Patent Grant
7553420
The present invention relates to a method and composition for controlling odors emanating from organic waste produced by metabolic processes, including human and animal waste, as well as industrial wastes, effluents, sewage, and the like.
The biogenic production of volatile compounds which cause objectionable odors is one of the problems associated with the collection and treatment of various waste materials. Domestic sewage is the largest source of such odorous compounds. Various reduced sulfur-containing compounds are common, with hydrogen sulfide being the most objectionable odor-causing compound in such wastes. Because of the magnitude of domestic sewage that is collected and treated and the prominence of the associated odorous sulfidic compounds, the present invention is particularly directed, but not limited to the control of hydrogen sulfide and other sulfide odors in municipal or industrial waste. As used herein, the term “sulfidic compounds” also includes hydrogen sulfide (H2S), mercaptans (RSH), and other related odoriferous sulfidic compounds.
The mixed biological population common to municipal or industrial waste utilizes the compounds found in the waste as a source of nutrient. In this process, oxygen is the preferred terminal electron acceptor, and the nutrient, commonly an organic compound, is oxidized. In highly nutrient loaded systems such as municipal sewage, bacterial action can result in a rapid consumption of oxygen in the water. In the absence of oxygen, bacteria require an alternate terminal electron acceptor.
In general, bacteria will utilize the terminal electron acceptor that provides them with the greatest amount of energy. Thus, there is a preferred selection order of a terminal electron acceptor by bacteria. This order is shown below.
O2>NO3−>Fe>SO4−2>CO3−2
As nitrate is not typically found in natural waters, the sulfate ion (SO4−2) is generally the preferred alternate. In the absence of oxygen, unless nitrate is added supplementally, those bacteria which can utilize sulfate as a terminal electron acceptor in their respiration process will predominate. The most well-characterized bacteria of this type is Desulfovibrio desulfuricans, and is most commonly referred to as sulfate-reducing bacteria, SRB. SRB are known to metabolize sulfate ion with organic matter to form H2S as shown in the following equation.
SO4−2+organic matter+SRB→H2S+CO2+H2O
H2S, responsible for the characteristic odor from rotten eggs, is toxic in low concentrations. Citizen complaints are often the driving force behind efforts to control odor. Such odors are generally regarded as a public nuisance and a health hazard.
Although H2S is a gas, H2S in water can dissociate with increasing pH as shown in the following equations. Thus at a given pH, the relative amount of dissolved H2S species can be predicted. The sulfide ion, S−2, and bisulfide ion, HS−, being ionic, are constrained to remain in the aqueous phase.
H2S+OH−→HS−+H2O
HS−+OH−→S−2+H2O
The FIGURE herein shows the relationship between these species, the evolution of the gas from aqueous solution being a function of pH. At the pH typically found in sewer systems, a significant percent of the H2S formed evolves from solution. The gas can redissolve on the crown of the sewer line, and the presence of Thiobacillus bacteria and others, metabolize the H2S, producing sulfuric acid, H2SO4. This can and has resulted in sewer line collapse and results in a significant cost in terms of their repair and replacement.
H2S is also corrosive towards steel and concrete. H2S is a gas, with the evolution of the gas from aqueous solution being a function of pH. At pHs often found in sewer systems, a significant percent of the H2S formed evolves from solution. The gas can redissolve on the crown of the sewer line, and the presence of Thiobacillus bacteria and others, metabolize the H2S, producing sulfuric acid, H2SO4. This can and has resulted in sewer line collapse and results in a significant cost in terms of their repair and replacement.
Various compounds, including hypochlorite (sodium or calcium), potassium permanganate, sodium nitrate, ferrous and ferric salts, hydrogen peroxide, chlorine, chlorine dioxide, and sodium chlorite have been widely used for the control of odor in wastes, and sewage waste in particular.
Sodium chlorite has been used alone for odor control. Several references to such use follow:
It is also known that nitrates added to sewage effect reduction in BOD and even suppress the formation of hydrogen sulfide gas via bacterial action.
U.S. Pat. No. 3,300,404 for example, cites the use of about 500 ppm of nitrate to prevent odor emanation from a lagoon.
U.S. Pat. No. 4,911,843 cites the use of cite the use of nitrate to remove existing sulfide. A dosage of 2.4 parts nitrate-oxygen per part of existing dissolved H2S is required.
U.S. Pat. Nos. RE36,651 and RE37,181E cite the use of nitrate to remove existing sulfide. A dosage of 2.4 parts nitrate-oxygen per part of existing dissolved H2S is required.
Even nitrite has been used to control sulfate reducing bacteria and associated odors:
U.S. Pat. No. 4,681,687 cites the use of sodium nitrite to control SRB and H2S in flue gas desulfurization sludge.
In addition, the use of some sulfide reactive chemicals in combination with nitrates is known:
For example, U.S. Pat. No. 3,966,450 cites the use of 5-500 mg/L of hydrogen peroxide and the addition of nitric acid to maintain a pH of 3.5-5.5 to enhance the nutrient value of the waste.
U.S. Pat. No. 4,108,771 cites the use of chlorate and nitrate coupled with an iron salt in pH<5 to control odors in a waste stream.
U.S. Pat. No. 4,446,031 cites the use of an aqueous solution of ferric sulfate and ferric nitrate in a ratio of from 1:0.5 to 1:3 to control odors in rising sewer mains. Optionally the composition may contain nitric acid.
U.S. Pat. No. 5,114,587 cites the use of nitrate in conjunction with oxygen, air, or iron salt, the dosage controlled by ORP, to reduce the concentration of soluble organic matter.
U.S. Pat. No. 5,200,092 cites the use of about 0.5 to about 10 weight percent potassium permanganate with about 0.5 to about 42 weight percent sodium nitrate for odor control. Feedrate of the product is such that the permanganate:sulfide ratio is maintained in the range of from about 2:1 to about 6:1.
U.S. Pat. No. 5,405,531 cites the use of nitrite and nitrate and/or molybdate for removal of H2S in an aqueous system.
U.S. Pat. No. 5,984,993 cites the use of a synergistic blend of 22.5 weight percent chlorite salt and 10 weight percent sodium nitrate for controlling odors.
A combination of nitrate and microorganisms is taught in the following patent:
U.S. Pat. No. 6,059,973 teaches an emulsion of nitrate and microorganisms of the Bacillus type for odor control in sewers.
Other compounds reactive with sulfide are known:
U.S. Pat. No. 3,959,130 cites the use of pH adjustment to a value over 7.0 and bringing the stream into contact with an ash product to control cyanide and hydrogen sulfide.
U.S. Pat. No. 4,501,668 cites the use of polycondensation products produced by the condensation of acrolein and formaldehyde to consume hydrogen sulfide in aqueous systems, such as waste water clarification plants.
The use of compounds to elevate pH to convert sulfide species to ionic species which remains in solution and minimizes H2S gas evolution is taught in the following patents:
U.S. Pat. No. 3,959,130, describes the use of fly ash to elevate the pH of a waste stream containing cyanide and possibly H2S to above 8.0.
U.S. Pat. No. 5,833,864, cites the use of magnesium oxide or magnesium hydroxide to elevate the pH to the range of 7.5-9.5, thus minimizing the amount of sulfide in the form of gaseous H2S.
The use of compounds to elevate pH to convert sulfide species to ionic species which remains in solution and minimizes H2S gas evolution is taught in the following patents:
U.S. Pat. No. 3,959,130, describes the use of fly ash to elevate the pH of a waste stream containing cyanide and possibly H2S to above 8.0.
U.S. Pat. No. 5,833,864, cites the use of magnesium oxide or magnesium hydroxide to elevate the pH to the range of 7.5-9.5, thus minimizing the amount of sulfide in the form of gaseous HxS.
Some of the treatments using specific chemicals have advantages in certain applications. However, they also suffer from various drawbacks, some of which are listed below. The chemicals are separated by their rate of reaction with sulfide or H2S.
In view of the disadvantages cited above, there is a need in the art for a method and composition for abating odor in waste materials that is cost effective, has the capability of consuming aqueous sulfide or H2S immediately, adjusts the pH into a range where H2S form is very low and provides long term control of biogenic sulfide production. Accordingly, it is an object of the present invention to address this need in the art. This and other objects of the present invention will become more apparent in light of the following summary and detailed description of the invention.
This invention relates to a method and composition for the elimination or reduction of sulfidic odors in sewer systems, municipal waste treatment plants and in other industrial waste applications. The composition comprises a synergistic combination of a rapid sulfide-consuming chemical, which is selected from the group comprising an iron salt, a hypochlorite, a permanganate, a persulfate, a perborate, a periodate, a percarbonate, a chlorite, a nitrite, a chlorate, a perchlorate, a peroxide and mixtures thereof and a nitrate salt from the group comprising an ammonium, alkali alkaline metal, or metal nitrate. The method according to the present invention comprises the step of contacting the waste products or their surrounding airspace with the composition.
Existing sulfides are consumed immediately by the sulfide-consuming chemical. The pH-elevating compound adjusts the pH into a range of 7.5-8.5, where the form of sulfide soluble only in aqueous solution is promoted. In addition, adjustment of the pH into this range promote growth of sulfide-oxidizing, nitrate-reducing bacteria, which grow best in this pH range. The nitrate then inhibits the biogenic production of H2S downstream by both promoting the growth of various sulfide-oxidizing bacteria and inhibiting the growth of anaerobic sulfate reducing bacteria by elevating the oxidation reduction potential into a range which do not provide an environment conducive to their growth. In systems where no sulfide-oxidizing bacteria exist, such bacteria or their enzymes may be incorporated into the formulation. Malodorous compounds can be destroyed and prevented easily, rapidly, at a reasonable cost and continue to be controlled with the composition according to the present invention.
The composition for controlling odor from waste products according to the present invention comprises a combination of a rapid-acting sulfide-consuming material and a longer acting material which prevents biogenic sulfide production. For water streams which do not contain sufficient sulfide-oxidizing bacteria, such bacteria are incorporated into the formulation. The rapid-acting sulfide consuming material is selected from the group which includes an iron salt, or a hypochlorite, a permanganate, a persulfate, a perborate, a periodate, a percarbonate, a chlorite, a nitrite, a chlorate, a perchlorate and a peroxide of ammonium, metal or alkali metal and mixtures thereof. The longer acting chemical which prevents the formation of biogenic sulfide is an ammonium, alkali, alkaline metal, or metal nitrate. As used herein, the term “controlling odor” means reducing and/or eliminating odor that is offensive to humans. Such odors are usually caused by volatile sulfides and other volatile odorous substances.
Exemplary of a bacterial microorganism useful for the herein disclosed invention is Thiobacillus denitrificans which has the ability to oxidize a variety of reduced sulfur compounds, including H2S (sulfide), S (elemental sulfur), S2O2−2 (thionite ion), S4O6−2 (dithionite ion), and SO3−2 (sulfite ion). The microorganism can function either aerobically or anaerobically with nitrate.
The waste products treatable with the present invention include, but are not limited to organic waste produced by metabolic processes, including human and animal waste, as well as industrial wastes, effluents, sewage, and the like. The preferred aqueous composition includes sodium chlorite at a weight percent of 0.01-0.39%, and sodium nitrate which may range in concentration from 40-80% weight percent, and water at 19.6-59.99 wt %. The preferred dry composition includes sodium chlorite at concentrations of 1-65%, sodium nitrate at 6-90%, magnesium hydroxide or magnesium oxide at 30-95%, a dry bacterial consortium containing mostly Thiobacillus denitrificans at concentrations of 0.001-2% by weight, and a blend of dry enzymes including mostly sulfide dehydrogenase at concentrations of 0.001-2% by weight.
The aqueous solution or the dry composition according to the invention can be employed to destroy and prevent the malodorous characteristics of odor causing compounds such as sulfides found in sewage and other waste products. The solution can be pumped into the material to be treated (liquid, sludge, or solid) or sprayed onto the surface or into the airspace surrounding the material. The dry material can be mixed into a slurry or solution at the point of application and applied in a similar manner.
A solution of sodium chlorite and sodium nitrate according to the invention can be employed to destroy and prevent the malodorous characteristics of odor causing compounds such as sulfides found in sewage and other waste products. The solution can be pumped into the material to be treated (liquid, sludge, or solid) or sprayed onto the surface or into the airspace surrounding the material.
Sodium chlorite is relatively non-reactive with the vast majority of compounds found in sewage. It will react rapidly with sulfide. Thus, the vast majority of the chlorite added to the sewage will consume sulfide, which allows such low levels to be used. The sodium chlorite provides rapid control of low levels of sulfides commonly found at upstream points early in the sewer line distribution system. The treatment concentration is directly dependent upon the amount of odor causing compounds with chlorite demand that are present in the waste.
The sodium nitrate prevents sulfate reducing bacteria from producing H2S. The arrest of H2S production using nitrate alone is not immediate, can take from 10-24 hours, and will remain until no nitrate is present. The concentration of nitrate salt present in the treatment solution may vary depending upon the amount of residual control of malodorous compounds that is required. Nitrate is less costly than chlorite and thus lowers the cost per pound of the treatment solution. Using a combination of nitrate plus chlorite treatment of sulfide odors also has an unexpected beneficial effect. It is expected that the treatment combination is capable of controlling sulfide odors much more effectively than the sum of the control when using either nitrate or chlorite alone.
As the nitrate requires the presence of nitrate-reducing, sulfide-oxidizing bacteria for it to be effective at consuming sulfide, in systems where no such bacteria reside, such nitrate-reducing, sulfide-oxidizing bacteria or their enzymes may be incorporated into the formulation.
The pH-elevating salt results in an increase in the pH of the waste to be treated, causing the H2S to revert to a soluble form of bisulfide ion, HS−, or sulfide ion, S−2. Controlling the pH of the waste in a range of above 7.5 has also been shown to promote the growth and metabolism of sulfide-oxidizing nitrate-reducing bacteria.
In another embodiment, it is desirable for one of the nitrates to be aluminum nitrate, as use of aluminum salts is known to be effective for phosphorous removal, which is a common problem in municipal wastewater treatment plants. Employment of aluminum nitrate as one of the nitrate salts in the above mentioned formulation can have additional positive benefits which include both rapid consumption of sulfide by the Al+3 ion and also promote the removal of phosphorous downstream in the wastewater treatment plant.
It is to be pointed out that U.S. Pat. No. 6,059,973 discloses a mixture of chlorite salt and nitrate salt, the ratios of the patent are different than those claimed herein. Note that the effective range of the herein disclosed invention employs more nitrate than chlorite.
Bacterial consortia is defined as meaning a group of bacteria as found in nature. That is in nature, bacteria do not exist independently of other bacteria. There is always a community required to survive. It is not always feasible nor possible to single out a bacterial strain of the mix. In the a consortia or community of this invention, the predominant bacteria is one like Thiobacillus denitrificans (although others are known), which has the ability to oxidize sulfide while using nitrate as the terminal electron acceptor.
In the processes of this invention, the aluminum ion also can react with sulfide in a 3:1 molar ratio and tie up the sulfide and prevent it from off-gassing to cause odor problems. So the aluminum has a double benefit. Tying up the sulfide short term and then precipitating with the phosphate later in the waste treatment plant.
In greater detail the herein disclosed invention is directed to a composition useful for reducing sulfidic odors comprising effective amounts of a sulfide consuming chemical and a nitrate compound. Effective amounts are those amounts herein disclosed. The sulfide consuming chemical may be a chlorite salt and the nitrate compound may be a nitrate salt, with the amount of nitrate compound being in excess of the sulfide consuming chemical. More specifically the chlorite salt is sodium chlorite present in an amount of 0.01-0.39% and the nitrate compound is sodium nitrate and is present in an amount of 40-80%.
The invention also involves a process for removing dissolved hydrogen sulfide and odoriferous reduced sulfur compounds found in waste systems comprising the step of adding to the waste system an aqueous composition comprising a combination of a sulfide consuming chemical, a nitrate salt, and bacterial consortia in a wt ratio comprising 2-10 parts sulfide consuming chemical, 40-80 parts of nitrate salt, 0.01-1 part bacteria or bacterial enzyme, and 9-57.99 parts water. The sulfide consuming chemical may be selected from the group comprising alkali metal salts of hypochlorite, chlorite, nitrite, peroxide, percarbonate, perborate, or ferrous or ferric iron salts, peroxy monosulfuric acid, chlorine, hydrogen peroxide, chlorine dioxide and mixtures thereof. The preferred alkali metal chlorite is selected from the group comprising sodium chlorite, calcium chlorite, potassium chlorite and mixtures thereof, and the most preferred alkali metal chlorite is sodium chlorite. The nitrate salt is selected from the group comprising sodium nitrate, calcium nitrate, potassium nitrate, ammonium nitrate, aluminum nitrate and mixtures thereof. A mixture of ammonium nitrate and other nitrate salts may be employed to achieve a desired crystallization temperature. In a specific embodiment an aluminum nitrate is one of the nitrate salts in the blend and is fed so that the aluminum has the benefit of reducing phosphate in the downstream wastewater plant. In the process the bacterial consortia are comprised of a mixture of nitrate reducing and sulfide-oxidizing bacteria, or enzymes produced by nitrate-reducing, sulfide-oxidizing bacteria. The preferred bacteria is Thiobacillus denitrificans, and the preferred enzyme is sulfide dehydrogenase. In the process the aqueous composition may be in the form of an aqueous solution and the composition may be added to provide sulfide consuming chemical in the ratio of 2-10 parts sulfide-consuming chemical per part sulfide to accomplish removal of sulfide. Further, the composition may be added to provide nitrate ion in the ratio of 10-30 parts nitrate ion per one part sulfide ion by weight. In a most specific process for removing dissolved odoriferous sulfidic compounds including all odoriferous reduced sulfur compounds found in wastewater including dissolved hydrogen sulfide comprises the steps of adding to the waste either as a dry solid or an aqueous composition comprising a combination of a sulfide consuming chemical, a nitrate salt, a salt for pH elevation, a bacterial consortia and enzyme blend added in such a manner that the applied dosage ratio comprises 1-10 parts by weight of sulfide consuming chemical, 10-30 parts by weight of nitrate salt, 10-100 parts by weight of a pH-elevating salt, 0.0001-1 parts by weight of a bacterial consortia, and 0.0001-1 parts by weight of a blend of bacterial enzymes per million parts by weight of water.
As used herein the sulfide consuming chemical is selected from the group comprising alkali metal salts of hypochlorite, chlorite, nitrite, peroxide, percarbonate, permanganate, perborate, ferrous or ferric iron salts, peroxy monosulfuric acid, chlorine, hydrogen peroxide, oxygen, air, chlorine dioxide and mixtures thereof.
In the process an aluminum nitrate is one of the nitrates in the blend and is fed so that the aluminum has the benefits of both consuming sulfide and reducing phosphate in the downstream wastewater plant. In the process a pH elevating salt is selected from the group comprising metal or alkali metal salts of carbonate ion or hydroxide ion or of metal or alkali metal oxides which react with water to form hydroxide ion, and metal or alkali. The preferred metal salts are selected from the group comprising magnesium hydroxide, calcium hydroxide, magnesium oxide, and calcium oxide and mixtures thereof.
The bacterial consortia are comprised of a mixture of nitrate reducing and sulfide-oxidizing bacteria and may include Thiobacillus denitrificans, a nitrate-reducing, sulfide-oxidizing bacteria.
An enzyme blend may be comprised of enzymes produced by nitrate-reducing, sulfide-oxidizing bacteria and more specifically the enzyme blend is comprised of sulfide dehydrogenase.
The composition is provided with sulfide consuming chemical in the weight ratio of 1-10 parts by weight of sulfide consuming chemical per part by weight of sulfide to accomplish removal of sulfide.
Further, the composition is added to provide nitrate ion in the weight ratio of 10-30 parts nitrate ion per million parts by weight of water to prevent biogenic generation of sulfide and the composition is added to provide pH-elevating salt in the weight ratio of 10-100 parts pH-elevating salt by weight per million parts by weight of waste.
The sulfide consuming chemical in the weight ratio of 1-10 parts by weight of sulfide consuming chemical per part by weight of sulfide is added to accomplish removal of sulfide.
The composition is added to provide nitrate ion in the weight ratio of 10-30 parts nitrate ion per million parts by weight of water to prevent biogenic generation of sulfide. The process involves a composition being added to provide pH-elevating salt in the weight ratio of 10-100 parts pH-elevating salt by weight per million parts by weight of waste.
Obviously, many modifications may be made without departing from the basic spirit of the present invention. Accordingly, it will be appreciated by those skilled in the art that within the scope of the appended claims, the invention may be practiced other than has been specifically described herein.
This application is a continuation of U.S. patent application Ser. No. 10/991,054 filed Nov. 17, 2004, now U.S. Pat. No. 7,285,217, which claims the benefit of U.S. Provisional Application No. 60/526,440 filed Dec. 2, 2003 both of these related applications are incorporated herein by reference.
| Number | Name | Date | Kind |
|---|---|---|---|
| 221232 | Hirsh | Nov 1879 | A |
| 1701825 | Seil | Feb 1929 | A |
| 1997252 | Fischer | Apr 1935 | A |
| 3219576 | Makabe | Nov 1965 | A |
| 3300404 | Howe et al. | Jan 1967 | A |
| 3401113 | Pruessner et al. | Sep 1968 | A |
| 3502566 | Raymond et al. | Mar 1970 | A |
| 3607736 | Miyaji | Sep 1971 | A |
| 3639263 | Troschinski et al. | Feb 1972 | A |
| 3867284 | Kappe et al. | Feb 1975 | A |
| 3930998 | Knopp et al. | Jan 1976 | A |
| 3959127 | Bartha et al. | May 1976 | A |
| 3959130 | Kloster et al. | May 1976 | A |
| 3966450 | O'Neil et al. | Jun 1976 | A |
| 4098690 | Semmens | Jul 1978 | A |
| 4108771 | Weiss | Aug 1978 | A |
| 4108777 | Kurita | Aug 1978 | A |
| 4115258 | Smith et al. | Sep 1978 | A |
| 4148726 | Smith | Apr 1979 | A |
| 4153547 | McLean | May 1979 | A |
| 4224154 | Steininger | Sep 1980 | A |
| 4297216 | Ishida et al. | Oct 1981 | A |
| 4446031 | List | May 1984 | A |
| 4501668 | Merk et al. | Feb 1985 | A |
| 4505819 | Barnes et al. | Mar 1985 | A |
| 4566469 | Semp et al. | Jan 1986 | A |
| 4612124 | Escrig | Sep 1986 | A |
| 4680127 | Edmondson | Jul 1987 | A |
| 4681687 | Mouchéet al. | Jul 1987 | A |
| 4725405 | Cassin et al. | Feb 1988 | A |
| 4760027 | Sublette | Jul 1988 | A |
| 4818404 | McDowell | Apr 1989 | A |
| 4911843 | Hunniford et al. | Mar 1990 | A |
| 5045213 | Bowers | Sep 1991 | A |
| 5114587 | Hägerstedt | May 1992 | A |
| 5200092 | Richards et al. | Apr 1993 | A |
| 5298174 | Momont et al. | Mar 1994 | A |
| 5336431 | Richards et al. | Aug 1994 | A |
| 5385842 | Weimer et al. | Jan 1995 | A |
| 5480550 | Sublette | Jan 1996 | A |
| 5482630 | Lee et al. | Jan 1996 | A |
| 5500368 | Tatnall | Mar 1996 | A |
| 5603832 | Høyvik et al. | Feb 1997 | A |
| 5833864 | Miller | Nov 1998 | A |
| 5948269 | Stone | Sep 1999 | A |
| 5984993 | Mainz et al. | Nov 1999 | A |
| RE36651 | Hunniford et al. | Apr 2000 | E |
| 6045695 | Janssen et al. | Apr 2000 | A |
| 6059973 | Hudson et al. | May 2000 | A |
| 6146522 | Fernholz et al. | Nov 2000 | A |
| 6221652 | Janssen et al. | Apr 2001 | B1 |
| RE37181 | Hunniford et al. | May 2001 | E |
| 6309597 | Ballinger, Jr. et al. | Oct 2001 | B1 |
| 6409926 | Martin | Jun 2002 | B1 |
| 6410305 | Miller et al. | Jun 2002 | B1 |
| 6419817 | Martin | Jul 2002 | B1 |
| 6576144 | Vineyard | Jun 2003 | B1 |
| 6620315 | Martin | Sep 2003 | B2 |
| 6623647 | Martin | Sep 2003 | B2 |
| 6660163 | Miklos | Dec 2003 | B2 |
| 6666975 | Chen et al. | Dec 2003 | B1 |
| 6716359 | Dennis, II | Apr 2004 | B1 |
| 6773604 | Walton et al. | Aug 2004 | B2 |
| 7087172 | Hunniford | Aug 2006 | B2 |
| 7138049 | Hunniford et al. | Nov 2006 | B2 |
| 7160712 | Christiansen | Jan 2007 | B2 |
| 7186341 | Hunniford et al. | Mar 2007 | B2 |
| 7285217 | Simpson et al. | Oct 2007 | B2 |
| 20020102229 | Wegner | Aug 2002 | A1 |
| 20040226891 | Dentel | Nov 2004 | A1 |
| 20050077251 | Rieth et al. | Apr 2005 | A1 |
| 20050142096 | Wegner | Jun 2005 | A1 |
| Number | Date | Country |
|---|---|---|
| 34 14556 | Oct 1985 | DE |
| 57187099 | Nov 1982 | JP |
| 10-328676 | Dec 1998 | JP |
| 11-156374 | Jun 1999 | JP |
| Number | Date | Country | |
|---|---|---|---|
| 20080041785 A1 | Feb 2008 | US |
| Number | Date | Country | |
|---|---|---|---|
| 60526440 | Dec 2003 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 10991054 | Nov 2004 | US |
| Child | 11859421 | US |
