WO2015197885A1 - Procédé thermochimique de transfert et de stockage d'énergie solaire concentrée - Google Patents

Procédé thermochimique de transfert et de stockage d'énergie solaire concentrée Download PDF

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Publication number
WO2015197885A1
WO2015197885A1 PCT/ES2015/000084 ES2015000084W WO2015197885A1 WO 2015197885 A1 WO2015197885 A1 WO 2015197885A1 ES 2015000084 W ES2015000084 W ES 2015000084W WO 2015197885 A1 WO2015197885 A1 WO 2015197885A1
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WO
WIPO (PCT)
Prior art keywords
storage
csp
energy
transfer
cao
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PCT/ES2015/000084
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English (en)
Spanish (es)
Inventor
José Manuel VALVERDE MILLÁN
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Universidad De Sevilla
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Publication date
Application filed by Universidad De Sevilla filed Critical Universidad De Sevilla
Publication of WO2015197885A1 publication Critical patent/WO2015197885A1/fr

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Classifications

    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S20/00—Solar heat collectors specially adapted for particular uses or environments
    • F24S20/20—Solar heat collectors for receiving concentrated solar energy, e.g. receivers for solar power plants
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F24—HEATING; RANGES; VENTILATING
    • F24S—SOLAR HEAT COLLECTORS; SOLAR HEAT SYSTEMS
    • F24S60/00—Arrangements for storing heat collected by solar heat collectors
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
    • F28D20/003—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using thermochemical reactions
    • 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
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage
    • 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
    • Y02E70/00—Other energy conversion or management systems reducing GHG emissions
    • Y02E70/30—Systems combining energy storage with energy generation of non-fossil origin

Definitions

  • the object of the present invention is the chemical transfer and storage of concentrated solar thermal energy through the use of a bed of granulated solids consisting of a mixture of inert solids, preferably sand, and CaCCVCaO fluidized by a controlled gas flow consisting of a mixture of inert gas, preferably air, and C0 2 in controlled proportion.
  • the area to which the invention corresponds is that of Energy and Environmental Technology, being the application sector in which the Renewable Energys would be applied.
  • the technique described in the present invention aims to improve the transfer and storage of concentrated solar energy (CSP).
  • CSP concentrated solar energy
  • thermal power plants (1), being its main advantage the possibility of generating electricity even in the absence of solar radiation during a certain period of autonomy compared to nature flashing of other types of renewable energy plants such as wind or photovoltaic solar.
  • conventional fossil thermal plants water vapor produced in a high pressure boiler is expanded in a turbine to generate mechanical work on its axis according to the Rankine cycle to be subsequently transformed into electrical energy by means of a generator.
  • the boiler is replaced by a concentrated solar radiation collector, the rest of the process (power cycle) being a thermal to electrical energy transformation similar to that of a fossil thermal.
  • HTF thermal transfer fluids
  • the first CSP with tower receiver technology (in operation since 2011) and thermal storage in HTF (molten salts) is the Gemasolar plant (19.9 MWe) located in Fuentes de Andaluc ⁇ a (Seville).
  • the molten salts heated in the tower are stored in a large capacity hot salt tank and conducted to a heat exchanger. Once they give heat to the power cycle they are transported to a tank of cold salts to be recirculated back to the tower.
  • the storage of heat in the hot salt tank allows an autonomy of electricity generation of up to 15 hours without solar input.
  • CSP technology has enormous potential for short-term growth, especially in countries in North Africa and the Middle East, as well as in the US, South Africa, Australia, Chile, India and China where they have been successfully completed or several commercial scale projects are underway (2). Spain has been a pioneer country in the development of this type of power plants and as of January 2014 it continues to be a world leader in CSP with an installed capacity of 2,204 MWt.
  • the development of efficient and low-cost HTFs is a key point for the commercial success of CSPs since the storage of solar thermal energy during long periods of low solar radiation would allow the generation of electric current continuously and on demand.
  • the CSP-HTF is integrated in a hybrid system with a fossil thermal power plant, whose energy is used to raise the temperature of the HTF in the case of prolonged periods of reduced solar radiation.
  • this temperature is limited by the degradation of the molten salts currently used as HTF and which decompose around 600 ° C.
  • Another drawback of the use of molten salts such as HTF is that they have freezing points at relatively high temperatures (between 120 ° C and 220 ° C) with the consequent risk of freezing and large heat losses during night hours in desert areas and / or of high altitude that have a very high insolation that make them ideal for the installation of CSP power plants.
  • This makes efficient thermal insulation necessary, limiting the flow of the fluid and eventually using energy to heat the salts in the cold tank in order to avoid freezing (in Gemasolar the temperature of the "cold" tank is maintained at 290 ° C).
  • the object of the present invention is the transfer and storage of concentrated solar thermal energy through the use of gas fluidized beds of granulated solids (FB): "Fluidized Beds".
  • FB granulated solids
  • the SOLTESS project (Solar Thermal Energy Solid Storage” carried out in Italy) has just demonstrated with the installation of a 0.1 MWt CSP-FB demonstration plant, the solid / gas fluidized bed system is very suitable for transfer and concentrated solar energy storage.
  • This bed uses a bed of fine siliceous sand fluidized with air (at speeds of the order of cm / s) as a means of reception, exchange and transfer of concentrated solar energy allowing to reach steam temperatures in the range 530-730 ° C With an autonomy of 10-15 h, that is, it can generate electricity efficiently during 24 hours (5).
  • the gas fluidized bed has a high coefficient of thermal transfer and diffusion that are adjustable through the control of the gas flow, while it is possible to achieve a high degree of storage in the granulated solids due to its high heat capacity.
  • the FB technology allows the gas combustion in the fluidized bed to be integrated into a hybrid system in order to heat it if necessary in long periods of absence of intense solar radiation.
  • the CSP-FB technology would also allow the avoidance of corrosion and contamination problems associated with the use of molten salts or mineral oils.
  • the sand is an inert material, abundant and readily available (especially in desert areas where the installation of CSP plants is indicated) which would contribute to the commercial expansion of the technology.
  • Figure 1 Scheme of the integration of concentrated solar thermal energy technologies with transfer and storage of thermal and chemical energy in a fluidized bed of granulated solids (mixture of inert materials with high heat capacity and thermal conductivity and CaC03 / CaO) by means of a controlled flow of gas containing C02 in a certain percentage.
  • This invention proposes the use of a bed of granulated solids consisting of a mixture of inert solids (for example sand) and CaCCyCaO (derived for example from natural limestone) fluidized by a controlled gas flow consisting of a mixture of inert gas (for example air) and C0 2 in order to transfer and store thermochemically concentrated solar energy.
  • the novelty of the invention is the use of CaC0 3 / CaO in the fluidized bed and C0 2 in the fluidization gas, which makes it possible to complement the storage of solar energy thermally in the sand with chemical storage by means of the endothermic decarbonation reaction of CaC0 3 .
  • CaC0 3 has a high energy density (1.7 MJ / kg of latent heat and 0.87 MJ / kg of sensible heat much higher than the typical values that have molten salts) and is a raw material that can be obtained from natural materials available in abundance and low cost (for example natural limestone).
  • both CaC0 3 and CaO can be stored for long periods of time in atmospheric conditions and without thermal losses as occurs with HTFs used in CSP technologies with storage in molten salts or mineral oils (CSP-HTF) or with the sand used in technology with solid fluidized bed / gas storage (CSP-FB).
  • CSP-HTF molten salts or mineral oils
  • CSP-FB solid fluidized bed / gas storage
  • the conversion values of CaO in the reaction of Carbonation in a fluidized bed exclusively of CaO oscillates in a very wide range of values (between 80% and 7%) depending significantly on the calcination / carbonation conditions (basically temperature, concentration of C0 2 and residence time of the gas in the bed) and the number of previous cycles.
  • Experimental results show that high temperature calcination causes the residual conversion (the one obtained after a high number of cycles) of CaO to fall below 10%, which would make it unfeasible to use CaL technology as the only storage method of concentrated solar energy.
  • CSP-FB-CaL In the present invention, the integration of CaL technology with CSP-FB fluidized bed storage technology is proposed in order to increase the storage autonomy and efficiency of the latter.
  • CSP-FB concentrated solar energy is stored exclusively in thermal form.
  • CSP integration -FB-CaL would allow the storage of energy in chemical form and therefore permanent to be used when the heat was necessary. This integration would therefore have the advantages of high thermal transfer and diffusion provided by the fluidized bed of sand with thermal storage on the one hand and, on the other, permanent storage in chemical form by means of CaL technology.
  • the transfer and storage of concentrated solar energy would be carried out in a fluidized bed formed by a mixture of inert granulated solids which is the thermal transfer medium (for example sand) with CaC0 3 / CaO, which is the medium where energy will be chemically stored.
  • the relative proportion of CaCOs / CaO can vary from 100% to 0%.
  • the fluidization gas velocities would be small (of the order of cm / s as in the current CSP-FB technology) so that the residence times of the gas in the bed are prolonged, which allows the calcination / carbonation reactions in around equilibrium reach advanced states.
  • the energy required to fluidize the material can be a limiting factor if very high volumes are required since the pressure drop across the bed of the applied gas flow must necessarily compensate for the total weight per unit area of the bed.
  • this integration proposed in the present invention could provide an advantage in a relevant aspect. in the commercial development of technology such as the energy needed to fluidize large volumes of material.
  • the CSP-FB technology offers the possibility of varying control parameters that regulate the thermal transfer such as the speed of the gas in order to counteract the effect of the variability of the intensity of solar radiation on the bed temperature of storage.
  • the present invention would have a new strategic control parameter (% C0 2 in the fluidization gas) in order to cause decarbonation or carbonation reactions as desired to reduce or increase the temperature of the bed depending on the intensity of solar radiation .
  • % C0 2 in the fluidization gas a new strategic control parameter in order to cause decarbonation or carbonation reactions as desired to reduce or increase the temperature of the bed depending on the intensity of solar radiation .
  • the carbonation during periods of low radiation using gas flows with high% C0 2 would allow the temperature to rise thus increasing the performance of the technology.
  • an optimum proportion of CaC0 3 can be chosen in the granular solids mixture.
  • the fluidizing gas may circulate in a closed circuit so that C0 2 emissions to the atmosphere are prevented.
  • CSP-FB it is necessary to divide the fluidized bed into compartments for receiving, exchanging and storing solar thermal energy for the selective control of the gas velocity in each of them in order to avoid minimizing the inevitable thermal losses.
  • the gas supply to the receiving compartment is cut off (to avoid heat leaks to the solar radiation receiving cavity) and to the storage compartment if its temperature falls below a critical value.
  • the absorption / release of chemical energy in the integrated CSP-FB-CaL technology proposed in the present invention can be selectively controlled along the fluidized bed by regulating the% C0 2 in the fluidization gas through each compartment which would contribute to reduce heat losses.
  • the possibility of adding a compartment for a fluidized bed exclusively of chemical energy storage CaC0 3 is considered .
  • the high thermal transfer in solid fluidized bed / gas would allow efficient transfer of excess heat to this compartment.
  • the CaO generated by calcination in this compartment can be used in the same plant if necessary to generate heat and increase the steam temperature or be transported if produced in excess for heat generation in other industrial applications.
  • FIG. 1 An exemplary embodiment of the invention based on the integration of CSP-FB-CaL technologies (thermochemical transfer and storage of concentrated solar energy in a fluidized bed of inert granulated solids and CaC0 3 / CaO) is shown in Figure 1.
  • Solar radiation (a) is collected by the fluidized bed (c) by a cavity in the same way as is done in the proven CSP-FB technology.
  • the bed of granulated solids is formed by a mixture of inert solids (for example fine siliceous sand) of high heat capacity and thermal conductivity and CaC0 3 / CaO (derived for example from natural limestone).
  • the bed is in a fluidized state by the application of a gas flow (b) consisting of a mixture of inert gas (for example air) and C0 2 at a rate and in an adjustable proportion in the control unit (d) .
  • a gas flow consisting of a mixture of inert gas (for example air) and C0 2 at a rate and in an adjustable proportion in the control unit (d) .
  • the possibility of introducing steam is contemplated in order to intensify the reactivity of the CaO if necessary.
  • the heat stored in the fluidized bed is transferred to the power cycle (f) for the generation of electric energy following the conventional procedure carried out in fossil plants. It is possible to divide the fluidized bed into different compartments (receiver, exchanger and energy storage) as in the CSP-FB technology.
  • the modification introduced in the present invention consists in the integration of CaL technology.
  • the CaO generated in this compartment can be used in the same plant to release heat by carbonation or be transported for use in other applications that require hot.
  • This CaO can be stored without energy losses for use when and where necessary.
  • fluidization allows a high degree of thermal transfer to be obtained, there is the possibility of applying techniques that intensify the transfer of heat and mass to enhance the carbonation of CaO.
  • One of these techniques of proven efficiency to enhance the carbonation of CaO in other applications in a high temperature fluidized bed reactor is the application of high intensity and low frequency sound that could be implemented in this invention.
  • the control of the% C0 2 used in the fluidization gas can be carried out in accordance with the equilibrium of the decarbonation / carbonation reaction of CaC0 3 represented in Fig. 2 and depending on the temperature distribution in the fluidized bed.
  • This diagram allows to anticipate the direction in which the reaction will move according to the% C0 2 in the fluidization gas and the temperature.
  • the system will release heat (carbonation of CaO) where and when the temperature drops below 750 ° C and absorb heat when the temperature rises above this value. (decarbonation of CaC0 3 ).
  • the regulation of% C0 2 in the fluidizing gas in the gas control unit would be used as a temperature control mechanism in the fluidized bed so that it is transferred with few oscillations to the power cycle.
  • the total amount of heat absorbed and released in the fluidized bed depends on the proportion of CaC0 3 and CaO used in the mixture of granulated solids that can also be variable depending on the incident solar radiation characteristic of the region where the plant is installed .
  • excess heat will be stored chemically permanently and stably in the form of CaO to be used when necessary.
  • This heat can come from the combustion of gas in the same fluidized bed as proposed in the CSP-FB technology in a hybrid system.
  • heat can only be stored temporarily in CSP-FB since the bed of inert solids (sand) will always have thermal losses.
  • the only possible solution in CSP-FB to prolong the transitory storage period is to increase the volume of the fluidized storage bed with the consequent loss of technology efficiency.
  • excess heat can be permanently stored chemically until it is necessary to recover it, so it is expected that this innovation will result in improved storage with respect to CSP technology.

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  • Engineering & Computer Science (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Sustainable Energy (AREA)
  • Combustion & Propulsion (AREA)
  • Sustainable Development (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engine Equipment That Uses Special Cycles (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Abstract

L'objet de la présente invention concerne le transfert et le stockage d'énergie thermosolaire concentrée par utilisation d'un lit de solides granulés composé d'un mélange de solides inertes, de préférence, du sable, et du CaCO3/CaO fluidifié par un flux de gaz contrôlé composé d'un mélange de gaz inerte, de préférence de l'air et du CO2 en proportion contrôlée. Le domaine de l'invention est celui de la technologie énergétique et environnementale, le secteur d'application dans lequel il s'applique étant celui des énergies renouvelables.
PCT/ES2015/000084 2014-06-26 2015-06-26 Procédé thermochimique de transfert et de stockage d'énergie solaire concentrée WO2015197885A1 (fr)

Applications Claiming Priority (2)

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ES201400520A ES2555329B2 (es) 2014-06-26 2014-06-26 Procedimiento termoquímico de transferencia y almacenamiento de energía solar concentrada
ESP201400520 2014-06-26

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105737658A (zh) * 2016-04-30 2016-07-06 华南理工大学 流态化钙基热化学高温储能/释能系统及其工作方法
DE102016217090A1 (de) * 2016-09-08 2018-03-08 Siemens Aktiengesellschaft Verfahren und System zum Speichern und Rückgewinnen von Wärmeenergie in einer Energieerzeugungsanlage
CN109520346A (zh) * 2018-12-14 2019-03-26 北方民族大学 一种利用石灰石进行热化学储能的方法
CN109566200A (zh) * 2018-11-30 2019-04-05 华中科技大学 一种基于流化床的农业大棚自给水系统
WO2021119752A1 (fr) * 2019-12-18 2021-06-24 Curtin University Batterie thermique
WO2021151758A1 (fr) * 2020-01-28 2021-08-05 Saltx Technology Ab Système et procédé de stockage d'énergie transportable et de capture de carbone

Citations (2)

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FR2418422A1 (fr) * 1978-02-24 1979-09-21 Fives Cail Babcock Procede de stockage et de restitution d'energie utilisant les reactions de decarbonatation du carbonate de calcium et de carbonatation de la chaux ainsi obtenue, et unites pour la mise en oeuvre de ce procede
US4894989A (en) * 1986-08-29 1990-01-23 Aisin Seiki Kabushiki Kaisha Heater for a stirling engine

Patent Citations (2)

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FR2418422A1 (fr) * 1978-02-24 1979-09-21 Fives Cail Babcock Procede de stockage et de restitution d'energie utilisant les reactions de decarbonatation du carbonate de calcium et de carbonatation de la chaux ainsi obtenue, et unites pour la mise en oeuvre de ce procede
US4894989A (en) * 1986-08-29 1990-01-23 Aisin Seiki Kabushiki Kaisha Heater for a stirling engine

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CHIRONE, R. ET AL.: "Development of a Novel Concept of Solar Receiver/Thermal Energy Storage System Based on Compartmented Dense Gas Fluidized Beds.", THE 14TH INTERNATIONAL CONFERENCE ON FLUIDIZATION - FROM FUNDAMENTALS TO PRODUCTS., 2013 *
FLAMANT, GILLES ET AL.: "Experimental aspects of the thermochemical conversion of solar energy; Decarbonation of CaCO3.", SOLAR ENERGY, vol. 24, no. 4, 1980, pages 385 - 395, XP025451818, ISSN: 0038-092x *
PARDO, P. ET AL.: "A review on high temperature thermochemical heat energy storage.", RENEWABLE AND SUSTAINABLE ENERGY REVIEWS, vol. 32, 5 February 2014 (2014-02-05), pages 591 - 610, XP055247587, ISSN: 1364-0321 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105737658A (zh) * 2016-04-30 2016-07-06 华南理工大学 流态化钙基热化学高温储能/释能系统及其工作方法
DE102016217090A1 (de) * 2016-09-08 2018-03-08 Siemens Aktiengesellschaft Verfahren und System zum Speichern und Rückgewinnen von Wärmeenergie in einer Energieerzeugungsanlage
CN109566200A (zh) * 2018-11-30 2019-04-05 华中科技大学 一种基于流化床的农业大棚自给水系统
CN109520346A (zh) * 2018-12-14 2019-03-26 北方民族大学 一种利用石灰石进行热化学储能的方法
CN109520346B (zh) * 2018-12-14 2020-08-07 北方民族大学 一种利用石灰石进行热化学储能的方法
WO2021119752A1 (fr) * 2019-12-18 2021-06-24 Curtin University Batterie thermique
WO2021151758A1 (fr) * 2020-01-28 2021-08-05 Saltx Technology Ab Système et procédé de stockage d'énergie transportable et de capture de carbone

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ES2555329B2 (es) 2016-04-26

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