Energy Storage System

Abstract

There is disclosed an energy storage system. In particular, there is disclosed a chemisorption based energy storage system, able to provide electricity, heating or cooling depending on the desired energy output. The energy storage system includes a first chemical reactor containing a first sorbent material and a second chemical reactor containing a second sorbent material. The first and second chemical reactors are in mutual fluid connection such that a refrigerant fluid can flow from the first chemical reactor to the second chemical reactor, and from the second chemical reactor to the first chemical reactor. The first and second chemical reactors are further provided with means for putting heat in to, or taking heat out of, the first and/or the second chemical reactors. A heat exchanger module is also provided. The heat exchanger module is configured to select from a plurality of available heat sources, a heat source having the highest temperature and an expander module selectively connected to the first chemical reactor and the second chemical reactor via the heat exchanger module. The heat source is arranged to heat the refrigerant fluid prior to the refrigerant fluid passing through the expander module, and the heat exchanger is configured to recover a surplus heat from the highest temperature heat source. The expander module is configured to expand the refrigerant fluid. The means for putting heat in to, or taking heat out of, the first and/or the second chemical reactors provides a flow of refrigerant fluid between the expander module and the first and second chemical reactors, and wherein the expander module is operable to expand the refrigerant fluid to provide a variable work output depending on energy storage requirements.

Claims

1. A chemisorption based energy storage device comprising: a first chemical reactor containing a first sorbent material and a second chemical reactor containing a second sorbent material, the first and second chemical reactors being in mutual fluid connection such that a refrigerant fluid can flow from the first chemical reactor to the second chemical reactor, and from the second chemical reactor to the first chemical reactor, the first and second chemical reactors being further provided with means for putting heat in to, or taking heat out of, the first and/or the second chemical reactors; a heat exchanger module, the heat exchanger module being configured to select from a plurality of available heat sources, a heat source having the highest temperature; and an expander module selectively connected to the first chemical reactor and the second chemical reactor via the heat exchanger module; wherein the heat source is arranged to heat the refrigerant fluid prior to the refrigerant fluid passing through the expander module, and wherein the heat exchanger is configured to recover a surplus heat from the highest temperature heat source, and the expander module is configured to expand the refrigerant fluid; wherein the means for putting heat in to, or taking heat out of, the first and/or the second chemical reactors provides a flow of refrigerant fluid between the expander module and the first and second chemical reactors, and wherein the expander module is operable to expand the refrigerant fluid to provide a variable work output depending on energy storage requirements.

2. An energy storage system according to claim 1, wherein the first sorbent material is a salt, and preferably, the first sorbent material is a metal halide.

3. An energy storage system according to claim 2, wherein the salt is a metal sulphide or a metal sulphate.

4. An energy storage system according to claim 1, wherein the first sorbent material is selected from the group: NiCl.sub.2, CaCl.sub.2, SrCl.sub.2, FeCl.sub.2, FeCl.sub.3, ZnCl.sub.2, MgCl.sub.2, MgSO.sub.4 and MnCl.sub.2

5. An energy storage system according to claim 1, wherein the second sorbent material is a salt, and preferably, the second sorbent material is a metal salt.

6. An energy storage system according to claim 5, wherein the salt is a metal halide.

7. An energy storage system according to claim 5, wherein the salt is a metal sulphide.

8. An energy storage system according to claim 5, wherein the salt is a metal sulphate.

9. An energy storage system according to claim 1, wherein the second sorbent material is selected from the group: CaCl.sub.2, SrCl.sub.2, BaCl.sub.2, NaBr, NH.sub.4Cl, PbCl.sub.2, LiCl, and Na.sub.2S.

10. An energy storage system according to claim 1, wherein the refrigerant fluid is selected from the group: ammonia, methanol, and steam.

11. A method of operating an energy storage system according to the first aspect, the method comprising: providing a first chemical reactor containing a first sorbent material and a second chemical reactor containing a second sorbent material, the first and second chemical reactors being in mutual fluid connection such that a refrigerant fluid can flow from the first chemical reactor to the second chemical reactor, and from the second chemical reactor to the first chemical reactor, the first and second chemical reactors being further provided with means for putting heat in to, or taking heat out of, the first and/or the second chemical reactors; providing a heat exchanger module, the heat exchanger module being configured to select from a plurality of available heat sources, a heat source having the highest temperature; and selectively connecting an expander module to the first chemical reactor and the second chemical reactor via the heat exchanger module; heating the refrigerant fluid via the selected highest temperature heat source and passing the refrigerant fluid through the expander module; recovering a surplus heat from the highest temperature heat source; and expanding the refrigerant fluid through the expander module; wherein the means for putting heat in to, or taking heat out of, the first and/or the second chemical reactors provides a flow of refrigerant fluid between the expander module and the first and second chemical reactors, and wherein the expander module is operable to expand the refrigerant fluid to provide a variable work output depending on energy storage requirements.

12. An energy storage system according to claim 1, wherein the refrigerant is selected from one of: ammonia, methanol or steam.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0049] Embodiments of the invention are further described hereinafter with reference to the accompanying drawings, in which:

[0050] FIG. 1 shows an example of a first half cycle for mechanical work output in an energy storage system;

[0051] FIG. 2 shows an example of a second half cycle for mechanical work output and a thermal transformer;

[0052] FIG. 3 shows an example of a second half cycle for mechanical work output;

[0053] FIG. 4 shows an example of a second half cycle for mechanical work output and cooling;

[0054] FIG. 5 shows a simulation result of the work output of the desorption-reheating process under conditions of different heat source temperature for different salt pairs when the heat sink temperature is at 25 C. Work output of the desorption-reheating process under conditions of different heat source temperature when the heat sink temperature is at 25 C. is shown: (a) MnCl.sub.2NaBr pair, the optimum desorption temperature of the first salt; (b) MnCl.sub.2NaBr pair, the optimum desorption temperature of the second salt; (c) MnCl.sub.2CaCl.sub.2 pair, the optimum desorption temperature of the first salt; (d) MnCl.sub.2CaCl.sub.2 pair, the optimum desorption temperature of the second salt;

[0055] FIG. 6 shows the ideal thermodynamic cycle of thermochemical power generation in an energy storage system using for example a salt pair of MnCl.sub.2CaCl.sub.2 and the ideal thermodynamic cycle of an ammonia based Rankine cycle in the diagram of the temperature versus entropy of the ammonia;

[0056] FIG. 7 shows ideal theoretical analysis of the desorption-expansion process in resorption power generation cycle.

DETAILED DESCRIPTION

[0057] Often, several heat sources or streams of waste heat are available in industrial processes. The heat sources often have different temperatures. The heat sources can be arranged and selected for the energy storage system based on optimum desorption temperatures for the first and second chemical reactor.

[0058] The energy storage system includes a first chemical reactor containing a material that can adsorb the refrigerant fluid when it is subject to a temperature lower than the first equilibrium temperature of the chemical reaction between the first sorbent material and the refrigerant fluid at a given working pressure. If the temperature is greater than the first equilibrium temperature the refrigerant fluid will desorb from the first chemical reactor.

[0059] A second chemical reactor is provided comprising a second sorbent material that can adsorb the refrigerant fluid when it is subject to a temperature lower than the equilibrium temperature of the reaction between the second sorbent material and the refrigerant fluid at a given working pressure. If the temperature is greater than the second equilibrium temperature the refrigerant fluid will desorb from the second chemical reactor.

[0060] The energy storage system has access to heat sources or alternatively, objects which require refrigeration.

[0061] The energy storage system further includes an expander module selectively connected to the first chemical reactor and the second chemical reactor via a heat exchanger module. The expander module is configured to expand the refrigerant fluid to produce mechanical work output. Refrigerant fluid, such as ammonia for example, flows between the expander module and the first and second chemical reactors. The expander module is able to expand the refrigerant fluid to provide a variable work output depending on energy storage requirements.

[0062] FIG. 1 shows an example of a first half cycle of an energy storage system. It has been found by the Applicants that and energy storage system as shown in FIGS. 1 to 4 comprising a first and second chemical reactor, has a first optimum desorption temperature range for the first chemical reactor and a second optimum desorption temperature range for the second chemical reactor under a given condition of heat source, heat sink and working pressure, whereby the refrigerant fluid desorbed from the first or the second chemical reactors can produce the maximum mechanical work output, leading to the improved energy efficiency. By incorporating a heat exchanger into each of the first half cycle and the second half cycle (see for example, FIGS. 1 to 4), several heat sources may be efficiently used within the energy storage system.

[0063] The optimum desorption temperature may be the same temperature as the available heat source, or the optimum desorption temperature may be higher or lower than the temperature of the available heat source.

[0064] The optimum temperature desorption is identified for the chemical reactor in order to obtain maximum power generation. In the first half cycle heat is put into the system at the first chemical reactor at the optimum desorption temperature Ts.sub.1 of the first chemical reactor. Ammonia is desorbed from the first chemical reactor at the desorption temperature Ts.sub.1, and is subsequently reheated by the heat exchanger by a higher temperature heat source, before the refrigerant fluid is expanded to generate mechanical energy. After the ammonia is expanded, the ammonia is adsorbed into the second chemical reactor.

[0065] FIG. 2 shows an example of a second half cycle of the energy storage system. Coupled with the first half cycle shown in FIG. 1, this arrangement is configured to provide continuous power generation and a batched thermal transformer in a complete cycle.

[0066] The second chemical reactor is heated up at the second optimum desorption so that ammonia is desorbed from the second reactor. The ammonia passes through the heat exchanger before the desorbed ammonia entrains to the expander and expands to generate mechanical energy. Exhausted ammonia from the expander is adsorbed into the first chemical reactor. The exhausted ammonia from the expander is at high temperature and high pressure, and therefore there is great potential for the ammonia adsorption in first chemical reactor to produce upgraded heat at higher temperature than the temperature of the available heat source.

[0067] FIG. 3 shows an alternative operation of the energy storage system, providing continuous optimum power generation in a complete cycle if coupled with the first half cycle shown in FIG. 1. The second chemical reactor is heated at the second optimum desorption temperature such that ammonia is desorbed from the second chemical reactor. The desorbed ammonia is subsequently reheated by the heat exchanger up to higher temperature by a heat source. The desorbed ammonia expands to generate mechanical energy before it is adsorbed into the first chemical reactor. Adsorption heat released from first chemical reactor is discharged to ambient environment thereby providing a heat source, or discharged to a cooler sink.

[0068] FIG. 4 shows a further alternative operation of the energy storage system, providing continuous optimum power generation and batched cooling in a complete cycle if coupled with the first half cycle shown in FIG. 1. The second chemical reactor extracts heat at the second optimum desorption temperature from the objects to be cooled and thereby produces a cooling effect for the objects. For some resorption metal salt working pairs, the optimum desorption temperature which is again identified to maximise work output by the expander, happens to be low enough to produce an additional cooling effect.

[0069] For example, using the metal salt pair of MnCl.sub.2 (first chemical reactor) and NaBr (second chemical reactor), the work output against desorption temperature in the first half cycle and the second half cycle is shown in FIG. 5 (a) and FIG. 5 (b), respectively. The Figure shows peaks at certain temperature points, depending on different waste heat source temperatures. The peaked temperature points in FIG. 5(b), represent the optimum desorption temperature of the second chemical reactor, and are lower than ambient temperatures (marked as the vertical dashed line in FIG. 5). This implies the potential of cooling generation. The red curves marked as basic process represent power generation of the prior art system, the TR-CAES system described in the background section of the present application.

[0070] Referring back to the example of the second half cycle shown in FIG. 4, after desorption of ammonia in the second chemical reactor, the desorbed ammonia is heated by available waste heat and subsequently the ammonia passes through the expander to generate mechanical energy. Adsorption heat is released from first chemical reactor and discharged to ambient environment or to a cooler sink.

[0071] The first chemical reactor may be considered as a high temperature salt chemical reactor and the second chemical reactor may be considered as a low temperature salt chemical reactor.

[0072] The desorption and reheating process can be conducted in an optimised manner by first identifying the first and second optimum desorption temperature of the first and second chemical reactors under a given condition of heat source and heat sink. In some situations, there is only one heat source at a certain temperature, the energy storage system may still use this single heat source in a heat exchange arrangement, e.g. the heat source firstly supplies reheating to the heat exchanger then the exhausted heat from the heat exchanger is used for the chemical reactor to instigate desorption of ammonia. Alternatively it is also possible to achieve the required temperature levels by controlling the flow rate of the heat source fluid or the heat exchanging fluid passing through the heat exchanger. Furthermore, if the optimum desorption temperature is lower than ambient temperature, refrigeration is achieved as shown in FIG. 4.

[0073] FIG. 6 shows the ideal thermodynamic cycle of a number of examples in a diagram of temperature versus entropy including the Rankine cycle using ammonia as the working fluid. In the Rankine cycle (shown as tracks 1-2-3-4-5), 2-3 shows the superheating process (from 80 degrees C. to 100 degrees C.) and the 3-4 is the isentropic expansion. Ammonia is a wet fluid and the thermodynamic state of the superheated ammonia vapour is still close to the saturation condition, therefore, the vapour expansion is limited, leading to limited work output.

[0074] The thermochemical power generation cycle using MnCl.sub.2CaCl.sub.2 pair without reheating process is shown as tracks 1-2-3-4-5-6, where 1-2 process is the isentropic expansion when the desorption temperature is at 100 C. (for example, 100 C. is the available highest heat source temperature) for MnCl.sub.2 ammoniate. Because the optimum desorption temperature of MnCl.sub.2 ammoniate is the same as the available highest heat source temperature (100 C.), no reheating is carried out in this first half cycle. 2-3 shows the isobaric adsorption in the CaCl.sub.2 reactor. In the second half cycle, 4-5 shows the isentropic expansion if the desorption temperature is at 100 C. for CaCl.sub.2 ammoniate without reheating, 5-6 shows the isobaric adsorption in the MnCl.sub.2 reactor. The thermochemical power generation cycle using MnCl.sub.2CaCl.sub.2 pair with reheating process is shown as tracks 1-2-3-4-5-6-7. Because the optimum desorption temperature of CaCl.sub.2 ammoniate in this example is lower than the available highest heat source temperature (100 C.), if the reheating process (4-5) is introduced in this second half cycle, e.g. when desorption temperature is at 80 C. and the reheat temperature is at 100 C., the work output increases to (5-6), higher than (4-5), much higher than (3-4). The equilibrium of the chemical reaction between salts and ammonia is far away from a saturation condition so that there is more potential of fluid expansion. Because there are two restricting factors for thermochemical power generation, the saturation condition and the backpressure (adsorption pressure on the other side), there is a balance between these two factors, therefore leading to an optimum condition of desorption temperature corresponding to different highest heat source temperature for maximum work output.

[0075] In an example, if the working pair MnCl.sub.2NaBr is used and the heat sink temperature is at 25 C., the first optimum temperature for the first sorbent material (MnCl.sub.2) ranges from 140 C. to 210 C. when the heat source is from 140 C. to 260 C.; the second optimum temperature for the second sorbent material (NaBr) ranges from 20 C. to 9 C. when the heat source temperature is from 40 C. to 180 C.

[0076] In another example, if the working pair MnCl.sub.2CaCl.sub.2 is used and the heat sink temperature is at 25 C., the first optimum temperature for the first sorbent material (MnCl.sub.2) ranges from 120 C. to 170 C. when the heat source is from 140 C. to 260 C.; the second optimum temperature for the second sorbent material (CaCl.sub.2) ranges from 14 C. to 45 C. when the heat source temperature is from 40 C. to 180 C.

[0077] It should be noted that for power generation, the resorption adsorbent pair can consist of two same salt, like CaCl.sub.2CaCl.sub.2 pair, MnCl.sub.2MnCl.sub.2 pair; for cooling and heating purpose, there must be two different salts to group a pair, like MnCl.sub.2CaCl.sub.2 pair, MnCl.sub.2NaBr pair.

[0078] The vapour isentropic expansion in the resorption cycle is limited by two factors. The first is the saturation condition of the working fluid (such as NH.sub.3), the other limiting factor is the expansion backpressure which relates to the equilibrium pressure of the salt-ammoniate adsorption.

[0079] FIG. 7 shows the resorption cycle using a CaCl.sub.2NaBr working pair in the energy storage system. FIG. 7 shows an ideal theoretical analysis of the first half cycle, CaCl.sub.2 is the first sorbent material (or the high temperature salt, HTS) while the NaBr is the second sorbent material (low temperature salt, LTS). Due to the limiting factors mentioned above, the expansion state should be located in the grey-colour-marked domain as shown in the graph of FIG. 7, which is the area on the right hand side of NH.sub.3 saturation line and above the adsorption equilibrium pressure line of NaBr ammoniate at a heat sink temperature (assumed 25 C. in this example).

[0080] This implies that the expansion exhaust remains in a vapour phase and at a pressure higher than the backpressure.

[0081] When the heat source is at a temperature of around 120 C. is used to heat the CaCl.sub.2 ammoniate (assuming that this is the highest temperature heat source available), the vapour expansion of the desorbed ammonia from CaCl.sub.2 ammoniate starts from the equilibrium state at point 1 as shown in FIG. 7. The isentropic expansion curve 1-2 therefore represents the ideal maximum potential of work generation when the 120 C. heat source is directly used for desorption.

[0082] If a reheating process is introduced, using a lower temperature for desorption (<120 C.) and then reheating the desorbed vapour isobarically to a higher temperature level with a 120 C. heat source, the final work output from the vapour expansion would change. There are three examples of reheating process shown in FIG. 7, where the Applicant has used different desorption temperatures but the same reheating temperature. The curve 1-2-3 represents the process of desorption at 110 C. and isobaric reheating process at 120 C., while the curve 1-2-3 represents the process of desorption at 85 C. and reheating at 120 C., the curve 1-2-3 represents the process of desorption at 70 C. and reheating at 120 C.

[0083] It is clear that the expansion potential in the order as (1-2-3)>(1-2-3)>(1-2)>(1-2-3). According to a calculation based on thermodynamic equilibrium of resorption process and isentropic expansion, the Applicant has found that the varying profile of the expansion work output against the desorption temperature is a peaked curve (as shown in FIG. 5). The work output firstly increases as the desorption temperature decreases and reaches its vertex at a certain desorption temperature. Afterwards the expansion work output starts to decrease as the desorption temperature further decreases. Therefore there is an optimal desorption temperature for maximum work output if a reheating process applies, as a result of the balancing between the two limiting factors as aforementioned in the resorption processes.

[0084] In another example, if the available heat source has a temperature equivalent to the optimum desorption temperature, there would be a monotone declining trend of the work output if a reheating applies and the desorption temperature decreases. The method to identify the optimum point applies for either case, and is necessary for identifying the optimum performance of the energy storage system.

[0085] It will be clear to a person skilled in the art that features described in relation to any of the embodiments described above can be applicable interchangeably between the different embodiments. The embodiments described above are examples to illustrate various features of the invention

[0086] Throughout the description and claims of this specification, the words comprise and contain and variations of them mean including but not limited to, and they are not intended to (and do not) exclude other moieties, additives, components, integers or steps. Throughout the description and claims of this specification, the singular encompasses the plural unless the context otherwise requires. In particular, where the indefinite article is used, the specification is to be understood as contemplating plurality as well as singularity, unless the context requires otherwise.

[0087] Features, integers, characteristics, compounds, chemical moieties or groups described in conjunction with a particular aspect, embodiment or example of the invention are to be understood to be applicable to any other aspect, embodiment or example described herein unless incompatible therewith. All of the features disclosed in this specification (including any accompanying claims, abstract and drawings), and/or all of the steps of any method or process so disclosed, may be combined in any combination, except combinations where at least some of such features and/or steps are mutually exclusive. The invention is not restricted to the details of any foregoing embodiments.

[0088] The invention extends to any novel one, or any novel combination, of the features disclosed in this specification (including any accompanying claims, abstract and drawings), or to any novel one, or any novel combination, of the steps of any method or process so disclosed.

[0089] The reader's attention is directed to all papers and documents which are filed concurrently with or previous to this specification in connection with this application and which are open to public inspection with this specification, and the contents of all such papers and documents are incorporated herein by reference.