CA1278566C - Chemical energy storage system - Google Patents

Abstract

ABSTRACT OF THE DISCLOSURE
A system for storing chemical energy comprises first and second vessels, the first containing a liquid solution of an alkali or alkaline earth metal hydroxide, halide, or thiocyanate, or ammonium halide or thiocynate at an initial concentration of between about 30% and about 80%, by weight, the second vessel containing liquid, a space about the liquid in each vessel and a conduit communicating between the spaces having a valve for selectively allowing liquid vapor to pass between the spaces, means for heating the solution to a temperature above about 80°F, means for cooling the liquid to a temperature below about 55°F, and heat exchange means for transferring heat from the heated solution and for transferring heat to the cooled liquid. Water is the preferred liquid although ammonia, lower alcohols, and polyols such as glycerol, glycols, polyglycols, glycol ethers, lower aliphatic amines and alkanol amines, and mixtures thereof, may be used.

Description

lZ7~ 66 With the high cost of electrical energy required to 6 operate air conditioners or heat pumps for cooling buildings, 7 and particularly with the heavy demands for commercial building 8 cooling systems at peak use hours, attention has been directed 9 to various types of thermal energy storage systems. Such energy storage is advantageous since the building cooling and/or 11 heating and process cooling may be generated and stored during 12 off-peak hours at night when most businesses are normally 13 closed, with the ambient outside temperatures being cooler and 14 municipal power requirements reduced.
Most state of the art thermal energy storage systems 16 are based on a solid to liquid phase change using energy storage 17 in a narrow temperature range. Water based systems using ice 18 storage are especially desirable because of low fluid costs and 19 availability. However, the disadvantages of such systems include low evaporator temperature requirements because thermal 21 gradient forces evaporator temperatures to a level far below 22 32F, also reducing the chiller efficiency, incomplete or low 23 phase change, often in the order of about 50% to 55%, and low 24 overall energy density of 80 BTU/lb. However, due to the excep-tional environmental acceptability qualities and large 26 availability, water is preferred above more corrosive, volatile, 27 expensive and less readily available energy storage materials.

~Z78~66 The present invention is directed to an energy stor- -age system utilizing the advantages of a phase change of gaseous and liquid water. The energy density of such a phase change is in excess of 1000 ~TU/lb. with no solidification or crystalli-zation required. Moreover, the present system utilizes relative-ly low cost and simple apparatus for taking advantage of the energy storage combined with state of the art heat exchange e~uipment normally found in modern residential and commercial buildings. These as well as other advantages will be evident from the following description of the invention.
According to one aspect of the present invention there is provided apparatus for transferring heat comprising a first vessel containing a liquid solution of a compound selected from the group consisting of alkali and alkaline earth metal hydroxide, halide and thiocyanate, ammonium halide and thiocyanate, and mixtures thereof, said solution having an initial concentration of between about 30% and about 80~, by weight of said compound, said liquid selected from the group consisting of water, ammonia an alcohol having between 1 and 8 carbon atoms, glycerol, glycols, polyglycols, glycol ethers, aliphatic amines and alkanol amines having between 1 and about 6 carbon atoms, and mixtures thereof, and a first space above the level of said liquid solution and means for pumping said liquid solution to distribution means for directing said liquid solution into said first space, a second vessel containing said liquid without said compound therein, and a second space above the level of said liquid and means for pumping said liquid to distribution means for directing said liquid into said second space, both said first and second vessels being closed to atmos-phere and capable of holding a vacuum, conduit means 1'~78~;fi~;

communi.cating between said first space and said second space forallowing liquid vapor and pressure changes to pass therebetween, and valve means cooperating with said conduit means for ~ermin-ating communication between said spaces, heating means for heating said solution to a temperature of above about 90F, and cooling means for cooling said liquid to a temperature below about 55F, first heat exchange means coope.rating with said first vessel for transferring heat from heated solution therein, and second heat exchange means cooperating with said second vessel for transferring heat to liquid therein.
According to a further aspect of the present inven-tion there is provided a heat exchange process utilizing the apparatus defined above comprising:
(a) opening said valve means, (b) heating said solution in said first vessel to a temperature of above about 85F and evaporating liquid there-from, directing the liquid vapor from the space in said first vessel to the space in said second vessel through said conduit means, concurrently cooling the liquid in said second vessel to a temperature below about 55F and condensing the water vapor in the space therein, and continuing said heating and cooling until the concentration of said material in said first vessel is between about 6% and about 25% greater than said initial con-centration, (c) terminating said heating of said solution and said cooling of said liquid and closing said valve means thereby closing communication between said spaces in said first and second vessels, ~ d) selectively opening said valve whereby liquid therein is evaporated thereby cooling said liquid in said second vessel - 2~a -1278~;66 as liquid vapor pressure differential between said first and second vessels is eliminated, (e) exposing said liquid in said second vessel to heat exchange means and pumping said liquid to said distribution means and spraying said pumped liquid into said second space; and (f) concurrently with step (e) exposing said solution in said first vessel to heat exchange means and pumping said solution to said distribution means and spraying said pumped solution into said first space.
The invention will be further described with refer-ence to the accompanying drawings showing, by way of example, embodiments of the invention in which:
Figure 1 is a schematic sectional view of a first embodiment of the system of the invention used in direct heat transfer;
Figure 2 is a schematic sectional view of the system of the invention using a direct expansion system; and Figure 3 is a schematic sectional elevation illus-trating a system for use in an indirect heat transfer system.
The hasic invention comprises charging the energy storage system by heating an aqueous salt solution and cooling water in separate vessels to a liquid temperature differential of at least 30 F, and preferably 50F or more up to about 180 F
differential. The vessels are separated although the space above each liquid in the respective vessels are in communication until the desired vapor mass transfer is completed. Thereafter - 2b -~Z'78566 1 the spatial communication is terminated until it is desired to 2 discharge the energy stored in the system as will be described 3 hereinafter.

4 In Fig. 1 there is shown an illustration of a first embodiment of the chemical thermal storage system of the 6 invention. The apparatus illustrated schematically comprises a 7 container lO having two cavities or vessels 12 and 14 separated 8 by a baffle or wall 24. The container must be air-tight so that 9 the two cells or cavities can selectively maintain different vapor pressures. It will be appreciated that although a single 11 container 10 is shown having the two vessels, different 12 containers may be used, the important consideration being that 13 two vessels or cavities are required for holding two different 14 liquids of the system with means for transferring water vapor and communicating vapor pressure differentials between the 16 vessels.
17 In the preferred embodiment shown, a valve 26 18 communicates between the spaces of the two vessels above the 19 liquid levels. The valve, conveniently located in wall 24, is preferably a butterfly valve with an orifice of several inches 21 and associated with convenient means for opening and closing the 22 valve. A first liquid composition 16 is located in first vessel 23 12 and fills the cavity only partially leaving a space 20 above 24 the liquid level. Similarly, in second vessel 14, liquid 18 only partially fills the cavity leaving a second space 22 above 26 the liquid level. It is the spaces 20 and 22 which are in 27 communication via valve 26 which can be selectively opened or lZ7~3~;66 1 closed to allow for water vapor to pass between the two spaces 2 thereby maintaining vapor pressure differential between the two 3 vessels when the valve is closed.
4 In the first vessel 12 is a liquid solution of an ammonium halide or thiocyanate, alkali or alkaline earth metal 6 halide, hydroxide or thiocyanate, or mixtures thereof, having 7 initial concentrations of between about 30 and about 80%, and 8 preferably between about 40% and 75%, by weightO In the second 9 vessel 14 is liquid 18. The preferred solvent in vessel 12 and liquid in vessel 14 is water although ammonia and ammonia/water 11 mixtures may be used for low temperature applications. In 12 addition, lower aliphatic amines, lower alkanol amines, 13 alcohols, glycerol, glycols, polyglycols, alkylene glycol ethers 14 and aqueous solutions or mixtures thereof may also be used in combination with water or ammonia. Useful alcohol~ are those 16 having between 1 and 12 carbon atoms. Lower alphatic amines and 17 alkanol amines are those of from 1 to about 6 carbon atoms.
18 Examples of the amines are methylamine, ethylamine, etc. while 19 ethanolamine and propanolamine are examples of alkanol amines.
Preferred glycols are ethylene glycol and propylene glycol while 21 suitable glycol ethers include ethylene glycol dimethyl ether, 22 diethylene glycol diethyl ether, etc.
23 Most preferred salts in aqueous systems are the alkali 24 or alkaline earth metal hydroxides especially those of sodium, potassium, cesium, magnesium, lithium, strontium and calcium.
26 Lithium or calcium chloride or bromide are also preferred.
27 Mixtures of the hydroxides may also be used together with i~78566 lithium chloride or lithium bromide or calcium chloride as well as nitrate salts of those metals as corrosion suppressing additives, in systems where corrosion may be a problem. For ammonium solvent systems, preferred salts include ammonium halides such as ammonium bromide and ammonium chloride, ammonium thiocyanate as well as ammonium metal halide salts, for example 4 4' ( 4)2 n 4 ( 4)3 C15. The above described organic additives may be used to increase the sorption rates and to increase the differential pressure, as well as to serve as freeze point suppressants in aqueous systems in vessels 12 and 14. For this purpose, plastic vessels or containers which are resistant to the aqueous hydroxide solutions are to be used as are plastic tubing or conduits. Other materials that are lined or coated with compositions which are not susceptible to cor-rosion when exposed to the strong hydroxide compositions may be used.
The apparatus also includes suitable conduits, pumps and spray nozzle systems for handling the liquids in the respec-tive cavities. Thus, conduits 30 and 32, and pump 34 direct aqueous solution 16 from vessel 12 to a heat exchanger, for ex-ample, a condenser of a heat pump or chiller or a waste heat source (not shown) or solar heat means for heating the solution to a desired temperature of at least 30F and preferably at least 50F higher than the temperature of water in second vessel 14.
Preferred solution temperatures are between about 85 and about 130 F although higher temperatures may be used. The heated solu-tion is then directed to first space 20. A preferred method of ~278~i6 1 returning the heated aqueous solution to the first vessel 2 incorporates a nozzle or spray nozzle system 36 which simply 3 sprays the heated aqueou~ composition in the form of droplets or 4 a fine mist into first space 20 above the surface of liquid 16 in vessel 12. Any suitable spray no7.zle means may be used for 6 this purpose. Similarly, in second vessel 14, water 18 is 7 pumped to a heat exchanger by pump 44 via line 42 where it is 8 cooled, for example, by an air conditioning or heat pump 9 evaporator, cooling tower or other evaporative cooling means or an air to air means after which the cooled water is directed via 11 pipe 40 to second space 22 above the water level using a spray 12 nozzle means 46.
13 In operating the above-described apparatus in a 14 storage system of the invention, preferably, during the night, or o~herwise at relatively low ambient temperature conditions 16 and when area or municipal use loads are at below peak or high 17 requirements, aqueous solution 16 is ~eated with condenser heat 18 from a building heat pump system, or otherwise heated 19 conveniently to a temperature of above about 85F up to about 130F. At the same time, water 18 i8 cooled to a temperature of 21 below about 55F, and preferably below 35F, using an evaporator 22 from a building heat pump or air conditioning system. Because 23 the vapor pressure of the aqueous solution, for example 42%
24 NaOH, by weight, at 120F is higher than the vapor pressure of water at 34F, the solution will desorb water in the form of 26 water vapor via open valve 26 into second space 22 which 27 condenses into the liquid water 18. This process continues ~78~66 1 until a solution concentration of approximately 52% of NaOH, by 2 weight, is achieved. ~t that point, the system is charged, and 3 valve 26 is closed to separate the first and second spaces in 4 the two vessels and maintain vapor pressure differential which thereby allows the charged system to remain stored for an indef-6 inite period of time.
7 When it is desired to utilize the stored energy in the 8 system created by the above-described charging process, the cold 9 water is circulated to a heat exchanger for the building, for example, passed through a cooling coil in an air handler for ll cooling the building. During this discharge period, again, the 12 water is pumped via pipe 42 using pump 44 to the building air 13 handler or other heat exchange cooling means, and returned via 1~ pipe 40 to second vessel 14 using the spray nozzle device 46.
The water thus becomes heated as it absorbs or picks up building 16 heat through the heat transfer system during this discharge 17 phase. Concurrently, hot aqueous solution 16 is pumped via pipe 18 32 and pump 34 to outside air heat exchangers or coolers such as 19 evaporative coolers, cooling towers and the like thereby cooling the aqueous solution which is then returned via pipe 30 and 21 discharged into first space 20 using a spray apparatus 36.
22 During this discharge cycle, valve 26 must be opened 23 and because of the difference in vapor pressure between the 24 first and second spaces, 20 and 22 respectively, water is evaporated in second space 22 to provide substantial cooling of 26 the liquid in second vessel 14. At the same time, the 27 evaporated water is passed into first space 20 where it is ~Z~3S66 1 absorbed into solution 16, which causes a heat of condensation 2 and solutions in first vessel 12, which heat is again exchanged 3 by the outside cooling means (not shown) previously discussed.
4 Alternatively, the heat of condensation and solutions in first vessel 12 may be used for heating purposes, for example in a 6 dual temperature storage capability for building heating and 7 cooling.
8 In Fig. 2 there is illustrated another variation or 9 embodiment of a system according to the invention in which a coolant, such as a refrigerant may be directly cooled or 11 condensed at low temperature during discharge of the energy 12 storage system of the invention. Again, a container 10 having 13 two vessels or cavities as illustrated in Fig. 1 may be used 14 with a divider 24 separating the two cavities. The liquid solu-tion 16 and water 18 in the respective containers are 16 substantially like that previously described as is the change of 17 vapor pressure and exchange of water vapor between the cavities 18 20 and 22, respectively, through valve 26, in both the charging 19 and discharging phases of the operation of the system. In this embodiment, the water is cooled during the charging phase by 21 direct exposure to evaporator coils of àn air conditioning 22 system evaporator. For example, the air conditioning system of 23 the building may utilize a cooling conduit 66 which is exposed 24 directly in second cavity 22 through which cold refrigerant is directed during the charging phase. At that time, water 18 will 26 be pumped via pump 60 and conduit 58 and sprayed through spray 27 nozzle apparatus 46 over the cold pipe or coil 66 to be cooled.

8~;66 1 Concurrently, with valve 26 open during the charginq phase, 2 aqueous solution 16 is heated by pumping the solution via pump 3 54 and conduit 52 through spray nozzle apparatus 36 over heated 4 pipe or coils 56 from a condenser 75 or other heating means including a heat exchanger of the HVAC (heating ventilation air 6 conditioning) equipment condensing the refrigerant. In that 7 case, hot refrigerant may be directed into pipe or coil 55 via 8 pump 74 from the heat exchanger 75. once the vapor mass 9 transfer between the liquid solution 16 and water 18 is achieved during this charge phase, further heating and cooling, 11 respectivel~ is terminated and valve 26 is closed thereby again 12 maintaining the energy charged in the respective li~uids stored 13 until its use is desired.
14 During discharge, valve 26 is opened, and the respective liquids are pumped through their respective nozzle 1~ sprayers over the heat exchange conduits present in the spaces 17 in the respective vessel. Refrigerant directed via conduit or 18 coil 66 is cooled by evaporation of water as water is sprayed 19 over the coil in space 22, the water gradually becoming heated as it picks up heat as it cools the refrigerant from heat 21 exchanger 72. Similarly, in this discharge phase of operation, 22 heat from solution i6 is removed by heat exchanger 75 which 23 similarly p~lmps a coolant via coil 56 present in space 20.
24 A third apparatus configuration utilizing an indirect heat transfer system is illustrated in Fig. 3. In this 26 apparatus, substankially like that described in Fig. 2, a heat 27 exchanger 76 is used for directly heating and cooling liquid 16 ~Z78566 1 in the charge and discharge phases, respectively of the 2 operation of the system by pumping a heat transfer fluid with 3 pump 74. The heat exchanger illustratad utilizing water with 4 the system is somewhat different in that pump 77 will direct a heat transfer material such as water, ammonia, methanol, 6 glycol-water mixtures, and the like through remote heat 7 exchanger 71, 73 and 79 at various locations throughout a 8 building in which the system is to operate. Pump 77 simply g pumps the secondary cooling material via pipe 70 to the respective heat exchangers, with the pipe 70 being exposed in 11 space 22 over which water is sprayed as previously discussed 12 regarding the apparatus shown in Fig. 2.
13 The specific types of heat exchangers and apparatus 14 used within the purview of the scope of the systems described herein are not so important, and other types of systems may be 16 used to achieve the same purpose. Thus, the specific design of 17 the systems shown and described herein are for the purpose of 18 illustration only and the invention is not to be necessarily 19 limited thereto. These as well as other modifications, variations and advantages of the system within the purview of 21 the invention will be evident to those skilled in the art.

Claims (23)

1. Claim 1. Apparatus for transferring heat comprising a first vessel containing a liquid solution of a compound selected from the group consisting of alkali and alkaline earth metal hydroxide, halide and thiocyanate, ammonium halide and thiocyante, and mixtures thereof, said solution having an initial concentration of between about 30% and about 80%, by weight of said compound, said liquid selected from the group consisting of water, ammonia an alcohol having between 1 and 8 carbon atoms, glycerol, glycols, polyglycols, glycol ethers, aliphatic amines and alkanol amines having between 1 and about 6 carbon atoms, and mixtures thereof, and a first space above the level of said liquid solution and means for pumping said liquid solution to distribution means for directing said liquid solution into said first space, a second vessel containing said liquid without said compound therein, and a second space above the level of said liquid and means for pumping said liquid to distribution means for directing said liquid into said second space, both said first and second vessels being closed to atmosphere and capable of holding a vacuum, conduit means communicating between said first space and said second space for allowing liquid vapor and pressure changes to pass therebetween, and valve means cooperating with said conduit means for terminating communication between said spaces, heating means for heating said solution to a temperature of above about 90°F, and cooling means for cooling said liquid to a temperature below about 55°F, first heat exchange means cooperating with said first vessel for transferring heat from heated solution therein, and second heat exchange means cooperating with said second vessel for transferring heat to liquid therein.
2. Claim 2. Apparatus of claim 1 wherein said first and second vessels comprise first and second chambers in a divided tank, respectively.
3. Claim 3. Apparatus of claim 2 wherein said conduit means comprises port means communicating between said first and second spaces, and wherein said valve means opens and closes said port means.
4. Claim 4. Apparatus of claim 1 including first pipe means and first pump means for directing said solution between said first vessel and said first heat exchange means, and second pipe means and second pump means for directing said liquid between said second vessel and said second heat exchange means.
5. Claim 5. Apparatus of claim 4 wherein said first heat exchange means comprises a heat pump condenser, and said second heat exchange means comprises a heat pump evaporator.
6. Claim 6. Apparatus of claim 1 wherein said first heat exchange means includes a first heat exchange pipe exposed in said first space and wherein said distribution means directs said solution over the first heat exchange pipe in said first space.
7. Claim 7. Apparatus of claim 6 including spray means for spraying said solution over said first heat exchange pipe.
8. Claim 8. Apparatus of claim 6 wherein said first heat exchange pipe comprises a condenser coil.
9. Claim 9. Apparatus of claim 1 wherein said second heat exchange means includes a second heat exchange pipe exposed in said second space and wherein said distribution means directs said liquid over said second heat exchange pipe.
10. Claim 10. Apparatus of claim 9 including spray means for spraying said liquid over said second heat exchange pipe.
11. Claim 11. Apparatus of claim 9 wherein said second heal exchange pipe comprises an evaporator coil.
12. Claim 12. Apparatus of claim 1 wherein said first heat exchange means include evaporative or air to air cooling means and first supplemental heat transfer means comprising a first conduit loop having heat transfer liquid therein and a pump cooperating therewith for pumping said heat transfer liquid through said first conduit loop, said first conduit loop extending between said first space and said evaporative or air to air cooling means.
13. Claim 13. Apparatus of claim 12 including spray means for spraying said solution over said first conduit loop in said first space.
14. Claim 14. Apparatus of claim 12 wherein said second heat exchange means includes a heat pump evaporator and second supplemental heat transfer means comprising a second conduit loop having a heat transfer liquid therein and a pump cooperating therewith for pumping said heat transfer liquid through said second conduit loop, said second conduit loop extending between said second space and said evaporator.
15. Claim 15. Apparatus of claim 14 including spray means for spraying said liquid over said second conduit loop in said second space.
16. Claim 16. Apparatus of claim 4 wherein said first heat exchanger means comprises waste heat or solar heat means.
17. Claim 17. A heat exchange process utilizing the apparatus of claim 1 comprising:
    (a) opening said valve means, (b) heating said solution in said first vessel to a tempera-ture of above about 85°F and evaporating liquid there-from, directing the liquid vapor from the space in said first vessel to the space in said second vessel through said conduit means, concurrently cooling the liquid in said second vessel to a temperature below about 55°F and condensing the water vapor in the space therein, and continuing said heating and cooling until the concentration of said material in said first vessel is between about 6% and about 25%
    greater than said initial concentration, (c) terminating said heating of said solution and said cool-ing of said liquid and closing said valve means thereby closing communication between said spaces in said first and second vessels, (d) selectively opening said valve whereby liquid therein is evaporated thereby cooling said liquid in said second vessel as liquid vapor pressure differential between said first and second vessels is eliminated, (e) exposing said liquid in said second vessel to heat exchange means and pumping said liquid to said distribution means and spraying said pumped liquid into said second space; and (f) concurrently with step (e) exposing said solution in said first vessel to heat exchange means and pumping said solution to said distribution means and spraying said pumped solution into said first space.
18. Claim 18. Process of claim 17 wherein said solution is heated to above 80°F in step (b) by directing said solution to a heat pump condenser or solar or waste heat source and exposing said solution to heated elements thereof.
19. Claim 19. Process of claim 17 wherein said liquid is cooled to below about 55°F in step (b) by directing said liquid to a heat pump evaporator and exposing said liquid to cooled elements thereof.
20. Claim 20. Process of claim 17 comprising providing elements of said first heat exchange means in said first space an providing elements of said second heat exchange means in said second space and spraying said liquid over said elements of said second heat exchange means in step (e) and spraying said solution over said elements of said first exchange means in step (f).
21. Claim 21. Process of claim 19 wherein said cooled liquid from step (e) is directed to a heat exchange evaporator for cooling elements thereof.
22. Claim 22. Process of claim 20 comprising providing said heat exchange elements in said second space and spraying said elements with said liquid.
23. Claim 23. Process of claim 18 wherein said liquid is cooled below about 55°F by directing said liquid to a heat pump evaporator and exposing said liquid to cooled elements thereof.