Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/02—Liquid carbonaceous fuels essentially based on components consisting of carbon, hydrogen, and oxygen only
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen; Reversible storage of hydrogen
  • C01B3/02—Production of hydrogen; Production of gaseous mixtures containing hydrogen
  • C01B3/06—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents
  • C01B3/065—Production of hydrogen; Production of gaseous mixtures containing hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen with inorganic reducing agents by reaction of inorganic compounds with hydrides
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
  • C10L1/1824—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms mono-hydroxy
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
  • C10L1/00—Liquid carbonaceous fuels
  • C10L1/10—Liquid carbonaceous fuels containing additives
  • C10L1/14—Organic compounds
  • C10L1/18—Organic compounds containing oxygen
  • C10L1/182—Organic compounds containing oxygen containing hydroxy groups; Salts thereof
  • C10L1/1822—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms
  • C10L1/1826—Organic compounds containing oxygen containing hydroxy groups; Salts thereof hydroxy group directly attached to (cyclo)aliphatic carbon atoms poly-hydroxy
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
  • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
  • H01M8/04186—Arrangements for control of reactant parameters, e.g. pressure or concentration of liquid-charged or electrolyte-charged reactants
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/06—Combination of fuel cells with means for production of reactants or for treatment of residues
  • H01M8/0606—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants
  • H01M8/065—Combination of fuel cells with means for production of reactants or for treatment of residues with means for production of gaseous reactants by dissolution of metals or alloys; by dehydriding metallic substances
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/08—Fuel cells with aqueous electrolytes
  • H01M8/083—Alkaline fuel cells
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/10—Fuel cells with solid electrolytes
  • H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/22—Fuel cells in which the fuel is based on materials comprising carbon or oxygen or hydrogen and other elements; Fuel cells in which the fuel is based on materials comprising only elements other than carbon, oxygen or hydrogen
  • H01M8/225—Fuel cells in which the fuel is based on materials comprising particulate active material in the form of a suspension, a dispersion, a fluidised bed or a paste
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
  • H01M8/00—Fuel cells; Manufacture thereof
  • H01M8/04—Auxiliary arrangements, e.g. for control of pressure or for circulation of fluids
  • H01M8/04082—Arrangements for control of reactant parameters, e.g. pressure or concentration
  • H01M8/04201—Reactant storage and supply, e.g. means for feeding, pipes
  • H01M8/04216—Reactant storage and supply, e.g. means for feeding, pipes characterised by the choice for a specific material, e.g. carbon, hydride, absorbent
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
  • Y02E60/30—Hydrogen technology
  • Y02E60/50—Fuel cells
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
  • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

• the present invention relates to suspension fuel compositions for use in electrochemical fuel cells, a method of producing electricity with the suspension fuel compositions, and a fuel cell using the suspension fuel compositions to generate electricity.
• a fuel cell is a device that converts the energy of a chemical reaction into electricity.
• a fuel cell produces electricity by bringing a fuel into contact with a catalytic anode while bringing an oxidant into contact with a catalytic cathode.
• the fuel When in contact with the anode, the fuel is oxidized at catalytic centers to produce electrons! The electrons travel from the anode to the cathode through an electrical circuit connecting the electrodes.
• the oxidant is catalytically reduced at the cathode, consuming the electrons generated at the anode.
• Mass balance and charge balance are preserved by the corresponding production of ions at either the cathode or the anode and the diffusion of these ions to the other electrode through an electrolyte with which the electrodes are in contact.
• a common type of fuel cell uses hydrogen as a fuel and oxygen as an oxidant.
• the protons pass through the electrolyte towards the cathode.
• the electrons travel from the anode, through an electrical load and to the cathode.
• the oxygen is reduced, combining with electrons and protons produced from the hydrogen to form water as shown in equation 2: (2) O 2 + 4H + +4e " - 2H 2 O
• liquid fuels have been proposed for use in fuel cells.
• Methods have been developed for converting liquid fuels such as methanol into hydrogen, in situ. These methods are not simple, requiring a fuel pre-processing stage and a complex fuel regulation system.
• Fuel cells that directly oxidize liquid fuels are the solution to this problem. Because the fuel is directly fed into the fuel cell, direct liquid-feed fuel cells are comparatively simple. Most commonly, methanol has been used as the fuel in these types of cells, as it is cheap, available from diverse sources and has a high specific energy (5020 Ampere hours per liter).
• the composition of the anolyte is an important design consideration.
• the anolyte must have both a high electrical conductivity and high ionic mobility at the optimal fuel concentration. Acidic solutions are most commonly used. Unfortunately, acidic anolytes are most efficient at relatively high temperatures, temperatures at which the acidity can passivate or destroy the anode. Anolytes with a pH close to 7 are anode-friendly, but have an electrical conductivity that is too low for efficient electricity generation. Consequently, most prior art direct methanol fuel cells use solid polymer electrolyte (SPE) membranes.
• SPE solid polymer electrolyte
• a proton exchange membrane that acts both as an electrolyte and as a physical barrier preventing leakage from the anode compartment wherein the liquid anolyte is contained.
• a membrane commonly used as a fuel cell solid electrolyte is a perfluorocarbon material sold by E. I. DuPont de Nemours (Wilmington, DE) under the trademark "Nafion".
• Fuel cells using SPE membranes have a higher power density and longer operating lifetimes than other anolyte-based fuel cells.
• a practical disadvantage of SPE membrane fuel cells arises from the tendency of high concentrations of methanol to dissolve the membrane and to diffuse through it.
• methanol supplied to the cell is not utilized for generation of electricity, but either is lost through evaporation or is oxidized directly at the cathode, generating heat instead of electricity.
• the problem of membrane penetration by the fuel is overcome by using anolytes with a low (at most 3%) methanol content.
• the low methanol content limits the efficiency of the fuel cell when measured in terms of electrical output as a function of volume of fuel consumed and raises issues of fuel transportation, dead weight and waste disposal.
• methanol is rather unreactive at room temperature, which limits the specific power output of a methanol fuel cell to about 15 milliwatts per square centimeter.
• Other organic compounds notably higher alcohols, hydrocarbons and acetates, have been proposed as fuels for fuel cells. See, for example, O. Savadogo and X. Yang, "The electrooxidation of some acetals for direct hydrocarbons fuel cell applications", Illrd International Symposium on Electrocatalysis, Slovenia, 1999, p. 57, and C.
• Inorganic water-soluble reducing agents such as metal hydrides, hydrazine and hydrazine derivatives also have been proposed as fuels for fuel cells. See, for example, S. Lei, "The characterization of an alkaline fuel cell that uses hydrogen storage alloys", Journal of the Electrochemical Society vol. 149 no. 5 pp. A603-A606 (2002), J. O'M. Bockris and S. Srinivasan, Fuel Cells: Their Electrochemistry, McGraw-Hill, New York, 1969, pp. 589- 593, and N. V. Korvin, Hydrazine, Khimiya, Moscow, 1980 (in Russian), pp. 205-224.
• Such compounds have high specific energies and are highly reactive.
• the alcohol inhibits decomposition of hydride species at the anode by at least one of two mechanisms.
• the first mechanism is that adsorption of alcohol molecules to the anode catalytic sites sterically obstructs access of the hydride species to the catalytic sites.
• the second mechanism is that alcohol molecules solvate the hydride species.
• capacity measured in Ampere hours
• capacity of a fuel cell that runs on hydride fuel would be a linear function of the hydride concentration.
• solubility of NaBH 4 in 3M KOH is 1.25 moles per liter
• NaBH in 3M NaOH is 4 moles per liter, so the capacity of a fuel cell that runs on 3M NaOH saturated with NaBH 4 would be expected to be four times that of a fuel cell that runs on 3M KOH saturated with NaBH Experimentally, this is not the case.
• FIG. 1 shows, schematically, a fuel cell 10 that consists of an electrolyte chamber
• Cathode 14 and anode 16 are shown connected by an electrical load 20 and by an ammeter 22 for measuring the electrical current drawn by electrical load 20.
• a fuel chamber 18 On the other side of anode 16 from electrolyte chamber 12 is. a fuel chamber 18 that contains a fuel solution. The oxidant is atmospheric oxygen that reaches cathode 14 on the other side of cathode 14 from electrolyte chamber 12.
• the volume of electrolyte chamber 12 was 2 cm 3
• the volume of fuel chamber 18 was 15 cm 3
• the area of each electrodes 14 and 16 was 4 cm 2 .
• Cathode 14 was made by screen-printing 20% platinum on activated carbon on waterproof paper.
• Anode 16 was made by screen-printing 20% platinum and 10% ruthenium on activated carbon on hydrophilic carbon paper.
• the capacity of fuel cell 10 was measured using different concentrations of NaBH 4 in a 3.3M aqueous NaOH fuel solution in fuel chamber 18 and using a 6M aqueous KOH electrolyte in electrolyte chamber 12.
• nip the effective mass of NaBH used, was determined as a function of initial NaBH 4 concentration using Faraday's law:
• a fuel composition including:
• a method of generating electricity including the steps of: (a) providing a fuel cell including a cathode and an anode;
• the fuel' composition including: (i) a solvent, (ii) a first portion of a fuel, dissolved in the solvent, and (iii) a second portion of the fuel, suspended in the solvent.
• the present invention is a fuel composition for fuel cells in which a first fuel is stored in two forms.
• a first portion of the first fuel is stored in solution in a solvent.
• a second portion of the first fuel is stored in suspension in the solvent.
• the effective concentration of the first fuel is the concentration of the first fuel in solution, and this concentration is kept low enough to preclude undesirable side effects such as decomposition of the first fuel at the anode and destruction of the anode.
• the effective mass of the first fuel is close to the total mass of the two portions of the first fuel.
• the solvent is a polar solvent such as water.
• the concentration of dissolved first fuel is the saturated concentration of the first fuel in the solvent. During the course of the operation of a fuel cell, as the dissolved first fuel is consumed, the suspended first fuel replaces the dissolved first fuel in solution and so maintains the dissolved portion of the first fuel at its saturated concentration.
• the first fuel is a salt whose anion is a product of a reduction half- reaction, in the solvent, that has a standard reduction potential more negative than the standard reduction potential of a hydrogen electrode in the solvent.
• BFLf the anion of NaBH
• BFLf the anion of NaBH
• HB0 3 " +5H 2 O+8e- ⁇ BH 4 -+8Off which has a standard reduction potential of -1.24 volts.
• the first fuel is a hydride such as LiAlRi, NaBH , LiBH 4 , (CH 3 ) 3 NHBH 3 ,
• the first fuel is NaBH t.
• Other preferred first fuels include Na 2 S 2 O 3 , Na2HPO3, Na 2 HPO 2 , K 2 S 2 O 3 , K 2 HPO 3 ,
• K HPO 2 , NaCOOH and KCOOH which, like the hydrides, are salts whose anions have standard reduction potentials in water that are more negative than the standard reduction potential of a hydrogen electrode in water.
• the preferred fuels for any specific solvent include salts whose anions have standard reduction potentials in that solvent that are more negative than the standard reduction potential of a hydrogen electrode in that solvent.
• the first fuel constitutes between about 0.1% and about 80% of the fuel composition by weight. Most preferably, the first fuel constitutes between about 5% and about 25% of the fuel composition by weight.
• the fuel composition of the present invention also includes an alcohol, for example methanol, ethanol, propanol, butanol, pentanol, hexanol, ethylene glycol or glycerol.
• an alcohol for example methanol, ethanol, propanol, butanol, pentanol, hexanol, ethylene glycol or glycerol.
• the alcohol constitutes between about 0.1% and about 50% of the fuel composition by weight.
• the alcohol constitutes between about 1% and about 25%o of the fuel composition by weight.
• the alcohol serves four functions:
• the alcohol is a second fuel that is oxidized along with the first fuel at the anode of the fuel cell.
• the alcohol controls the solubility of the first fuel in the solvent, to ensure that the saturated concentration of the first fuel is not too high.
• the alcohol inhibits the decomposition of the first fuel at the anode of the fuel cell. 4.
• the alcohol stabilizes the suspension by being present, in the solution of the first fuel in the solvent, in a proportion that makes the density of the solution substantially equal to the density of the suspended portion of the first fuel, so that the suspended portion of the first fuel neither precipitates nor floats, but remains suspended.
• the fuel composition of the present invention includes an additive for stabilizing the dissolved portion of the first fuel in the solvent.
• this additive is an alkali such as LiOH, NaOH or KOH, or a basic salt.
• this additive is present in the solvent in a concentration between about 0.1 mole/liter and about 12 mole/liter. Most preferably, this additive is present in the solvent in a concentration between about 0.2 mole/liter and about 5 mole/liter.
• Osborg are of hydrogen carriers that are dissolved in the base fuel. There is no indication in Osborg of any utility to both dissolving and suspending a hydrogen carrier in the base fuel.
• the scope of the present invention also includes a fuel cell that is fueled by the fuel composition of the present invention, as well as a method of generating electricity using such a fuel cell.
• FIG. 1 is a schematic diagram of a fuel cell
• FIG. 2 is a plot of the effective mass of NaBH 4 vs. initial NaBH 4 concentration in a series of prior art fuel compositions
• FIG. 3 shows plots of electrical currents and capacities of the fuel cell of FIG. 1, for a fuel composition of the present invention vs. a prior art fuel composition.
• the present invention is of a fuel composition which can be used to generate electricity in a fuel cell. Specifically, the present invention allows a hydride fuel to be used efficiently by a fuel cell.
• Figure 1 in addition to illustrating a prior art fuel cell, also serves to illustrate a fuel cell of the present invention, with a fuel composition of the present invention substituted for the prior art fuel solution in fuel chamber 18.
• a fuel composition of the present invention was prepared by preparing a saturated solution of NaBH in 3M aqueous KOH and adding solid powdered NaBFL and agitating with a magnetic stirrer to create a suspension of NaBH 4 in the NaBEL t -saturated KOH solution.
• the mean NaBH 4 particle size was about 10 microns, and 90% of the NaBH 4 particles were smaller than 100 microns.
• the suspension was stabilized by the addition of
• the 10% glycerol by volume to act as a dispersant.
• the 10% glycerol dispersant by giving the NaBH 4 -saturated KOH solution a density of 1.12 g/cm , also keeps the NaBFL t particles uniformly dispersed in suspension.
• the glycerol dispersant also keeps the NaBO 2 reaction product in suspension, thereby preventing the reaction product from reducing the catalyst activity in anode 16 and also preventing the reaction product from reducing the fuel utilization efficiency.
• the initial ratio of suspended NaBH to dissolved NaBH 4 was 1:1.
• the electrical current produced by fuel cell 10, as well as the corresponding capacity (integrated current), were measured with fuel cell 10 fueled by this fuel composition vs.

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• 2002
  • 2002-08-29 US US10/230,204 patent/US6773470B2/en not_active Expired - Fee Related
• 2003
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  • 2003-07-29 RU RU2005105320/04A patent/RU2334784C2/ru not_active IP Right Cessation
  • 2003-07-29 EP EP03741048A patent/EP1530621A4/en not_active Withdrawn
  • 2003-07-29 PL PL03374251A patent/PL374251A1/xx unknown
  • 2003-07-29 BR BR0309301-8A patent/BR0309301A/pt not_active IP Right Cessation
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  • 2003-07-29 CA CA002492362A patent/CA2492362A1/en not_active Abandoned
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  • 2003-07-29 IL IL16433103A patent/IL164331A0/xx unknown
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