Patent Grant
8251694
1. Field of the Invention
The present invention relates generally to a method for reducing byproducts emissions from combustion reactions, and, more particularly, to a method for reducing flue gas acidity in combustion furnaces.
2. Description of the Prior Art
Acidity Decrease
The flue gas of power generation plants has long been recognized as a source of atmospheric pollution. In the combustion of fossil fuels, some of the naturally present elements are oxidized to form acids, such as SO3, NOx, HCl, HF, and the like. These acids, especially SO3, can become a problem if their concentrations exceed certain thresholds. For example, as the SO3 concentration increases, the acid dewpoint temperature of the flue gas increases. If the temperature of the flue gas is less than the acid dewpoint temperature of the flue gas, the SO3 in the gas will condense and react with water to form H2SO4, causing corrosion problems inside the furnace. Also, flue gases exiting a furnace cool immediately and SO3 and other acids in the gas condense, creating localized acid rain, which is the condensation and precipitation of SO3 and other acids onto the surrounding land with subsequent corrosion. Excessive SO3 will condense into small droplets, creating a visible plume as it exits the furnace, which becomes an esthetic and local political problem. If NH3-like compounds are present in the flue gas, they can react with SO3 to form ammonium bisulfate (NH3HSO4) which then fouls the air heater.
Thus, a need exists to decrease the acid dewpoint temperature of the flue gases such that the acid dewpoint temperature is lower than the flue-gas temperature in the coolest parts of the furnace, such as the ducts and stack. A further need exists to lower the acid content of the flue gases such that the localized acid rain and other problems associated with high-acid flue gas are minimized.
SO3 Increase
The particulate matter carried in the flue gas can be removed by electrostatic precipitators that cause the individual particles to accept an electrical charge and then use that charge to attract them to collector plates for disposal. The efficiency of such electrostatic precipitators is dependent upon the ability of the individual particles to take a charge, that is, the resistivity of the particles. It has been found that the presence of SO3 in the flue gas effectively reduces the resistivity of the particles, making them easier to charge electrostatically.
In the combustion of coal, some of the naturally present sulfur is converted to SO3. On the other hand, the effectiveness of SO3 in reducing the resistivity of the particulate matter in the flue gas depends upon the concentration of the SO3, with about 15 to 20 parts per million (ppm) giving optimal results. Therefore, precipitator efficiency is affected by the ability to adjust the amount of SO3 in the flue gas, regardless of the sulfur content of the coal being burned, to provide an overall SO3 concentration in the optimal range.
SO3 is also produced in SCR (catalyst) installations by the oxidation of SO2 and often exceeds the optimal 15 to 20 ppm optimal concentrations. The catalyst blends typically used in the SCR to reduce NOx to N2 (in the presence of ammonia) also oxidize SO2 to SO3. The rate of this reaction is strongly temperature dependent and, at higher temperatures, can convert more than 1 percent of SO2 to SO3. High sulfur U.S. coal generates anywhere from 2,000 to 3,000 ppm of SO2 in the boiler, and therefore can result in 20 to 30 ppm of SO3 out of the SCR. The problem is that as much as 50 percent, or 10 to 15 ppm, of the SO3 coming out of the SCR will make it past the scrubber and out of the stack. At about 8 to 10 ppm, depending upon the particulate concentration, SO3 becomes visible as a blue plume.
Furthermore, SO3 can also be produced catalytically on other boiler surfaces through interaction with elements/chemicals such as Vanadium.
Therefore, because any SO3 formed prior to the SCR adds to the effluent SO3, reducing the SO3 formed prior to the SCR is important for reducing the effluent SO3 and permits the use of SCR for the reduction of NOx for gases without generating excessive amounts of SO3.
SO3 Control
If the SO3 concentration is too low, the precipitator will operate at less than optimal efficiency. On the other hand, if the SO3 concentration is too high, the flue gas becomes highly acidic, creating a “blue plume” and contributing to acid rain. In addition, acidic flue gases contribute to corrosion of the pipes carrying the flue gas, and, when combined with NH3-type chemicals, can clog the air heater.
Furthermore, an SCR is often only intended to be used for six months per year (during the summer ozone control season), and are bypassed during the winter. This creates seasonal variability in the SO3 concentrations at the precipitator, in the duct work, and out of the exhaust stack.
It is therefore desirable to control the concentrations of SO3 in the flue gas depending upon whether the SCR is in use or not. SO3 concentrations approaching 40 ppm produce severe adverse local acid problems that are not necessarily regulated, but create local political problems for the facility. The U.S. EPA has indicated that future regulations on SO3 emissions are to be expected.
It is desirable, therefore, to have an SO3 flue gas system that is capable of adjusting the concentrations of SO3 in a flue gas with or without an SCR installed to maintain the SO3 concentration at an optimal level for increased ESP performance, without increased localized SO3 emissions.
Staging
Combustion staging is the process of burning a fuel, i.e., coal, in two or more stages. A fuel-rich stage, or simply, rich stage, is one in which not enough air is available to fully burn the fuel. A fuel-lean stage is one in which there is sufficient or extra air to fully burn the fuel. Staging is used in the prior art to reduce NOx by a) reducing peak temperatures (thermal NOx) and b) providing a reducing environment (NOx reduction). Macro-staging is the dividing of whole sections of a furnace into rich and lean stages and is accomplished through the use of such techniques as Over-Fired Air (OFA). Micro-staging is the creation of proximal microenvironments with functionally different characteristics, such as reduction potential, temperature, and the like. Micro-staging in a furnace can be achieved, for example, in the first stage of the furnace through the use of Low-NOx burners with adjustment of spin-vane settings and registers. Increased staging increases the residence time in a reducing atmosphere and increases the effect of the reducing atmosphere.
Prior art has used micro-staging to reduce NOx emissions in combustion furnaces. Low-NOx burners (LNB) stage by delivering high-fuel-content primary air into the furnace that mixes with secondary air flowing through one or more secondary air registers. LNB primarily use micro-staging. The flow through a LNB is designed such that the volatile components of the coal mix with the available near-field air at a stoichiometric ratio near unity (1.0), thus anchoring the flame. The net combustion in the central core near the burners is overall fuel rich and does not produce much thermal NOx, as the temperatures are low. The coal is eventually consumed over the depth of the furnace as more and more air slowly mixes into the central core. The majority of the NOx created in this region is from the fuel-bound nitrogen reacting to NO through the intermediate HCN. The rate at which the outer secondary air mixes into the core flow is set by the dampers and the spin vanes, as well as the spin vane in the coal pipe. LNB systems decrease NOx by staging since there is a continuous mixing of the rich products of combustion and secondary air throughout the combustion zone. Staging is increased by decreasing the mixing rate between the rich core flow and the outer secondary air flow.
Prior art has used macro-staging to reduce emissions in combustion furnaces. Macro-staging consists of highly mixed fuel and air in the lower furnace, mixed to a stoichiometric ratio below unity for a large part of the flow. Excess oxygen is ultimately required to assure that all of the fuel has burned and to reduce explosion risks. In a macro-staged furnace, excess air is introduced downstream of the burners. Increased staging is achieved by increasing the residence time, temperature, or reducing quality of the combustion products in the absence of oxygen.
Prior art used both micro-staging (LNB) and macro-staging (OFA) to reduce NOx emissions in combustion furnaces. In the case of both micro-staging and macro-staging, components of each of the above are used and adjusted to achieve NOx emissions reduction.
Staging has nowhere been taught in the prior art for flue gas acidity reduction, acid dewpoint temperature control or SO3 concentration control in combustion gases.
The present invention is directed to a method for reducing the acidity of flue gases in combustion systems and methods.
The present invention is further directed to a method for reducing the acid dewpoint temperature of flue gases in combustion systems and methods.
It is therefore an aspect of the present invention to provide a method for reducing the acidity of flue gases in combustion systems and methods, including the steps of:
Another aspect of the present invention provides a method for reducing the acid dewpoint temperature of flue gases in combustion systems and methods with staging.
Still another aspect of the present invention provides a method of lowering the acid dewpoint temperature of flue gas, including the steps of:
Still another aspect of the present invention provides a combustion furnace operated with a method for reducing the acidity of the flue gas, the method steps including:
These and other aspects of the present invention will become apparent to those skilled in the art after a reading of the following description of preferred embodiment(s) when considered with the drawings.
In the following description, like reference characters designate like or corresponding parts throughout the several views. Also in the following description, it is to be understood that such terms as “forward,” “rearward,” “front,” “back,” “right,” “left,” “upwardly,” downwardly,” and the like are words of convenience and are not to be construed as limiting terms. In the present invention, “reducible acid” refers to acids in which the acidity can be reduced or eliminated by the electrochemical reduction of the acid. “Chemically reduce” shall refer to a chemical reaction where one substrate “gains an electron” or there is an “electron addition”.
The present invention is directed to a method for in-furnace decrease and control of the acid dewpoint temperature using combustion staging. The present invention is further directed to a method for in-furnace reduction and control of SO3 using combustion staging. Increased staging is advantageously used to simultaneously decrease the acidity, decrease the acid dewpoint temperature and reduce the SO3 levels of the flue gas.
Acidity, Acid Dewpoint Temperature and SO3 Reduction Through Micro-Staging
Similar to how NOx is reduced back to N2 in a rich “reducing” environment, SO3 is reduced back to SO2 in a reducing environment. With macro-staging, the center of the furnace below the OFA ports is largely fuel-rich. This staged environment can be adjusted to be even less mixed to create reducing micro-stages within the first stage of the furnace. The mixing can be reduced by reducing the spin vane velocity settings of the primary air and coal flow, or additionally or otherwise, the secondary air spin vane and register settings, thus creating reducing micro-stages, or additionally or otherwise, the relative exit velocities between the primary air and coal flow and the secondary air flow can be changed.
While the majority of fuel-bound sulfur forms SO2, some forms SO3 directly during combustion of the fuel-bound sulfur. SO2 can react to form more SO3 through the following oxidative reaction:
SO2+O(+M)→SO3(+M)
However, this three-body reaction is very slow. An additional source for SO3 production in an oxidative environment is through the reaction:
SO2+O2→SO3+O
This reaction does not require three bodies to simultaneously collide; however, it is very sensitive to temperature, requiring high temperatures, and it is susceptible to reverse reaction:
SO3+O→SO2+O2
None of the above three reactions occur in any significant quantity in a reducing environment due to the lack of O and O2 species. In a reducing environment, the direct conversion of SO3 to SO2 takes place through the following general “reducing” reaction:
SO3+R→SO2+RO
Where R is any reducing radical species. The primary radical in fossil fuel combustion is the H radical.
SO3+H→SO2+OH
Many radicals and molecules can be functional in a reducing environment; e.g., H, OH, C, CO, CH, CH2 C2H, CH3, CnHm, N, NHi, and many others.
The above SO3 reducing reactions are very fast when there are significant concentrations of the reducing radicals (“R”). Sufficient concentrations exist primarily in reducing environments within the first (fuel-rich) stage of the furnace.
In a fuel-rich staged, reducing environment, oxidative chemistry terminates due to greatly decreased (extinguished) concentrations of oxidative combustion species; e.g., OH, O, O2, HO2, H2O2, and many others. In this environment, species are very competitive for any available oxygen species. Molecules with oxygen atoms that exist in relatively small concentrations are consumed by oxygen-wanting species that exist in high concentration; e.g., the oxygen in NO is consumed by other species like C, CO, H, and CH. Molecules that have multiple oxygen atoms are particularly at risk; i.e., SO3 will quickly revert to SO2 through oxygen abstraction by just about anything around, most notably H atoms.
Thus, in a reducing environment, the SO3 reduction reaction is very fast virtually irreversible while the reducing environment is maintained.
Surprisingly and importantly, with the present invention methods and systems, the net effect is that any SO3 that is formed during combustion is quickly reduced to SO2 in the first stage and SO3 is not reformed by oxidation to SO2 because there is not enough residence time at sufficiently high temperature in the furnace in the latter, fuel-lean stages. Thus, the present invention advantageously uses the differences in reaction rates to reduce and maintain the SO3 levels in the flue gas.
Increased staging increases the residence time in a reducing atmosphere, or increases the reducing potential of the atmosphere, to decrease SO3 concentration and thereby lower the dewpoint temperature. Therefore, to increase the reduction of SO3, the residence time can be increased or the reducing potential in the flue gases can be increased.
To increase residence time, several methods are available.)
To increase the reducing potential in the flue gases, several methods are available.
Mixing within a stage also influences the reduction process. A perfectly mixed stage with a stoichiometric mixture is the best, since these reaction conditions will give the highest temperature, while still maintaining the reducing environment; i.e., minimizing oxidation radicals like O radicals. But, since perfect mixing is impractical, in practice a stoichiometric ratio less than one is used, which minimizes the occurrence of localities with a stoichiometric ratio greater than one. However, as mixing is reduced, a longer residence time and/or higher temperature is needed to achieve a similar reduction of the total acidity, acid dewpoint temperature, and/or SO3 concentration. However, the temperature of the combustion gases is dependent to a certain extent on the level of mixing, going down if mixing is decreased. Therefore, if an increased temperature is desired for a given degree of mixing, temperature must be increased by other means, such as preheating air, changing heat transfer characteristics of furnace, and the like. Alternatively or additionally, the residence time in the reducing environment can be increased by delaying lean stage air introduction, such as OFA injection.
Note that SO3 is formed by the oxidation of SO2 in a catalyst because a catalyst enables the oxidation of SO2 though the following reaction:
SO2+½O2→SO3
Production of SO3 in a catalyst is independent of the SO3 concentration in the gas, since the catalyzed reaction is only dependent on the SO2 and O2 concentration. Therefore, any SO3 that is reduced by the present invention independently reduces the exit SO3 and is not affected by and does not affect SO3 production in a catalyst.
The present invention thus provides a method for controlling and reducing flue gas acidity, specifically the flue gas concentrations of SO3, in order to beneficially (1) affect the efficiency of an electrostatic precipitator, and more particularly, (2) to reduce the concentration of SO3 and other reducible acids in the flue gas in order to reduce the flue gas acidity and acid dewpoint, thereby reducing air heater pluggage, duct corrosion, and SO3 emissions to the environment, which can be a source of visible plumes and localized acid rain.
As seen in
In a preferred embodiment of the present invention, macro-staging to regulate furnace acidity and SO3 levels is achieved through the use of OFA. In another preferred embodiment, micro-staging to regulate furnace acidity and SO3 levels is achieved through the use of low-NOx burners. In yet another preferred embodiment, macro-staging and micro-staging through the use of OFA and low-NOx burners in combination are used to regulate furnace acidity and SO3 levels. For furnaces with SCRs in operation, the acidity is preferably regulated to reduce total flue gas acidity. For furnaces without SCRs or with by-passed SCRs, the SO3 is preferably regulated such that the SO3 levels going to the ESP enhance or favor precipitation. For current ESPs, SO3 levels between about 10 to about 15 ppm (by volume) in the exhaust is desirable for best ESP efficiency.
The dewpoint temperature is a convenient parameter for estimating and/or adjusting the reducing environment variables in order to achieve adequate reduction of acidity and/or desired SO3 levels. For a desired level of SO3 and operating relative humidity, the dewpoint can be determined and the reducing environment variable adjusted accordingly to achieve the desired dewpoint. Other methods of determining acidity and/or SO3 level can be used for the same purpose without departing from the scope of the invention.
As seen in
As seen in
In a preferred embodiment of the present invention, a power plant is operated to provide a deeply-staged, micro-stage or macro-stage reducing environment in the lower furnace. The OFA in the upper furnace provides the necessary oxygen to ensure an acceptable level of burnout of the remaining unburned fuel, combustion intermediates, and CO. Additionally, an SCR can be used to reduce NOx. Thus, an embodiment of the present invention includes a combustion furnace with OFA and low NOx burners for use with sulfur containing fuels to lower the dewpoint temperature and to reduce the SO3 concentration. Additionally, an SCR can be provided to reduce NOx. The low NOx burners are preferably of a grade that provides adequate mixing in the primary stage to provide adequate acid dewpoint temperature reducing and SO3 concentration reduction, thus permitting the use of an SCR, if necessary. Thus, an embodiment of the present invention includes a combustion furnace with high-grade low NOx burners for the purpose of reducing the flue gas acidity, lowering the acid dewpoint temperature and reducing the flue gas SO3 concentration. This embodiment can further include an SCR.
An adequate reducing environment according to the present invention is one that will reduce SO3 to SO2 in less than about 2 seconds, more preferably, in less than about 0.5 seconds. In the present invention, such a reducing environment can be achieved when the first stage flue gas temperature is greater than or equal to 900 Kelvin (1160 degrees F.), more preferably greater than about 1255 K (1800 degrees F.), even more preferably greater than about 1650 K (2500 degrees F.). A reducing environment is one where the ratio of the concentrations of reducing radicals to oxidizing radicals is greater than about 1; more specifically, the ratio of the concentrations of H radicals to O radicals is greater than about 1. A better reducing environment is one where the ratio of the concentrations of reducing radicals to oxidizing radicals is greater than about 10; more specifically, the ratio of the concentrations of H radicals to O radicals is greater than about 10.
Thus, a method for operating a furnace according to the present invention involves the steps of:
Alternatively, in another embodiment according to the present invention, a method of lowering the acid dewpoint temperature of flue gas includes the steps of:
The following examples illustrate the results that can be achieved using methods according to the present invention. Methods according to the present invention were used to reduce flue gas acidity and lower acid dewpoint at 3 different power plants. Because SO3 is the predominant acid in coal furnace emissions, SO3 emissions were measured and used as an indicator of acidity and dewpoint. The experimental data shown in Tables 1 and 2 were achieved through the use of high-velocity over-fired air and were measured by third-party companies.
For the “shallow” staging cases, the over-fired air ports were nearly closed, but still contained cooling flow (around 10% of the total air). For the “mid” staging case, the over-fired air ports made up nearly 20% of the total air flow. For the “deep” staging cases, the over-fired air ports made up nearly 30% of the total air flow. All three units were corner-fired units and the OFA system was located well above the burner zone.
Thus, the experimental data demonstrate the ability to regulate the SO3 level, which is the predominant acid in coal furnace emissions and an indicator of flue gas acidity and acid dewpoint, using methods according to the present invention.
Certain modifications and improvements will occur to those skilled in the art upon a reading of the foregoing description. All modifications and improvements have been deleted herein for the sake of conciseness and readability but are properly within the scope of the following claims.
This nonprovisional utility patent application claims the benefit of a prior filed provisional application 60/544,724 filed Feb. 14, 2004, which is incorporated herein by reference in its entirety.
| Number | Name | Date | Kind |
|---|---|---|---|
| 3105540 | Hardgrove | Oct 1963 | A |
| 3528797 | Funk et al. | Sep 1970 | A |
| 3565757 | Warshaw et al. | Feb 1971 | A |
| 3773897 | Fields et al. | Nov 1973 | A |
| 3847564 | Marion et al. | Nov 1974 | A |
| 3860384 | Vulliet et al. | Jan 1975 | A |
| 3900554 | Lyon | Aug 1975 | A |
| 3970739 | Shiraishi et al. | Jul 1976 | A |
| 4021188 | Yamagishi et al. | May 1977 | A |
| 4029752 | Cahn | Jun 1977 | A |
| 4039446 | Ban et al. | Aug 1977 | A |
| 4080423 | Smith et al. | Mar 1978 | A |
| 4089639 | Reed et al. | May 1978 | A |
| 4119702 | Anuhata et al. | Oct 1978 | A |
| 4150631 | Frey et al. | Apr 1979 | A |
| 4154581 | Nack et al. | May 1979 | A |
| 4173454 | Heins | Nov 1979 | A |
| 4196057 | May et al. | Apr 1980 | A |
| 4208386 | Arand et al. | Jun 1980 | A |
| 4213944 | Azuhata et al. | Jul 1980 | A |
| 4294178 | Borio et al. | Oct 1981 | A |
| 4325924 | Arand et al. | Apr 1982 | A |
| 4375949 | Salooja | Mar 1983 | A |
| 4381718 | Carver et al. | May 1983 | A |
| 4469050 | Korenberg | Sep 1984 | A |
| 4502633 | Saxon | Mar 1985 | A |
| 4504211 | Beardmore | Mar 1985 | A |
| 4506608 | Strohmeyer, Jr. | Mar 1985 | A |
| 4507075 | Buss et al. | Mar 1985 | A |
| 4507269 | Dean et al. | Mar 1985 | A |
| 4565137 | Wright | Jan 1986 | A |
| 4582122 | Fan | Apr 1986 | A |
| 4584948 | Syred et al. | Apr 1986 | A |
| 4624840 | Dean et al. | Nov 1986 | A |
| 4627965 | Hegemann et al. | Dec 1986 | A |
| 4672900 | Santalla et al. | Jun 1987 | A |
| 4704084 | Liu et al. | Nov 1987 | A |
| 4751065 | Bowers | Jun 1988 | A |
| 4777024 | Epperly et al. | Oct 1988 | A |
| 4780289 | Epperly et al. | Oct 1988 | A |
| 4824441 | Kindig | Apr 1989 | A |
| 4842834 | Burton | Jun 1989 | A |
| 4873930 | Egnese et al. | Oct 1989 | A |
| 4915036 | DeVita | Apr 1990 | A |
| 4927612 | Bowers | May 1990 | A |
| 4962711 | Yamauchi et al. | Oct 1990 | A |
| 4978514 | Hofmann et al. | Dec 1990 | A |
| 4985218 | DeVita | Jan 1991 | A |
| 4992249 | Bowers | Feb 1991 | A |
| 5017347 | Epperly et al. | May 1991 | A |
| 5032154 | Wright | Jul 1991 | A |
| 5039507 | Sturm | Aug 1991 | A |
| 5048432 | Hogmann | Sep 1991 | A |
| 5052921 | Hemsath | Oct 1991 | A |
| 5057293 | Epperly et al. | Oct 1991 | A |
| 5105747 | Khinkis et al. | Apr 1992 | A |
| 5139754 | Luftglass et al. | Aug 1992 | A |
| 5146858 | Tokuda et al. | Sep 1992 | A |
| 5240404 | Hemsath et al. | Aug 1993 | A |
| 5261602 | Brent et al. | Nov 1993 | A |
| 5286467 | Sun et al. | Feb 1994 | A |
| 5310334 | Sprios | May 1994 | A |
| 5336081 | Saito et al. | Aug 1994 | A |
| 5342592 | Hoblyn et al. | Aug 1994 | A |
| 5345883 | Panos | Sep 1994 | A |
| 5489419 | Diep et al. | Feb 1996 | A |
| 5536482 | Diep et al. | Jul 1996 | A |
| 5585081 | Chu et al. | Dec 1996 | A |
| 5690039 | Monroe et al. | Nov 1997 | A |
| 5707596 | Lewandowski et al. | Jan 1998 | A |
| 5728357 | von Harpe | Mar 1998 | A |
| 5809910 | Svendssen | Sep 1998 | A |
| 5853684 | Fang et al. | Dec 1998 | A |
| 5854173 | Chang et al. | Dec 1998 | A |
| 6019068 | Tsuo et al. | Feb 2000 | A |
| 6042371 | Mitani et al. | Mar 2000 | A |
| 6109911 | Tamminen et al. | Aug 2000 | A |
| 6190628 | Carter | Feb 2001 | B1 |
| 6213032 | Breen et al. | Apr 2001 | B1 |
| 6230664 | Janka et al. | May 2001 | B1 |
| 6280695 | Lissianski et al. | Aug 2001 | B1 |
| 6315551 | Salzsieder et al. | Nov 2001 | B1 |
| 6357367 | Breen et al. | Mar 2002 | B1 |
| 6398039 | Xue et al. | Jun 2002 | B1 |
| 6485289 | Kelly et al. | Nov 2002 | B1 |
| 6527828 | Flippo et al. | Mar 2003 | B2 |
| 6532905 | Belin et al. | Mar 2003 | B2 |
| 6818043 | Change et al. | Nov 2004 | B1 |
| 6953494 | Nelson, Jr. | Oct 2005 | B2 |
| 7198769 | Cichanowicz | Apr 2007 | B2 |
| 7335014 | Higgins | Feb 2008 | B2 |
| 7537743 | Higgins | May 2009 | B2 |
| 20030110948 | Gaita et al. | Jun 2003 | A1 |
| 20040045437 | Chang et al. | Mar 2004 | A1 |
| 20040120872 | Fan et al. | Jun 2004 | A1 |
| 20040185399 | Moberg | Sep 2004 | A1 |
| 20040185401 | Moberg | Sep 2004 | A1 |
| 20040185402 | Moberg | Sep 2004 | A1 |
| 20040253161 | Higgins | Dec 2004 | A1 |
| 20050000901 | Campbell et al. | Jan 2005 | A1 |
| 20050002841 | Moberg | Jan 2005 | A1 |
| 20050013755 | Higgins | Jan 2005 | A1 |
| 20090188782 | Genuario et al. | Jul 2009 | A1 |
| Number | Date | Country |
|---|---|---|
| 28 37 156 | Mar 1979 | DE |
| 0 287 224 | Oct 1988 | EP |
| 0 326 943 | Jan 1989 | EP |
| 0 287 224 | Oct 1998 | EP |
| 0936405 | Aug 1999 | EP |
| 2 001 419 | Jul 1978 | GB |
| 53-112273 | Sep 1978 | JP |
| 2003 31322 | Jan 2003 | JP |
| WO8703507 | Jun 1987 | WO |
| WO 8703507 | Jun 1987 | WO |
| WO2005079305 | Sep 2005 | WO |
| Number | Date | Country | |
|---|---|---|---|
| 20050181318 A1 | Aug 2005 | US |
| Number | Date | Country | |
|---|---|---|---|
| 60544724 | Feb 2004 | US |
