WO2012162438A2 - Fluides supercritiques, systèmes et procédés d'utilisation - Google Patents

Fluides supercritiques, systèmes et procédés d'utilisation Download PDF

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Publication number
WO2012162438A2
WO2012162438A2 PCT/US2012/039217 US2012039217W WO2012162438A2 WO 2012162438 A2 WO2012162438 A2 WO 2012162438A2 US 2012039217 W US2012039217 W US 2012039217W WO 2012162438 A2 WO2012162438 A2 WO 2012162438A2
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WIPO (PCT)
Prior art keywords
fluid
working fluid
heat exchanger
disorder
energy storage
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PCT/US2012/039217
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English (en)
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WO2012162438A3 (fr
Inventor
Kelly HERBST
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Navitasmax, Inc.
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Application filed by Navitasmax, Inc. filed Critical Navitasmax, Inc.
Priority to US13/686,886 priority Critical patent/US20130333385A1/en
Publication of WO2012162438A2 publication Critical patent/WO2012162438A2/fr
Publication of WO2012162438A3 publication Critical patent/WO2012162438A3/fr

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F01—MACHINES OR ENGINES IN GENERAL; ENGINE PLANTS IN GENERAL; STEAM ENGINES
    • F01K—STEAM ENGINE PLANTS; STEAM ACCUMULATORS; ENGINE PLANTS NOT OTHERWISE PROVIDED FOR; ENGINES USING SPECIAL WORKING FLUIDS OR CYCLES
    • F01K25/00—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for
    • F01K25/06—Plants or engines characterised by use of special working fluids, not otherwise provided for; Plants operating in closed cycles and not otherwise provided for using mixtures of different fluids
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03G—SPRING, WEIGHT, INERTIA OR LIKE MOTORS; MECHANICAL-POWER PRODUCING DEVICES OR MECHANISMS, NOT OTHERWISE PROVIDED FOR OR USING ENERGY SOURCES NOT OTHERWISE PROVIDED FOR
    • F03G6/00—Devices for producing mechanical power from solar energy
    • F03G6/06—Devices for producing mechanical power from solar energy with solar energy concentrating means
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/04—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa
    • C09K5/041—Materials undergoing a change of physical state when used the change of state being from liquid to vapour or vice versa for compression-type refrigeration systems
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F03—MACHINES OR ENGINES FOR LIQUIDS; WIND, SPRING, OR WEIGHT MOTORS; PRODUCING MECHANICAL POWER OR A REACTIVE PROPULSIVE THRUST, NOT OTHERWISE PROVIDED FOR
    • F03G—SPRING, WEIGHT, INERTIA OR LIKE MOTORS; MECHANICAL-POWER PRODUCING DEVICES OR MECHANISMS, NOT OTHERWISE PROVIDED FOR OR USING ENERGY SOURCES NOT OTHERWISE PROVIDED FOR
    • F03G7/00—Mechanical-power-producing mechanisms, not otherwise provided for or using energy sources not otherwise provided for
    • F03G7/04—Mechanical-power-producing mechanisms, not otherwise provided for or using energy sources not otherwise provided for using pressure differences or thermal differences occurring in nature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2205/00—Aspects relating to compounds used in compression type refrigeration systems
    • C09K2205/10—Components
    • C09K2205/102—Alcohols
    • 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
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/40—Solar thermal energy, e.g. solar towers
    • Y02E10/46—Conversion of thermal power into mechanical power, e.g. Rankine, Stirling or solar thermal engines
    • 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
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/54—Improvements relating to the production of bulk chemicals using solvents, e.g. supercritical solvents or ionic liquids

Definitions

  • thermal energy storage There are various types of approaches for thermal energy storage, which may be broadly classified under sensible heat storage, latent heat storage and chemical energy storage.
  • Storage and removal of energy using sensible heat storage involves a temperature change of the storage medium in solid, liquid or gaseous form.
  • Storage and removal of energy using latent heat storage involves a state change of the storage medium, e.g., liquid to gas.
  • Storage and removal of energy using chemical energy storage involves a chemical change in the storage medium, e.g., burning hydrogen.
  • phase change materials in contrast, rely on the latent heat energy and can therefore store substantially large amounts of heat. Thermal energy technologies having phase change materials may require large heat transfer areas.
  • Sensible heat storage materials e.g. molten salt
  • Phase change materials may be limited to low temperatures ( ⁇ 200 °C).
  • the invention provides energy storage systems that benefit from improved heat capacities in relation to other systems, while minimizing materials and operating costs and expenses.
  • Some embodiments provide a supercritical fluid mixture that comprises carbon dioxide.
  • the supercritical fluid mixture can include other components, such as hydrocarbons.
  • Provided herein are efficient, high energy density, cost effective, reliable and maintainable thermal energy storage systems.
  • supercritical fluid mixtures are provided having substantial increase in heat capacity in relation to other systems.
  • the substantial increase in heat capacity may be on the order of at least 1.1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, or 10 over other fluid mixtures.
  • supercritical fluid mixtures provided herein comprising C0 2 and one or more secondary components may have heat capacities on the order of at least 1.1, 1.5, 2, 3, 4, 5, 6, 7, 8, 9, or 10 over a supercritical fluid that only includes C0 2 .
  • supercritical fluids mixtures include two or more components.
  • a supercritical fluid includes carbon dioxide and other fluids.
  • supercritical fluid mixtures are provided with heat capacities that are targeted to increase over broad temperature ranges.
  • Such supercritical fluid mixtures may be tailored for particular applications— for example, for concentrating solar power, the mixtures may be able to store significant energy up to a temperature of about 600 °C. For geothermal processes, lower temperatures may be acceptable.
  • supercritical fluid mixtures are provided with substantially high heat capacities, but configured to operate in a manner that does not substantially increase system pressure. This advantageously reduces containment costs, which may decrease overall system and operating costs.
  • supercritical fluid mixtures are provided for use as working fluids and thermal energy storage mediums in energy storage systems that operate per a Brayton cycle.
  • supercritical fluid mixtures are provided for use as thermal energy storage mediums in energy storage systems that operate per a Rankine cycle.
  • An aspect of the invention provides a system, comprising a circulatory fluid flow path having (a) a compressor configured to accept a working fluid and increase the pressure of the working fluid, wherein the working fluid is a supercritical fluid mixture comprising carbon dioxide and at least one disorder-inducing species; (b) a heat exchanger downstream of the compressor, the heat exchanger adapted to accept the working fluid from the compressor and provide heat to the working fluid; and (c) a power generator downstream of the heat exchanger, the power generator adapted to generate power upon the flow of the working fluid through the power generator, and direct the working fluid to the compressor.
  • the system (i) circulates the working fluid along the circulatory fluid flow path, and (ii) increases the pressure and/or temperature of the working fluid to above the critical pressure and critical temperature of the working fluid.
  • the system further comprises an another circulatory fluid flow path for circulating an another working fluid, the another fluid flow path comprising: (a) an another heat exchanger for providing energy to the another working fiuid; (b) a pump downstream of the another heat exchanger, the pump adapted to accept an another working fluid and increase the pressure of the another working fluid; and (c) the heat exchanger.
  • the heat exchanger accepts the another working fluid and transfers energy from the another working fluid to the working fiuid.
  • the system further comprises an energy source in thermal communication with the another heat exchanger.
  • the energy source provides energy to the another heat exchanger.
  • the energy source is a combustion system, nuclear reactor or solar concentrator.
  • the another working fluid comprises a supercritical fluid mixture comprising carbon dioxide and at least one disorder- inducing species.
  • the system further comprises (d) an another heat exchanger downstream of the power generator, the another heat exchanger adapted to (i) accept the working fluid from the power generator, (ii) remove heat from the working fluid and (iii) direct the working fluid to the compressor.
  • the at least one disorder- inducing species is selected from the group consisting of an alkane, alkene, alcohol, aldehyde, ketone, ether, ester, water, fluorinated hydrocarbons, nitromethane, aromatic hydrocarbons and carboxylic acid.
  • the compressor increases the pressure of the working fluid at or above a critical pressure of the working fluid.
  • the heat exchanger maintains or increases the temperature of the working fluid at or above a critical temperature of the working fluid.
  • the working fluid is a supercritical fluid mixture comprising carbon dioxide and at least one disorder-inducing species; (b) a pump downstream of the first heat exchanger.
  • the pump accepts the working fluid from the first heat exchanger and increases the pressure of the working fluid; and (c) a second heat exchanger downstream of the pump, the second heat exchanger adapted to accept the working fluid from the pump and transfer energy from the working fluid to a secondary fluid.
  • the system circulates the working fluid along the circulatory fluid flow path.
  • the system further comprises an energy source in thermal communication with the first heat exchanger.
  • the energy source provides energy to the first heat exchanger.
  • the energy source is a combustion system, nuclear reactor of solar concentrator.
  • the system maintains the pressure and temperature of the working fluid at a supercritical pressure and supercritical temperature, respectively, of the working fluid.
  • the at least one disorder-inducing species is selected from the group consisting of an alkane, alkene, alcohol, aldehyde, ketone, ether, ester, water, fluorinated hydrocarbons, nitromethane, aromatic hydrocarbons and carboxylic acid.
  • Another aspect of the invention provides a thermal energy storage fluid, comprising carbon dioxide and at least one disorder-inducing species.
  • the proportion of carbon dioxide to the at least one disorder-inducing species in the thermal energy storage fluid is sufficient to induce disorder in the thermal energy storage fluid at or above a critical point of the thermal energy storage fluid.
  • the at least one disorder-inducing species is selected from the group consisting of an alkane, alkene, alcohol, aldehyde, ketone, ether, ester, water, fluorinated hydrocarbons, nitromethane, aromatic hydrocarbons and carboxylic acid.
  • the thermal energy storage fluid has a heat capacity of at least about 1 Kilojoule
  • the proportion is at least about 0.5: 1. In another embodiment, the proportion is at least about 1 : 1. In another embodiment, the proportion is at least about 2: 1.
  • Another aspect of the invention provides a method for forming a thermal energy storage fluid, comprising providing a fluid mixture having carbon dioxide and at least one disorder- inducing species in a vessel at a proportion of carbon dioxide to the at least one disorder- inducing species that is selected to induce disorder in the thermal energy storage fluid at or above a critical point of the thermal energy storage fluid.
  • the at least one disorder-inducing species is selected from the group consisting of an alkane, alkene, alcohol, aldehyde, ketone, ether, ester, water, fluorinated hydrocarbons, nitromethane, aromatic hydrocarbons and carboxylic acid.
  • the thermal energy storage fluid has a heat capacity of at least about 1 KJ/Kg*K, 2 KJ/Kg*K, 3 KJ/Kg*K, 4 KJ/Kg*K, 5 KJ/Kg*K, 6 KJ/Kg*K, 7 KJ/Kg*K, 8 KJ/Kg*K, 9 KJ/Kg*K, 10 KJ/Kg*K, 15 KJ/Kg*K, 20 KJ/Kg*K, 25 KJ/Kg*K, 30 KJ/Kg*K, 40 KJ/Kg*K, or 50 KJ/Kg*K.
  • the proportion is at least about 0.5: 1.
  • the proportion is at least about 1 : 1.
  • the proportion is at least about 2: 1.
  • FIG. 1 shows a phase diagram of carbon dioxide
  • FIG. 2 shows a plot of the heat capacity of carbon dioxide along specified isotherms (Tr);
  • FIG. 3 shows a phase diagram of a fluid
  • FIG. 4 is a phase diagram of a fluid mixture, showing the critical line
  • FIG. 5 is an exemplary plot of heat capacity (Cp) as a function of temperature (T) and component composition (X) for a fluid mixture comprising nitromethane and isobutanol;
  • FIG. 6 is a cross-section of the plot of FIG. 5;
  • FIG. 7 is a system configured to generate power, in accordance with an embodiment of the invention.
  • FIGs. 8A and 8B show pressure- volume and temperature-entropy diagrams for a system operating under a Brayton cycle
  • FIG. 9 shows a system configured to generate power, in accordance with an embodiment of the invention.
  • FIG. 10 shows a system configured to store energy and generate power, in accordance with an embodiment of the invention.
  • FIG. 11 shows a system for storing thermal energy, in accordance with an embodiment of the invention.
  • fluid generally refers to a substance that continually deforms or flows under an applied shear stress.
  • a fluid can have various phases, such as solid phase, liquid phase, gas phase, or supercritical phase.
  • a fluid can include a liquid, gas, plasma, or semi-solid, such as a gel-like substance, or a mixture of fluids, such as a gas-liquid mixture.
  • a fluid can be selected from water, alcohols (e.g., methanol, ethanol), aldehydes, ketones, carboxylic acids, and combinations thereof, such as a water-alcohol mixture (e.g., water-methanol mixture).
  • a fluid can be a fluid mixture having two or more components.
  • supercritical fluid generally refers to a substance at a temperature and pressure above its critical point, where distinct liquid and gas phases do not exist.
  • supercritical fluid can effuse through solids like a gas, and dissolve materials in a manner similar to a liquid. In addition, close to the critical point, small changes in pressure or temperature can result in large changes in fluid density. Examples of supercritical fluids include carbon dioxide (C0 2 ) and water.
  • secondary fluid refers to a fluid for use in removing heat from, or adding heat to, another fluid.
  • a secondary fluid can be a liquid, gas, gas-solid or gas- liquid mixture. In some cases, a secondary fluid is air.
  • disorder-inducing species generally refers to an atom or molecule, or a mixture of atoms and/or molecules, which is adapted to generate disorder in a fluid at or above the critical point of the fluid.
  • the disorder-inducing species can generate disorder in the fluid mixture at or above the critical point of the fluid mixture. This may be effected, for example, by reduced (or disrupted) intermolecular interactions between atoms or molecules of the fluid, such as between CO 2 molecules, and in some cases increased attractive interactions between C0 2 or disorder- inducing species, which may result in local inhomogeneities and extended disorder at or above the critical point.
  • a disorder-inducing species in a fluid mixture comprising CO 2 can disrupt the interaction between CO 2 molecules in the fluid mixture.
  • a disorder-inducing species introduces disorder in a fluid mixture comprising supercritical CO 2 .
  • the disorder-inducing species is an organic species, such as an alkane, alkene, alcohol, aldehyde, ketone, ether, ester, water, fluorinated hydrocarbons, nitromethane, aromatic hydrocarbons and carboxylic acid.
  • cycle refers to a system having one or more components (or unit operations, also “units” herein) for facilitating fluid flow and/or fluid phase change, such as pumps, compressors, fluid separators, heat exchangers and reservoirs (or vessels).
  • a cycle can be a circulatory flow system. In the context of such circulatory flow systems, the terms
  • downstream and upstream are used to indicate the location of one component in relation to another component along a fluid flow path that brings the components in fluid communication with one another.
  • Components can be interconnected with the aid of fluid flow paths (or fluid streams, also “streams” herein), which can include channels, fluid passages or conduits for aiding in fluid flow from one unit to another.
  • FIG. 1 is a phase diagram of carbon dioxide as a function of pressure (bar) and temperature (Kelvin, K). Below the critical temperature, e.g., 280K, C0 2 exists as a gas, liquid or solid, depending on the pressure. As the pressure increases, the gas compresses and eventually (at just over 40 bar) condenses into a much denser liquid.
  • the system of FIG. 1 includes two phases in equilibrium, a dense liquid and a low density gas. As the critical temperature is approached (300K), the density of the gas at equilibrium becomes denser, and that of the liquid lower.
  • FIG. 2 is a plot of the heat capacity of carbon dioxide along specified isotherms (Tr).
  • the invention provides supercritical fluid mixtures that can have both broadened and increased heat capacities with minimal system pressure increases.
  • a supercritical fluid may be generated by increasing the pressure of a fluid at a constant temperature above the critical temperature; increasing the temperature of the fluid at a constant pressure above the critical pressure; or increasing the temperature and the pressure of the fluid to a point above the critical temperature and critical pressure.
  • the pressure of the fluid can be increased at constant (or substantially constant) volume.
  • a fluid may be pressurized with the aid of a compressor or pump.
  • C0 2 may be compressed by a single or multi-stage compressor to a pressure above the critical pressure of C0 2 to generate supercritical C0 2 .
  • the invention provides fluid mixtures that are based on the unexpected realization that by introducing disorder in a supercritical fluid mixture, the thermal energy properties, such as heat capacity, of the fluid mixture can be tailored for use in a given application, such as a thermal energy storage application.
  • Such fluid mixtures can be used in energy storage systems, such as systems adapted for use in a Brayton or Rankine Cycle.
  • an ultra- thermally dense thermal energy storage fluid is provided by enhancing critical fluctuations and introducing disorder to tailor the properties of supercritical fluids over a wide range in pressure (P), temperature (T) and composition (X). Fluid mixtures provided herein can demonstrate extended thermal capacity along the critical line of the fluid mixtures and throughout the adjacent critical surface.
  • a fluid mixture comprises a primary component (atom or molecule) and one or more secondary components.
  • the primary component can be a non- carcinogenic and/or an environmentally friendly species, and the one or more secondary components can be disorder-inducing species.
  • the secondary components may be non- carcinogenic and/or environmentally friendly.
  • the primary component is selected from C0 2 and H 2 0. In an example, the primary component is C0 2 . In another example, the primary component is H 2 0. In another example, the primary component is a mixture of C0 2 and H 2 0. The temperature, pressure and composition of the fluid are selected such that the fluid mixture is supercritical.
  • An aspect of the invention provides a thermal energy storage fluid comprising carbon dioxide and at least one disorder-inducing species.
  • the proportion of carbon dioxide to the at least one disorder-inducing species in the thermal energy storage fluid is selected such that disorder is induced in the thermal energy storage fluid at or above a critical point of the thermal energy storage fluid. In some cases, disorder is induced at or above a critical point of C0 2 .
  • the fluid with the disorder-inducing species can be at a pressure and temperature such that C0 2 is in a supercritical state.
  • the thermal energy storage fluid has a heat capacity of at least about 0.1 Kilojoules (KJ)/Kg*K, 1 KJ/Kg*K, 2 KJ/Kg*K, 3 KJ/Kg*K, 4 KJ/Kg*K, 5 KJ/Kg*K, 6 KJ/Kg*K, 7 KJ/Kg*K, 8 KJ/Kg*K, 9 KJ/Kg*K, 10 KJ/Kg*K, 15 KJ/Kg*K, 20 KJ/Kg*K, 25 KJ/Kg*K, 30 KJ/Kg*K, 40 KJ/Kg*K, or 50 KJ/Kg*K.
  • the thermal energy storage fluid may have a heat capacity from about 1 KJ/Kg*K and 100 KJ/Kg*K, or 3 KJ/Kg*K and 50 KJ/Kg*K.
  • the proportion of carbon dioxide to the at least one disorder- inducing species is at least about 0.1 : 1, or at least about 0.5: 1, or at least about 1 : 1, or at least about 2: 1, or at least about 3: 1, or at least about 4:1, or at least about 5: 1, or at least about 10: 1, or at least about 20: 1, or at least about 30: 1, or at least about 40: 1, or at least about 50: 1, or at least about 100: 1.
  • Supercritical fluid mixtures of the invention are based on the unexpected realization that heat storage properties of fluids, such as heat capacities, may be increased by inducing inhomogeneities at or above the critical point (see FIG. 3).
  • a supercritical fluid may experience an improved heat capacity in the supercritical portion of the phase diagram of the fluid along, for example, a "ridge” extending from the critical point, separating "liquid-like” and “vapor-like” region.
  • Such improved heat capacity may be experienced along other paths in the critical region.
  • the properties of the fluid mixture extending away from a critical line to a plane may be adjusted to enhance the heat capacity of the fluid mixture.
  • the composition of a fluid mixture comprising carbon dioxide and one or more disorder-inducing species may be selected to enhance the heat capacity of the fluid mixture. This may provide increases in intrinsic heat capacity of the fluid mixture in the vicinity of the critical point (line), and provide extended enhancement of the heat capacity into the supercritical region.
  • carbon dioxide is mixed with a disorder-inducing species to form a fluid mixture, and the pressure and/or temperature of the fluid mixture is increased to a point such that the fluid mixture is in a supercritical regime. In some cases, this is achieved via a trans-critical process with fluid properties (e.g., pressure, temperature, composition) selected to bring the fluid to supercritical conditions. In some cases, this is above a critical point
  • the thermal energy storage fluid has a disorder-inducing species at a composition (mole %) between 0.1% and 70%>, or between about 1% and 60%>, or between about 5%> and 50%>. In some situations, the thermal energy storage fluid has a disorder-inducing species at a composition of at least about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%), 30%), 40%), 50%o, or 60%>.
  • the balance of the fluid mixture is C0 2 .
  • a supercritical fluid mixture comprises about 60%> C0 2 and 40%> ethanol.
  • a fluid mixture comprises 80% C0 2 and 20% ethanol.
  • a fluid mixture comprises 90% C0 2 and 10% nitromethane.
  • a fluid mixture comprises 95% C0 2 and 5% acetic acid.
  • the thermal energy storage fluid has two or more disorder- inducing species at a composition (mole %) between 0.1% and 70%, or between about 1% and 60%), or between about 5% and 50%. In some situations, the thermal energy storage fluid has two or more disorder-inducing species at a composition of at least about 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 15%, 20%, 30%, 40%, 50%, or 60%.
  • the balance of the fluid mixture is C0 2 .
  • a supercritical fluid mixture comprises about 60% C0 2 and 20% methanol and 20% ethanol.
  • the disorder-inducing species comprises one or more organic compounds.
  • An organic compound can be selected from alkanes, alkenes, alkynes, alcohols, carboxylic acids, ketones, aldehydes, or combinations thereof.
  • a fluid mixture comprising carbon dioxide and one or more disorder-inducing species can include one or more, two or more, three or more, four or more, five or more, or six or more disorder-inducing species.
  • a fluid mixture can comprise carbon dioxide and ethanol, or carbon dioxide, ethanol and propanol (e.g., isopropanol).
  • anomalously high heat capacities are achieved at or above the critical point, which may arise from extended density inhomogeneities as may be produced with the aid of disorder-inducing species.
  • the length scale is characterized by a correlation length ( ⁇ ) much greater than the molecular scale and is due to enhanced attractive interactions
  • clustering between molecules near the critical point. Maximization of heat capacity and its persistence in some cases is achieved by maximizing disorder in fluid systems.
  • the heat capacity of a fluid mixture comprising C02 and one or more other components may be continuously tuned by varying the fluid mixture composition. In some cases, this may provide at least a 2, 3, 4, 5, 6, 7, 8, 9 or 10-fold increase in heat capacity at the critical point with respect to the pure components, and a significant enhancement of heat capacity in the
  • FIG. 5 is an exemplary plot of heat capacity (Cp) as a function of temperature (T) and component composition (X) for a fluid mixture comprising nitromethane and isobutanol.
  • FIG. 6 is a cross-section of the plot of FIG. 5 taken at 291 K.
  • FIGs. 5 and 6 show a substantial increase in Cp at a temperature of about 291 Kelvin (K) and a fluid mixture composition of about 45 mole % nitromethane.
  • Another aspect of the invention provides a circulatory fluid flow system configured to store energy and/or generate power.
  • the system employs a fluid mixture comprising a supercritical fluid and a disorder-inducing species.
  • the fluid mixture is both a thermal energy storage fluid and a working fluid.
  • the supercritical fluid in some cases is C0 2 .
  • the system employs a fluid mixture comprising a supercritical fluid and a disorder-inducing species.
  • the fluid mixture in such a case is the thermal energy storage material.
  • the system employs a separate working fluid, which may be a supercritical fluid.
  • a supercritical fluid is the working fluid of a power generation system.
  • the supercritical fluid is the thermal energy storage medium of a power generation system.
  • FIG. 7 shows a system 700 configured to generate power, in accordance with an embodiment of the invention.
  • the system 700 comprises a compressor 701, heat exchanger 702 and power generator 703.
  • the power generator 702 may be a turbine adapted to generate electricity, such as, for example, via electromagnetic induction.
  • the system 700 includes an energy source 704, such as a renewable energy source.
  • the system 700 is a circulatory fluid flow system in which a working fluid comprising a fluid mixture having a supercritical fluid, such as C0 2 , and one or more secondary components, such as a disorder- inducing species, is directed through a fluid flow path having the compressor 701, heat exchanger 702 and power generator 703.
  • the direction of fluid flow in the circulatory fluid flow system is indicated by arrows between the unit operations of the system 700.
  • the renewable energy source can be configured to direct thermal energy to the heat exchanger 702 or a fluid in fluid communication with the heat exchange 702.
  • the renewable energy source 704 can be a solar concentrator that collects solar radiation and directs thermal energy collected from collected solar radiation to the heat exchanger 702, either directly, such as with the aid of optics, or with the aid of a secondary fluid or thermal energy storage material, such as, for example, molten salt or a supercritical fluid adapted to store thermal energy.
  • Solar concentrators are described in, for example, WO/2011/116141 to Joseph et al, which is entirely incorporated herein by reference.
  • the working fluid is compressed by the compressor 701 and directed into the heat exchanger 702, where heat is applied to the working fluid.
  • the compressor 701 compresses the working fluid to a pressure at or above the critical pressure of the working fluid, and the heat exchanger 702 supplies heat to the working fluid, which may increase the temperature of the working fluid to a temperature at or above the critical temperature of the working fluid.
  • the working fluid is directed to the power generator 703, which generates electricity. In some situations, heat is removed from the working fluid, such as in the power generator 703 and/or another heat exchanger between the power generator 703 and the compressor 701.
  • the working fluid is operated at or above a critical point of the working fluid from the point the system 700 is initiated.
  • the system 700 can initiate with the working fluid in a supercritical regime of the working fluid.
  • the compressor and/or heat exchanger may be used to increase the pressure and temperature of the working fluid from a first point (Pi, Ti) in the supercritical regime to a second point (P 2 , T 2 ) in the supercritical regime.
  • FIGs. 8A and 8B show pressure- volume and temperature-entropy diagrams for a system operating under a Brayton cycle, in accordance with an embodiment of the invention.
  • the system of FIGs. 8A and 8B operates with the aid of a working fluid comprising a supercritical fluid mixture.
  • supercritical fluid mixture in some cases includes C0 2 and one or more secondary fluids, such as one or more disorder-inducing species.
  • step 1 the working fluid is compressed, such as with the aid of a compressor.
  • step 2 heat is added to the compressed working fluid.
  • heat is added to the working fluid with the aid of a heat exchanger in thermal
  • the working fluid is directed to a power generator, which is used to generate electricity from the working fluid.
  • the working fluid undergoes expansion and a reduction in pressure.
  • heat is rejected from the working fluid. Heat can be removed from the working fluid with the aid of a heat exchanger. Heat rejected from the working fluid can be directed to a secondary fluid, such as water to generate steam.
  • the secondary fluid may be a supercritical fluid, such as supercrirical C0 2 and, in some cases, a disorder-inducing species.
  • heat can be added to the working fluid (e.g., supercritical fluid) from an energy source, such as heat generated from combustion (e.g., fuel or coal combustion), a nuclear reactor or a solar concentrator.
  • an energy source such as heat generated from combustion (e.g., fuel or coal combustion), a nuclear reactor or a solar concentrator.
  • heat from the energy source may be stored in a thermal energy storage material, which may be brought in thermal communication with the working fluid to transfer heat from the thermal energy storage material to the working fluid.
  • the thermal energy storage material is brought in direct contact with the working fluid to transfer energy.
  • energy is introduced to the working fluid in the form of heat from step 2 to step 3.
  • energy may be introduced to the working fluid in the form of work upon compression from step 1 to step 2.
  • An increase in C p by a factor of 10 can effectuate an increase in the amount of energy stored in the system by about the same factor without an increase in temperature. This avoids operation at higher temperature and some of the associated materials and maintenance issues.
  • Heat loss may decline as the thermal gradient to the ambient is significantly reduced.
  • Efficiency may be improved with reduced containment insulation. Overall cycle efficiency can also directly improve as input enthalpy is increased.
  • a working fluid comprising a supercritical fluid mixture having C0 2 and one or more secondary species (or components), such as one or more disorder-inducing species, is directed through a closed-loop cycle comprising a compressor, heat exchanger in thermal communication with a source of energy, and a turbine.
  • the pressure of the working fluid is increased with the aid of the compressor.
  • the working fluid is directed to the heat exchanger that is in thermal communication with the source of energy, such as a solar concentrator for collecting and concentrating solar radiation, a source of combustion, or nuclear reactor. In the heat exchanger, heat is added to the working fluid.
  • the working fluid is directed to the power generator, such as a turbine, to generate electricity. From step 4 to step 1, the working fluid is directed from the power generator to the compressor, and heat is removed from the working fluid.
  • Supercritical fluid mixtures provided herein can be tailored to decrease the cost of systems operating under the Brayton cycle.
  • a supercritical working fluid with a high heat capacity can decrease the operating pressure and/or temperature of the system, leading to savings in materials and maintenance costs and expenses.
  • FIG. 9 shows a system 900 comprising a renewable energy source 901, a compressor 902, a first fluid storage vessel 903, a second fluid storage vessel 904, a power generator 905, an electricity (or power) grid 906 and an electrical load 907, in accordance with an embodiment of the invention.
  • the renewable energy source 901 can include one or more solar concentrators, wind turbines, wave generators, or geothermal energy sources.
  • the system 900 can include a heat exchanger between the compressor 902 and the second fluid storage vessel 904.
  • the heat exchanger can be configured to direct energy to the working fluid.
  • the energy can be provided by way of an energy source, such as a renewable energy source (e.g., solar concentrator).
  • the compressor 902, first fluid storage vessel 903, second fluid storage vessel 904 and power generator 905 define a close-loop power generation cycle.
  • the cycle in some cases can operate under the Brayton cycle (see below).
  • the cycle can operate with the aid of a working fluid that comprises a primary fluid and one or more secondary fluids.
  • the working fluid is a supercritical fluid mixture that comprises C0 2 as the primary fluid and one or more secondary fluids, such as one or more disorder-inducing species (e.g., ethanol, isopropanol), as described elsewhere herein.
  • the renewable energy source 901 generates electricity, which may be directed to the electricity grid 906 and subsequently directed to the electrical load 907.
  • electricity from the renewable energy source is used to power the compressor 902, which compresses a fluid from the first fluid storage vessel 903 and directs the compressed fluid to the second fluid storage vessel 904.
  • the renewable energy source 901 is used to compress the fluid from the first storage vessel 903 to the second storage vessel 904 in off-peak (or low electricity demand) conditions.
  • the compressed fluid from the second fluid storage vessel 904 is directed to the power generator 905, which generates electricity. Electricity generated by the power generator 905 may be directed to the power grid 906 and subsequently directed to the electrical load 907.
  • a circulatory fluid flow system having a fluid mixture comprising a supercritical fluid and a disorder-inducing species.
  • the fluid mixture in such a case is the thermal energy storage material.
  • the system employs a separate working fluid, which may be a supercritical fluid.
  • FIG. 10 shows a system 1000 configured to generate electricity, in accordance with an embodiment of the invention.
  • the system 1000 includes a first circulatory fluid flow cycle comprising a compressor 1001, first heat exchanger 1002 and power generator 1003.
  • a fluid flow path directs a first working fluid from the compressor 1001 to the first heat exchanger, from the first heat exchanger 1002 to the power generator 1003, and subsequently from the power generator 1003 to the compressor 1001.
  • the first circulatory fluid flow cycle can include another heat exchanger between the power generator 1003 and the compressor 1001, which is configured to remove heat from the first working fluid of the first circulatory fluid flow cycle.
  • the first circulatory fluid flow cycle may operate under the Brayton cycle.
  • the system 1000 also includes a second circulatory fluid flow cycle that comprises the first heat exchanger 1002, a second heat exchanger 1004 and pump 1005.
  • a fluid flow path directs a second working fluid of the second circulatory fluid flow cycle from the first heat exchanger 1002 to the second heat exchanger 1004, and subsequently from the second heat exchanger 1004 to the pump 1005.
  • Flow of the second working fluid through the second circulatory fluid flow path can be facilitated with the aid of the pump 1005.
  • the first circulatory fluid flow cycle and the second circulatory fluid flow cycle can operate under the
  • the system 1000 in some cases includes an energy source 1006 configured to supply energy to the second heat exchanger 1006.
  • the energy source 1006 can be a combustion furnace, nuclear reactor or solar concentrator or other source of energy.
  • the energy source 1006 is configured to supply thermal energy to the second heat exchanger 1002, which is subsequently directed to the second working fluid of the second circulatory fluid flow cycle.
  • the first working fluid is water, a hydrocarbon or other organic species.
  • the first working fluid is an alkane or alkene, such as n-pentane or toluene.
  • the first working fluid is a supercritical fluid.
  • the second working fluid is a supercritical fluid mixture.
  • the supercritical fluid mixture includes supercritical C0 2 and one or more secondary components, such as one or more disorder-inducing species.
  • the properties of the second working fluid in some cases are selected to optimize the heat capacity of the second working fluid.
  • the second working fluid of the second circulatory fluid flow cycle is heated in the second heat exchanger 1004 with the aid of thermal or electrical energy provided by the energy source 1006 and directed to the first heat exchanger 1002 with the aid of the pump 1005.
  • energy is transferred from the second working fluid to the first working fluid of the first circulatory fluid flow cycle.
  • the first working fluid is then directed to the power generator 1003, which generates power from the first working fluid.
  • the first working fluid is then directed to the compressor 1001, which compresses the first working fluid and directs the first working fluid to the first heat exchanger 1002.
  • the system comprises a supercritical fluid.
  • the supercritical fluid is a fluid mixture comprising carbon dioxide and one or more disorder-inducing species.
  • the disorder- inducing species can be as described elsewhere herein.
  • FIG. 11 shows a system 1100 for storing thermal energy, in accordance with an embodiment of the invention.
  • the system 1100 includes a first vessel 1101 in thermal communication with a source of energy 1102.
  • the source of energy 1102 may be a combustion system, nuclear reactor or renewable energy source (e.g., solar concentrator).
  • a pump 1103 directs a working fluid from the first vessel 1101 to a second vessel 1104.
  • a combustion system e.g., nuclear reactor or renewable energy source (e.g., solar concentrator).
  • a pump 1103 directs a working fluid from the first vessel 1101 to a second vessel 1104.
  • a working fluid from the first vessel 1101 to a second vessel 1104.
  • the working fluid is a supercritical fluid comprising carbon dioxide and one or more disorder-inducing species.
  • the disorder-inducing species can be as described elsewhere herein.
  • the pump can select the pressure of the working fluid to be at or above the critical pressure of the working fluid.
  • the temperature of the working fluid can be selected to be at or above the critical temperature with the aid of the source of energy 1102.
  • the first vessel 1101 and/or the second vessel 1104 can be a storage vessel for storing the working fluid for later use.
  • the first vessel 1101 and/or the second vessel 1104 can be detachable from a fluid flow path having the first vessel 1101, the pump 1103 and the second vessel 1104. This may permit energy to be transferred to the working fluid, which may be transported to another location (e.g., remote location) for use.
  • one or both of the first vessel 1101 and the second vessel 1104 is a heat exchanger adapted to facilitate the transfer of energy to the working fluid or from the working fluid to another fluid, such as a secondary fluid (e.g., water).
  • a secondary fluid e.g., water
  • Systems and methods provided herein can be implemented with the aid of a controller having a processor (e.g., central processing unit) that executes machine-executable instructions, which may be located on a memory location (e.g., read-only memory, random-access memory, flash memory) of the controller.
  • the controller can be a feedback controller.
  • the controller can regulate various system parameters, such as system pressure, temperature, and flow rate.
  • the controller may be programmed to monitor fluid pressure and/or temperature and maintain system and/or fluid parameters to achieve a given system performance. For instance, the controller can be programmed to maintain system pressure and/or temperature to maximize the heat capacity of the thermal energy storage medium or working fluid.
  • Example 1
  • a supercritical fluid mixture comprises carbon dioxide C0 2 and ethanol in a composition (mole %) of about 90% C0 2 and 10% ethanol.
  • the composition is selected to provide a heat capacity of the fluid mixture that may be suitable for use with thermal energy storage.
  • a system such as the system 700 of FIG. 7, is used to generate power.
  • the working fluid is a fluid mixture comprising Supercritical C0 2 and ethanol at a composition (mole %) of about 90% C0 2 and 10% ethanol.
  • the temperature of the working fluid is about 305 K.
  • the supercritical working fluid is directed to a heat exchanger, which supplies heat to the working fluid.
  • the working fluid is directed to a turbine to generate power.
  • heat is removed from the working fluid, in some cases with the aid of another heat exchanger. The working fluid is then returned to the compressor.

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  • Combustion & Propulsion (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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Abstract

L'invention concerne un fluide supercritique qui comprend du dioxyde de carbone et au moins une espèce induisant une perturbation. La proportion de dioxyde de carbone par rapport à la ou les espèces induisant une perturbation dans le fluide supercritique peut être suffisante pour induire une perturbation dans le fluide. L'invention concerne des systèmes de production d'énergie et des systèmes de stockage d'énergie thermique conçus pour utiliser le fluide supercritique.
PCT/US2012/039217 2011-05-24 2012-05-23 Fluides supercritiques, systèmes et procédés d'utilisation WO2012162438A2 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6813895B2 (en) * 2003-09-05 2004-11-09 Carrier Corporation Supercritical pressure regulation of vapor compression system by regulation of adaptive control
US20070161095A1 (en) * 2005-01-18 2007-07-12 Gurin Michael H Biomass Fuel Synthesis Methods for Increased Energy Efficiency
JP2009536020A (ja) * 2006-02-23 2009-10-08 フリーズランド ブランズ ビー．ブイ． 超臨界媒体を使用する乾燥された粒子の調製方法
US20100024421A1 (en) * 2006-12-08 2010-02-04 United Technologies Corporation Supercritical co2 turbine for use in solar power plants
EP2157317A2 (fr) * 2008-08-19 2010-02-24 ABB Research LTD Système de stockage d'énergie thermoélectrique et procédé de stockage d'énergie thermoélectrique
US20110061387A1 (en) * 2009-09-17 2011-03-17 Held Timothy J Thermal energy conversion method

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6813895B2 (en) * 2003-09-05 2004-11-09 Carrier Corporation Supercritical pressure regulation of vapor compression system by regulation of adaptive control
US20070161095A1 (en) * 2005-01-18 2007-07-12 Gurin Michael H Biomass Fuel Synthesis Methods for Increased Energy Efficiency
JP2009536020A (ja) * 2006-02-23 2009-10-08 フリーズランド ブランズ ビー．ブイ． 超臨界媒体を使用する乾燥された粒子の調製方法
US20100024421A1 (en) * 2006-12-08 2010-02-04 United Technologies Corporation Supercritical co2 turbine for use in solar power plants
EP2157317A2 (fr) * 2008-08-19 2010-02-24 ABB Research LTD Système de stockage d'énergie thermoélectrique et procédé de stockage d'énergie thermoélectrique
US20110061387A1 (en) * 2009-09-17 2011-03-17 Held Timothy J Thermal energy conversion method

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