Patent Application
20100012590
The present invention relates to water treatment and more particularly to the provision of treated water substantially free of both organic and ionic contaminants.
High purity water is required for many purposes, including use in analysis, medicine and biology, as well as for personal use such as drinking and cleaning. Standards for water purity for various uses have been established by a number of professional organizations. The American Society for Testing and Materials (ASTM), for example, classifies purified water into Types I, II, III, and IV, based upon maximum allowable impurities. One measurement commonly employed for quantifying the quality of water is specific resistivity, which is measured by electrical resistance, expressed in megohm/cm at 25° C., as a measure of ionic contamination. Pure water has a theoretical resistivity of 18.2 and water can be provided to various resistivities approaching this value. Non-ionic contaminants such as organic materials and particulates are monitored by other analytical techniques and maximum values are sometimes specified.
Water is purified by a number of techniques, which are often used in combinations, for providing the highest purity. These techniques include filtration, single or multiple distillation, sorption and ion exchange. Water initially treated by distillation or reverse-osmosis filtration is often “polished” or further purified by passage through activated carbon beds to sorb residual materials, principally organics, mixed beds of anion and cation exchange resins to remove residual ions, and then finally filtered through a microporous filter media to remove residual particulates. Water of 18 megohm/cm resistivity and comprising low organic content can be thus provided by the aforementioned techniques.
Unfortunately, activated carbons may contain ionic impurities, and also may collect microorganisms, which are subsequently released into the water. They are therefore normally used prior to treatment of the water with mixed ion (cation and anionic) exchange resins which remove the ions released. These resins, however, are organic and may release trace quantities of organic contamination into the water. Such contamination is usually small, measured in the parts per billion range, and presents no undue problems for many uses. However, for some applications, for example trace organic analysis by high performance liquid chromatography (HPLC), such contamination can produce significant interference. Further, in home or commercial cleaning applications, trace contaminates may leave residue on evaporated water. Thus, cleaning surfaces cannot be left to dry but must be wiped down to remove contamination residue.
The need for improved techniques to reduce organic contaminants for critical applications is described in an article by Poirer and Sienkilwicz, entitled “Organic-free Water”, American Laboratory, December 1980, pages 69-75. This article describes a device utilizing oxidation by ultraviolet light to reduce organics. While apparently effective, this treatment is relatively expensive and such devices restrict total water output.
Presently, there does not appear to be any system or method for filtering water to the extent that such water is able to evaporate from the cleaned surface so that the surface does not contain any remaining film or residue.
In addition, there is at present a great need to provide for drinking water purification systems. Presently, a commercially available, stand alone or in-line water purification system that provides a high level of purity of drinking water for consumers does not appear to be readily available.
Further, emergency desalinization systems for use on boats and other water craft are not readily available or known. Such a system may be used in emergencies, for example, where a ship's drinking water supply has been contaminated or depleted and drinking water is needed to survive until the ship's passengers and crew are rescued. In such a case, no readily available commercial system presently is known that provides a portable desalinization system where a significant volume of sea water may be filtered through the system and then used safely for drinking by the ship's occupants.
A water filtration system and device is herein disclosed and described that effectively treats water such that the water evaporates with virtually no film, reside, or spots. In one aspect, a water filtration system and device is herein disclosed and described that provides a high level of purity in an in-line or portable water filtration system.
In another aspect, a water desalinization system and device for use in emergency situations where sea water (or brackish water) is treated and safely provided to be consumed by the ship's occupants is herein disclosed and described.
In yet another aspect, a system and method for treating water in a dwelling is herein disclosed and described that effectively treats the supply-water such that contaminates are removed or reduced and then provides improved palatability to the water prior to its dispensing for consumption.
Thus, in a first embodiment, a device for treating water is provided. The device comprises a housing comprising an inlet for receiving a volume of water; and an outlet for discharging the volume of water. A first filter media, positioned within the housing, comprises an acidic cation exchange resin capable of exchanging at least a portion of metal cations in the volume of water with non-metal cations such that the volume of water exiting the first filter media is reduced in metal cation content. A second filter media, positioned within the housing, comprises a weakly basic anion exchange resin capable of exchanging at least a portion of the basic anions in the volume of water. The first filter media or the second filter media are optionally mixed with a particulate activated carbon. In an aspect of the first embodiment, the second filter media receives the volume of water after exiting the first filter media.
In combination with any of the aspects of the first embodiment, the device further comprises at least one water-permeable casing separately containing the first filter media or the second filter media.
In combination with any of the aspects of the first embodiment, the acidic cationic exchange resin is selected from the group consisting of crosslinked polystyrenes functionalized with sulphonic acid groups.
In combination with any of the aspects of the first embodiment, the weakly basic anionic resin is selected from the group consisting of crosslinked polystyrenes functionalized with tertiary amine.
In combination with any of the previous aspects of the first embodiment, the device comprises about 60-90 volume % acidic cation in combination with about 40-10 volume % weakly basic anion resin, optionally with about 5-10% activated carbon.
In combination with any of the aspects of the first embodiment, the device further comprises at least one unit in fluid communication with the housing, the at least one unit adapted to receive the volume of water prior to contact with the first filter media. The at least one unit comprises a particulate filter media capable of reducing the level of particulates in the volume of water; and a redox filter media capable of chemically reducing or chemically oxidizing at least one component in the volume of water.
In combination with the previous aspect of the first embodiment, the particulate filter media is silica having a bulk density of about 24-26 pounds per cubic foot, and a density of about 2.25 grams per cubic centimeter.
In combination with the previous aspects of the first embodiment, the redox filter media is a copper-zinc alloy.
In combination with any of the aspects of the first embodiment, the device of any of the preceding claims, further comprising a third filter media comprising a carbonate salt of calcium, wherein the third fluid media receives the volume of water after exiting the second filter media.
The use of the device is provided for drinking water for a dwelling, for spotless washing, or for desalinating water.
In a second embodiment, a method of treating water is provided. The method comprises the steps of (i) contacting a volume of water with a first filter media optionally mixed with activated carbon, wherein at least a portion of metal cations present in the volume of water are exchanged with non-metal cations in the first filter media such that the volume of water exiting the first filter media is reduced in metal cation content; and (ii) contacting the volume of water with a second filter media comprising a weakly basic anion exchange resin optionally mixed with activated carbon, wherein at least a portion of anions present in the volume of water are exchanged with anions of the second filter media, the first and second filter media being in fluid communication with each other. The volume of water provided by the method evaporates without leaving a visible residue.
In combination with any of the aspects of the second embodiment, the volume of water exits the first filter media before contacting the second filter media, where the volume of water exiting the second filter media is reduced in metal cations and halogen anions such that the volume of water evaporates essentially spotless.
In combination with any of the aspects of the second embodiment, the method further comprising contacting the volume of water after contacting the second filter media with a carbonate salt of calcium, where at least a portion of the volume of water is increased in the amount of calcium cation, whereby the palatability of the volume of water is improved.
In combination with any of the aspects of the second embodiment, the first filter media is an acidic cationic exchange resin selected from the group consisting of crosslinked polystyrenes functionalized with sulphonic acid groups, the first filter media exchanging at least some protons with the metal cations of the volume of water. The second filter media is a weakly basic anionic resin selected from the group consisting of crosslinked polystyrenes functionalized with tertiary amine, the second filter media exchanging at least some hydroxide ions with the halogen anions of the volume of water.
In yet another embodiment, a supply water treatment system is provided comprising a Point of Entry unit fluidically coupled to a Point of Use unit. The Point of Entry unit is fluidically coupled to a dwelling's supply water and comprises a particulate filter media capable of reducing the level of particulates in the volume of water; and a redox filter media capable of chemically reducing or chemically oxidizing at least one component in the volume of water. The Point of Use system comprises a first filter media comprising an acidic cation exchange resin capable of exchanging at least a portion of metal cations in the volume of water with non-metal cations such that the volume of water exiting the first filter media is reduced in metal cation content, and a second filter media comprising a weakly basic anion exchange resin capable of exchanging at least a portion of the basic anions in the volume of water. The first filter media or the second filter media are optionally mixed with a particulate activated carbon.
Features and advantages of the present invention will become more apparent in light of the following detailed description of some embodiments thereof, as illustrated in the accompanying figures. As will be realized, the invention is capable of modifications in various respects, all without departing from the spirit and scope of the invention. Accordingly, the drawings and the description are to be regarded as illustrative, and not as restrictive in nature.
The invention will now be described with reference to the accompanying drawings which illustrate disclosed embodiments of the ratcheting tool of the present invention falling within the scope of the appended claims.
A device for treating water is provided. The device generally comprises a housing having an inlet for receiving a volume of supply water; and an outlet for discharging a volume of exiting water. The volume of water enters the housing through the inlet and is urged into contact with a first filter media. The first filter media comprises an acidic cation exchange resin where the first filter media is capable of exchanging at least a portion of metal cations in the volume of water with non-metal cations such that the volume of water exiting the first filter media is reduced in metal cation content. Suitable acidic cationic exchange resins may include materials selected from crosslinked polystyrenes functionalized with sulphonic acid groups. Other acidic cation exchange resins may be used provided they are capable of exchanging at least a portion of metal cations in the volume of water with non-metal cations, preferably, hydrogen ions.
The volume of water after having been contacted with the first filter media is urged into contact with a second filter media. The second filter media, positioned within the housing, comprises a weakly basic anion exchange resin capable of exchanging at least a portion of the basic anions in the volume of water. Suitable weakly basic anionic resins may include materials selected from crosslinked polystyrenes functionalized with tertiary amine. Other weakly basic anion exchange resins may be used provided they are capable of exchanging at least a portion of the basic anions in the volume of water, preferably providing hydroxide ion. The first filter media or the second filter media may optionally be mixed with a particulate activated carbon. Multiple layers of the first and second filter media may be arranged within the housing, such that the volume of water is urged into contact with the acidic filter media followed by the weakly basic filter media. This particular arrangement of filter media may be repeated as desired in the housing to achieve the level of water treatment required.
The device is useful for spotless washing as the supply water, upon contact with the filter media arranged as described, is reduced of dissolved or suspended components, which upon evaporation would otherwise remain as a residue, usually a visible residue. Moreover, the device is also useful for desalinating water in an emergency, as the sediments and salts of the otherwise non-potable supply water are reduced or removed to provide potable water.
In a second embodiment, a water treatment system is provided that is adaptable to a dwelling, such as a public, residential, or commercial establishment, building or structure. The system comprises a Point of Entry (POE) unit and optionally at least one auxiliary Point of Use (POU) unit. The POE unit is adapted to receive a volume of water entering the dwelling and is further adapted for fluid communication with the existing water-supply lines of the dwelling. At least one POU units are adapted for fluid communication with the water-supply lines and may be positioned in proximity to typical water dispensing devices, such as spigots, sinks, home appliances, etc. In a preferred aspect, at least one POU unit is adapted for providing water for drinking, cooking, and for servicing a home appliance, such as a refrigerator.
In one aspect of the second embodiment, the water treatment system is designed to receive a volume of water and to cause contact of the water with one or more materials in a sequential or staged manner. In one aspect, the system is adapted to contain materials for treating the water in one or more replaceable containers.
In one aspect, the system removes a portion of heavy metals, metal salts, VOC's, chlorine, pharmaceuticals, pesticides, herbicides, fungicides, sediment, etc., and additionally may “soften” the water. The removal of metals and their salts providing may prevent mineral buildup in equipment associated with the water system of the dwelling, such as water heaters, toilets, appliances, and interior plumbing.
In one aspect of the second embodiment, the device and method of water treatment for a dwelling comprises at least two tanks in fluid communication with each other, each of the tanks comprising one or more filter medias contained in one or more canisters. The bottom of one canister is configured to fluidically engage with the top of another canister. In one aspect, the tanks are fluidically connected in series such that the volume of water and its flow path is at least partially controlled as it migrates through the filter medias.
In another aspect, each of the canisters is configured to be removed and replaced, for example, by the dwelling owner or service provider. Means are provided for rapid replacement of the canisters with minimal or no spillage of the filter media.
Referring now in more detail to the drawings in which like numbers indicate like parts throughout the several views,
The lid 14 is removable from the collar 15. The collar 15, as shown in more detail in
Lid 14, as shown in more detail in
Lid 14 also has an inner ring 80. Ring 80 has base 82 and tip 84. The inner radial surface 86 of ring 80 is tapered so that base 82 of ring 80 where it is joined to the lid body 30 is thicker than tip 84 of the ring. The ring 80 interacts with the collar 15 in use to form a fluid seal.
The base 16 of the housing 12 is fixed to the pipe 18 by means of a slip fit and adhesive, as shown in
The base body 50 is made up of a base floor 62 and a series of base walls 64 extending upward from the base floor, as shown in
In one aspect, two filter medias are located within the housing 12, as shown in
Likewise a second filter media casing is filled with a second filter media 68. In one aspect, the first filter media composition 66 comprises a mixture of activated carbon and a strongly acidic cation gel ion exchange polymer. The particulate composition of the first filter media may comprises a strong acidic cation gel ion exchange resin, (for example, SST60 manufactured by Purolite), the remainder being activated carbon. The resin and carbon may be randomly dispersed therein or they may be layered. In a preferred aspect, the carbon is randomly dispersed in the acidic resin by mixing or commutating.
The second filter media 68 is prepared in a similar manner to that of the first filter media, and may be made of the same or similar casing. In a preferred embodiment, the second filter media casing is also 100% polyester knit, (Carriff Corporation, part no. FA-04355C Red). The casing for the second filter media 68 holds a second filtration particulate composition 76. In one aspect, the second filtration particulate composition 76 comprises a mixture of activated carbon and a weak base anion macroporous ion exchange resin. For example, an exemplary second filtration particulate mixture comprises 5% by volume activated carbon and 25% by volume weakly base anion macroporous ion exchange resin. In a preferred aspect, the weakly basic resin is a crosslinked polystyrene resin having tertiary amine functional groups, for example, A113S manufactured by Purolite, and the activated carbon is coconut shell-derived, for example, 1230 cc manufactured by United States Resin Company.
In the event that the supply water is intended for drinking, the relative proportions of cation and anion resins, and carbon may be varied. For example, for treating supply water for drinking, the relative volume proportions of cation resin and the basic anion resin with carbon may be approximately 40%, 55% and 5% respectively.
The overall interior volume of a container may be measured, and a margin of 20% of the measure volume may be deducted to allow for later expansion of the filter media and the corresponding casing. In one aspect, at least a portion of the remaining 80% volume of the container after the margin of 20% is determined is occupied by the second filter media. Thus, for example, 60% of the remaining volume, or 48% of the total volume, may be occupied by the first filter media, and a corresponding 40% of the remaining volume, or 32% of the total volume, may be occupied by the second filter media. The volume % range of the acidic cation and anion resins and carbon may be between 60-90%, 40-10% and 5%, respectively, with a margin of ±5% when treating water for cleaning purposes. In one preferred aspect, the acidic cation resin filter media casing is devoid of carbon and the basic anion resin filter media includes carbon. Thus, the ratio of cation resin, anion resin with carbon may be 60%, 40% and 5% respectively; 70%, 25% and 5% respectively; 80%, 20% and 5% respectively; or 90%, 10% and 5% respectively, with a margin of ±5%, with the carbon mixed with the basic anion resin in the second filter media. In a preferred aspect, the ratio of cation resin, anion resin with carbon is preferably 70%, 25% and 5% respectively, with the carbon mixed with the basic anion resin in the second filter media. These ratios are observed to provide acceptable surface cleaning and spot-free drying for a wide range of supply water.
As a result of the supply water contacting the filter media, one or both of the filter medias may be altered in terms of their relative volume. The resin may expand until its activity is diminished. Thus, the device disclosed and described herein is adapted to exploit this feature in its design and for providing user-indication of the replacement interval.
Referring to
Once both filter medias and casings are inserted into the housing 12 the lid 14 may be secured to the collar 15. This is done by placing the lid 14 over the collar 15. The lid 14 is positioned relative to the collar 15 so that the collar lips 20 and the lid ledges 38 are spaced apart. The lid 14 is then rotated by the user at the handle 32 in a counterclockwise direction so as to rotate the ledges 38 underneath the collar lips 20. As the lid 14 is rotated, each ledge 38 moves underneath a corresponding lip 20 until the ledge meets the stop member 28 of the corresponding lip 20, as shown in
The fully assembled device is then connected to a supply water source via inlet 21, for example, a garden hose which is threaded to the water inlet 21. In use, the supply water passes through the water inlet 21 and into the housing 12. As the water enters the housing 12, the water contacts first filter media 66 housed within the casing 70. The first filtration media interacts with the water to bond or otherwise reduce or remove various compounds present in the supply water. While not being held to any particular theory, it is believed that many minerals typically present in most water supplies have a positive charge associated to them. These positively charged contaminates may become electrostatically attracted to certain electrolytic compounds in the first filter media and are thus removed or reduced from the water, at least a portion of the mineral cations being exchanged for non-metallic cations, preferably protons. As a result, as the water exits the first filter media, many of the positively charged contaminates, such as metallic or mineral cation contaminates originally present in the supply water, are removed or reduced, and remain within the first filtration particulate mixture. As the first filter media is acidic, it is likely that the overall pH of the water as it exits the first filter media may be acidic (e.g., pH range of less than 7) or in any event, more acidic than the supply water. In use, the pH of the water exiting the first filter media casing may range from 3-6 depending on the level of exhaustion of the acidic cation resin.
Subsequently, the water that has exited the first filter media 66 then passes through the second filter media 68. As it passes through the second filter media 68, which interacts with certain other contaminates in the supply water so as to remove or reduce at least a portion of these contaminates, preferably contaminates having associated therewith a negative charge, such as for example, chloride and other halogen ions. In addition to halogen ions, silicas, bicarbonates and other weak acids may be substantially removed or reduced from the water during contact with the second filter media 68. As the second filter media 68 is primarily basic in its pH, the water exiting the first filter media 66 and contacting the second filter media is substantially neutralized, typically providing exiting water with a pH between 6 and 6.8.
In a preferred aspect, the device is configured such that the supply water substantially first contacts the acidic cationic resin and then contacts the supply water contacts the weakly basic anion resin. The pH level of the water exiting the acidic cation resin in the first filter media 66 will likely be between 3-6. The basic anion resin in the second filter media 68 will likely add hydroxide to the free hydrogen from the acidic cation resin in the first filter media 66 and combine to form water. This reaction results in adjusting the pH of the exiting water (for example, to a slightly acid, neutral level, around between 6 and 6.8).
Once the water has passed through the second filter media 68 it moves through the tortuous pathway formed by the base walls 64 and out through the water outlet 52. The water may be used as drinking water or applied to cleaning surfaces, such as cars or boats. In this use, the quality of the water is such that the discharged water will evaporate from the cleaned surface and leave substantially no residue or spots.
The present system and method are focused, in part, on treating water that will not leave any spots or residue when it evaporates on a particular surface. For this reason, small amounts of neutrals and gases may remain in the exiting water as they generally do not impact on spotting.
A diagrammatic depiction of the process of treating supply water as herein disclosed and described is depicted schematically in
Without being held to any particular theory, it is believed that the activated carbon present in the filter media helps to remove or reduce undesirable properties of the supply water, such as odor and taste, as well as removing or reducing the level of mineral salts, chlorines and other components that would otherwise leave a residue upon evaporation of the water. The use of admixed activated carbon may also help to extend the life of the resin media. In one aspect, the coconut shell activated carbon disclosed herein is preferred as providing a greater surface area for reacting with the incoming water than other activated carbons.
In the second embodiment and by way of example illustrated by
The first canister 206a comprises treaded opening 232 at one end, and nipple 240 at the opposite end, as shown in
Upon exiting first canister 206a, the volume of water may then urged into an optional second canister 206b in first tank 208a. The second canister is in fluidic communication with the first canister via lid 232 such that the first and second canisters are arranged in series. Second canister 206b may comprise the same filter media 250 as the first canister, such as Filter media AG, or optionally may also comprise a bed of crushed calcium carbonate, for example, should the volume of water have a low pH. It is generally believed that in this arrangement of the first and second canisters there is substantial removal of the aforementioned sediments and iron salts in the volume of water prior to contact with the subsequent downstream filter media of the system. For example, as will become apparent in the disclosure below, dirt, silt, and oxidized iron will likely have a detrimental effect on the ability of the filter media in subsequent canisters, and should otherwise be avoided.
Upon exiting the second canister via second orifice 230 of base plate 218, the volume of water is then urged into a second tank 208b via conduit 214, second tank 208b comprising a third and optionally a fourth canister (206c, 206d). The third canister 206c is in fluidic communication with the fourth canister 206d such that the third and fourth canisters are arranged in series. Third canister 208c comprises filter media 260 comprising finely granulated material capable of oxidizing and reducing contaminates in the water (a redox media) together with granular activated carbon (GAC). The redox media may comprise finely granulated copper and zinc alloys. Suitable alloys include, for example, KDF 55 or KDF 85 (Fluid Treatment, Inc.). The redox media and GAC may be mixed in any proportions suitable for effective and efficient removal of the contaminates in the volume of water. Thus, in one aspect, the volume ratio of the material of the third canister comprises about 50% KDF 55 (or KDF 85) and 50% GAC. The GAC preferably is an arsenic free carbon, or one that is not from a coal source. The particular KDF may be chosen based on the source of the volume of water. For example, if the volume of water is provided by a municipality, KDF 55 may be used such that effective and efficient conversion of chlorine to chloride ion may be achieved, which when further contacted with the weakly basic filter media of the POU component of the system would be at least partially exchanged for another ion as previously described. If the volume of water is supplied by a well, for example, then a mixture of 50% KDF 85 and 50% GAC may be used, such that ferrous salts and hydrogen sulfide may be effectively and efficiently removed or reduced. In one aspect, the KDF Filter Media is used in a layered arrangement. In another aspect, to get the amount of through flow and the most amounts of usable gallons through the filter media, it is preferred to mix the KDF and GAC together in about a 50% to 50% ratio by volume.
Upon exiting the third canister 206c, the volume of water is then urged into the optional fourth canister 206d in the second tank. The third and fourth canisters may be stacked upon each other as described above and configured to urge the volume of water in a predetermined manner through the system. The fourth canister may comprise generally the same filter media and filter media arrangement as in the third canister. For at least one reason, the third and fourth canisters may comprise the same filter media in the event of a constant or intermittent high flow condition where there may be some leakage or the filter media of the third canister is loosing some of its activity. As the volume of water contacts the filter media of the third and fourth canisters, at least a portion of the contamination present in the volume of water is oxidized and/or reduced upon contact with the redox media. The volume of water exiting the system is thus reduced in metal cation content and halogen anions, providing improved supply water. The volume of water leaving the Point of Entry Unit via conduit 224 may be used through the entire dwelling and can be used as a universal unit for any number of applications. Preferably, the volume of water is sent to at least one POU device as now described.
The POU device is essentially configured as the first embodiment device as previously described. Thus, referring to
A comparative example demonstrating the improved exit water quality achieved using the embodiments described and disclosed with that of a commercially available system water treatment system were performed. Thus, a CR Spotless unit by Spotless Water Systems of San Diego, Calif., which is believed to comprise a mixture of de-ionizing resins, not otherwise separated, including a strongly basic anionic resin, were compared to the system herein disclosed and described. The CR Spotless unit was subjected to the same tests and testing equipment for spotting and TDS in ppm vs. Total Flow in gallons. The comparison data of the two systems are graphically depicted in
Experiments were preformed using the filter media composition and arrangement as described above for sample 4 using a sample of the Atlantic Ocean as supply water. The quality of the exit water obtained is summarized below. TDS of the exit water was reduced from 35,500 ppm to 364, the palatability of the water was rendered acceptable, and the pH was slightly raised. Thus, for at least certain emergencies of a temporary duration, the system herein disclosed and described may provide for substantial improvement of ocean or brackish supply water suitable for drinking.
As the water supplies both city and rural are being stressed with the growing population, it is desirable for each individual dwelling owner or municipality to ensure the quality of the water consumed by persons from water problems both harmful or of a nuisance.
The water processing system as herein disclosed and described does not require that the user add regenerating chemicals, such as salt to the system. Nor is it necessary to “backwash” or otherwise “regenerate” the system, which provides for improved water conservation. Moreover, because the system does not need electricity, it also provides for energy conservation. The canisters that contain the filter media are designed and configured to be reversibly installed and removed for replacement of the filter media and thus can be reused again and again. The filter materials are generally recyclable as well. Thus, it is generally believed that the environmental impact for the above disclosed water treatment system is minimized, for example, when compared to other types of systems typically used for water treatment of dwellings.
The following claims are in no way intended to limit the scope of the invention to the specific embodiments described. It should be understood by those skilled in the art that the foregoing modifications as well as various other changes, omissions and additions may be made without parting from the spirit and scope of the present invention.
This application claims the benefit of U.S. Provisional Application No. 61/051,926 filed May 9, 2008, the entire disclosures of which is incorporated herein by reference in their entirety.
| Number | Date | Country | |
|---|---|---|---|
| 61051926 | May 2008 | US |
