaust channels 21, replacing conventional catalytic converters with one or more screens 10 reduces the complexity of the typical vehicular exhaust system (as well as its weight) and potentially simultaneously decreases the effective back pressure and cost as well.
The screen 10 may also capture particulate matter, such as via the porous nature of the fibrous material 16. In these cases, the catalyst material 18 may be utilized to facilitate oxidation of the particulate matter at relatively low temperatures. In exhaust streams with high concentrations of particulate matter, the fibrous layer 16 will be called upon to efficiently trap and store soot, ash, and other particulate matter contributions without significantly increasing exhaust stream back pressure. Further, the catalyst material 18 is typically selected to oxidize soot and ash as well as exhaust gasses; this may be accomplished via the judicious selection of a single catalyst material 18 or by selecting a combination of catalyst materials 18 matched to the various pollutants desired to be catalyzed. Since particulate filtration is typically a more depth-oriented process than non-particulate conversion, the catalyst 18 is typically applied not just on the surface of the fibrous layer 16 but also into the porosity extending away from the surface.
In operation, pollutant-containing exhaust gas from the engine 25 typically flows through the exhaust gas pathway 26, flows through the screen 10 positioned therein. The screen 10 acts to catalytically remove some of the pollutants from the gas flowing therethrough, such that less-polluted exhaust gas 27 then flows from the screen 10 to the atmosphere. Since the fibrous nonwoven refractory material layer 16 portion of the screen is typically substantially porous, diffusion forces urge the exhaust gas into the pores of the substantially fibrous porous nonwoven refractory material layer 16. The fibrous nonwoven refractory material layer 16 is typically thick enough to provide substantial surface area for significant exhaust gas 25 contact, but not so thick so as to significantly impeded the flow of exhaust fluids from the engine to the atmosphere and thus contribute to an unacceptable build-up of back pressure. Typically, the fibrous nonwoven refractory material layer 16 is between about 5 and about 10 millimeters thick, although the thickness may vary with exhaust system size, positioning in the pathway 10, and the like.
Typically, the exhaust gas 25 does not penetrate completely into the substantially fibrous porous nonwoven refractory material layer 16, since the diffusion forces are relatively weak as compared to the pressure differential between the engine and the atmospheres, thereby urging the cleaned exhaust gas 27 along and out of the pathway 10 and into the atmosphere. Also, the substantially fibrous porous nonwoven refractory material layer 14 tends to become denser and less porous moving from its inner surface (adjacent the exhaust gas) to its outer surface (adjacent the backbone 14 portion), so exhaust gas is less likely to fully penetrate.
Due to the typically very high surface area to volume ratio of the screen 10, the exhaust gas transfers heat into the substantially fibrous porous nonwoven refractory material layer 16, which tends to quickly raise the temperature of at least the inner surface of layer 16 until it is in equilibrium with the exhaust gas temperature, since the substantially fibrous porous nonwoven refractory material layer 16 typically has a low thermal conductivity value. If a catalyst 18 material is present thereon, its temperature is likewise quickly increased into its operating range, whereupon the catalyst material 18 begins to convert pollutants in the exhaust gas into relatively harmless nonpollutant gasses. If the screen 10 is located sufficiently close to the engine, the exhaust gasses will not have had time to significantly cool, and the screen 10 may thus be nearly instantaneously heated to its operating temperature. Furthermore, the screen 10 may be preheated, such as by a resistance heater or the flow of electricity therethrough (i.e., the backbone 14 and/or the fibrous material 16 is the resistance heater) so as to further shorten the light-off time.
The screen 10 may be used with any source of pollutant fluids, such as gasoline and diesel engines, including those in automobiles, motorcycles, lawn mowers, recreational equipment, power tools, chemical plants, and the like, to further reduce pollution emissions therefrom. Further, as mentioned above, the screen 10 provides an additional function of trapping particulate emissions in fibrous nonwoven refractory material layer 16 for later burnout or removal. The system may be present in the form of an insert into an existing exhaust system 16, as an add-on screen 10 having couplings or connectors 22 operationally connected at one or both ends (see
Referring now to
Generally, catalytic screen 10 has a mesh backbone support structure 14 on which substantially porous nonwoven fibrous refractory material 16 is disposed. Catalytic material 18 is likewise coated on the fibrous material 16. The catalyst material 18 composition is typically specifically selected to perform a particular catalytic function. Fibrous material 16 is typically disposed over the entire backbone structure 14, more typically including the areas 21 between the solid portions of the mesh 14. It will be appreciated that overall catalytic conversion efficiency and backpressure may be manipulated by adjusting the density of support mesh 14 (i.e., the solid area to aperture area ratio), porosity and thickness of the fibrous material 16, and the amount of catalytic material 18 used.
In yet another alternate configuration, as illustrated in
While the preceding examples relate generally to screen devices 10 for the removal of pollutants (both gaseous and particulate) from exhaust gas streams, and more specifically to screen filters 10 for use with internal combustion engines, the screens 10 may also be used in a variety of other applications wherein fluids are desired to be treated or processed. For example, a screen 10 may be useful in low temperature catalytic air filtration applications (such as in vehicular cabin air conditioning/heating applications). Moreover, various fluids may be filtered through a screen 10, including liquids, emulsions, suspensions, potable fluids (such as beer, beer flavorants, wine, juice, water, milk and whey) laboratory grade water, wastewater, pharmaceuticals, medicines, and cosmetics. The screens 10 may be generally useful in the fields of chemistry, biotechnology, gene technology, environmental protection and in general laboratory work. Filters 10 may be utilized in cross-flow and other filtration units for the recovery of valuable material, for the separation of substances such as macromolecules and biomolecules, for the depyrogenation and sterilization of solutions, for the separation of corrosive substances from fluids, for the filtration and concentration of biological solutions, for the separation of microorganisms such as bacteria, yeasts, virus and cell components, for the desalination of protein solutions and other biological media, nano-materials, precious metals, catalysts, hot metals, and the like. By means of example, filters 10 may be utilized in such endeavors as Fischer-Tropsch synthesis, catalytic cracking and reforming, isomerization, fuel-cells technology, molecular sieves, shape selective reactions, biosynthetic reactions such as growth and repair of tissues, ozone abatement in high flying aircraft, nitrous oxide decomposition, low-temperature oxidation, and the like.
In an alternate embodiment, the screen 10 is incorporated into an emissions control system where active regeneration is employed. The temperature of the screen 10 is raised in a controlled fashion using techniques known in the art (such as by the injection of excess unburnt fuel into the exhaust stream, via electrical or microwave heaters, through pressure buildup, or the like) until soot caught in the screen 10 ignites and is substantially completely burnt off. The system could also contain control systems that would allow the onboard diagnostics computer to conduct thermal management of the exhaust system.
Another use for the screen 10 is as a component of a cross-flow filter. Cross flow filters utilize the preferential attraction or filtration potential of a porous material to separate two fluids (such as separating oil from air or water) or condensed matter (e.g. particulates) from a fluid stream. In a typical cross-flow filter, the inlet channels and the outlet channels run perpendicular to each other, and typically lie on a different plan from each other. The inlet and the outlet channels may contain blocks that would prevent easy flow of material in the channels. The walls of the cross-flow filter could be coated with a reactive agent 18, such as a membrane, chemical coating, or a catalyst coating. The role of the reactive agent 18 is to have a particular attraction/affinity for certain molecules or material and not for others. For example, a pore-specific membrane may allow smaller molecules to pass through the membrane but not larger molecules, thereby separating smaller molecules from larger molecules. In such an example, a mixture of small and large molecules could enter in a fluid stream into the inlet channels and as the fluid flows in the inlet channel, and over the separation membrane, the small molecules may diffuse into the membrane and emerge into the outlet channel where they could flow perpendicular to the inlet flow and be extracted at the outlet channels. The larger molecules will continue to flow down the inlet channels and exit at the other end. The entire system, in this manner, works to separate one set of species from other species.
The reactive agents 18 could contain chemically active components or materials that have attraction to hydrophilic or hydrophobic molecules. Similarly, the reactive agent could wholly or only partially cover the walls. The reactive agent 18 could exist only on the surface of the wall or be embedded throughout the wall thickness. The reactive agent 18 could be layered such that each layer contains a different composition or the same composition but in different concentrations. The cross-flow filters are efficient filters, which work to continuously separate fluids or particulates from fluids. Once the crow-flow filters are packed or clogged, they can either be cleaned or replaced in the filtration system.
Substantially fibrous nonwoven gas permeable materials 16 offer great advantages to cross-flow filtration. Such substrates may be readily formed into desired shapes and forms, have very high porosities and/or permeabilities, offer easy control of pore-size, contribute relatively little backpressure, have a high filtration capacity, are typically suitable for hosting a number of reactive agents 18, are characterized by chemical stability, and are typically refractory. Moreover, the open fibrous network reduces or minimizes the likelihood of clogging the system during filtration or separation are very low, thereby prolonging the time required before replacement or cleanup.
While the invention has been illustrated and described in detail in the drawings and foregoing description, the same is to be considered as illustrative and not restrictive in character. It is understood that the embodiments have been shown and described in the foregoing specification in satisfaction of the best mode and enablement requirements. It is understood that one of ordinary skill in the art could readily make a nigh-infinite number of insubstantial changes and modifications to the above-described embodiments and that it would be impractical to attempt to describe all such embodiment variations in the present specification. Accordingly, it is understood that all changes and modifications that come within the spirit of the invention are desired to be protected.
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3788935 | Shyne | Jan 1974 | A |
3795524 | Sowman | Mar 1974 | A |
3827238 | Hayashi | Aug 1974 | A |
3869267 | Gaylor | Mar 1975 | A |
3916057 | Hatch | Oct 1975 | A |
3920404 | Gandhi | Nov 1975 | A |
3927152 | Kyrias | Dec 1975 | A |
3935060 | Blome | Jan 1976 | A |
3945803 | Musall | Mar 1976 | A |
3952083 | Fletcher | Apr 1976 | A |
3953646 | Fletcher | Apr 1976 | A |
3957445 | Foster | May 1976 | A |
3969095 | Kurahashi | Jul 1976 | A |
3978567 | Vroman | Sep 1976 | A |
4001996 | Byrd, Jr. | Jan 1977 | A |
4004649 | Shimada | Jan 1977 | A |
4007539 | Nishio | Feb 1977 | A |
4012485 | Meguerian | Mar 1977 | A |
4014372 | Dichiara | Mar 1977 | A |
4020896 | Mold | May 1977 | A |
4038175 | Bhasin | Jul 1977 | A |
4039292 | Morini | Aug 1977 | A |
4041199 | Cartwright | Aug 1977 | A |
4041592 | Kelm | Aug 1977 | A |
4056654 | Kompanek | Nov 1977 | A |
4065046 | Roberts | Dec 1977 | A |
4092194 | Green | May 1978 | A |
4094644 | Wagner | Jun 1978 | A |
4094645 | Bailey | Jun 1978 | A |
4098580 | Shimizu | Jul 1978 | A |
4148962 | Frosch | Apr 1979 | A |
4156533 | Close | May 1979 | A |
4192402 | Nakagawa | Mar 1980 | A |
4206177 | Otsubo | Jun 1980 | A |
4208374 | Foster | Jun 1980 | A |
4239733 | Foster | Dec 1980 | A |
4276071 | Outland | Jun 1981 | A |
4290501 | Tanaka | Sep 1981 | A |
4297328 | Ritscher | Oct 1981 | A |
4319556 | Schwartz | Mar 1982 | A |
4324572 | Erdmannsdorfer | Apr 1982 | A |
4329162 | Pitcher, Jr. | May 1982 | A |
4335023 | Dettling | Jun 1982 | A |
4338368 | Lovelace | Jul 1982 | A |
4343074 | Bailey | Aug 1982 | A |
4345430 | Pallo | Aug 1982 | A |
4348362 | Foss | Sep 1982 | A |
4349055 | Dichiara | Sep 1982 | A |
4358480 | Ecord | Nov 1982 | A |
4379109 | Simpson | Apr 1983 | A |
4398931 | Shevlin | Aug 1983 | A |
4404992 | Sasaki | Sep 1983 | A |
4410427 | Wydeven | Oct 1983 | A |
4415342 | Foss | Nov 1983 | A |
4417908 | Pitcher, Jr. | Nov 1983 | A |
4427418 | Kogiso | Jan 1984 | A |
4456457 | Nozawa | Jun 1984 | A |
4457895 | Prigent | Jul 1984 | A |
4483108 | Howard | Nov 1984 | A |
4495399 | Cann | Jan 1985 | A |
4508256 | Radel | Apr 1985 | A |
4529718 | Dupin | Jul 1985 | A |
4550034 | Shimrock | Oct 1985 | A |
4554195 | Ormiston | Nov 1985 | A |
4557773 | Bonzo | Dec 1985 | A |
4584003 | Oda | Apr 1986 | A |
4601868 | Radel | Jul 1986 | A |
4608108 | Goll | Aug 1986 | A |
4609563 | Shimrock | Sep 1986 | A |
4647477 | DeLuca | Mar 1987 | A |
4650775 | Hill | Mar 1987 | A |
4671911 | Garnier | Jun 1987 | A |
4682470 | Shaff | Jul 1987 | A |
4686128 | Gentilman | Aug 1987 | A |
4696711 | Greszczuk | Sep 1987 | A |
4710487 | Koch | Dec 1987 | A |
4711009 | Cornelison | Dec 1987 | A |
4722920 | Kimura | Feb 1988 | A |
4732593 | Kondo | Mar 1988 | A |
4732879 | Kalinowski | Mar 1988 | A |
4735756 | Rausch | Apr 1988 | A |
4737326 | Wirth | Apr 1988 | A |
4749674 | Dejaifve et al. | Jun 1988 | A |
4761323 | Muhlratzer | Aug 1988 | A |
4818625 | Lavendel | Apr 1989 | A |
4828774 | Andersson | May 1989 | A |
4847506 | Archer | Jul 1989 | A |
4849399 | Joy, III | Jul 1989 | A |
4858117 | Dichiara | Aug 1989 | A |
4865877 | Yamaguchi | Sep 1989 | A |
4885679 | Webster, Jr. | Dec 1989 | A |
4890285 | Dichiara | Dec 1989 | A |
4894070 | Keidel | Jan 1990 | A |
4915981 | Traskos | Apr 1990 | A |
4916897 | Hayashi | Apr 1990 | A |
4925561 | Ishii | May 1990 | A |
4928645 | Berneburg | May 1990 | A |
4928714 | Shannon | May 1990 | A |
4929429 | Merry | May 1990 | A |
4934142 | Hayashi | Jun 1990 | A |
4935178 | Esposito | Jun 1990 | A |
4940523 | Takeshima | Jul 1990 | A |
4942020 | Whittenberger | Jul 1990 | A |
4952896 | Dawson, Jr. | Aug 1990 | A |
4955164 | Hashish | Sep 1990 | A |
4957773 | Spencer | Sep 1990 | A |
4968383 | Volkmann | Nov 1990 | A |
4970035 | Baarsch | Nov 1990 | A |
4976760 | Helferich | Dec 1990 | A |
4976929 | Cornelison | Dec 1990 | A |
4988290 | Forster | Jan 1991 | A |
5006021 | Wheetley | Apr 1991 | A |
5007475 | Kennedy | Apr 1991 | A |
5008086 | Merry | Apr 1991 | A |
5013405 | Izard | May 1991 | A |
5015610 | Dwivedi | May 1991 | A |
5021369 | Ackerman | Jun 1991 | A |
5024979 | Debaig-Valade | Jun 1991 | A |
5028397 | Merry | Jul 1991 | A |
5043244 | Cairncross | Aug 1991 | A |
5053062 | Barris | Oct 1991 | A |
5062911 | Hampton | Nov 1991 | A |
5063029 | Mizuno | Nov 1991 | A |
5065757 | Dragisic | Nov 1991 | A |
5066432 | Gabathuler | Nov 1991 | A |
5070591 | Quick | Dec 1991 | A |
5075160 | Stinton | Dec 1991 | A |
5079082 | Leiser | Jan 1992 | A |
5087272 | Nixdorf | Feb 1992 | A |
5089236 | Clerc | Feb 1992 | A |
5106397 | Jaroszczyk | Apr 1992 | A |
5114901 | Tsang | May 1992 | A |
5117939 | Noguchi | Jun 1992 | A |
5124302 | Lachman | Jun 1992 | A |
5151819 | Stephens | Sep 1992 | A |
5154373 | Scott | Oct 1992 | A |
5154894 | MacFarlane | Oct 1992 | A |
5154901 | Yoshida | Oct 1992 | A |
5167934 | Wolf | Dec 1992 | A |
5168085 | Addiego | Dec 1992 | A |
5171341 | Merry | Dec 1992 | A |
5173349 | Yavuz | Dec 1992 | A |
5174969 | Fischer | Dec 1992 | A |
5179061 | Haerle | Jan 1993 | A |
5180409 | Fischer | Jan 1993 | A |
5186903 | Cornwell | Feb 1993 | A |
5194078 | Yonemura | Mar 1993 | A |
5195319 | Stobbe | Mar 1993 | A |
5196120 | White | Mar 1993 | A |
5210062 | Narula | May 1993 | A |
5231409 | Astier | Jul 1993 | A |
5232671 | Brunson | Aug 1993 | A |
5238386 | Cunningham | Aug 1993 | A |
5244852 | Lachman | Sep 1993 | A |
5248481 | Bloom | Sep 1993 | A |
5248482 | Bloom | Sep 1993 | A |
5250094 | Chung | Oct 1993 | A |
5258150 | Merckel | Nov 1993 | A |
5258164 | Bloom | Nov 1993 | A |
5260125 | Copes | Nov 1993 | A |
5262129 | Terada | Nov 1993 | A |
5266548 | Koradia | Nov 1993 | A |
5270551 | Kamimura | Dec 1993 | A |
5271906 | Yuuki | Dec 1993 | A |
5272125 | Weible | Dec 1993 | A |
5279737 | Sekhar | Jan 1994 | A |
5290350 | Besnard | Mar 1994 | A |
5294409 | Cohen | Mar 1994 | A |
5294411 | Breuer | Mar 1994 | A |
5298046 | Peisert | Mar 1994 | A |
5303547 | Mieville | Apr 1994 | A |
5304520 | Dwivedi | Apr 1994 | A |
5334570 | Beauseigneur | Aug 1994 | A |
5338903 | Winberg | Aug 1994 | A |
5339629 | Winberg | Aug 1994 | A |
5376598 | Preedy | Dec 1994 | A |
5380580 | Rogers | Jan 1995 | A |
5380621 | Dichiara | Jan 1995 | A |
5391428 | Zender | Feb 1995 | A |
5393499 | Bagley | Feb 1995 | A |
5401614 | Dichiara | Mar 1995 | A |
5408827 | Holtermann | Apr 1995 | A |
5409669 | Smith | Apr 1995 | A |
5429780 | Prin | Jul 1995 | A |
5436216 | Toyao | Jul 1995 | A |
5449654 | Prin | Sep 1995 | A |
5451444 | DeLiso | Sep 1995 | A |
5453116 | Fischer | Sep 1995 | A |
5455594 | Blasing | Oct 1995 | A |
5456965 | Machida | Oct 1995 | A |
5458944 | Austin | Oct 1995 | A |
5463206 | Abe | Oct 1995 | A |
5466917 | Matsuki | Nov 1995 | A |
5482538 | Becker | Jan 1996 | A |
5482817 | Dichiara | Jan 1996 | A |
5486399 | Brydon | Jan 1996 | A |
5487865 | Hampton | Jan 1996 | A |
5501842 | Rajnik | Mar 1996 | A |
5504281 | Whitney | Apr 1996 | A |
5511747 | Parrot | Apr 1996 | A |
5516580 | Frenette | May 1996 | A |
5519191 | Ketcham | May 1996 | A |
5523059 | Langer | Jun 1996 | A |
5526462 | Kondo | Jun 1996 | A |
5536562 | Tran | Jul 1996 | A |
5540981 | Gallagher | Jul 1996 | A |
5551239 | Feeley | Sep 1996 | A |
5552360 | Farrauto | Sep 1996 | A |
5553455 | Craig | Sep 1996 | A |
5554485 | Dichiara | Sep 1996 | A |
5567536 | Lintz | Oct 1996 | A |
5569441 | Engler | Oct 1996 | A |
5582805 | Yoshizaki | Dec 1996 | A |
5589143 | Mori | Dec 1996 | A |
5593647 | Kirby | Jan 1997 | A |
5599510 | Kaminsky | Feb 1997 | A |
5601259 | Dichiara | Feb 1997 | A |
5611832 | Suzuki | Mar 1997 | A |
5614155 | Abe | Mar 1997 | A |
5618500 | Wang | Apr 1997 | A |
5626951 | Hogenson | May 1997 | A |
5629067 | Kotani | May 1997 | A |
5629186 | Yasukawa | May 1997 | A |
5632320 | Atmur | May 1997 | A |
5637399 | Yoshikawa | Jun 1997 | A |
5656048 | Smith | Aug 1997 | A |
5660778 | Ketcham | Aug 1997 | A |
5666804 | Sekiya | Sep 1997 | A |
5674802 | Sheppard | Oct 1997 | A |
5686039 | Merry | Nov 1997 | A |
5686368 | Wong | Nov 1997 | A |
5687046 | Mathews | Nov 1997 | A |
5687787 | Atmur | Nov 1997 | A |
5691736 | Hunn | Nov 1997 | A |
5692373 | Atmur | Dec 1997 | A |
5702494 | Tompkins | Dec 1997 | A |
5702761 | Dichiara, Jr. | Dec 1997 | A |
5705118 | Hayes | Jan 1998 | A |
5705129 | Takahashi | Jan 1998 | A |
5705444 | Tompkins | Jan 1998 | A |
5721188 | Sung | Feb 1998 | A |
5730096 | Atmur | Mar 1998 | A |
5732555 | Gracyalny | Mar 1998 | A |
5736107 | Inomata | Apr 1998 | A |
5742254 | Bassaler | Apr 1998 | A |
5744763 | Iwasa | Apr 1998 | A |
5749223 | Kreucher | May 1998 | A |
5750026 | Gadkaree | May 1998 | A |
5766458 | Sekhar | Jun 1998 | A |
5772154 | Stewart | Jun 1998 | A |
5773143 | Vermilion | Jun 1998 | A |
5780126 | Smith | Jul 1998 | A |
5783515 | Sakurai | Jul 1998 | A |
5795456 | Friedman | Aug 1998 | A |
5801806 | Dichiara | Sep 1998 | A |
5814397 | Cagliostro | Sep 1998 | A |
5827577 | Spencer | Oct 1998 | A |
5830250 | Shirk | Nov 1998 | A |
5842342 | Strasser | Dec 1998 | A |
5844200 | Leader | Dec 1998 | A |
5849375 | Smith | Dec 1998 | A |
5849406 | Daws | Dec 1998 | A |
5851647 | Foster | Dec 1998 | A |
5853675 | Howorth | Dec 1998 | A |
5853684 | Fang | Dec 1998 | A |
5856263 | Bhasin | Jan 1999 | A |
5866210 | Rosynsky | Feb 1999 | A |
5872067 | Meng | Feb 1999 | A |
5876529 | Grant | Mar 1999 | A |
5879640 | Atmur | Mar 1999 | A |
5882608 | Sanocki | Mar 1999 | A |
5883021 | Beer | Mar 1999 | A |
5884864 | Sunne | Mar 1999 | A |
5907273 | Ross, Jr. | May 1999 | A |
5910095 | Strasser | Jun 1999 | A |
5925156 | Motoki | Jul 1999 | A |
5928448 | Daws | Jul 1999 | A |
5928775 | Dichiara, Jr. | Jul 1999 | A |
5932496 | Morris | Aug 1999 | A |
5939141 | Cagliostro | Aug 1999 | A |
5943857 | Ansell | Aug 1999 | A |
5948146 | Thomaides | Sep 1999 | A |
5948257 | Custer | Sep 1999 | A |
5955177 | Sanocki | Sep 1999 | A |
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0044716 | Jan 1982 | EP |
0047525 | Mar 1982 | EP |
0187256 | Jul 1986 | EP |
0278597 | Aug 1988 | EP |
0244109 | Sep 1990 | EP |
0412315 | Feb 1991 | EP |
0124863 | Apr 1991 | EP |
0421159 | Apr 1991 | EP |
0433582 | Jun 1991 | EP |
0202733 | Jul 1991 | EP |
0441401 | Aug 1991 | EP |
0251150 | Dec 1991 | EP |
0471590 | Feb 1992 | EP |
0561019 | Mar 1992 | EP |
0500154 | Aug 1992 | EP |
0554104 | Aug 1993 | EP |
0236071 | Oct 1993 | EP |
0345795 | Nov 1993 | EP |
0570698 | Nov 1993 | EP |
0431648 | Mar 1995 | EP |
0848535 | Apr 1995 | EP |
0588182 | May 1995 | EP |
0600971 | Nov 1995 | EP |
0704241 | Apr 1996 | EP |
0618353 | Jul 1996 | EP |
0727567 | Aug 1996 | EP |
0734757 | Oct 1996 | EP |
0737859 | Oct 1996 | EP |
0750971 | Jan 1997 | EP |
0769822 | Apr 1997 | EP |
0692995 | Jul 1997 | EP |
0790216 | Aug 1997 | EP |
0819459 | Jan 1998 | EP |
0599595 | Apr 1998 | EP |
0835368 | Apr 1998 | EP |
0884459 | Dec 1998 | EP |
0668252 | Jan 2000 | EP |
1052010 | Nov 2000 | EP |
1085352 | Mar 2001 | EP |
1125704 | Aug 2001 | EP |
1163970 | Dec 2001 | EP |
1180390 | Feb 2002 | EP |
0958874 | May 2002 | EP |
1205228 | May 2002 | EP |
0856645 | Jul 2002 | EP |
1254715 | Nov 2002 | EP |
1222661 | May 2003 | EP |
1326012 | Jul 2003 | EP |
1331118 | Jul 2003 | EP |
1032755 | Nov 2003 | EP |
1366801 | Dec 2003 | EP |
1342889 | Sep 2005 | EP |
WO-9014224 | Nov 1990 | WO |
WO9303262 | Feb 1993 | WO |
WO9416134 | Jul 1994 | WO |
WO-9500235 | Jan 1995 | WO |
WO9620787 | Jul 1996 | WO |
WO-9639244 | Dec 1996 | WO |
WO-9702413 | Jan 1997 | WO |
WO9701599 | Jan 1997 | WO |
WO-9748890 | Dec 1997 | WO |
WO-9802649 | Jan 1998 | WO |
WO9927206 | Jun 1999 | WO |
WO9955459 | Nov 1999 | WO |
WO0008315 | Feb 2000 | WO |
WO0021903 | Apr 2000 | WO |
WO0070915 | Nov 2000 | WO |
WO0071863 | Nov 2000 | WO |
WO0154801 | Aug 2001 | WO |
WO0172663 | Oct 2001 | WO |
WO0173126 | Oct 2001 | WO |
WO0183956 | Nov 2001 | WO |
WO0194760 | Dec 2001 | WO |
WO0197952 | Dec 2001 | WO |
WO03053542 | Jul 2003 | WO |
WO03068362 | Aug 2003 | WO |
WO03069595 | Aug 2003 | WO |
WO2004011783 | Feb 2004 | WO |
WO2004011785 | Feb 2004 | WO |
WO-2004018079 | Mar 2004 | WO |