The present invention relates to a thermochemical device for producing refrigeration at very low temperature.
A system composed of a thermochemical dipole using two reversible thermochemical phenomena is a known means for producing refrigeration. The thermochemical dipole comprises an LT reactor, an HT reactor and means for exchanging a gas between LT and HT. The two reactors are the site of reversible thermochemical phenomena chosen so that, at a given pressure in the dipole, the equilibrium temperature in LT is below the equilibrium temperature in HT.
The reversible phenomenon in the HT reactor involves a sorbent S and a gas G and may be:
The thermochemical phenomena currently used enable refrigeration to be produced at a negative temperature in LT, but they do not fulfill the above criteria with the objective of producing refrigeration at very low temperature (Tf typically from −20° C. to −40° C.) for long-lasting foodstuff preserving and freezing applications from a heat source, with the thermal potential of which is around 60 to 80° C., the heat sink generally composed of the ambient medium being at a temperature To of around 10° C. to 25° C. These phenomena either require, during the regeneration, a temperature Tc well above 70° C. to operate with a heat sink at the ambient temperature To, or they require a heat sink at a temperature below To if a heat source at Tc=60-80° C. is used.
For example, to produce refrigeration at −30° C. using a heat source at 70° C., when LT is the site of an L/G phase change of ammonia NH3, and HT is the site of a chemical sorption of NH3 by a reactive solid S: if S is BaCl2, a heat sink at 0° C. would be needed for the reactor LT during the refrigeration production step, whereas if S is CaCl2, a heat sink at −5° C., that is to say at a temperature well below To, would be needed during the regeneration step.
Solar energy or geothermal energy are advantageous heat sources, but they supply heat at a low temperature level which is not, in general, above 60-70° C. when a low-cost collection technology is used, such as for example flat collectors conventionally used for producing domestic hot water. The use of these types of energy consequently does not enable the intended aim to be achieved.
The inventors have now found that it was possible to produce refrigeration at a temperature Tf below −20° C. from a heat source at a temperature Th between 60 and 80° C., and from a heat sink at the ambient temperature To varying from 10° C. to 25° C., by combining two dipoles D1 and D2 so that:
The object of the present invention is consequently to provide a method and a device for producing refrigeration at a temperature Tf below −20° C., from a heat source at a temperature Th of around 60-80° C. and from a heat sink at the ambient temperature To of around 10° C. to 25° C.
a and 1b illustrate the method for producing refrigeration according to the first embodiment.
a and 2b illustrate the method for producing refrigeration according to the second embodiment.
The device for producing refrigeration according to the present invention comprises a refrigeration-producing dipole D2 and an auxiliary dipole D1, and it is characterized in that:
In the remainder of the text, the expressions “the elements” of a dipole will be used to denote both the reactor and the evaporator/condenser of the dipole.
As an example of thermochemical phenomena used in the present invention, mention may be made of the L/G phase change of ammonia (NH3), of methylamine (NH2CH3) or of H2O in the evaporators/condensers. For the reactors, mention may be made of:
The method for producing refrigeration at the temperature Tf from a heat source at the temperature Th and from a heat sink at the ambient temperature To consists in operating the device according to the invention from an initial state in which the dipole D2 is in the regenerated state, and the dipole D1 is to be regenerated, the two elements of a given dipole being isolated from one another, said method comprising a series of successive cycles made up of a refrigeration production step and a regeneration step;
In this method, the dipoles therefore operate in phase opposition: one of the dipoles is in a phase of gas absorption in the sorbent, whereas the other is in a phase of gas desorption by the sorbent.
The various steps may be carried out continuously or on demand. At the beginning of one step, the elements of one and the same dipole must be connected, so that the thermochemical phenomena can occur. In order to operate the device continuously, it is sufficient to supply, at the end of one step, the appropriate amount of heat to the appropriate reactor to start the following step. If the device is intended to be operated in batch mode, it is sufficient to isolate the elements of each dipole by insulation means, at the end of a refrigeration production step or a regeneration step.
The method may be implemented permanently if the heat at the temperature Th is available permanently, for example if it is geothermal energy. The operation will be in batch mode if the heat source is not permanent, for example if it is solar energy whose availability varies throughout a day.
In a first embodiment, the coupling of the dipoles is carried out thermally between the evaporator/condenser EC1 of the dipole D1 and the evaporator/condenser EC2 of the dipole D2, and the thermochemical phenomena are chosen such that, in this coupling phase, T(EC1)<T(EC2)<T(R1)<T(R2). In this case, G1 and G2 are different.
The thermal coupling between EC1 and EC2 may be carried out, for example, by a coolant loop, by a heat pipe or by direct contact.
The method of this first embodiment is characterized in that, during the second step, the evaporators/condensers EC1 and EC2 are thermally coupled, and at the same time heat at the temperature Th is supplied to the reactor R2 to cause the endothermic desorption of G2 in R2 and the exothermic condensation of G2 in EC2, the heat generated in EC2 being transferred to the reactor EC1, which causes an endothermic evaporation of G1 in EC1 and a concomitant exothermic absorption of G1 by S1 in R1.
In this embodiment, the device produces refrigeration at the temperature Tf during the refrigeration production step of the dipole D2 concomitant to the regeneration step of the auxiliary dipole D1.
During the regeneration step of the dipole D2, refrigeration may be produced at the temperature Ti below To in EC1 by the dipole D1, if the heat required during this step for the evaporation phase in EC1 is greater than the heat supplied by the condensation phase in EC2.
The method for producing refrigeration according to the first embodiment is illustrated in the
During the refrigeration production step, the evaporation of G2 in EC2 (point E2 of the straight line 3) extracting heat from the ambient medium to be cooled at Tf therefore produces refrigeration at this temperature. Gaseous G2 thus produced is transferred into R2 to be absorbed by S2 releasing heat at a temperature above the ambient temperature To (point R2S on the straight line 2). At the same time, a supply of heat at the temperature Th to R1 (point R1D on the curve 1) causes the release of G1 which is transferred into EC1 for the condensation of G1 (point C1 on the curve 0), releasing heat into the environment at To.
During the regeneration step of the dipole D2, which corresponds to the regeneration step of the device, heat at the temperature Th is supplied to R2 (point RD2 on the straight line 2) which releases gaseous G2 that will be condensed in EC2 (point C2 on the straight line 3) by releasing heat at the temperature Ti, said heat being transferred toward EC1 in order to trigger therein the release of gas G1 (point E1 on the curve 0), said gas G1 flowing into R1 for the synthesis step (point R1S on the curve 1). If the heat supplied by EC2 to EC1 is insufficient to release all the gas in EC1, the heat is extracted from the environment, which will produce refrigeration at the temperature Ti below the ambient temperature.
In a preferred form of the first embodiment, each of the elements EC is composed of an assembly comprising an evaporator E and a condenser C connected by a line enabling the flow of gas or liquid. Furthermore, in order to limit the heat losses and to improve the efficiency of the regeneration of the dipole D1, the elements involved in the thermal coupling, that is to say E1 and C2, are thermally isolated from the ambient medium.
In a second embodiment, the two dipoles operate with the same gas G. In this embodiment, the dipoles D1 and D2 of the device according to the invention are coupled, during the regeneration phase of the dipole D1, by a mass coupling which allows the flow of gas between the reactor R1 of the dipole D1 and the reactor R2 of the dipole D2 on the one hand, and between the evaporators/condensers EC1 and EC2 on the other hand. Moreover, the thermochemical phenomena are chosen so that T(EC1)=T(EC2)<T(R1)<T(R2).
The method for producing refrigeration according to this second embodiment is characterized in that, at the beginning of the second step, the connection between EC2 and R2 is stopped, and R1 and R2 are connected, and at the same time heat at the temperature Th is supplied to the reactor R2, which causes the endothermic desorption of G by S2 in R2, and by cooling the reactor R1, which causes absorption of the gas G in R1. Cooling may be carried out by using coolant circuits. Cooling may also be controlled by external conditions, for example by natural nighttime cooling, in the absence of the sun.
During the method, EC1 and EC2 are connected to make G flow in liquid form from EC1 toward EC2. This operation may be carried out during an additional step. It may, in addition, be carried out during the first or the second step, if the device comprises an expansion valve on the line connecting EC1 and EC2.
The method for producing refrigeration of this second embodiment is illustrated in the
During the refrigeration production step, the evaporation of G in EC2 (point E of the straight line 0) extracts heat at Tf from the ambient medium and produces refrigeration at this temperature. Gaseous G thus released is transferred into R2 for the synthesis step with S2 releasing heat at a temperature above the ambient temperature To (point R2S on the straight line 2). At the same time, a supply of heat at the temperature Th to R1 (point R1D on the curve 1) causes the release of G which is transferred into EC1 for the condensation of G (point C on the curve 0), releasing heat into the environment at To.
During the regeneration step, heat at the temperature Th is supplied to R2 (point R2D on the straight line 2) which releases gaseous G that is transferred into R1 for the synthesis with S1 (point R1S on the line 0).
The present invention is illustrated by the following examples, to which it is not however limited.
This example illustrates a device for producing refrigeration, in which the dipoles interact by a thermal coupling. Each of the elements EC is composed of a condenser and an evaporator connected by a line enabling the flow of gas or liquid, and denoted by C1, C2, E1 and E2. A schematic representation of the device is given in
In accordance with
R1 is the site of a reversible chemical sorption of methylamine (gas G1) on CaCl2.2NH2CH3 (the reactive solid S1), C1 and E1 being the site of a condensation/evaporation phenomenon of methylamine (the gas G1). R2 is the site of a reversible chemical sorption of NH3 (the gas G2) on CaCl2.4NH3 (the solid S2), C2 and E2 being the site of a condensation/evaporation phenomenon of the gas NH3.
The thermochemical phenomena are as follows:
The operation of the device comprising these reactants is represented in
The parts of the device that are active during the refrigeration production step are represented in
The parts of the devices that are active during the regeneration step of the device are represented in
Such a device enables refrigeration to be produced at a temperature Ti halfway between To and Tf during the regeneration step of the device. For example, referring to
This example illustrates a device for producing refrigeration, in which the dipoles interact by mass coupling. EC1 and EC2 are respectively a condenser C1 and an evaporator E2. A schematic representation of the device is given in
In accordance with
R1 and R2 are connected by a line which is placed before the valves 11 and 12, and which is equipped with a valve 8. C1 is connected by a line to a reservoir which is itself connected to E2 by a line equipped with an expansion valve 9 which may be, for example, controlled and activated by a drop in the pressure or liquid level in E2.
The active parts of the device during the refrigeration production step are represented in
The active parts of the device during the regeneration step are represented in
Such a device may be implemented using ammonia as gas G, CaCl2.4NH3 as solid S2 in R2 and BaCl2 as solid S1 in R1.
The thermochemical phenomena are as follows:
NH3(gas)⇄NH3(liquid)
(CaCl2.4NH3)+4NH3⇄(CaCl2.8NH3)
(BaCl2)+8NH3⇄(BaCl28NH3)
The operation of the device comprising these reactants is represented in
The refrigeration production step is embodied by the positions 1 and 2 of the dipoles D1 and D2. D1 is in regeneration phase due to the introduction of available heat at the temperature Th of around 70° C., to cause the decomposition of (BaCl2.8NH3) in R1 with release of NH3 which will be condensed in C1 releasing heat into the heat sink constituted by the surroundings at To=25° C. Concomitantly, D2 is in refrigeration production phase, extracting heat from the medium to be cooled to a temperature Tf of around −30° C.
The regeneration step of D2 is embodied by the position 3. The supply of the available heat at the temperature Th of around 70° C. causes the decomposition of (CaCl2.8NH3) releasing NH3, which is transferred into R1 to cause therein the synthesis of BaCl2.8NH3. At this stage, the reactors R1 and R2 are in the state required for a regenerated device, and the opening of the valve 9 enables C1 and E2 to be put into the required state for complete regeneration of the device.
Number | Date | Country | Kind |
---|---|---|---|
04 11766 | Nov 2004 | FR | national |
Filing Document | Filing Date | Country | Kind | 371c Date |
---|---|---|---|---|
PCT/FR2005/002748 | 11/4/2005 | WO | 00 | 10/9/2007 |
Publishing Document | Publishing Date | Country | Kind |
---|---|---|---|
WO2006/048558 | 5/11/2006 | WO | A |
Number | Name | Date | Kind |
---|---|---|---|
4623018 | Takeshita et al. | Nov 1986 | A |
4944159 | Crozat | Jul 1990 | A |
5083607 | Lebrun et al. | Jan 1992 | A |
5174367 | Nasako et al. | Dec 1992 | A |
5351493 | Hiro et al. | Oct 1994 | A |
5857346 | Goetz | Jan 1999 | A |
Number | Date | Country |
---|---|---|
WO 9740328 | Oct 1997 | WO |
WO 2005108880 | Nov 2005 | WO |
Number | Date | Country | |
---|---|---|---|
20090094996 A1 | Apr 2009 | US |