US20050269211A1 - Method of and apparatus for producing hydrogen using geothermal energy - Google Patents

Method of and apparatus for producing hydrogen using geothermal energy Download PDF

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US20050269211A1
US20050269211A1 US10/861,350 US86135004A US2005269211A1 US 20050269211 A1 US20050269211 A1 US 20050269211A1 US 86135004 A US86135004 A US 86135004A US 2005269211 A1 US2005269211 A1 US 2005269211A1
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producing
geothermal
electrolysis
hydrogen
solution
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Oron Zachar
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Ormat Technologies Inc
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Assigned to ORMAT TECHNOLOGIES, INC. reassignment ORMAT TECHNOLOGIES, INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ORMAT INDUSTRIES LTD.
Priority to PCT/IL2005/000596 priority patent/WO2005121409A2/en
Priority to NZ551788A priority patent/NZ551788A/en
Publication of US20050269211A1 publication Critical patent/US20050269211A1/en
Priority to IS8581A priority patent/IS8581A/en
Priority to US11/790,343 priority patent/US7891188B2/en
Priority to US13/031,456 priority patent/US20110138810A1/en
Priority to US13/045,074 priority patent/US20110277468A1/en
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    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00Operating or servicing cells
    • C25B15/08Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25BELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B1/00Electrolytic production of inorganic compounds or non-metals
    • C25B1/01Products
    • C25B1/02Hydrogen or oxygen
    • C25B1/04Hydrogen or oxygen by electrolysis of water
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/36Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • This invention relates to a method and apparatus for producing hydrogen using geothermal energy, and more particularly, to a method and apparatus for producing hydrogen via electrolysis using geothermal energy.
  • U.S. Pat. No. 5,661,977 discloses a system for generation of electricity from geothermal energy wherein one or more substances are transported down a well to a depth at which geothermal heat (whether from brine or steam reservoirs or hot, dry rock) is sufficient to cause an endothermic reaction or an electrolysis reaction to occur among substances.
  • a system is disclosed for the generation of electricity from geothermal energy wherein one juncture of a thermocouple is transported down a well to a depth at which geothermal heat is sufficient to create a temperature difference, relative to the temperature of the other juncture of the thermocouple.
  • Such systems are rather complicated to construct so that the costs for constructing such system could be high.
  • Geothermal energy is conventionally produced using a constant flow rate of the geothermal fluid. Due to this, such a geothermal power plant operates at a fixed production level, while on the other hand, consumer power demand varies significantly between peak hours and off-peak hours. As a result, operation of such geothermal power plants is not cost effective.
  • Fouillac et al. (2003) discuss the use of geothermal heat to pre-heat the solution for high temperature (around 900° C. or more) electrolysis with additional energy sources such as coal- or gas-fired power being combined for such a use. In this paper, it is suggested that the geothermal energy could be combined with nuclear power plant energy.
  • the present inventive subject matter is drawn to apparatus for producing hydrogen using geothermal energy comprising: heating means apparatus for heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution; and electrolysis means apparatus for producing hydrogen by electrolysis of said heated solution.
  • the present invention also relates to a method for producing hydrogen using geothermal energy comprising: heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution; and producing hydrogen by electrolysis of said heated solution.
  • apparatus for producing hydrogen using geothermal energy comprising: heating means for heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution; electrolysis means apparatus for producing hydrogen by electrolysis of said heated solution; and power producing means utilizing the pressure of said hydrogen for producing power.
  • a method for producing hydrogen using geothermal energy comprising: heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution; producing hydrogen by electrolysis of said heated solution; and utilizing the pressure of said hydrogen for producing power.
  • geothermal and electrolysis plants of the present invention as described herein is advantageous since the efficiency of the integrated or combined geothermal and electrolysis plant is higher than independently operated plants. This is achieved by using the heat present in the geothermal fluid for heating the solution prior to electrolysis and also permitting the use of the pressure of the hydrogen and/or oxygen electrolysis products in the pumping of brine to be injected into the injection well of the geothermal power plant.
  • the method and apparatus of the present invention permits the integrated or combined geothermal and electrolysis plant to have flexible modes of operation during peak and off-peak demand hours.
  • the hydrogen and oxygen produced by the electrolysis system of the present invention are energy storage vehicles that enable the shift of off-peak geothermal power to be sold and consumed during periods of peak power demand.
  • the local use of the electrolysis hydrogen and oxygen products make it unnecessary to use high-pressure storage or transportation of these gases. Consequently, the available pressure of the electrolysis produced hydrogen and oxygen can be used for other purposes.
  • the above-mentioned flexibility of operation of the integrated or combined plant is achieved while the geothermal fluid pumping rate remains substantially constant. This is achieved by using a combination of valves that permits the variable diversion of the geothermal fluid from the geothermal power plant to the electrolysis system.
  • FIG. 1 is a graphical representation of a combined power plant
  • FIG. 2 is a graphical representation of a further embodiment of a combined power plant
  • FIG. 3 is a graphical representation of an additional embodiment of a combined power plant.
  • FIG. 4 is a graphical representation of a still further embodiment of a combined power plant.
  • FIG. 1 represents an embodiment of a combined power plant that operates in accordance with the present invention.
  • numeral 10 A designates a combined power plant for the production of hydrogen using geothermal energy.
  • Combined power plant 10 A includes vaporizer 12 A of geothermal power plant 15 A for vaporizing working fluid present in the vaporizer using heat present in geothermal liquid or brine supplied thereto, the geothermal liquid or brine being produced by a separator (not shown) that separates the geothermal liquid or brine as well as geothermal steam from geothermal fluid extracted from production well 11 A.
  • Working fluid vapor exiting vaporizer 12 A is supplied to vapor turbine 14 A where it is expanded and power is produced as well as expanded working fluid.
  • vapor turbine 14 A drives electric generator 16 A for producing electric power.
  • Expanded working fluid vapor exiting vapor turbine 14 A is supplied to condenser 17 A, which is an air-cooled condenser or a water-cooled condenser, and working fluid condensate is produced which is supplied to vaporizer 12 A using cycle pump 18 A.
  • an organic working fluid is used for working fluid of geothermal power plant 15 A.
  • organic working fluids are butane, i.e. n-butane, or iso-butane, pentane, i.e. n-pentane, or iso-pentane, hexane, i.e. n-hexane, or iso-hexane, etc. and mixtures of the above-mentioned fluids, preferably, pentane, i.e. n-pentane, or iso-pentane.
  • heat depleted geothermal liquid or brine exiting vaporizer 12 A is supplied to heat exchanger 22 A of electrolysis system 25 A for heating water or solution supplied thereto.
  • heat exchanger 22 A of electrolysis system 25 A for heating water or solution supplied thereto.
  • specific advantages of using electrolysis together with a fuel cell are described in U.S. Pat. No. 6,127,055.
  • the further heat-depleted geothermal liquid or brine is supplied to injection well 21 A using pump 20 A.
  • the heated water or heated solution exiting heat exchanger 22 A is supplied to electrolysis unit 24 A wherein electrolysis of the heated water or heated solution is carried out.
  • hydrogen and oxygen are produced in hydrogen supply means 28 A and oxygen supply means 29 A.
  • Hydrogen may be used in utilization device 30 A to produce e.g. in electricity using e.g. fuel cells, combustion processes such as in gas turbines, steam turbines, internal combustion engines, etc. Alternatively, the hydrogen produced can be used to produce methanol or ammonia. Oxygen produced can be used in utilization device 32 A e.g. in combustion processes such as in gas turbines or steam turbines, or used together with hydrogen in a fuel cell to produce electricity.
  • part of the heat of condensation of the organic Rankine cycle turbine can be used for pre-heating the water to be used in electrolysis.
  • this embodiment is very similar to the embodiment of the present invention described with reference to FIG. 1 except that heater 19 B can be used for pre-heating water with heat present in expanded vapors exiting turbine 14 B prior to supplying the water to heat exchanger 22 B for further heating the water with geothermal fluid.
  • combined power plant 10 B includes vaporizer 12 B of geothermal power plant 15 B for vaporizing working fluid present in the vaporizer using heat present in geothermal liquid or brine supplied thereto, the geothermal liquid or brine being produced by a separator (not shown) that separates the geothermal liquid or brine as well as geothermal steam from geothermal fluid extracted from production well 11 B.
  • Working fluid vapor exiting vaporizer 12 B is supplied to vapor turbine 14 B where it is expanded and power is produced as well as expanded working fluid.
  • vapor turbine 14 B drives electric generator 16 B for producing electric power.
  • Expanded working fluid vapor exiting vapor turbine 14 B is first of all supplied to pre-heater 19 B where it heats water supplied to pre-heater 19 B and heat depleted working fluid vapor exiting pre-heater 19 B is supplied to condenser 17 B, which is an air-cooled condenser or a water-cooled condenser.
  • the working fluid condensate produced in condenser 17 B is then supplied to vaporizer 12 B using cycle pump 18 B.
  • an organic working fluid is used for working fluid of geothermal power plant 15 B. Examples of such organic working fluids are butane, i.e. n-butane, or iso-butane, pentane, i.e.
  • n-pentane, or iso-pentane hexane, i.e. n-hexane, or iso-hexane, etc., and mixtures of the above-mentioned fluids, preferably, pentane, i.e. n-pentane, or iso-pentane.
  • heat depleted geothermal liquid or brine exiting vaporizer 12 B is supplied to heat exchanger 22 B of electrolysis system 25 B for further heating water or solution supplied thereto from pre-heater 19 B. Thereafter, the further heat-depleted geothermal liquid or brine is supplied to injection well 21 B using pump 20 B.
  • the further heated water exiting heat exchanger 22 B is supplied from heat exchanger 22 B to electrolysis unit 24 B wherein electrolysis of the heated water or heated solution is carried out.
  • hydrogen and oxygen are produced in hydrogen supply means 28 B and oxygen supply means 29 B. Hydrogen may be used in utilization device 30 B to produce e.g. in electricity using e.g.
  • the hydrogen produced can be used to produce methanol or ammonia.
  • Oxygen produced can be used in utilization device 32 B e.g. in combustion processes such as in gas turbines or steam turbines, or used together with hydrogen in a fuel cell to produce electricity.
  • the embodiment of the present invention can be used in any of the other embodiments of the present invention.
  • FIG. 3 represents a further embodiment of a combined power plant that operates in accordance with the present invention.
  • numeral 10 C designates a combined power plant for the production of hydrogen using geothermal energy.
  • Combined power plant 10 C includes vaporizer 12 C of geothermal power plant 15 C for vaporizing working fluid present in the vaporizer using heat present in geothermal liquid or brine supplied thereto, the geothermal liquid or brine being produced by a separator (not shown) that separates the geothermal liquid or brine as well as geothermal steam from geothermal fluid extracted from production well 11 C.
  • Working fluid vapor exiting vaporizer 12 C is supplied to vapor turbine 15 C where it is expanded and power is produced as well as expanded working fluid.
  • vapor turbine 14 C drives electric generator 16 C for producing electric power.
  • Expanded working fluid vapor exiting vapor turbine 14 C is supplied to condenser 17 C, which is an air-cooled condenser or a water-cooled condenser, and working fluid condensate is produced which is supplied to vaporizer 12 C using cycle pump 18 C.
  • an organic working fluid is used for working fluid of geothermal power plant 15 C.
  • organic working fluids are butane, i.e. n-butane, or iso-butane, pentane, i.e. n-pentane, or iso-pentane, hexane, i.e. n-hexane, or iso-hexane, etc., and mixtures of the above mentioned fluids, preferably, pentane, i.e. n-pentane, or iso-pentane.
  • heat present in heat depleted geothermal liquid or brine exiting the vaporizer of the geothermal power plant is used in the electrolysis system.
  • heat depleted geothermal liquid or brine exiting vaporizer 12 C is supplied to heat exchanger 22 C of electrolysis system 25 C for heating water or solution supplied thereto.
  • the further heat-depleted geothermal liquid or brine is supplied to injection well 21 C using pump 20 C.
  • the heated water or heated solution exiting heat exchanger 22 C is supplied to electrolysis unit 24 C wherein electrolysis of the heated water or heated solution is carried out.
  • hydrogen and oxygen are produced in hydrogen supply means 28 C and oxygen supply means 29 C.
  • the hydrogen or portion thereof may be used also here to produce e.g. electricity using e.g. fuel cells, combustion processes such as in gas turbines, steam turbines, internal combustion engines, etc.
  • the hydrogen produced or portion thereof can be used to produce methanol or ammonia.
  • Oxygen produced or portion thereof can be used also here e.g. in combustion processes such as in gas turbines or steam turbines, or used together with hydrogen in a fuel cell to produce electricity.
  • hydrogen produced or portion thereof is used to operate expander 34 C for expanding the hydrogen from its present pressure to a lower pressure such that expander 34 C runs pump 19 C for supplying at least portion of further heat-depleted geothermal liquid exiting heat exchanger 22 C to the injection well.
  • oxygen produced or portion thereof is used to operate expander 36 C for expanding the oxygen from its present pressure to a lower pressure such that expander 36 C runs pump 19 C for supplying at least portion of further heat-depleted geothermal liquid exiting heat exchanger 22 C to the injection well.
  • the hydrogen and/or oxygen produced by the electrolysis system can be stored for use at a different time e.g. during peak hours of electricity demand rather than using the hydrogen online as produced.
  • the operation of this embodiment is similar to that of the embodiment described with reference to FIG. 1 utilizing geothermal power plant 15 D and electrolysis system 25 D except that the hydrogen and/or oxygen produced by electrolysis system 25 D is stored in hydrogen storage apparatus 40 D and in oxygen storage apparatus 42 D respectively for later use.
  • Such later use can be e.g. during peak hours of electricity demand and the hydrogen and/or oxygen produced can be used in utilization devices 30 D and 32 D for producing electricity using e.g.
  • Oxygen produced can be used in utilization device 32 D e.g. in combustion processes such as in gas turbines or steam turbines, or used together with hydrogen in a fuel cell to produce electricity.
  • the hydrogen and/or oxygen can be stored for local used to that low-pressure (e.g. approximately between 3-10 atmospheres) storage can be used.
  • Combined power plant 10 D includes vaporizer 12 D of geothermal power plant 15 D for vaporizing working fluid present in the vaporizer using heat present in geothermal liquid or brine supplied thereto, the geothermal liquid or brine being produced by a separator (not shown) that separates the geothermal liquid or brine as well as geothermal steam from geothermal fluid extracted from production well 11 D.
  • Working fluid vapor exiting vaporizer 12 D is supplied to vapor turbine 14 D where it is expanded and power is produced as well as expanded working fluid.
  • vapor turbine 14 D drives electric generator 16 D for producing electric power.
  • Expanded working fluid vapor exiting vapor turbine 14 D is supplied to condenser 17 D, which is an air-cooled condenser or a water-cooled condenser, and working fluid condensate is produced which is supplied to vaporizer 12 D using cycle pump 18 D.
  • an organic working fluid is used for working fluid of geothermal power plant 15 D.
  • organic working fluids are butane, i.e. n-butane, or iso-butane, pentane, i.e. n-pentane, or iso-pentane, hexane, i.e.
  • n-hexane or iso-hexane, etc.
  • mixtures of the above-mentioned fluids preferably, pentane, i.e. n-pentane, or iso-pentane.
  • heat depleted geothermal liquid or brine exiting vaporizer 12 D is supplied to heat exchanger 22 D of electrolysis system 25 D for heating water or solution supplied thereto. Thereafter, the further heat-depleted geothermal liquid or brine is supplied to injection well 21 D using pump 20 D.
  • the heated water or heated solution exiting heat exchanger 22 D is supplied to electrolysis unit 24 D wherein electrolysis of the heated water or heated solution is carried out.
  • hydrogen and oxygen are produced in hydrogen supply means 28 D and oxygen supply means 29 D.
  • the embodiments of the present invention described with reference to FIG. 1 , FIG. 2 and FIG. 3 can also be used in the present embodiment.
  • the hydrogen and/or oxygen produced can be first expanded in expanders like 34 C and 36 C (see FIG. 3 ) for driving pump 19 C for supplying further heat-depleted geothermal liquid or brine to the injection well prior to storing the hydrogen and/or oxygen.
  • the stored hydrogen and oxygen can be used and often transported, if preferred, in e.g. certain industries, e.g. the manufacture of methanol or ammonia.
  • the ratio of geothermal liquid supplied to geothermal power plant 15 D and to electrolysis system 25 D can be changed and controlled using valve 50 D (and valve 52 D) so that more geothermal liquid can be supplied to electrolysis system 25 D during e.g. off-peak electricity demand so that more hydrogen can be stored and subsequently used e.g. during peak hours of electricity demand to produce electricity.
  • the efficiency of the electrolysis process is increased.
  • the pressure of the hydrogen and/or oxygen produced in accordance with the present invention less electric power has to be used for such a purpose.
  • the present invention permits increased production of electricity during e.g. periods of peak demand for electricity.
  • the hydrogen and/or oxygen can be used locally, without having to substantially transport the gases, hydrogen and oxygen can be used at relatively low pressures and their use does not suffer from various market barriers which are often associated with hydrogen transport and prolonged storage.
  • geothermal Flash Steam Power Plants geothermal Steam Power plants
  • EGS Enhanced Geothermal Systems
  • HFR Hot Fractured Roc
  • HDR Hot Dry Rock
  • the present invention is particularly advantageous for use with low to medium temperature geothermal resources and geothermal fluids and does not need to rely on supercritical geothermal steam or vapor. Furthermore, the present invention can be used preferably for low temperature and intermediate temperature electrolysis for solution temperatures up to 350° C.

Abstract

The present inventive subject matter is drawn to apparatus for producing hydrogen using geothermal energy comprising: heating means for heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution; and electrolysis means for producing hydrogen by electrolysis of said heated solution. The present invention also relates to a method for producing hydrogen using geothermal energy comprising: heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution; and producing hydrogen by electrolysis of said heated solution. In addition, in accordance with the present invention, apparatus for producing hydrogen using geothermal energy is provided comprising: heating means for heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution; electrolysis means for producing hydrogen by electrolysis of said heated solution; and power producing means utilizing the pressure of said hydrogen for producing power.

Description

    BACKGROUND OF THE INVENTION
  • 1. Technical Field
  • This invention relates to a method and apparatus for producing hydrogen using geothermal energy, and more particularly, to a method and apparatus for producing hydrogen via electrolysis using geothermal energy.
  • 2. Background of the Invention
  • Recently an increasing interest has been developing in methods of producing renewable energy that produces little or minimal pollution. One of the ways is using hydrogen to produce power or electricity. However, the methods of producing hydrogen at present are rather expensive and also can cause pollution.
  • U.S. Pat. No. 5,661,977 discloses a system for generation of electricity from geothermal energy wherein one or more substances are transported down a well to a depth at which geothermal heat (whether from brine or steam reservoirs or hot, dry rock) is sufficient to cause an endothermic reaction or an electrolysis reaction to occur among substances. In a second embodiment of the invention disclosed in this US Patent, a system is disclosed for the generation of electricity from geothermal energy wherein one juncture of a thermocouple is transported down a well to a depth at which geothermal heat is sufficient to create a temperature difference, relative to the temperature of the other juncture of the thermocouple. Such systems are rather complicated to construct so that the costs for constructing such system could be high.
  • Geothermal energy is conventionally produced using a constant flow rate of the geothermal fluid. Due to this, such a geothermal power plant operates at a fixed production level, while on the other hand, consumer power demand varies significantly between peak hours and off-peak hours. As a result, operation of such geothermal power plants is not cost effective.
  • As far as room temperature electrolysis operated at atmospheric pressure is concerned, the energy requirements are relatively high. Thus, electrolysis is a relatively expensive method of producing hydrogen.
  • Fouillac et al. (2003) discuss the use of geothermal heat to pre-heat the solution for high temperature (around 900° C. or more) electrolysis with additional energy sources such as coal- or gas-fired power being combined for such a use. In this paper, it is suggested that the geothermal energy could be combined with nuclear power plant energy.
  • It is therefore an object of the present invention to provide a new and improved method of and apparatus for producing hydrogen and operation of geothermal power plants wherein the disadvantages as outlined above are reduced or substantially overcome.
  • SUMMARY OF THE INVENTION
  • The present inventive subject matter is drawn to apparatus for producing hydrogen using geothermal energy comprising: heating means apparatus for heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution; and electrolysis means apparatus for producing hydrogen by electrolysis of said heated solution.
  • The present invention also relates to a method for producing hydrogen using geothermal energy comprising: heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution; and producing hydrogen by electrolysis of said heated solution.
  • In a further embodiment of the present invention, apparatus for producing hydrogen using geothermal energy is provided comprising: heating means for heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution; electrolysis means apparatus for producing hydrogen by electrolysis of said heated solution; and power producing means utilizing the pressure of said hydrogen for producing power.
  • In this embodiment, a method for producing hydrogen using geothermal energy is also provided comprising: heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution; producing hydrogen by electrolysis of said heated solution; and utilizing the pressure of said hydrogen for producing power.
  • The integration of geothermal and electrolysis plants of the present invention as described herein is advantageous since the efficiency of the integrated or combined geothermal and electrolysis plant is higher than independently operated plants. This is achieved by using the heat present in the geothermal fluid for heating the solution prior to electrolysis and also permitting the use of the pressure of the hydrogen and/or oxygen electrolysis products in the pumping of brine to be injected into the injection well of the geothermal power plant.
  • Furthermore, the method and apparatus of the present invention permits the integrated or combined geothermal and electrolysis plant to have flexible modes of operation during peak and off-peak demand hours. In particular, the hydrogen and oxygen produced by the electrolysis system of the present invention are energy storage vehicles that enable the shift of off-peak geothermal power to be sold and consumed during periods of peak power demand. The local use of the electrolysis hydrogen and oxygen products make it unnecessary to use high-pressure storage or transportation of these gases. Consequently, the available pressure of the electrolysis produced hydrogen and oxygen can be used for other purposes. More importantly, the above-mentioned flexibility of operation of the integrated or combined plant is achieved while the geothermal fluid pumping rate remains substantially constant. This is achieved by using a combination of valves that permits the variable diversion of the geothermal fluid from the geothermal power plant to the electrolysis system.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • A description of the present inventive subject matter including embodiments thereof is presented and with reference to the accompanying drawings, the description is not meant to be considered limiting in any manner, wherein:
  • FIG. 1 is a graphical representation of a combined power plant;
  • FIG. 2 is a graphical representation of a further embodiment of a combined power plant;
  • FIG. 3 is a graphical representation of an additional embodiment of a combined power plant; and
  • FIG. 4 is a graphical representation of a still further embodiment of a combined power plant.
  • Like reference numerals and designations in the various drawings refer to like elements.
  • DETAILED DESCRIPTION
  • Turning now to the Figures, FIG. 1 represents an embodiment of a combined power plant that operates in accordance with the present invention. As can be seen from the figure, numeral 10A designates a combined power plant for the production of hydrogen using geothermal energy. Combined power plant 10A includes vaporizer 12A of geothermal power plant 15A for vaporizing working fluid present in the vaporizer using heat present in geothermal liquid or brine supplied thereto, the geothermal liquid or brine being produced by a separator (not shown) that separates the geothermal liquid or brine as well as geothermal steam from geothermal fluid extracted from production well 11A. Working fluid vapor exiting vaporizer 12A is supplied to vapor turbine 14A where it is expanded and power is produced as well as expanded working fluid. Preferably, vapor turbine 14A drives electric generator 16A for producing electric power. Expanded working fluid vapor exiting vapor turbine 14A is supplied to condenser 17A, which is an air-cooled condenser or a water-cooled condenser, and working fluid condensate is produced which is supplied to vaporizer 12A using cycle pump 18A. Preferably, an organic working fluid is used for working fluid of geothermal power plant 15A. Examples of such organic working fluids are butane, i.e. n-butane, or iso-butane, pentane, i.e. n-pentane, or iso-pentane, hexane, i.e. n-hexane, or iso-hexane, etc. and mixtures of the above-mentioned fluids, preferably, pentane, i.e. n-pentane, or iso-pentane.
  • In accordance with this embodiment of the present invention, heat depleted geothermal liquid or brine exiting vaporizer 12A is supplied to heat exchanger 22A of electrolysis system 25A for heating water or solution supplied thereto. Specific advantages of using electrolysis together with a fuel cell are described in U.S. Pat. No. 6,127,055. Thereafter, the further heat-depleted geothermal liquid or brine is supplied to injection well 21A using pump 20A. The heated water or heated solution exiting heat exchanger 22A is supplied to electrolysis unit 24A wherein electrolysis of the heated water or heated solution is carried out. During electrolysis of the heated water or heated solution using electrodes 26A hydrogen and oxygen are produced in hydrogen supply means 28A and oxygen supply means 29A. Hydrogen may be used in utilization device 30A to produce e.g. in electricity using e.g. fuel cells, combustion processes such as in gas turbines, steam turbines, internal combustion engines, etc. Alternatively, the hydrogen produced can be used to produce methanol or ammonia. Oxygen produced can be used in utilization device 32A e.g. in combustion processes such as in gas turbines or steam turbines, or used together with hydrogen in a fuel cell to produce electricity.
  • In an additional embodiment, see FIG. 2, part of the heat of condensation of the organic Rankine cycle turbine can be used for pre-heating the water to be used in electrolysis. Thus, this embodiment is very similar to the embodiment of the present invention described with reference to FIG. 1 except that heater 19B can be used for pre-heating water with heat present in expanded vapors exiting turbine 14B prior to supplying the water to heat exchanger 22B for further heating the water with geothermal fluid. In this embodiment combined power plant 10B includes vaporizer 12B of geothermal power plant 15B for vaporizing working fluid present in the vaporizer using heat present in geothermal liquid or brine supplied thereto, the geothermal liquid or brine being produced by a separator (not shown) that separates the geothermal liquid or brine as well as geothermal steam from geothermal fluid extracted from production well 11B. Working fluid vapor exiting vaporizer 12B is supplied to vapor turbine 14B where it is expanded and power is produced as well as expanded working fluid. Preferably, vapor turbine 14B drives electric generator 16B for producing electric power. Expanded working fluid vapor exiting vapor turbine 14B is first of all supplied to pre-heater 19B where it heats water supplied to pre-heater 19B and heat depleted working fluid vapor exiting pre-heater 19B is supplied to condenser 17B, which is an air-cooled condenser or a water-cooled condenser. The working fluid condensate produced in condenser 17B is then supplied to vaporizer 12B using cycle pump 18B. Preferably, an organic working fluid is used for working fluid of geothermal power plant 15B. Examples of such organic working fluids are butane, i.e. n-butane, or iso-butane, pentane, i.e. n-pentane, or iso-pentane, hexane, i.e. n-hexane, or iso-hexane, etc., and mixtures of the above-mentioned fluids, preferably, pentane, i.e. n-pentane, or iso-pentane.
  • In accordance with this embodiment of the present invention, heat depleted geothermal liquid or brine exiting vaporizer 12B is supplied to heat exchanger 22B of electrolysis system 25B for further heating water or solution supplied thereto from pre-heater 19B. Thereafter, the further heat-depleted geothermal liquid or brine is supplied to injection well 21B using pump 20B. The further heated water exiting heat exchanger 22B is supplied from heat exchanger 22B to electrolysis unit 24B wherein electrolysis of the heated water or heated solution is carried out. During electrolysis of the further heated water or further heated solution using electrodes 26B, hydrogen and oxygen are produced in hydrogen supply means 28B and oxygen supply means 29B. Hydrogen may be used in utilization device 30B to produce e.g. in electricity using e.g. fuel cells, combustion processes such as in gas turbines, steam turbines, internal combustion engines, etc. Alternatively, the hydrogen produced can be used to produce methanol or ammonia. Oxygen produced can be used in utilization device 32B e.g. in combustion processes such as in gas turbines or steam turbines, or used together with hydrogen in a fuel cell to produce electricity. In accordance with the present invention, the embodiment of the present invention can be used in any of the other embodiments of the present invention.
  • FIG. 3 represents a further embodiment of a combined power plant that operates in accordance with the present invention. As can be seen from the figure, numeral 10C designates a combined power plant for the production of hydrogen using geothermal energy. Combined power plant 10C includes vaporizer 12C of geothermal power plant 15C for vaporizing working fluid present in the vaporizer using heat present in geothermal liquid or brine supplied thereto, the geothermal liquid or brine being produced by a separator (not shown) that separates the geothermal liquid or brine as well as geothermal steam from geothermal fluid extracted from production well 11C. Working fluid vapor exiting vaporizer 12C is supplied to vapor turbine 15C where it is expanded and power is produced as well as expanded working fluid. Preferably, vapor turbine 14C drives electric generator 16C for producing electric power. Expanded working fluid vapor exiting vapor turbine 14C is supplied to condenser 17C, which is an air-cooled condenser or a water-cooled condenser, and working fluid condensate is produced which is supplied to vaporizer 12C using cycle pump 18C. Preferably, an organic working fluid is used for working fluid of geothermal power plant 15C. Examples of such organic working fluids are butane, i.e. n-butane, or iso-butane, pentane, i.e. n-pentane, or iso-pentane, hexane, i.e. n-hexane, or iso-hexane, etc., and mixtures of the above mentioned fluids, preferably, pentane, i.e. n-pentane, or iso-pentane.
  • Also in accordance with this embodiment of the present invention, heat present in heat depleted geothermal liquid or brine exiting the vaporizer of the geothermal power plant is used in the electrolysis system. Thus, heat depleted geothermal liquid or brine exiting vaporizer 12C is supplied to heat exchanger 22C of electrolysis system 25C for heating water or solution supplied thereto. Thereafter, the further heat-depleted geothermal liquid or brine is supplied to injection well 21C using pump 20C. The heated water or heated solution exiting heat exchanger 22C is supplied to electrolysis unit 24C wherein electrolysis of the heated water or heated solution is carried out. During electrolysis of the heated water or heated solution using electrodes 26C hydrogen and oxygen are produced in hydrogen supply means 28C and oxygen supply means 29C. The hydrogen or portion thereof may be used also here to produce e.g. electricity using e.g. fuel cells, combustion processes such as in gas turbines, steam turbines, internal combustion engines, etc. Alternatively, also here, the hydrogen produced or portion thereof can be used to produce methanol or ammonia. Oxygen produced or portion thereof can be used also here e.g. in combustion processes such as in gas turbines or steam turbines, or used together with hydrogen in a fuel cell to produce electricity. However, in accordance with this embodiment of the present invention, hydrogen produced or portion thereof is used to operate expander 34C for expanding the hydrogen from its present pressure to a lower pressure such that expander 34C runs pump 19C for supplying at least portion of further heat-depleted geothermal liquid exiting heat exchanger 22C to the injection well. Likewise, oxygen produced or portion thereof is used to operate expander 36C for expanding the oxygen from its present pressure to a lower pressure such that expander 36C runs pump 19C for supplying at least portion of further heat-depleted geothermal liquid exiting heat exchanger 22C to the injection well.
  • In a further embodiment, see e.g. FIG. 4, the hydrogen and/or oxygen produced by the electrolysis system can be stored for use at a different time e.g. during peak hours of electricity demand rather than using the hydrogen online as produced. Basically, the operation of this embodiment is similar to that of the embodiment described with reference to FIG. 1 utilizing geothermal power plant 15D and electrolysis system 25D except that the hydrogen and/or oxygen produced by electrolysis system 25D is stored in hydrogen storage apparatus 40D and in oxygen storage apparatus 42D respectively for later use. Such later use can be e.g. during peak hours of electricity demand and the hydrogen and/or oxygen produced can be used in utilization devices 30D and 32D for producing electricity using e.g. fuel cells or combustion apparatus such as gas turbines or steam turbines, internal combustion engines, etc. Oxygen produced can be used in utilization device 32D e.g. in combustion processes such as in gas turbines or steam turbines, or used together with hydrogen in a fuel cell to produce electricity. In such a case, the hydrogen and/or oxygen can be stored for local used to that low-pressure (e.g. approximately between 3-10 atmospheres) storage can be used. Combined power plant 10D includes vaporizer 12D of geothermal power plant 15D for vaporizing working fluid present in the vaporizer using heat present in geothermal liquid or brine supplied thereto, the geothermal liquid or brine being produced by a separator (not shown) that separates the geothermal liquid or brine as well as geothermal steam from geothermal fluid extracted from production well 11D. Working fluid vapor exiting vaporizer 12D is supplied to vapor turbine 14D where it is expanded and power is produced as well as expanded working fluid. Preferably, vapor turbine 14D drives electric generator 16D for producing electric power. Expanded working fluid vapor exiting vapor turbine 14D is supplied to condenser 17D, which is an air-cooled condenser or a water-cooled condenser, and working fluid condensate is produced which is supplied to vaporizer 12D using cycle pump 18D. Preferably, an organic working fluid is used for working fluid of geothermal power plant 15D. Examples of such organic working fluids are butane, i.e. n-butane, or iso-butane, pentane, i.e. n-pentane, or iso-pentane, hexane, i.e. n-hexane, or iso-hexane, etc., and mixtures of the above-mentioned fluids, preferably, pentane, i.e. n-pentane, or iso-pentane.
  • In accordance with this embodiment of the present invention, heat depleted geothermal liquid or brine exiting vaporizer 12D is supplied to heat exchanger 22D of electrolysis system 25D for heating water or solution supplied thereto. Thereafter, the further heat-depleted geothermal liquid or brine is supplied to injection well 21 D using pump 20D. The heated water or heated solution exiting heat exchanger 22D is supplied to electrolysis unit 24D wherein electrolysis of the heated water or heated solution is carried out. During electrolysis of the heated water or heated solution using electrodes 26D hydrogen and oxygen are produced in hydrogen supply means 28D and oxygen supply means 29D.
  • Also, the embodiments of the present invention described with reference to FIG. 1, FIG. 2 and FIG. 3 can also be used in the present embodiment. Thus, e.g. the hydrogen and/or oxygen produced can be first expanded in expanders like 34C and 36C (see FIG. 3) for driving pump 19C for supplying further heat-depleted geothermal liquid or brine to the injection well prior to storing the hydrogen and/or oxygen. However, in a further option, the stored hydrogen and oxygen can be used and often transported, if preferred, in e.g. certain industries, e.g. the manufacture of methanol or ammonia.
  • In addition, in this embodiment, if preferred, the ratio of geothermal liquid supplied to geothermal power plant 15D and to electrolysis system 25D can be changed and controlled using valve 50D (and valve 52D) so that more geothermal liquid can be supplied to electrolysis system 25D during e.g. off-peak electricity demand so that more hydrogen can be stored and subsequently used e.g. during peak hours of electricity demand to produce electricity.
  • By use of the present invention to heat the solution to be used in electrolysis with heat from geothermal fluid, the efficiency of the electrolysis process is increased. In addition, by using the pressure of the hydrogen and/or oxygen produced in accordance with the present invention, less electric power has to be used for such a purpose.
  • Furthermore, the present invention, particularly as described in the embodiment of the present invention with reference to FIG. 4, permits increased production of electricity during e.g. periods of peak demand for electricity. Moreover, the hydrogen and/or oxygen can be used locally, without having to substantially transport the gases, hydrogen and oxygen can be used at relatively low pressures and their use does not suffer from various market barriers which are often associated with hydrogen transport and prolonged storage.
  • In addition, while the embodiment of the present invention described with reference to FIG. 4 describes the use of a binary cycle organic Rankline cycle turbine for producing electricity from the geothermal fluid in e.g. a peaking power configuration, other power systems can be used instead, e.g. geothermal Flash Steam Power Plants, geothermal Steam Power plants, Enhanced Geothermal Systems (EGS) Power Plants, Hot Fractured Roc (HFR) and Hot Dry Rock (HDR) Power Plants. In such geothermal Flash Steam Power Plants, geothermal Steam Power plants, geothermal steam produced from the geothermal fluid can be used.
  • It should be pointed out that the present invention is particularly advantageous for use with low to medium temperature geothermal resources and geothermal fluids and does not need to rely on supercritical geothermal steam or vapor. Furthermore, the present invention can be used preferably for low temperature and intermediate temperature electrolysis for solution temperatures up to 350° C.
  • It is believed that the advantages and improved results furnished by the method and apparatus of the present invention are apparent from the foregoing description of the invention. Various changes and modifications may be made without departing from the spirit and scope of the invention as described in the claims that follow.

Claims (53)

1. Apparatus for producing hydrogen using geothermal energy comprising:
a) heating means apparatus for heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution; and
b) electrolysis means apparatus for producing hydrogen by electrolysis of said heated solution.
2. The apparatus according to claim 1 wherein said heating means for heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution comprises an indirect heat exchanger for transferring heat from said geothermal fluid to a solution for heating said solution.
3. Apparatus according to claim 1 including supply means for supplying said heated solution to said electrolysis means for producing hydrogen by electrolysis of said heated solution.
4. Apparatus according to claim 2 further including a separator for separating said geothermal fluid into geothermal steam and geothermal liquid and a pump for pumping geothermal liquid of said geothermal fluid.
5. Apparatus according to claim 4 further including power producing means that includes a vaporizer for vaporizing working fluid present in said vaporizer and producing working fluid vapor using heat present in said geothermal liquid, a vapor turbine for expanding said working fluid vapor and producing power, and a condenser for condensing the expanded working fluid exiting said vapor turbine and producing working fluid condensate and a cycle pump for supplying said working fluid condensate to said vaporizer.
5. Apparatus according to claim 4 wherein said working fluid is an organic working fluid.
6. Apparatus according to claim 4 further including supply means for supplying heat depleted geothermal liquid exiting said vaporizer to said indirect heat exchanger for heating said solution and producing said heated solution for electrolysis.
7. Apparatus according to claim 6 wherein said pump pumps further heat depleted geothermal liquid exiting said indirect heat exchanger to an injection well.
8. Apparatus according to claim 1 including further means for producing oxygen by electrolysis of said heated solution.
9. Apparatus according to claim 8 including further means for utilizing said oxygen for producing power.
10. Apparatus according to claim 8 including storage means for storing said oxygen for later use.
11. Apparatus according to claim 1 including further means for utilizing said hydrogen for producing power.
12. Apparatus according to claim 1 including storage means for storing said hydrogen for later use.
13. Apparatus according to claim 12 including apparatus for producing power using stored hydrogen stored in said storage means.
14. Apparatus according to claim 13 including apparatus for producing power using stored hydrogen stored in said storage means during period of peak electricity demand.
15. Apparatus for producing hydrogen using geothermal energy comprising:
a) heating means for heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution;
b) electrolysis means for producing hydrogen by electrolysis of said heated solution; and
c) power producing means utilizing the pressure of said hydrogen for producing power.
16. The apparatus according to claim 15 wherein said heating means for heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution comprises an indirect heat exchanger for transferring heat from said geothermal fluid to a solution for heating said solution.
17. Apparatus according to claim 15 including supply means for supplying said heated solution to said electrolysis means for producing hydrogen by electrolysis of said heated solution.
18. Apparatus according to claim 15 wherein said power producing means utilizing the pressure of said hydrogen for producing power includes a separator for separating said geothermal fluid into geothermal steam and geothermal liquid and a pump using the pressure of said hydrogen in pumping geothermal liquid of said geothermal fluid.
19. Apparatus according to claim 18 wherein said power producing means utilizing the pressure of said hydrogen for producing power further includes a vaporizer for vaporizing working fluid present in said vaporizer and producing working fluid vapor using heat present in said geothermal liquid, a vapor turbine for expanding said working fluid vapor and producing power, and condenser for condensing the expanded working fluid exiting said vapor turbine and producing working fluid condensate and a cycle pump for supplying said working fluid condensate to said vaporizer.
20. Apparatus according to claim 19 wherein said working fluid is an organic working fluid.
21. Apparatus according to claim 18 further including supply means for supplying heat depleted geothermal liquid exiting said vaporizer to said indirect heat exchanger for heating said solution and producing said heated solution for electrolysis.
22. Apparatus according to claim 21 wherein said pump pumps further heat depleted geothermal liquid exiting said indirect heat exchanger to an injection well.
23. Apparatus according to claim 15 including further means for producing oxygen by electrolysis of said heated solution.
24. Apparatus according to claim 23 including further means for utilizing the pressure of said oxygen for producing power.
25. Apparatus according to claim 24 wherein said further means for utilizing the pressure of said gas for producing power includes a separator for separating said geothermal fluid into geothermal steam and geothermal liquid, power producing means using said geothermal liquid to produce power and means using the pressure of said oxygen for pumping geothermal liquid of said geothermal fluid.
26. A method for producing hydrogen using geothermal energy comprising:
a) heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution;
b) producing hydrogen by electrolysis of said heated solution; and
c) utilizing the pressure of said hydrogen for producing power
27. The method according to claim 26 wherein the step of heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution is carried out by supplying said geothermal fluid to an indirect heat exchanger for transferring heat from said geothermal fluid to a solution for heating said solution.
28. A method according to claim 26 including supplying said heated solution to apparatus for use of said heated solution in electrolysis for producing hydrogen.
29. A method according to claim 26 wherein the step of utilizing the pressure of said hydrogen for producing power includes separating said geothermal fluid into geothermal steam and geothermal liquid, using geothermal liquid to produce power and using the pressure of said hydrogen in pumping geothermal liquid of said geothermal fluid.
30. A method according to claim 26 including the further step of producing oxygen by electrolysis of said heated solution.
31. A method according to claim 29 including the further step of utilizing the pressure of said oxygen for producing power.
32. A method according to claim 31 wherein the further step of utilizing the pressure of said oxygen for producing power includes separating said geothermal fluid into geothermal steam and geothermal liquid, using said geothermal liquid to produce power and using the pressure of said oxygen in pumping geothermal liquid of said geothermal fluid.
33. A method according to claim 30 including the further step of producing power using said oxygen.
34. A method according to claim 26 including the further step of producing power using said hydrogen.
35. Apparatus for producing hydrogen using geothermal energy comprising:
(a) heating means for heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution;
(b) electrolysis means for producing hydrogen by electrolysis of said heated solution; and
(c) storage means for storing said hydrogen for later use.
36. Apparatus according to claim 35 including apparatus for producing power using stored hydrogen stored in said storage means.
37. Apparatus according to claim 36 including apparatus for producing power using stored hydrogen stored in said storage means during period of peak electricity demand.
38. A method for producing hydrogen using geothermal energy comprising:
a) heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution;
b) producing hydrogen by electrolysis of said heated solution; and
c) storing said hydrogen for later use.
39. A method according to claim 38 wherein the further step of storing said hydrogen for later use is carried out by storing said hydrogen during off-peak periods of electricity demand for use during periods of peak electricity demand.
40. A method according to claim 38 including the further step of using said stored hydrogen for producing electricity.
41. Apparatus for producing hydrogen using geothermal energy comprising:
(a) heating means for heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution;
(b) electrolysis means for producing hydrogen by electrolysis of said heated solution; and
(c) power producing means for producing power using heat present in said geothermal fluid.
42. The apparatus according to claim 41 wherein said heating means for heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution comprises an indirect heat exchanger for transferring heat from said geothermal fluid to a solution for heating said solution.
43. Apparatus according to claim 42 further including a separator for separating said geothermal fluid into geothermal steam and geothermal liquid and a pump for pumping geothermal liquid of said geothermal fluid.
44. Apparatus according to claim 43 wherein said power producing means includes a vaporizer for vaporizing working fluid present in said vaporizer and producing working fluid vapor using heat present in said geothermal liquid, a vapor turbine for expanding said working fluid vapor and producing power, and a condenser for condensing the expanded working fluid exiting said vapor turbine and producing working fluid condensate and a cycle pump for supplying said working fluid condensate to said vaporizer.
45. Apparatus according to claim 44 wherein said working fluid is an organic working fluid.
46. Apparatus according to claim 45 further including supply means for supplying heat depleted geothermal liquid exiting said vaporizer to said indirect heat exchanger for heating said solution and producing said heated solution for electrolysis.
47. A method for producing hydrogen using geothermal energy comprising:
a) heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution;
b) producing hydrogen by electrolysis of said heated solution; and
c) producing power using heat present in said geothermal fluid.
48. The method according to claim 47 wherein the step of heating a solution for use in electrolysis with heat from geothermal fluid and producing a heated solution is carried out by supplying said geothermal fluid to an indirect heat exchanger for transferring heat from said geothermal fluid to a solution for heating said solution.
49. A method according to claim 47 including the steps of separating said geothermal fluid into geothermal steam and geothermal liquid, producing power from said geothermal liquid and pumping the geothermal liquid of said geothermal fluid.
50. A method according to claim 49 wherein the step of producing power from said geothermal liquid is carried out by supplying said geothermal liquid to a vaporizer of a power producing means for vaporizing working fluid present in said vaporizer and producing working fluid vapor using heat present in said geothermal liquid, said power producing means further comprising a vapor turbine for expanding said working fluid vapor and producing power, and a condenser for condensing the expanded working fluid exiting said vapor turbine and producing working fluid condensate and a cycle pump for supplying said working fluid condensate to said vaporizer.
51. A method according to claim 50 wherein the step of vaporizing working fluid present in said vaporizer and producing working fluid vapor using heat present in said geothermal liquid for expansion in said vapor turbine of said power producing means and production of power is carried out by vaporizing an organic working fluid present in said vaporizer.
52. A method according to claim 51 further including supplying heat depleted geothermal liquid exiting said vaporizer to said indirect heat exchanger for heating said solution and producing said heated solution for electrolysis.
US10/861,350 2004-06-07 2004-06-07 Method of and apparatus for producing hydrogen using geothermal energy Abandoned US20050269211A1 (en)

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NZ551788A NZ551788A (en) 2004-06-07 2005-06-06 Apparatus for producing hydrogen using geothermal energy to superheat water before electrolysis
PCT/IL2005/000596 WO2005121409A2 (en) 2004-06-07 2005-06-06 Method of and apparatus for producing hydrogen using geothermal enerby
IS8581A IS8581A (en) 2004-06-07 2006-12-15 Method and apparatus for producing hydrogen with geothermal energy
US11/790,343 US7891188B2 (en) 2004-06-07 2007-04-25 Apparatus for producing power using geothermal liquid
US13/031,456 US20110138810A1 (en) 2004-06-07 2011-02-21 Apparatus for producing power using geothermal liquid
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US7891188B2 (en) 2011-02-22
US20070251237A1 (en) 2007-11-01

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