WO1991006612A1

WO1991006612A1 - Thermal storage medium

Info

Publication number: WO1991006612A1
Application number: PCT/GB1990/001634
Authority: WO
Inventors: Malcolm George Clulow; David Frederick Winnett
Original assignee: Clulow Malcom George; David Frederick Winnett
Priority date: 1989-10-27
Filing date: 1990-10-24
Publication date: 1991-05-16
Also published as: DE69009771T2; IL96123A0; EP0497827B1; IE903853A1; FI921829A0; GR900100774A; IN179313B; GB2237629B; ZA908613B; AU6622790A; ATE106934T1; HUT56952A; GB2237629A; CA2071535A1; PT95699A; ES2057597T3; EP0497827A1; GB9023135D0; DE69009771D1; AU641705B2

Abstract

A storage medium is intended to store thermal energy in a high capacity manner with relatively high heat transfer. The medium includes activated alumina and an aqueous medium and the storage medium may be usable at low temperatures and up to about 200 °C. Heat exchange with the storage medium utilises the specific heat of the medium and enthalpy arising out of reversible endothermic and exothermic chemical changes to give high thermal storage capacities which can be enhanced if the range includes a phase change. The thermal storage medium can be used in storage systems such as air conditioning and in systems where the thermal energy is utilised at locations remote from the charging station.

Description

Thermal Storage Medium

This invention relates to thermal storage media and in particular to thermal storage media having a high thermal storage capacity for a range of applications.

It has been proposed to utilise thermal storage medium for a range of applications from storage of heat at relatively high temperatures for heating purposes and at relatively low temperatures for air conditioning and other low temperature uses.

In selecting a thermal storage medium there are a number of related factors to consider, amongst which is the storage capacity of the medium which capacity is related to the specific heat and, -sometimes, the latent heat, if a phase change of the medium is involved. For example water may be used as a storage medium. Water has a high specific heat and in the phase change to ice or steam a high latent heat is involved. Water also is safe in use. However utilisation of the latent heat characteristics of water usually requires that the temperature range over which it is used includes a phase change. When the temperature range desired is, say, below the freezing point of water such latent heat characteristics cannot be utilised.

Other thermal storage media have also been used but they have often involved large masses of the material because of their low specific heat characteristics and/or the inability to use any latent heat characteristics of the material.

A wide range of applications awaits any improved thermal storage medium. Such a medium would open up applications in which intermittent cold or heat supply is required. A source of cold or heat could then be used to supply the thermal storage medium at a substantially constant rate and the cold or heat could be abstracted on an intermittent basis according

SUBSTITUTE SHEET to demand.

For example an air conditioning system which requires cooling at peak demand for a few hours per day could be supplied by a refrigeration system operating at substantially constant rate below peak demand, peak demand being supplied in part from the refrigeration system and in part from a thermal storage unit.

However in order for the thermal storage unit to be effective it should be compact which means it must have a high thermal storage capacity per unit volume. It should also be cost effective and include relatively low cost materials. Preferably the unit should not include toxic materials, that is the materials should not have high alkalinity or acidity, give off toxic vapours and should otherwise not be a hazard to the environment.

An object of the invention is to provide a thermal storage medium and method which provides an enhanced thermal storage capacity greater than that which is possible from the contribution of latent heat and/or specific heat of the medium.

According to one aspect of the invention a method of storing thermal energy comprises passing fluid in heat exchange relationship through a mass of thermal storage medium including activated alumina or aluminium oxide combined with an acqueous medium at a temperature whereby to cause the water content of the acqueous medium to be associated with and disassociated from the alumina in an enthalpy change. Conveniently the water content of the acqueous medium constitutes up to 100% by weight of the alumina. Preferably the water content is less than 70% by weight. The temperature may be in a range of up to 200°C, preferably up to 170°C.

The acqueous medium may be substantially wholly water or water

SUBSTITUTE SHEET combined with a material which affects the temperature at which a phase change of the medium takes place. Such material may be selected from glycol, sodium chloride, clathrates or the like.

The alumina may be activated by subjecting aluminium hydrate to heat in the equation:-

2A1(0H)₃ = A1₂0₃ + 3H₂0 to derive the activated aluminium oxide which is capable of being associated and disassociated with water by the addition or removal of heat in the presence of water.

The upper temperature limit of the heat exchange medium is preferably below 170°C to ensure that the alumina does not begin to be converted to sintered alumina in which form the desired enthalpy change is absent or reduced.

If the desired temperature range for the medium is in excess of the vaporisation temperature of the acqueous medium the medium may be maintained under pressure to inhibit such vaporisation.

Other materials may be incorporated into the thermal storage medium such as powdered sintered alumina which may be interspersed between the bodies of activated alumina, sintered alumina having a high specific heat, but without the benefit of enthalpy for the medium.

The temperature range may include a temperature at which the mass fuses to thereby obtain further thermal storage benefit arising from the latent heat of fusion.

The invention also provides a thermal storage medium for a thermal storage system comprising activated alumina or aluminium oxide and an acqueous medium intimately associated with the alumina.

The acqueous medium may be in the proportion 10-100% by weight

SUBSTITUTE SHEET of the alumina or, preferably, 20-80% by weight. At low proportions of acqueous medium there is insufficient water for take up by the alumina. At high proportions there is more water than can be taken up by the alumina. But the proportion of acqueous medium will differ according to the temperature range to be utilised.

The alumina may be in divided particulate, granular or spheroidal form having a size in the range 1mm to lOcms, preferably 4mms. Conveniently the alumina is Fl, F200, T60, T162 or CPN alumina obtainable from Aluminium Company of America (Alcoa) and is porous to the water content of the acqueous medium.

According to a further aspect of the invention there is provided a thermal storage system comprising a mass of thermal storage medium enclosed within an envelope container and having heat exchange means whereby heat is exchanged with said mass of thermal storage medium, the thermal storage medium comprising activated alumina or aluminium oxide and acqueous medium in intimate association with the alumina, whereby upon heat exchange with the mass thermal energy is transferred to and from the mass utilising enthalpy in the mass.

Preferably the container is an insulated container for the thermal storage medium and includes conduits for heat exchange fluid material to pass through the thermal storage medium.

The thermal storage medium of the invention has a relatively high specific heat and thermal conductivity. Moreover in raising and lowering the temperature of the medium the thermal storage capacity of the medium is in excess of that expected from a specific heat calculation alone. This is due to the enthalpy arising from chemical changes occurring between the activated alumina and the water content of the medium which results in the exchange of relatively large quantities of heat when a heat exchange is set up. Thus the chemical changes

SUBSTITUTE SHEET result in exothermic and endothermic reactions within the medium.

The chemical changes are wholly reversible at least over certain temperature ranges which means that the medium can be used as a thermal storage medium in which thermal energy is constantly and cyclically added to and substracted from the medium.

The chemistry of the exothermic and endothermic chemical reactions of the medium remains to be fully evaluated but it appears it is connected with the reaction between the activated alumina and the water molecules and it involves ion exchange. It is believed that the exothermic and endothermic reactions occur over a range of temperatures from well below the freezing point of the water. Surprisingly even when the water or other acqueous medium is in solid form the chemical reaction takes place when the medium changes in temperature. The endothermic changes occur at somewhat different temperatures from the exothermic changes but, providing the utilised temperature range involves both reactions, the chemical change is reversed.

The thermal storage medium is chemically non-toxic, plentiful and relatively cheap to obtain.

The thermal storage medium may include only water as the acqueous medium in which case if the temperature range of the heat exchange application covers 0°C the full benefit of using the latent heat of fusion of the water is utilised. By adding other materials to the water the temperature at which fusion takes place can be varied and the most useful temperature range can be obtained. Thus the acqueous medium can be brine to lower the fusion temperature. Glycol can also be added for the same purpose. Other additives which can be useful in this respect include sodium sulphates and clathrates. It will be appreciated that the thermal storage capacity of the medium

SUBSTITUTE SHEET can be improved by the use of such acqueous medium depending on the application, but particularly in cases in which the thermal storage medium is to be used at low temperatures for refrigeration, air conditioning and similar purposes.

In the case of refrigeration a source of heat exchange fluid may be refrigeration means and the fluid acts as a coolant when the thermal storage medium is to be cooled. When the cold in the medium is to be abstracted the coolant or another fluid can be used to remove stored coldness from the medium. This would normally occur when the demand for refrigeration exceeds the capacity of the refrigeration means.

Thus the refrigeration capacity of the refrigeration means may be substantially less tha the maximum refrigeration requirement of the system and such refrigeration requirement is provided for limited periods by the thermal storage system. During periods of low or zero refrigeration requirement the refrigeration means is able to operate to cool the mass of medium to replenish the source of refrigeration. Thus refrigeration means is provided which may be a capacity substantially less than the peak requirement but which is, through the thermal storage medium, able to satisfy peak requirements.

For example a refrigeration plant may have a requirement of say lOOkw for 8 hours in 24 hours, the requirement during the remaining 16 hours being zero. Instead of having a lOOkw capacity refrigeration plant to meet this requirement the plant may have a capacity of 33V3kw and operates for 24 hours i.e. continuously.

During a refrigeration requirement of lOOkw the capacity is provided at 66²/3kw from the thermal storage medium and at 33¹/3kw from the refrigeration plant.

The mass of thermal storage medium may be a combination of

SUBSTITUTE SHEET different materials each of which contributes to providing the desired thermal properties over the range of temperature required. Such materials may be contained in the form of a cell or enclosed body of material through which a heat exchange medium is passed either to cool or to be cooled depending on the mode of operation of the system. During the passage of the heat exchange fluid the thermal storage medium is cooled or warmed and it may change its phase from liquid to solid, or vice versa, and is chemically changed to absorb or give up heat. The different materials of the thermal storage medium may be arranged to provide the necessary changes over different parts of the desired temperature range to enhance the thermal storage characteristics of the system.

Thus a relatively small system with a small mass of materials may provide a relatively large thermal capacity with a relatively high heat"exchange rate. Moreover, the system may be operated within the desired heat exchange and heat storage cycle without the need for high capacity heating or refrigeration means.

The refrigeration or heating means may be operated at efficient, full loads because a lower capacity refrigeration or heating means may be operated at full load and the thermal energy stored, even when the refrigeration or heating requirement is low or non-existent.

The cell or enclosed body of thermal storage medium may be cooled or charged at a position remote from that at which its thermal storage properties are to be used. In this case the heat exchange fluid is passed through the cell at one location having the refrigeration or heating means and, at another location, the cell may be connected to a heat exchange fluid whereby the thermal storage capacity of- the cell is utilised.

The thermal storage medium may be used at the relatively higher temperatures, for example for storage of heat for hot

SUBSTITUTE SHEET water heating purposes. For this purpose materials may be added to the acqueous medium to elevate the temperature at which the acqueous medium may boil or vaporize. Alternatively or in addition the medium may be contained in a pressurised envelope to provide such elevated temperature. As a further alternative the gas or vapour may be allowed to be generated and then contained in a receiver, possibly pressurised, in order to be able to utilise the latent heat of vaporisation and reverse the vaporisation process.

To illustrate the benefit of the invention tests have been conducted and the following is an example:-

Example

A thermal storage medium consisted of 73.64kg of activated alumina saturated and intimately mixed with 36.67kg of water.

The alumina was F200 alumina as supplied by Alcoa.

The water was obtained from public supply in Telford, England.

The activated alumina was in the form of spheroidal alumina having a mean size of 3mm diameter. It had been produced by heating aluminium hydrate to drive off the water according to the equation.

2A1(0H)₃ = A1₂0₃ + 3H₂0 alumina water (aluminium oxide)

The initially dry alumina was intimately mixed with the water in a calorimeter which consisted of an insulated container in which were .laid a series of parallel conduits for heat exchange fluid. The thermal storage medium was located within the container to surround the conduits and heat exchange fluid was passed along the conduits to change the temperature of the medium over the range -20°C to +42°C in thirty hours. During these temperature changes the amount of heat required to bring about the changes in temperature was measured.

The measured heat input to raise the temperature of the alumina/water mixture from -20°C to +42°C in thirty hours was 28.37kw.

This heat input can be compared with the calculated heat requirement for raising the temperature of dry alumina added to the heat requirement for water, through the same temperature range, using the known specific heat of the components and the latent heat of fusion of water. Thus using the following data:-

Specific heat of water below freezing

- 2.095 kj/kg/°C. Specific heat of alumina

- 0.4 kj/kg/°C.

Latent heat of fusion of water

- 335kj/kg.

Specific heat of water above freezing

- 4.187kj/kg/°C .

The total theoretical heat requirement for raising the temperature from -20°C to 0°C is : -

Water 36.67kg x 2.095kj/kg/°C x 20 = 1536.47kj Alumina 73.64kg x 0.4kj /kg/°C x 20 = 589 . 12ki

Total 2125.59kj

The total heat requirement due to the latent heat of fusion is:-

Water 36.67kg x 335 j/kg = 12284.45kj

Alumina NIL

The total theoretical heat requirement for raising the temperature from 0°C to 42°C is:-

Water 36.67kg x 4.187 j/kg/°C x 42 = 6448.57kj Alumina 73.64kg x 0.4kj/kg/°C x 42 = 1237.15ki

SUBSTITUTE SHEET Total 7685.72kj

Therefore the total comparable heat requirement is:- 2125.59 + 12284.45 + 7685.72 = 22095.76kj.

In thirty hours this would require a heat input of 6.137kw.

This compares with an actual heat input requirement of the alumina mixed with water of 28.37kw.

Thus it is shown that 20.233kw of the heat input can be attributed to enthalpy arising from a chemical reaction within the mixture. It has been found that the endothermic/exothermic reversible reaction is not specific to a given temperature but is a continuous heat input/output over the specified temperature range.

Examples of an application of the thermal storage medium in a thermal storage system will now be described with reference to the drawings in which:-

Figure 1 is a sectional plan view of a thermal storage cell, Figure 2 is a sectional side elevation of the cell of Figure

1,

Figure 3 is a schematic diagram showing the incorporation of a thermal storage cell in a thermal storage system,

Figure 4 is a diagram of an alternative thermal storage system,

Figure 5 is a schematic diagram showing the use of a thermal storage cell at a thermal storage charging station, and

Figure 6 is a schematic diagram showing a thermal storage cell when in use at refrigeration location, and

Figure 7 is a perspective view of a further form of thermal storage cell.

Referring to the drawings and firstly to Figures 1 and 2 a thermal storage cell 10 is shown which may be of a size

SUBSTITUTE SHEET according to the thermal storage capacity required. Moreover the cell may be associated with other cells in a series or parallel arrangement to provide flexibility. The cell 10 is an insulated enclosure having insulated sides 11 and the enclosure contains a plurality of serpentine or embossed plate coils 19 for heat exchange fluid, which coils are series or parallel connected.

The spaces between the walls 11 and the coils 19 are filled with particulate, granular or spheroidal activated alumina 15. Sintered alumina or other suitable material of smaller size, such as powder, may fill the spaces between the bodies of activated alumina. Water on its own or water and phase change material, such as sodium chloride, is added to saturate the alumina so as to be in intimate contact with the alumina.

The coils 19 are supported side by side and embedded in the alumina and acqueous medium, and in the illustrated arrangement the coils are connected in parallel to common headers 17 and 18 for reverse return to balance flows, or the coils may be connected in series to one another.

Thus the cell provides a thermal storage unit in which thermal storage medium comprising the alumina and the acqueous medium is cooled or heated by passage of the heat exchange fluid through the coils acting as a coolant. The cell after charging can then be used as a source of cooling or heating capacity by passing heat exchange fluid therethrough to remove the charge from the medium.

Referring now to Figure 3 a cell 10 is shown in an installation including refrigeration means 20 communicating with the cell 10 to pass coolant around the coils 19. A three-way valve 21 controls the flow of heat exchange fluid through the cell 10, through a heat load 22 and via a pump 23 back to the refrigeration means 20. Operation of the valve 21 enables the installation to operate to cool the cell 10 only

SU_BSTITUTE SHEET and/or to pass coolant through the heat load 22. The refrigeration means 20 may be replaced by a source of heat to heat the storage medium.

Referring to Figure 4 a heat exchange cell 10 is incorporated into a chiller 30 and primary refrigerant is used for transferring heat to the cell 10. ^* A flooded type heat exchanger 31 is added to enable cooling to take place i the thermal storage medium 15, and the exchanger 31 is connected in series with an evaporator 32. Changeover valves 33 enable a refrigeration compressor 34 to cool the cell during charging. By this means the system has increased efficiency. Fluids such as glycol are not required in the secondary coolant circuit if the application of the system does not require it, for example if the system is providing chilled water at +5°C.

Referring now to Figures 5 and 6 an installation is shown in which the cell 10 is charged at a location different from the location at which its heat storage capacity is utilised. In Figure 5 the cell is connected to refrigeration means or heat generation means 20 through releasable connectiions 25 whereby coolant or heating fluid is passed through the cell by a pump 23.

After release of the connections 25 the cell 10 may be moved to the other location, Figure 6, at which the cell is connected releasably to a load 22 which requires to be cooled or heated and heat exchange fluid is passed from the cell through the load by a pump 26 transferring heat or cold from the load to the cell.

The location at which the cooling or heating effect of the cell is utilised may be remote^* from the refrigeration or heating means 20 in an inaccessible place.

The releasable connections will incorporate suitable self- closing valves for retaining the heat exchange fluid when the cell is disconnected.

After depletion of the cooling or heating effect of the cell the cell is recharged at the refrigeration location.

It will be appreciated that the heat storage medium of the invention may be located and arranged in a different manner to that described with provision for a heat exchange fluid from refrigeration or heating means to cool or heat the medium. A different heat exchange medium may be used to deplete or increase the heat storage capacity of the material simultaneously or at a different time from the cooling or heating operation.

There are many applications of the thermal storage medium in a refrigeration mode^" or in a heating mode.

As an example in the refrigeration mode the thermal storage medium can be used in food storage or processing. In a food storage system, for example in a retail unit, a central refrigeration plant may be utilised. The demand on the refrigeration plant changes between opening and closing hours so the thermal storage medium can be used in a thermal storage system in the central refrigeration plant to store the thermal requirements of the individual refrigeration units in the purchasing areas of the retailing unit.

The supply of coolant for the food refrigeration units is from the thermal storage system and such coolant may be different coolant from that supplied by the refrigeration plant to the storage system.

Referring to Figure 7 the thermal storage medium can also be used in a closed envelope or package 40 as coolant after cooling in a refrigerated location, the package being subjected directly to such refrigeration. Such a cooled

SUBSTITUTE SHEET package would find use as an 'ice pack' for sports injuries or otherwise to provide a long life source of coldness. The package 40 may be insulated over one side at 40A which is the side away from the side to be applied to the injured area. The envelope is made of flexible material to conform to the desired shape.

Such a package 40 can also find application as a heat source, for example in keeping food hot.

Claims

1. A method of storing thermal energy which comprises passing fluid in heat exchange relationship through a mass of thermal storage medium including activated alumina or aluminium oxide combined with an acqueous medium at a temperature whereby to cause the water content of the acqueous medium to be associated with and disassociated from the activated alumina in an enthalpy change.

2. A method according to claim 1 wherein the temperature of the medium is in the range up to 200°C

3. A method according to claim 1 or 2 wherein the acqueous medium includes water constituting up to 100% by weight of the activated alumina.

4. A method according to claim 3 wherein the water constitutes up to 70% by weight of the activated alumina.

5. A method according to claim 1, 2 , 3 or 4 wherein the acqueous medium includes phase change material whereby the temperature at which a phase change of the water takes place is altered.

6. A method according to claim 5 wherein the phase change material is selected from glycol, sodium chloride and clatherate.

7. A method according to any one of the preceding claims wherein the activated alumina is formed by subjecting aluminium hydrate to heat in the equation:-

2A1(0H)₃ = A1₂0₃ + 3H₂0 whereby the activated alumina is aluminium oxide having the facility to be associated or disassociated with water by the addition or removal of heat.

8. A method according to any one of the preceding claims wherein the temperature range includes one or both of the

SUBSTITUTE SHEET fusion and vaporisation phase changes.

9. A method according to any one of the preceding claims wherein the activated alumina is in divided particulate, granular or spheroidal form having a size in the range 1mm to lOcms.

10. A thermal storage medium for a thermal storage system which medium comprises activated alumina and an acqueous medium intimately associated with the activated alumina.

11. A medium according to claim 10 wherein the acqueous medium is in the proportion 10-100% by weight of the activated alumina.

12. A medium according to claim 10 or 11 wherein the activated alumina is in divided particulate, granular or spheroidal form having a size in the range 1mm to 10cms.

13. A medium according to claim 10, 11 or 12 comprising sintered aluminium interspersed within the activated alumina to occupy the spaces between the bodies of activated alumina.

14. A medium according to any one of claims 10-13 wherein the acqueous medium includes a phase change material whereby the fusion and/or vaporisation temperature of the medium is changed.

15. A thermal storage system which comprises a mass of thermal storage medium enclosed within an envelope or container and having heat exchange means whereby heat is exchanged with the mass of thermal storage medium, the thermal storage medium comprising activated alumina and acqueous medium in intimate association with the activated alumina, whereby upon heat exchange with the mass thermal energy is transferred to and from the mass utilising enthalpy in the mass.

SUBSTITUTE SHEET 1~-

16. A thermal storage system according to claim 15 wherein the container is an insulated container for the thermal storage medium and includes conduits for heat exchange fluid material to pass through the thermal storage medium.

17. A system according to claim 16 wherein fluid in the conduits communicates with a source of thermal energy to heat or cool the thermal storage medium.

18. A system according to claim 15, 16 or 17 wherein the container is chargeable with thermal energy at a location remote from its discharge location.

19. A system according to any one of claims 16-18 wherein the container has releasable inlet and outlet connections for the admission of heat exchange fluid to the conduits.

20. A system according to claim 17 wherein the source of thermal energy is refrigeration means and the primary refrigerant is passed through said conduits.

21. A thermal storage system substantially as described with reference to the drawings.