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    • 专利摘要:
    The object of the present invention is the transfer and storage of concentrated thermosolar energy by the use of a bed of granulated solids consisting of a mixture of inert solids, preferably sand, and caco3/cao fluidized by a controlled gas flow consisting of a mixture of inert gas, preferably air, and co2 in a controlled proportion. The area to which the invention corresponds is that of energy and environmental technology, being the application sector in which the renewable energy would be applied. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2555329A1
    申请号:ES201400520
    申请日:2014-06-26
    公开日:2015-12-30
    发明作者:José Manuel VALVERDE MILLÁN
    申请人:Universidad de Sevilla；
    IPC主号:
    专利说明:

    In 2009 located in Sanlúcar La Mayor, Seville, generating 11 and 20 MWe, respectively, of electrical power), heat is used directly to generate water vapor that is stored at high pressure and conducted to the power cycle. This design only allows a period of autonomy of electricity generation around 1 h. New designs already in operation in commercial plants incorporate thermal transfer fluids (HTF) with high heat capacity and transfer heat to water through heat exchangers. 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 Andalucía (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. In CSPs with parabolic trough technology, sunlight is concentrated on a collecting cylinder located in the focus of a row of parabolic section reflectors. The collecting cylinder contains a mineral oil that acts as HTF. Solana, the largest CSP (280 MWt) with parabolic trough technology recently completed in the US It has an autonomy of 6h of storage. 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. Alternatively, there are projects in which 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. According to the Rankine cycle (thermodynamic process that takes place in the power cycle in a steam power plant), the efficiency of heat conversion into mechanical energy increases with the temperature of the water vapor produced. In fossil plants, this temperature is limited by the resistance of the materials used in the steam conduction system. Standardized steam turbines can operate at steam temperatures around 550 ° C. An important field of research focuses on the development of materials with very high resistance in order to increase the efficiency of electric power production and thus reduce CO2 emissions from fossil power plants. Recently, the American Society of Mechanical Engineers (ASME) has approved the use of a NiCr-Co alloy (Inconel® 740) for the manufacture of steam conduction materials capable of withstanding temperatures up to 700 ° C (2). In CSP-HTF with parabolic trough technology, the temperatures reached in the collector are limited to values around 400 ° C, so it is not possible to obtain a high thermoelectric efficiency. Mineral oils used as HTF decompose at higher temperatures and have a freezing point around 12-20oC. On the other hand, the Gemasolar plant (Fuentes de Andalucía, Sevilla) with central tower technology operates at steam temperatures close to 550 ° C, which makes it possible to use standardized steam turbines commonly used in fossil thermal plants although potentially attainable temperatures in the collector of this type of CSP power plants could reach 900 ° C. In principle, the possibility of reaching higher temperatures would increase the conversion efficiency of solar energy concentrated in electricity (2). However, 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 necessitates efficient thermal insulation, limiting the fluid path 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). An additional problem associated with the use of mineral oils or molten salts such as HTF is generally its high corrosive and contaminating power. Valves, pipes, instruments, joints and standard monitoring systems are not suitable for the conduction of such HTFs, which implies an additional cost that makes CSP-HTF technology more expensive. The development of materials compatible with the limitations imposed by the use of molten salts or mineral oils as well as the synthesis of new HTFs with improved thermal properties (increased heat capacity, reduced freezing point and increased decomposition temperature) (3 , 4) are current research topics of great interest. In the CSP EOS project (Cyprus) it is planned to build a commercial scale plant (50 MW) in which the storage and heat transfer medium consists of solid graphite blocks with high melting point and specific heat. The commercial expansion of CSP technology necessarily involves enhancing its competitiveness even lower compared to fossil thermal power plants (2). The most urgent challenge to achieve this goal is to improve the efficiency of storage and transfer of concentrated solar energy. It is therefore a completely open field and in great development. 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". As the SOL TESS 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 fluidized / gas bed system is very suitable for transfer and storage of concentrated solar energy. In this plant a bed of fine siliceous fluid sand with air (at speeds of the order of cm / s) is used 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. As an added advantage, 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 easily available (especially in desert areas where the installation of CSP plants is indicated) which would contribute to commercial expansion
    of technology The high performance of the demonstration plant built in Italy suggests that CSP-FB power plants could be sold in small modules depending on the demand of the region where they are installed. This feature will facilitate the commercial development of CSP technology because it exceeds the need for CSP-HTF based on central tower and parabolic trough technology to have a relatively large minimum size (around 10MWe) to achieve acceptable performance which It makes the installation cost too high. Currently, the group that has executed the SOL TESS project projects the construction of a commercial module CSP-FB of 1.85MWt and that will supply 0.65MWe. This year 2014, another 2 industrial projects have been initiated in the United States (US Solar Holdings) and United Arab Emirates (SANDSTOCK) in which the sand / gas fluidized bed technology will also be analyzed with the final objective of building a CSP-FB plant to commercial scale These studies demonstrate that CSP-FB integration has significant potential for the development of concentrated solar energy on a commercial scale. The object of the present invention is a method that will foreseeably improve the energy storage capacity by means of this innovative technology.
    References
    (one) V. S. Reddy, S. Kaushik, K. Ranjan, and S. Tyagi, "State-of-the-art of solar thermal power plants: a review," Renewable and Sustainable Energy Reviews, vol. 27, pp. 258-273, 2013.
    H.L. Zhang, J. Baeyens, J. Degreve, G. Caceres, "Concentrated solar power plants: Review and design methodology", Renewable and Sustainable Energy Re views, vol. 22, pp. 466-481, 2013.
    (2) JT Hinkley, JA Hayward, B. Curtin, A. Wonhas, R. Boyd, C. Grima, A. Tadros, R. Hall, and K. Naicker, "An analysis of the costs and opportunities for concentrating solar power in Australia, "Renewable Energy, vol. 57, pp. 653661,2013.
    (3) D. Shin and D. Banerjee, "Enhanced specific heat of silica nanofluid," Journal of Heat Transfer, vol. 133, p. 024501, 2011.
    (4) Andy Skumanich, "Csp: Developments in heat transfer and storage materials," Renewable energy focus, pp. 40-43, September / October 2010.
    (5) R. Chirone, P. Sala tino, P. Ammendo / a, R. SoJimene, M. Magaldi, R. Sorrenti,
    G. D. Michele, and F. Donatini, "Development of a novel concept of solar receiverlthermal energy storage system based on compartmented dense gas f1uidized beds," in The 14th International Conference on Fluidization From Fundamentals to Products, Engineering Conferences Internationa /, 2013. Description of the figures
    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.
    (to) Solar radiation incident.
    (b) Controlled gas flow containing C02.
    (C) Mixture of inert granulated solids and CaC03 / CaO.
    (d) Unit of control of the composition and gas flow.
    (and) Heat exchanger.
    (F) Power cycle
    Figure 2.- Concentration values (% by volume) of C02 in the gas and temperature that determine the displacement of the reaction CaC03 = CaO + C02 in order to store or obtain energy through this reaction in a fluidized bed.
    Description of the invention This invention proposes the use of a bed of granulated solids consisting of a mixture of inert solids (for example sand) and CaC03 / CaO (derived for example from natural limestone) fluidized by a controlled gas flow consisting of a mixture of inert gas (for example air) and CO2 in order to transfer and store thermochemically concentrated solar energy. The novelty of the invention is the use of CaC03 / CaO in the fluidized bed and CO2 in the fluidization gas, which makes it possible to complement the storage of solar thermal energy in the sand with chemical storage by means of the endothermic decarbonation reaction of CaC03. When the temperature reached at certain points of the bed is excessively high and cannot be used in the power cycle, the control of the proportion of CO2 in the gas flow would cause the endothermic decarbonation of CaC03. Conversely, when this temperature dropped below a desired value due to long periods of low solar radiation, it would be possible to carbonate the CaO by exothermic reaction that would provide the heat previously used in decarbonation to transfer it to the power cycle. In this way it would be possible to increase autonomy and thermoelectric efficiency. Likewise, chemical storage would reduce the volume of solid fluidized bed / gas that can become excessively high if it is only operated with thermal storage. The chemical storage of solar energy would not present losses as occurs with thermal storage. In this novel procedure, the advantages of the use of fluidized bed associated with high values of thermal transfer and diffusion with the high heat capacity of inert solids for thermal storage and the high latent and sensitive heat values of CaC03 are integrated into the same technology
    Chemical storage of energy stably. the mixture of CaC03 with an inert material such as silica would also increase the reversibility of the decarbonation / carbonation reactions as silica favors the thermal stability of CaC03 / CaO. Likewise, if a hybrid system is chosen including the combustion of gas in the fluidized bed, the decarbonation / carbonation of the CaC03 will allow the excess heat to be chemically stored for later use according to demand. Finally, the use of additional fluidized beds exclusively of CaC03 would allow not only storing but also transporting concentrated solar energy (in the form of Ca O) without loss for use in other applications, which would expand the range of possibilities of use of CSP plants and thus help its commercial development.
    The use of concentrated solar energy to calcine CaC03 at high temperature, this heat being able to be recovered when necessary by carbonation of CaO, has already been proposed as a method of storing solar energy. The CaC03 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 of molten salts) and is a raw material that can be obtained from natural materials available in abundance and low cost (for example natural limestone). In addition, both CaC03 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 sand used in solid / gas fluidized bed storage technology (CSP-FB).
    Thus, the decarbonation (or calcination) and carbonation cycle of CaC03 / CaO (Cal): "Ca-Iooping") has recently been proposed in an integrated concept (CSP-Cal) in order to store and transfer concentrated solar energy According to this concept, the CaO and CO2 generated by the calcination of CaC03 would be transported separately, and when the demand made it necessary the carbonation of the CaO would serve to transfer heat to a gas stream used for the production of electricity by means of a turbine gas However, the results suggest that CSP-Cal integration would only be advantageous with respect to CSP-HTF technology in a limited range of CaO conversion values between 20% and 30% (percentage of CaO converted to CaC03 in the reaction carbonation), which constitutes an important practical limit for the possible implementation of CSP-Cal technology, which has not yet been proven in practice. Normally, the values of the conversion of CaO in the carbonation reaction in a fluidized bed exclusively of CaO range in a very wide range of values (between 80% and 7%) depending significantly on the calcination / carbonation conditions (basically temperature, CO2 concentration 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. On the other hand, although there are synthetic materials based on CaO / CaC03, and treatment methods that can reactivate the CaO derived from natural limestone, the use of such techniques would make more expensive a technology whose greatest potential advantage should lie in its low cost and abundance of a non-polluting raw material. In the present invention, the integration of the Cal technology with the CSP-FB fluidized bed storage technology is proposed in order to increase the storage autonomy and efficiency of the latter. In CSP-FB concentrated solar energy is stored exclusively in thermal form. Although the use of large volumes of inert material such as sand (which can be a problem due to the size of the bed in relation to the power generated) can be a solution to extend the transitory period of storage, 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.
    In the CSP-FB-Cal integration proposed in the present invention, 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 CaC03 / CaO, which is the medium where energy will be chemically stored. The relative proportion of CaCOJCaO 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. Since the calcination would take place slowly at temperatures close to equilibrium as soon as this is exceeded, the reactivity of the regenerated CaO will not be significantly diminished, as is the case in Cal technology where CaC03 suddenly heats up at temperatures well above that of Balance. Likewise, mixing CaC03 with inert granulated solids such as silica (sand) contributes to thermally stabilize limestone according to experimental observations.
    the fluidization of sand / CaC03 / CaO in contact with the solar collector using a CO2 / air mixture in percentages that can vary from 0% (if you want to calcine at temperatures below approximately 700 ° C) up to 100% (if I would like to carbonate at high temperatures), it would result in the calcination of CaC03 at temperatures above a desired critical value and the exothermic carbonation of CaO when the temperature dropped below a certain value which would allow increasing the autonomy of this storage method and homogenize the heat delivery to the power cycle. In addition, the volume of material that would be necessary to use to maintain a sufficiently high storage bed temperature could be reduced. In the CSP-FB pilot device of
    0.1 MWt in current operation (SOL TESS project) employs around 15,000 kg in the storage bed to maintain its temperature between approximately 530 ° C and 780 ° C in night / day cycles and thus allow continuous operation of the unit power with a global efficiency of solar energy transformation to the power unit around 70% (much higher than in CSP with parabolic trough and central tower technology that is set at around 20%). With 15,000 kg of sand, an autonomy of operation is achieved around 10/15 h. It is to be expected, however, that the need to use volumes of sand that are too high represents a problem in the higher level scaling of CSP-FB technology. In addition, 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. Taking into account the high latent and sensitive heat of the CaC03, it is foreseeable that the total mass of material needed in the CSP-FB-Cal technology can be reduced so that 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. On the other hand, 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. Through the CSP-FB-Cal integration that we propose in the present invention, a new strategic control parameter (% C02 in the fluidization gas) would be had in order to cause the decarbonation or carbonation reactions as desired to reduce or increase the bed temperature depending on the intensity of solar radiation. Carbonation during periods of low radiation using gas flows with high% C02 would allow the temperature to rise thereby increasing the performance of the technology. Depending on the intensity of solar radiation, an optimal proportion of CaC03 can be chosen in the granular solids mixture. The fluidization gas can circulate in a closed circuit so that CO2 emissions to the atmosphere are avoided.
    In 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. During the night, for example, 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 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% C02 in the fluidization gas through each compartment. which would help reduce heat losses. In addition, the possibility of adding a compartment for a fluidized bed exclusively of chemical energy storage CaC03 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.
    The effectiveness of the CSP-FB-CaL integration described in the present invention would critically depend on the reactivity of the regenerated CaO in each cycle by calcination. Results obtained in our laboratory show that it is possible to maintain a high cyclic reactivity of the regenerated CaO under certain calcination / carbonation conditions such as calcination in an air atmosphere and carbonation in an atmosphere with a high concentration of CO2 at temperatures between 600 ° C and 900 ° C. The possibility of introducing H20 vapor, around 20% by volume, into the fluidized bed would also contribute to increasing the reactivity of CaO as experimental results show. Taking into account the range of temperature oscillation in the current CSP-FB technology, these conditions would be compatible with an efficient CSP-FB-CaL integration. Embodiment of the invention
    An 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 mixture and CaC03 / CaO) is shown in Figure 1. The 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 CaC03 / 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 CO2 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. Through heat exchangers (e), 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. In a division in compartments of the fluidized bed it is possible to use mixtures of inert solids / CaC03 / CaO in varying proportions in each of the compartments in order to intensify the exothermic carbonation in the regions close to the exchangers and thus increase more Efficient steam temperature. There is also the possibility of passing gas flows with different% C02 through each compartment in order to intensify decarbonation in the higher temperature region by reducing% C02 (usually the reception compartment during the day) and intensifying carbonation by the application of a flow with high% C02 (usually in the exchanger and the storage unit if the temperature is too low). An exclusive chemical storage compartment consisting of a fluidized bed of CaC03 can also be added. 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 heat. This CaO can be stored without energy losses for use when and where necessary. Although 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% C02 used in the fluidization gas can be carried out in accordance with the equilibrium of the decarbonation / carbonation reaction of the CaC03 shown in Fig. 2 Y 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% C02 in the fluidization gas and the temperature. Thus, if for example the% C02 is maintained at around 10%, 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 CaC03). The regulation of% C02 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 CaC03 and CaO used in the mixture of granulated solids that can also be variable depending on the incident incident solar radiation characteristic of the region in which the plant is installed . At all times, 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. However, 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. In the CSP-FB-CaL concept proposed in the present invention, 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. FB
    权利要求:
    Claims (6)
    [1]
     Claims
    one. Thermochemical process for transferring and storing concentrated solar energy characterized in that it consists in subjecting to concentrated solar radiation a bed of granulated solids fluidized by gas and which is divided into compartments for the reception, exchange and storage of energy depending on the proportion of the mixture .
    [2]
    2. Thermochemical process for transferring and storing concentrated solar energy according to claim 1, characterized in that the granulated solid is constituted by a mixture of inert granulated solids, preferably sand, and CaCOiCaO, preferably derived from natural limestone.
    [3]
    3. Thermochemical process for transferring and storing concentrated solar energy according to claims 1 and 2, characterized in that the gas flow used for fluidization is formed by a mixture of inert gas, preferably air, and CO2 in controlled proportion such that above a Critical temperature value, preferably 700 ° C, chemical energy is stored by decarbonation of CaC03.
    [4]
    Four. Thermochemical process for transferring and storing concentrated solar energy according to claims 1 and 2 characterized in that the gas flow used for fluidization is formed by a mixture of inert gas, preferably air and CO2 in controlled proportion such that below a value Critical temperature, preferably 700 ° C, chemical energy is released by carbonation of CaO.
    [5]
    5. Thermochemical process for transferring and storing concentrated solar energy according to claim 4, characterized in that the incorporation of controlled quantities around 20% by volume of H20 vapor in the gas flow allows to increase the reactivity of CaO.
    [6]
    6. Thermochemical energy transfer and storage method according to claim 1, characterized in that the application of sound waves on the fluidized bed intensifies the transfer of heat and mass in the fluidized bed.
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    同族专利:
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    引用文献:
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    FR2418422A1|1978-02-24|1979-09-21|Fives Cail Babcock|Storing and recovering heat energy - by decomposing calcium carbonate and recombining the products elsewhere|
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