WO2018162614A1 - Use of mof in a system for cooling/heating by adsorption for a thermal battery - Google Patents

Abstract

The invention relates to a trithermal method or system for cooling/heating by adsorption for a thermal battery, based on MOF as a solid adsorbent, in certain specific operating ranges. The invention also relates to air-conditioning or refrigerating systems that implement the method or comprise the system according to the present invention.

Description

 USE OF MOF IN A COOLING / ADSORPTION HEATING SYSTEM

 FOR THERMAL BATTERY Field of the invention

 The present invention relates to a trithermal adsorption cooling / heating method for a thermal battery based on MOF as a solid adsorbent in certain specific operating ranges.

The invention also relates to air conditioning or refrigeration systems, implementing the method or comprising the system according to the present invention.

State of the art

 The principles of operation of cold machines using solid adsorbents in a trithermal (closed) system are known. For example, the companies Vaillant, Viesman, Sortech, Mycon market such type cold machines.

If we consider a trithermal adsorption system, with the internal temperature To at which the evaporation is produced cold Qo, T _c the intermediate temperature heat rejection Q _c (condensation and adsorption), and finally the inner temperature TA of the hot source which provides Q _g for the regeneration of the adsorbent.

The efficiency of the process is determined by the amount of refrigerant vapor that can be reversibly exchanged between adsorption and desorption (coefficient of performance, "COP" or "coefficient of performance" in English) and the cycling time covering the phases. of adsorption and regeneration (or desorption) (specific cooling power: "SCP" or "specifies cooling power"). See Figure 1.

 Thus, the efficiency of the thermal transformation process is expressed:

 (i) By the coefficient of performance (COP)

COP ⁼ Qo / Qg ⁼ QEvaporation / QDsorption

COP is directly related to the cyclized (adsorbed-desorbed) fluid mass variation in the trithermal cycle. In general, the fluids that offer the best potential are those with high latent heat / heat of vaporization such as water and short alcohols (methanol, ethanol). (i) By the power of the machine which is expressed in terms of specific cooling capacity (SCP) by volume (V) or weight (m) of the device (device = adsorbent + adsorber)

 SCP = 1 / V x Qo / t

or

 The SCP is directly related to the speed of the transfer phenomena, ie. the transfer of material (time required for the phenomenon to occur, the rate of transport of the fluid in the adsorbent is an element) and heat transfer (time required for the transfer of heat quantities from one element to another, whose rate of conduction / convection of heat is an element).

The performance (SCP) of a cold machine can be limited by:

 1) the small amount of cycled refrigerant in a cycle (eg silica gel as adsorbent) = COP

2) the low adsorption / desorption kinetics of the refrigerant in the adsorbent (eg silica gel ("silica gel" in English)) - material transport

3) the poor quality of heat transfer = heat conduction of the adsorbent and the adsorber and its interface. To minimize the thermal loads or the size of the cold-machine devices, adsorbents with high adsorption capacity under operating conditions, as well as fast adsorption and desorption kinetics, are required. Thus, the adsorbent and the configuration of the adsorber have a significant impact on performance.

The adsorbent commonly used is silica gel ("silica gel" in English). It is a poorly performing adsorbent, i.e. at low COP. The disadvantage of silica gel in terms of process efficiency is its relatively low cycling capacity during adsorption / desorption cycles which requires large amounts of silica gel. This leads to large devices with relatively low power (SCP) and efficiency (COP) values. (J. Bauer et al., J. Energy Res 2009; 33: 1233-1249 [1]). The application of MOFs (metal-organic material, or "Metal Organic Framework" in English), which are porous coordination polymers, in particular Basolite A520, in cold machines has been mentioned in EP2230288 [2] and EP2049549

[3].

However, MOFs are not equivalent in all possible applications for adsorption cooling / heating systems. In particular, some MOFs are not fully adapted to certain types of cooling / heating (eg air conditioning systems), depending on their adsorption characterization (IUPAC classification isotherm profile), temperatures and pressures partial steam operation.

 There is therefore a need to develop trithermal cold adsorption cooling / heating processes and systems which are perfectly optimized, that is to say which allow the optimization of the following three criteria:

 1) quantity of refrigerant cycled in a cycle (COP) 2) kinetics of adsorption / desorption of the refrigerant in the adsorbent

3) heat transfer quality = heat conduction between the adsorbent and the adsorber.

Description

 The present invention responds precisely to this need by selecting certain particular MOFs for association with particular modes of operation of trithermal adsorption cooling / heating processes and systems, thereby enabling optimized operation of these methods / systems.

In one aspect, the present invention relates to a trithermal closed thermal adsorption cooling / heating method or system comprising: at. a refrigerant (F) consisting of water;

b. a condensation module (C) of said refrigerant (F), in thermal connection with a coolant circuit (CWi-medium) whose temperature of the coolant at the outlet of the circuit is T _c ^ext ;

vs. an evaporation module (E) of said refrigerant (F), in thermal connection with a coolant circuit (CWi-low) whose temperature of the coolant at the outlet of the circuit is T _e ^ext ;

 d. at least one adsorption / desorption module (AD) containing a solid adsorbent (A) consisting of a porous hybrid metallo-organic material (MOF) selected from di-, tri- or tetra-carboxylate MOFs, the modulus of adsorption / desorption

(AD) alternately in fluid connection with said condensation module (C) and said evaporation module (E), which MOF material can adsorb or desorb the refrigerant (F) depending on the adsorption / desorption module (AD ) is in fluid connection with the evaporation module (E) or condensation module (C), respectively, and according to the temperature TMOF to which the MOF material is subjected; characterized in that the system is operated alternately in adsorption / desorption mode according to the following operating parameters: in adsorption mode: the adsorption / desorption module (AD) is in fluid connection with the evaporation module (E) at an internal evaporation temperature T _e ;

- 0 ° C <T _e <15 ° C;

the MOF material is subjected to a temperature TMOF = T _C where T _C = T _E + 35 ° C.

± 5 ° C; and

0.05 <pe / _her p t (e) ≤ 0, 1 1; more preferably pe / p _S at (e) = 0.08;

in which :

p _e represents the pressure of the refrigerant (F) in the gas phase in the evaporation module (E); Psat (e) represents the saturation vapor pressure of the refrigerant (F) at the adsorption temperature thereof by the porous hybrid metallo-organic material;

and pe / _her p t (e) represents the ratio between the evaporation pressure of the refrigerant fluid (F) in the evaporation unit (E) and the saturation pressure in the refrigerant adsorption temperature (F) the porous hybrid metallo-organic material (or the relative humidity value). This ratio is also called the relative evaporation pressure (with respect to the saturation pressure in the adsorber); in desorption mode: the adsorption / desorption module (AD) is in fluid connection with the condensation module (C) at an internal condensing temperature T _c ;

 the MOF material is subjected to a temperature TMOF = Tr = Tc + (Tc-Te + 10 ° C) ± 5 ° C;

0.05 <pe / _her p t (e) ≤ 0, 11; more preferably pe / p _its t (e) = 0.08; and

in which :

p _c represents the pressure of the refrigerant (F) in the gas phase in the condensation module (C);

 Psat (c) represents the saturation vapor pressure of the refrigerant (F) at the desorption temperature thereof of the porous hybrid metallo-organic material.

and pc / p _S at (c) represents the ratio of the condensing pressure of the refrigerant (F) in the condensation module (C) and the saturation pressure of the refrigerant (F) to the desorption temperature of the metallo material -organic hybrid porous (or relative humidity). This ratio is also called the relative pressure of condensation (relative to the saturation pressure in the desorber);

In the following :

T _e refers to the internal evaporation temperature (ie, within the evaporation module (E)). The temperature Te can be controlled by means of a valve between the evaporator and the adsorber which makes it possible to regulate the flow of refrigerant between the evaporator and the adsorber (FIG. 3) or via the Evaporator supply valve (Figure 4). T _e ^ext refers to the temperature of the heat transfer fluid at the outlet of the coolant circuit (CWi-low) passing through the evaporation module (E). The difference between T _e and T _e ^ext is related to the efficiency of the heat exchanger in the evaporation module (E), and responds to the applicable thermodynamic laws (heat transfer coefficient, exchange surface, etc.). . Generally, the difference Te ^ext- Te is of the order of 2 to 5 ° C depending on the quality of the evaporator.

T _c refers to the internal temperature of condensation (ie, inside the condensation module (C)).

T _c ^ext refers to the temperature of the heat transfer fluid at the outlet of the coolant circuit (CWi-medium) passing through the condensation module (C). The difference between T _c and T _c ^ext is related to the efficiency of the heat exchanger in the condensation module (C). Generally, the difference Tc-Tc ^ext is of the order of 2 to 5 ° C depending on the quality of the condenser.

Advantageously, the solid adsorbent (A) consisting of a porous hybrid metallo-organic material (MOF) is chosen from aluminum, zirconium di-, tri- or tetracarboxylate MOFs.

 The heat transfer fluid of each of CWi-medium and CWi-low circuits can be any suitable heat transfer fluid known to those skilled in the art. Advantageously, the coolant of each of the CWi-medium and CWi-low circuits may be water or an aqueous solution, optionally containing one or more additives such as glycols; or air. Advantageously, the heat transfer fluid may be an aqueous solution such as a conventional cooling fluid for a heat engine. Typically, a coolant contains additives such as glycols. Advantageously, the adsorption / desorption operating parameters are as follows:

in adsorption mode: the adsorption / desorption module (AD) is in fluid connection with the evaporation module (E) in the absence of any non-adsorbable inert gas by the porous hybrid metallo-organic material (essentially, the air); the presence of gas non-adsorbable can create a plug capable of blocking the adsorption of the refrigerant (F) by the porous hybrid metallo-organic material;

- 0 ° C <T _e <15 ° C;

MOF material is subjected to a temperature TMOF = T where _C T = _C T _E + 35 ° C ± 5 ° C; and

0.05 <pe / _her p t (e) ≤ 0, 1 1; more preferably pe / p _its t (e) = 0.08; in desorption mode: the adsorption / desorption module (AD) is in fluid connection with the condensation module (C) in the absence of any non-adsorbable inert gas by the porous hybrid metallo-organic material (essentially air ); the presence of non-adsorbable gas can form a plug capable of blocking the condensation of the refrigerant (F) in the condensation module (C); the MOF material is subjected to a temperature TMOF = Tr = Tc + (Tc-Te + 10 ° C) ± 5 ° C;

0.05 <pe / _her p t (e) ≤ 0, 1 1; more preferably pe / p _its t (e) = 0.08; and

Advantageously, in the desorption mode, the MOF adsorbent can be regenerated (ie, subjected to the temperature TMOF = Tr = Tc + (Tc-Te + 10 ° C.) ± 5 ° C. by a heat source (for example, heat fatalities of different origins such as thermal battery, solar panels, electrical circuit etc ...) For example, it may be: recovery of fatal heat, for example on independent electric heat engines by an external circuit, for example example using electric resistors

 embedded fuel cell

 thermal heat from solar panels

Advantageously, the system is implemented so that the AD module is alternately put in adsorption then desorption mode. Advantageously, the system may contain a single module alternately serving as a condensation module (C) and an evaporation module (E). See Figure 3 for an example embodiment.

 Advantageously, the system may contain a condensation module (C) and a separate evaporation module (E). See Figure 4 illustrating a mode of implementation.

Advantageously, the system can contain two adsorption / desorption modules (AD) and (AD '), each alternately in fluid connection with the condensation (C) and evaporation (E) modules, so that when (AD) is in fluid connection with the condensation module (C) while (AD ') is in fluid connection with the evaporation module (E), and vice versa. An example of configuration of such a system in which the coolant is for example water, is shown in Figure 5.

Advantageously, in any one of the preceding variants, the refrigerant (F) may be water.

 The term "thermally connected" as used herein refers to a connection means for the exchange of heat between the elements to which it refers. For example, it may be a connection means for heat exchange between the condensation module (C) and the coolant circuit (CWi-medium) or between evaporation module (E) and the coolant circuit (CWi-low). For example, the thermal connection can be made via a heat exchanger. Alternatively, the thermal connection can be made by passing the heat transfer fluid circuit in the condensation module (C) or the evaporation module (E), thus allowing the transfer of the heat released in the condensation module (C) in the heat transfer fluid circuit therethrough, or conversely allowing the transfer of the heat absorbed into the evaporation module (E) in the heat transfer fluid circuit passing therethrough. The coolant may be any suitable coolant known to those skilled in the art, for example water or an aqueous solution, optionally containing one or more additives such as glycols; or air.

The term "fluid connection" as used herein refers to a connection means for the transfer of refrigerant between the elements. to which he refers. For example, it may be a connection means for the transfer of refrigerant vapor from an adsorption / desorption module (AD) to the condensation module (C). It can also be a connection means for the transfer of refrigerant vapor from the evaporation module to an adsorption / desorption module (AD) as shown in FIG. 5. Advantageously, this fluid connection can be controlled by an "all or nothing" valve, which can be either in the closed position (no transfer of refrigerant vapor from one module to another), or in the open position. Alternatively, the fluid connection can be controlled by a controlled variable flow valve (regulator) to control the steam flow during evaporation and thus control the temperature in the evaporator. It will be said that one module is in fluid connection with another when the valve or valve connecting them is open (transfer of refrigerant vapor from one module to another). Advantageously, when the system has two modules (AD) and (AD '), the two adsorption / desorption modules can contain the same solid MOF adsorbent. In this case, advantageously, the two adsorption / desorption modules are simultaneously but separately in fluid connection with the condensation module (C) and the evaporation module (E). In other words, when the first adsorption / desorption module AD is in fluid connection with the condensation module (C), then the second adsorption / desorption module AD 'is simultaneously in fluid connection with the evaporation module ( E).

An advantage of the MOFs used in the context of the present invention over conventional adsorbents is that they can be regenerated at lower temperatures. Advantageously, in desorption mode, the MOF adsorbent may be subjected to a temperature TMOF such that TMOF = Tr = Tc + (Tc-Te + 10 ° C.) ± 5 ° C., where Tr represents the high range of the temperature at which the MOF is regenerated (ie it desorbs the refrigerant molecules). Of course, Tr will be below the temperature at which the MOF is likely to decompose or degrade. The value of Tr depends on the MOF used as well as the operating conditions. Typically, a temperature Tr of at least 75 ° C. will make it possible to regenerate the MOFs that may be used in the context of the present invention. Advantageously, Tr may be between 60 ° C and 120 ° C, preferably between 70 ° C and 100 ° C, more preferably between 75 ° C and 90 ° C. Advantageously, the MOF used as adsorbent (A) will be adapted to the fatal heats of the system concerned. For example, if it is a heat engine, the MOF adsorbent will preferably be stable at 90-100 ° C. (in fact, typically, the cooling fluid of a heat engine generally has a temperature below 110 ° C, most often 90 to 100 ° C, when the engine is hot). For example, zirconium fumarate MOFs, such as MOF-801, or aluminum MOF furanedicarboxylates, such as MIL-160 are suitable for this type of application.

Advantageously, when the adsorption / desorption module (AD) (or one of the adsorption / desorption modules when the system comprises two) is in desorption mode, the heat source, at Tmax, for heating the material MOF at temperature T _max >TMOF> T _c is chosen from fatal heats, for example on heat engines, independent electric heating, and / or solar panels. Advantageously, in desorption mode, TMOF = Tr = Tc + (Tc-Te + 10 ° C.) ± 5 ° C.

 Advantageously, the thermal connection between the refrigerant (F) and the coolant circuits (CWi-medium) and (CWi-low) of the condensation and evaporation modules, respectively, is provided by a heat exchanger (ET). Advantageously, the heat transfer fluid of each of CWi-medium and CWi-low circuits may be water, or air. MOF material

 Porous hybrid metallo-organic (MOF) materials are known, and are described for example in U.S. 5,648,508, EP-A-0790253, M. O'Keeffe et al, J. Sol. State Chem, 152 (2000), page 3-20 H. Li et al, Nature 402 (1999), page 276 M. Eddaoudi et al, Topics in Catalysis 9 (1999), pp. 105-111 B. Chen et al, Science 291 (2001), DE-A-101 11 230, DE-A 10 2005 0534, WO-A 2007/054 581, WO-A

2005/049892 and WO-A 2007/023134.

Advantageously, the MOF material used as solid adsorbent (A) is chosen from aluminum or zirconium di-, tri- or tetracarboxylate MOFs having an S-shaped water adsorption isotherm (Type V such that classi fi ed by IUPAC, Pure & Appl Chem., vol 57, No. 4, 603-619, 1985) characterized in that the adsorption isotherm has the greatest slope at the relative humidity value p / p _its t between 0.05 and 0.11. Advantageously, the MOF material used as solid adsorbent (A) is chosen from aluminum or zirconium di-, tri- or tetracarboxylate MOF having an S-shaped water adsorption isotherm, characterized in that isotherm adsorption exhibits the greatest slope at the relative humidity value p / p _its t = 0.08. The advantage of MOFs which exhibit an S-isotherm at a relative pressure of between 0.05 and 0.11 is that for a given value of Tc-Te compatible with the relative pressure of the S-curve (typically 35 ° C. ), they make it possible to operate at a lower regeneration temperature than the adsorbents having a classic I type isotherm according to the IUPAC classification.

The MOF material used as solid adsorbent (A) may be prepared according to any known process for the preparation of di-, tri- or tetracarboxylated MOF, for example under hydrothermal or solvothermal conditions, in the microwave, or in the presence of a cylinder crusher.

The corresponding protocols are those known to those skilled in the art. Nonlimiting examples of protocols that can be used for hydrothermal or solvothermal conditions are described, for example, in K. Byrapsa, et al. "Handbook of Hydrothermal Technology," Noyes Publications, Parkridge, New Jersey USA, William Andrew Publishing, LLC, Norwich NY USA, 2001 [7]. For the microwave synthesis, nonlimiting examples of usable protocols are described for example in G. Tompsett, et al. ChemPhysChem. 2006, 7, 296 [8]; in S.-E. Park, et al. Catal. Survey Asia 2004, S, 91 [9]; in CS Cundy, Collect. Czech. Chem. Common. 1998, 63, 1699 [10]; or in SH Jhung, et al. Bull. Kor. Chem. Soc. 2005, 26, 880 [11]. The hydrothermal or solvothermal conditions, whose reaction temperatures can vary between 0 and 220 ° C, are generally carried out in glass (or plastic) containers when the temperature is below the boiling point of the solvent. When the temperature is higher or when the reaction is carried out in the presence of fluorine, Teflon bodies inserted into metal bombs are used [7]. Advantageously, the MOF material used as solid adsorbent (A) is in a form having an improved surface area and / or adsorption capacity, for example in the form of micron powders, especially in the form of micron powder of homogeneous size.

 By "micronic" is meant a particle of size less than lmrnr

Nonlimiting examples of protocols that can be used for the preparation of MOF in the form of micron powders are described for example in WO 2009/77670. Thus, the MOF material used as solid adsorbent (A) can be prepared according to a process comprising the steps of:

 A) mixture in a polar solvent system:

 (i) at least one inorganic metal precursor in the form of a metal M, a metal salt M or a coordination complex comprising the metal ion

M ^{z +} ;

 (ii) at least one precursor ligand The aliphatic or aromatic organic di-, tri- or tetra-dentate comprising 1 to 18, preferably 1 to 10 carbon atoms and comprising 2, 3 or 4 groups capable of forming a binding of carboxylate coordination with the metal M; and

 B) allowing the mixture obtained in step A) to react optionally with the addition of external energy; to obtain said nanoparticles.

The carboxylate MOFs and their methods of preparation are well known. The reader may in particular refer, for example, to the teaching described in patent documents EP2230288, WO2009 / 077670 and WO2009 / 077671, to name a few. Advantageously, the MOF material used as solid adsorbent (A) is a di-, tri- or tetracarboxylate of aluminum or zirconium, and the metal ion M ^{z +} may advantageously be chosen from Zr ⁴⁺ or Al ³⁺ .

 The synthesis of MOF materials may preferably be carried out in the presence of energy which may be provided, for example, by heating, for example hydrothermal or solvothermal conditions, but also by microwaves, ultrasonics, grinding, a process involving a supercritical fluid, etc. The corresponding protocols are those known to those skilled in the art.

Advantageously, the solvents used are generally polar. In particular, the following solvents may be used: water, alcohols, dimethylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofuran, diethylformamide, chloroform, cyclohexane, acetone, cyanobenzene, dichloromethane, nitrobenzene, ethylene glycol, dimethylacetamide or mixtures of these solvents. One or more co-solvents may also be added at any stage of the synthesis for better solubilization of the compounds of the mixture. These may include monocarboxylic acids, such as acetic acid, formic acid, benzoic acid, and the like.

 When the co-solvent is a monocarboxylic acid, the latter, in addition to a solubilizing effect, also makes it possible to stop the crystalline growth of the MOF solid. Indeed, the carboxylic function coordinates with the metal, which can not bind to another metal atom for lack of the presence of a second -COOH function on the co-solvent molecule. Thus, the growth of the crystal lattice is slowed down and stopped. The addition of a monocarboxylic co-solvent, such as acetic acid, formic acid, benzoic acid, etc., thus makes it possible to reduce the size of the MOF solid particles obtained. The use of a monocarboxylic co-solvent can therefore promote the production of micron powders (particles of size <1 mm).

 The synthesis of MOF materials can preferably be carried out under experimental conditions conducive to the formation of micron powders. For example, a control of the following parameters may be important for the production of nanoparticles of MOF solids according to the invention:

 - reaction temperature,

 - reaction time,

 L-ligand and inorganic metal precursor concentrations and / or

 - addition of one or more additives such as pH modifiers (acids, bases), mineralizers, or agents promoting the stopping of crystal growth (mono carboxylic acid).

The ranges of preferred values for each of these parameters may vary depending on whether the synthesis of the nanoparticles is carried out by the hydro / solvothermal route, by ultrasound or by microwaves. For example, a higher reaction temperature will generally be used for the hydro / solvothermal route (about 20-150 ° C) than for the ultrasound route (about 0 ° C). The MOF materials that can be used in the context of the invention can be obtained in ranges of temperature, reaction time and concentrations, and with amounts of additives, varying around the operating conditions illustrated in this document, depending on the size and desired polydispersity.

For example, the following conditions can be used:

 Solvent pathway

 the reaction temperature is preferably between 20 and 200 ° C., more particularly between 50 and 100 ° C., especially between 60 and 70 ° C.

 the reaction time is between 30 minutes and 72 hours, more particularly between 30 minutes and 12 hours, especially between 1 and 4 hours;

 the concentration of ligand L 'and inorganic metal precursor is between 1 and 200 mmol / L, more particularly between 30 and 100 mmol / L, especially between 60 and 70 mmol / L

 a mono carboxylic acid can be added, preferably acetic acid. It is understood that other additives such as pH modifiers (acids, bases), mineralizers may also be added.

Ultrasonic way

 the reaction temperature is preferably between -5 ° C. and 20 ° C., more particularly between -5 ° C. and 10 ° C., particularly preferably between -5 ° C. and 5 ° C.

 the reaction time is between 15 minutes and 2 hours, more particularly between 15 minutes and 1 hour, especially between 15 and 45 minutes.

the concentration of ligand L 'and inorganic metal precursor is between 10 mol / l and 10 ^-2 mol / l, more particularly between 1 and 10 ^-2 mol / l, especially between 50 and 200 mmol / l

a mono carboxylic acid is added, preferably acetic acid. It is understood that other additives such as H modifiers (acids, bases), mineralizers can also be added. microwaves

 the reaction temperature is preferably between 30 ° C and 300 ° C, more preferably between 30 ° C and 150 ° C, most preferably between 50 ° C and 120 ° C

 the reaction time is between 1 minute and 3 hours, more particularly between 10 and 50 minutes, especially between 1 and 30 minutes

the concentration of ligand L 'and inorganic metal precursor is between 200 mol / l and 10 ^-2 mol / l, more particularly between 100 and 10 ^-2 mol / l, especially between 10 and 10 ^-2 mol / l.

 a pH modifier is added, preferably hydrochloric acid. It is understood that other additives such as pH modifiers (acids, bases), mineralizers or agents promoting the stopping of crystal growth (mono carboxylic acid) can also be added. The various MOF materials used as solid adsorbent (A) according to the present invention can be obtained in the form of nanoparticles under similar operating conditions, using the aforementioned temperature ranges, reaction time and concentration, and with the possible addition of additives such as those mentioned above.

The structure and composition of an MOF (nature of metal sites and ligands) can be determined by X-ray diffraction.

Advantageously, the MOF material used as solid adsorbent (A) is chosen from aluminum or zirconium di-, tri- or tetracarboxylate MOFs characterized by a pore diameter of between 0.4 and 0.7 nm, preferably between 0.5 and 0.6 nm, and a microporous volume of between 0.2 and 0.5 cm ³ / g, preferably between 0.3 and 0.45 cm ³ / g.

In the context of the invention, the microporous volume means the accessible volume for the molecules of gas and / or liquid. The porous network is preferentially three-dimensional, that is to say that the pores are connected to each other in the 3 dimensions of the space (longitudinal, lateral, depth). Connected pores can form porous channels. The pore diameter is between 0.4 and 0.7 nm, preferably between 0.5 and 0.6 nm. The pore volume (Vp) is 0.2 to 0.5 cm ³ / g, preferably 0.3 to 0.45 cm ³ / g.

The pore volume can be determined by nitrogen adsorption at 77 K after activation of the 12 hour MOF material at 383 K under vacuum. Measurement of the microporous volume can be carried out by "t-plot" analysis from a 77K dinitrogen adsorption isotherm (a method well known to those skilled in the art). Advantageously, aluminum or zirconium di-, tri- or tetracarboxylate MOFs characterized by the above-mentioned pore diameter and pore volume have an S-shaped water adsorption isotherm (Type V as classified). by IUPAC) characterized in that the adsorption isotherm exhibits the greatest slope at the relative humidity value p / p _its t = 0.08 ± 0.03; preferably at the relative humidity value p / p _sat = 0.08.

The water adsorption isotherms can be obtained by gravimetric or volumetric methods, well known to those skilled in the art, which are commercially available (eg Micromeretics, Bel Japan, Setaram). Advantageously, in the MOFs that may be used in the context of the present invention, the di-, tri- or tetracarboxylate ligand can be chosen from aliphatic or aromatic organic di-, tri- or tetra-dentate ligands comprising 1 at 18, preferably 1 to 10 carbon atoms and comprising 2, 3 or 4 carboxylate groups. Advantageously, it may include ligands selected from: C ₂ H ₂ (C02 ^~) 2 (fumarate), C ₂ H ₄ (C0 ₂ ^") 2 (succinate), C ₃ H ₆ (C0 ^~ ₂₎ 2 ( glutarate), C ₄ H ₄ (C0 ₂ ^" ) 2 (muconate), C ₄ H ₈ (C0 ₂ ^")

) ₂ (adipate), CvHi ₄ (CO ₂ ^" ) 2 (azelate), CsH ₃ S (CO ₂ ^" ) 2 (2,5-thiophene dicarboxylate), 2,5-furandicarboxylate, CeH ₄ (CO ₂ ^" ) 2 ( terephthalate), C6H ₂ N ₂ (CO ₂ ^" ) 2 (2,5-pyrazine dicarboxylate), C 10 H 6 (CO ₂ ^" ) 2 (naphthalene-2,6-dicarboxylate), C ₂ H 8 (CO ₂ ^" ) 2 (biphenyl) - 4,4'-dicarboxylate), Ci ₂ H8N ₂ (C0 ₂ ^") 2 (azobenzènedicarboxylate), C 6 H ₃ (C0 ^~ _{2) 3} (benzene-1, 2,4-tricarboxylate), C 6 H ₃ (C0 ^~ _{2) 3} (benzene-1,3,5-tricarboxylate),

C ₂₄ Hi5 (C0 ₂ ^" ) 3 (benzene-1,3,5-tribenzoate), C6H ₂ (C0 ₂ ^" ) 4 (benzene-1,2,4,5 tetracarboxylate, CioFÎ4 (C02 ^~) 4 (naphthalene-2,3,6,7-tetracarboxylate), CioFÎ4 (C02 ^~) 4 (naphthalene-1, 4,5,8-tetracarboxylate), Ci2FÎ6 (C02 ^~) 4 (biphenyl -3,5,3 ', 5'-tetracarboxylate), and modified carboxylate ligands selected from the group consisting of 2-aminoterephthalate, 2-nitroterephthalate, 2-methylterephthalate, 2-chloroterephthalate, 2-bromoterephthalate, 2,5-dihydroxyterephthalate, tetrafluoroterephthalate, tetramethylterephthalate, dimethyl-4,4'-biphenydicarboxylate, tetramethyl-4,4'-biphenydicarboxylate, dicarboxy-4,4'-biphenydicarboxylate, 2,5-pyrazyne dicarboxylate.

Advantageously, among the di-, tri- or tetra-carboxylate organic ligands mentioned above, those whose molar mass is <260 g / mol, preferably <211 g / mol, more preferably <160 g / mol, may be selected.

Advantageously, the organic ligands constituting the MOFs that may be used in the context of the present invention are dicarboxylate ligands, preferably fumarate or furanedicarboxylate, more preferably fumarate or 2,5-furanedicarboxylate.

Advantageously, the MOFs that may be used in the context of the present invention are chosen from zirconium fumarates or aluminum furanedicarboxylates.

Advantageously, the MOFs that may be used in the context of the present invention are chosen from MOF-801 or MIL-160.

These two MOFs respond at once:

- the criterion isothermal water adsorption S-shaped characterized in that the adsorption isotherm exhibits the greatest slope at the relative humidity value p / p _sat = 0.08 ± 0.03 ; and the pore diameter criterion of between 0.4 and 0.7 nm, preferably between 0.5 and 0.6 nm, and a microporous volume of between 0.2 and 0.5 cm ³ / g, preferably between 0.3 and 0.45 cm ³ / g. Indeed, MOF Zr-UiO-fumarate (ie, MOF 801) has a water adsorption isotherm such as that illustrated in FIG. 2, and a pore diameter of 0.5-0.7 nm and a porous volume. Vp = 0.45 cm ³ / g.

The MOF MIL-160 has a water adsorption isotherm with an inflection point of about 0.08 (see FIG. 2B), and a porous 3D network consisting of pore diameter square-shaped sinusoidal channels. ~ 5 Å and a pore volume Vp = 0.40 cm ³ / g.

MIL-160: 2,5-Furandicarboxylate (FDCA) aluminum, the FDCA ligand having a molar mass = 156 g / mol. Zr-UiO-fumarate = zirconium fumarate, the fumarate ligand having a molar mass = 116 g / mol.

The MOF-801 and MIL-160 materials are known, and their synthesis and characterization have been reported in the literature:

 1) Zr-fumarate (MOF-801): ref [4] and Wipmann et al., Microporous

 mesoporous mater., 2012, 152, 64 [5]

 2) MIL-160: Cadiau et al, Advanced Materials, 2015, 27, pp. 4775-4780 [12]

The MOF adsorbent may be shaped by any method known in the art of trithermal adsorption cooling / heating systems (eg, fixed bed, adhesive or composite coating). The composite can be based on any load conventionally used in the field. For example, it may be a composite based on expanded natural graphite (GNE).

Advantageously, for thermal battery applications, the MOF adsorbent can be shaped (in English enbodiment). In this case, the more advantageous shaping methods include granulation, extrusion and pelletizing. The shapes of the resulting objects can be grains, balls, cylinders, pellets or even parallelograms of any size that can facilitate the implementation of the thermal battery (filling the tank or operating mode). Ref [13]: D. Bazer-Bachi, Towards industrial use of metal-organic framework: Impact of shaping on the MOF properties, Powder Technology Volume 255, March 2014, Pages 52-59

 Ref [14]: S. Kaskel, Ed Book: Wiley-VCH, The Chemistry of Metal-Organic Frameworks: Synthesis, Characterization, and Applications lst Edition - ISBN-13: 978-3527338740, ISBN-10: 3527338748

Advantageously, when the MOF adsorbent is shaped as an adhesive coating on a surface (eg, on a heat exchanger), it can be shaped on a metal surface by a method allowing the growth of the MOF directly on the surface. surface of the metal support (ie, without binder, adhesive or composite). It may be for example a method for growing MOF on the surface of a metal support, comprising:

 (i) oxidizing the metal of the surface of the metal support to cover it with a metal oxide layer;

(ii) preparing a precursor solution / suspension of MOF material comprising mixing in a polar solvent (a) a metal inorganic precursor in the form of metal M, metal salt M or coordination comprising the metal ion M wherein M is a metal ion selected from Al ³⁺ , Zr ²⁺ , Zr ⁴⁺ ; preferably Zr ⁴⁺ or Al ³⁺ ; and (b) at least one ligand L selected from a di-, tri- or tetracarboxylate ligand selected from: C ₂ H ₂ (CO ₂ ) ₂ (fumarate), C ₂ H ₄ (CO ₂ ) ₂ ( succinate), C ₃ H ₆ (CO ₂ ) ₂ (glutarate), C ₄ H ₄ (CO ₂ ) ₂ (muconate), C ₄ H ₈ (CO ₂ ) ₂ (adipate), C ₇ H ₄ (C0 ₂ ) ₂ (azelate), C ₅ H ₃ S (CO ₂ ^" ) ₂ (2,5-thiophene dicarboxylate), 2,5-furandicarboxylate, C ₆ H ₄ (CO ₂ ^" ) ₂ (terephthalate), C ₆ H ₄ (CO ₂ ^" ) ₂ (isoterephthalate), C ₆ H ₂ N ₂ (CO ₂ ^" ) ₂ (2,5-pyrazine dicarboxylate), C ₁₀ H ₆ (CO ₂ ^" ) ₂ (naphthalene-2,6-dicarboxylate), Ci ₂ Hs (C0 ₂ ^" ) ₂ (biphenyl-4,4'-dicarboxylate), Ci ₂ H8N ₂ (CO ₂ ^" ) ₂ (azobenzenedicarboxylate), C ₆ H ₃ (CO ₂ ^" ) ₃ (benzene-1,2,4-tricarboxylate), C ₆ H ₃ (C0 ₂ ^") ₃ (benzene-1, 3,5-tricarboxylate), C ₂₄ Hi ₅ (C0 _{^2") 3} (benzene-1, 3, 5-tribenzoate), C ₆ H ₂ (C0 ₂ ^" ) ₄ (benzene-1,2,4,5-tetracarboxylate, CioH ₄ (CO ₂ ^" ) ₄ (naphthalene-2,6,7,7-tetracarboxylate), CioH ₄ (CO ₂ ^" ) ₄ (naphthalene- 1,4,5,8-tetracarboxylate), Ci ₂ H 6 ( C0 ₂ ^" ) ₄ (biphenyl-3,5,3 ', 5'-tetracarboxylate), 2-aminoterephthalate, 2- nitroterephthalate, 2-methylterephthalate, 2-chloroterephthalate, 2-bromoterephthalate, 2,5-dihydroxyterephthalate, tetrafluoroterephthalate, tetramethylterephthalate, dimethyl-4,4'-biphenydicarboxylate, tetramethyl-4,4'-biphenydicarboxylate, dicarboxy-4,4'-biphenydicarboxylate, or 2,5-pyrazyne dicarboxylate;

 (iii) immersing the oxidized metal support obtained in step (i) in the

 solution / suspension obtained in step (ii);

 (iv) heating the mixture of step (iii) to 100-140 ° C, preferably 110-130 ° C, preferably 120 ° C for 24-36 hours, preferably 12-36 hours, preferably at least 6 hours;

 (v) Remove the metal support from the solution / suspension precursor of MOF material,

 (vi) Rinse the support with an appropriate solvent

 (vii) Dry in air at 40-60 ° C, preferably 45-55 ° C, preferably at 50 ° C.

The aforementioned method implements the prior oxidation of the surface of the metal support before it comes into contact with the solution / suspension containing the metal ion and the constituent ligand of the MOF, which differs from certain methods reported in the prior art. involving the use of a temperature gradient at the metal interface / MOF precursor solution. By the aforementioned prior oxidation process, a metal support coated with a layer of MOF anchored to the metal surface is obtained directly via an intermediate layer of metal oxide, without organic spacer. In other words, the metal oxide layer formed on the metal surface serves as anchoring to the MOF layer covering, in whole or in part, the surface of the metal. Advantageously, the ligand L may represent C ₂ H 2 ^(~ C0 ₂₎ 2 (fumarate), or 2,5 furandicarboxy late.

Advantageously, the metal support can be made of copper, aluminum or stainless steel, and can be in the form of a plate, a honeycomb shape, or any form used in heat exchangers. heat, for example a flat tube with fins. In the prior art are reported processes for coating fine-woven copper woven fabrics with MOFs, for example woven copper mesh 400 mesh. This type of wire cloth Mesh woven mesh is typically not suitable for structures intended to be used as a heat exchanger.

Advantageously, step (i) can be carried out by any means known to those skilled in the art, for example by a thermal and / or chemical treatment of the metal surface, and which is specific and adapted to the metal used and the material of the art. the adsorbent. Step (i) prior oxidation excludes cleaning processes (washing) of metal surfaces, for example with a solvent such as acetone or a dilute inorganic acid such diluted HCl, these cleaning processes typically aimed at remove traces of grease (washing with acetone), and / or traces of oxide on the surface of the metal (washing with dilute HCl). Step (i) prior oxidation also excludes annealing processes, which consist of a step of gradual rise in temperature followed by controlled cooling. This procedure, common in metallurgy, redistributes metal atoms and eradicates dislocations in metals. This action is particularly used to facilitate the relaxation of the stresses that can accumulate in the core of the material, under the effect of mechanical or thermal stresses, involved in the steps of synthesis and shaping of materials. In the case of an oxidizable metal, the annealing is typically carried out under an inert atmosphere to prevent oxidation of the metal surface.

 For example, when the metallic support is made of copper, step (i) can be carried out by placing the copper support in an oven at a temperature and for a lapse of time sufficient to effect the oxidation of the surface of the support. copper. For example, the baking can be performed at 100 ° C under ambient atmosphere.

In another example, when the metallic support is aluminum, step (i) can be carried out by treating the support in a solution of sodium hydroxide, in a dilute solution of nitric acid (to deoxidize the surface of aluminum), and then air-drying at a temperature and for a period of time sufficient to effect oxidation of the surface of the aluminum support. For example, air drying can be performed at 60 ° C. The preparation of the precursor solution / suspension of MOF materials may preferably be carried out in the presence of energy which may be provided, for example, by heating, for example hydrothermal or solvothermal conditions, but also by microwaves, ultrasounds, grinding, a process involving a supercritical fluid, etc. Reference may be made to the "MOF Material" section previously described for relevant citations and details of embodiments.

Thus, advantageously, step (iv) can be carried out in a teflon body inserted in a metal bomb ("teflonlined stainless steel autoclave").

 The solvents used in step (ii) are generally polar. In particular, the following solvents may be used: water, alcohols, dimethylformamide, dimethylsulfoxide, acetonitrile, tetrahydrofuran, diethylformamide, chloroform, dichloromethane, dimethylacetamide or mixtures of these solvents. Advantageously, it may be water or a hydroalcoholic solution. The above solvents can also be used in the rinsing step (vi).

One or more additives may also be added during the preparation of the MOF material precursor solution / suspension in step (ii) to modulate the pH of the mixture. These additives may advantageously be chosen from inorganic or organic acids or mineral or organic bases. In particular, the additive may be selected from HF, HCl, FnO 3, H 2 SO 4, NaOH, KOH, lutidine, ethylamine, methylamine, ammonia, urea, EDTA, tripropylamine, pyridine, etc. Advantageously, FnO 3, H 2 SO 4, NaOH may be used.

 The method described above has the advantage of making it possible to obtain metal supports coated with a thin layer of MOF material, without the use of binders, adhesives or composite to ensure the adhesion of the MOF to the surface of the support. The MOF material adheres to the metal oxide layer generated on the surface of the metal support during step (i) of the process. In heat exchanger applications, where the MOF material functions as an adsorbent (eg, heat batteries), this MOF shaping in a layer directly on the metal support makes it possible to optimize the quality of the heat transfer, and to reduce the heat transfer. adsorbent layer mass (since no binder, adhesive or composite is needed).

However, it is known that, in the case of surface heat exchangers coated with adsorbent, of course, the exchange surface is important, but generally the surface is imposed less to ensure thermal power than to ensure the amount of adsorbent necessary because the thickness of the adsorbent layers is limited. In other words, a reducing the adsorbent mass by a factor of 2 can result in a reduction of the exchange surfaces by a factor close to 2 and the volume of each adsorber would also be greatly reduced.

 The above method adjusts the advantage of allowing MOF adsorbent to be deposited to form an effective coated surface with an appropriate thickness of adsorbent. Another advantage of this method is to allow optimization of the water mass cycled during a cycle, when a heat exchanger coated with MOF according to the method of the invention is used. Indeed, typically, in the heat of regeneration, the sensible heat can represent the third and latent heat two-thirds. By way of example, a reduction of the adsorbent and metal masses by a factor of two would reduce the sensible heat by a factor of two if the temperature conditions are the same. The gain of the COP would then be between 15 and 20% which is very significant. In summary, using this method, MOF-coated heat exchangers are accessed with advantageous performance in terms of cycled mass, COP and SCP.

B. Device

 Advantageously, the system implementing the method according to the invention can be implemented according to several variants.

 1. Thermal battery comprising a single module alternately serving condensation module (C) and evaporation module (E)

 For example, the system may comprise a single adsorption / desorption module (AD) and a single module alternately operating as a condensation module (C) and evaporation module (E). See Figure 3.

Advantageously, the adsorber (adsorption / desorption module (AD)) and the evaporator (ie the module operating alternately as a condensation module (C) and an evaporation module (E)) can be connected by a valve. "All or nothing" or, preferably, by a variable flow valve (regulator) controlled to control the steam flow during evaporation and thus control the temperature in one evaporator. This regulator and the on-off valve may possibly be connected in parallel: only the on-off valve is used during condensation and only the expansion valve is used during evaporation. Advantageously, the adsorber may be provided with devices enabling it to be heated during the regeneration / condensation phase and to be cooled during the adsorption / evaporation phase.

 For its part, the evapo-condenser can also be cooled during the condensation (this heat source can possibly be used in the case of a hot thermal battery) and be heated during the evaporation phase which allows to produce the cold (in the form of chilled water or fresh air) useful for air conditioning.

The: heating of the adsorbent in the AD module

The heating of the adsorption / desorption module (AD) containing the solid adsorbant (A) of MOF type can be provided by any means known to those skilled in the field.

 For example, the heating can be provided by heat transfer fluid or electric heating.

Heating the adsorber by heat transfer fluid

 Since the regeneration temperature of the MOFs used is low, generally less than 100 ° C. but still less than 120 ° C., the water or an aqueous solution may advantageously be used as heat transfer fluid, for example at a pressure of less than 2 bar. In this case, the adsorber may advantageously be provided with a heat exchanger, in good thermal contact with the MOF, comprising a coolant circulation circuit, this circuit being connected to the external source of heat (generally a source of heat recovery). The source of heat can be fatal heats in the case of implementation, for example with heat engines or solar panels. Typically, the coolant of a heat engine generally has a temperature below 110 ° C, typically 90 to 100 ° C, when the engine is hot. In this case, Tr (regeneration temperature of the adsorbent) is less than 110 ° C, and may be of the order of 90 to 100 ° C.

Heating of the adsorber by an electrical resistance

Advantageously, electrical resistors can be conveniently arranged inside the adsorption / desorption module (AD) (the adsorber) in order to heat the MOF as homogeneously as possible while avoiding very hot spots that may damage the adsorbent (Figure 3). Advantageously, the resistance and the intensity of the current flowing therethrough are chosen so that the electrical resistance releases a temperature corresponding to the desired TMOF temperature for the desorption mode.

 In the case of heating the adsorber by an electrical resistance, the regeneration temperature may be greater than 100 ° C. l .b: cooling of the adsorption / desorption (AD) module

 The cooling of the adsorption / desorption (AD) module (the adsorber) can be ensured by any suitable means, for example using a suitable heat transfer fluid, such as water or an aqueous solution, possibly containing one or more additives such as glycols; or by simple ventilation (air). Thus, the cooling of the adsorber can be ensured for example either by circulation of water or by air ventilation. Cooling of the adsorber by circulation of water

 When a coolant circuit exists in the adsorber, a circulation of water, itself advantageously cooled while circulating through an air cooler, can be used to ensure the cooling of the adsorber. Cooling of the adsorber by ventilation

 When the adsorber is provided with electrical resistances, cooling by simple ventilation is advantageously used. l .c: Use of the cold produced by the evaporator

Depending on the intended application, the produced cold can be used in the form of ventilation

(natural or forced) or in the form of chilled water production.

 If ventilation is used, a heat exchanger (e.g., fins) may conveniently be conveniently installed on the outer surface of the evaporator to improve heat exchange.

To produce chilled water, the evapo-condenser can be equipped with an internal heat exchanger in which the water to be cooled circulates. l .d: Cooling of the evapo-condenser When the evapo-condenser is in its function of condenser, it can be cooled by ventilation or by circulation of water if it is provided with an internal heat exchanger.

2. Thermal battery comprising an adsorption / desorption module (AD), an evaporation module (E) and a condensation module (C)

 The components correspond to those previously described except that the evaporation and condensation functions each have their specific component (see Figure 4). Advantageously, at the outlet of the condensation module (C), the refrigerant (F) can be stored in a tank instead of being accumulated in the condensation module. With this device, an HP side (high pressure) and a LP side (low pressure) are created. This makes it possible to improve the performance of the evaporation module and to control the liquid flow rate entering the evaporation module (and not the steam flow at the outlet of the evaporation module as in the previous case) with the aid of a pressure reducer (for example a thermostatic expansion valve).

3. Operation of the cycle

The principle will firstly be described in the case of a single module alternately serving evaporation module and then condensation module (combined evapo-condensation module). In a second step, we will indicate the few differences in the case where the evaporator and the condenser are distinct.

3.a Adsorption / desorption module + combined evapo-condensation module (Fig 3) Let us consider the starting state of the cycle in which the adsorption / desorption module has just completed its adsorption, and therefore its production of cold. The adsorption / desorption module and evapacondenser assembly is at the low evaporation pressure with the communication valve in the open position.

In order to carry out the regeneration, the adsorption / desorption module is heated and the evapo-condenser is placed in a condition that it can be cooled (either by circulation of water or by ventilation). On heating up, the adsorption / desorption module causes the pressure to increase. When the pressure reaches the value of the condensing pressure (saturated vapor pressure corresponding to the cooling temperature of the evaporator-condenser), condensation begins and continues as the temperature of the adsorber increases. The optimal time of this regeneration phase is predefined. When the regeneration is complete, the heating is interrupted and the fluid communication valve with the evapo-condenser is closed. During this heating / desorption phase, the adsorption / desorption module desorbed a quantity of water.

 All, the adsorption / desorption module with regenerated adsorbent + evapocondenser containing the refrigerant (F) + closed communication valve can remain in the state as long as necessary: it is the storage function. In doing so, the adsorption / desorption module which is no longer heated cools and the temperature of the evaporator removes the temperature of the environment. When the stored cold is to be used, the adsorption / desorption module is placed in a position to be cooled (by circulation of water or ventilation) and the evaporator is conditioned so that the produced cold is useful ( by connection to the chilled water circuit or by ventilation). The adsorption / desorption module is then cooled and the fluid connection valve with the evapo-condenser is opened. Evaporation begins with the production of cold and the temperature of the evaporator drops. When the temperature of the evaporator reaches the desired temperature, the open of the valve is controlled to maintain this evaporation temperature as close as possible to the target temperature. This evaporation can continue as long as the temperature of the evaporator is constant. When this temperature rises by more than a predefined value (typically 2 ° C), the production of cold is complete. The system is then ready to start a new regeneration / condensation phase. 3.b: Adsorber plus evaporator and condenser separated (Fig 4)

 The cycle is the same as previously described but the implementation is slightly different due to the existence of separate HP and BP parts.

During the regeneration phase, the fluid connection valve between the adsorption / desorption module and the evaporator is closed as well as that between the reservoir and the evaporator, while that between the adsorption / desorption module and the condenser is open. At the end of this regeneration phase, the valve between the condenser and the adsorber is closed. During the storage period, the valves are closed.

 During the cold production phase, the valve between the adsorption / desorption module and the evaporator is opened while that between the adsorption / desorption module and the condenser is closed. The expansion valve of the liquid between the tank and the evaporator is open and plays its role of feeding the evaporator. At the end of this evaporation phase, all the valves are closed.

4. Thermal battery comprising two adsorption / desorption modules, with almost continuous production of cold In this case, when one adsorber is in adsorption / production of cold, the other is in desorption / condensation. See for example Figure 5, and the patent application US2008 / 0066473 for the description of an exemplary embodiment and principle of operation. C. Uses / applications

 According to another aspect, the invention also relates to an air conditioning or refrigeration system implementing a method or comprising a system according to the invention, in any of the variants and embodiments described herein. The refrigeration system may be suitable for the preservation / conservation of perishable food, food, pharmaceutical or veterinary products such as vaccines, biological samples, blood, etc ... or any material that can be preserved by the cold.

 According to another aspect, the invention relates to a use of the method or system according to the invention, in any one of the variants and embodiments described herein, in an air conditioning system for a cabin or passenger compartment of a vehicle automobile (light, utility, or heavy vehicle) or nautical vehicle. The size of the system according to the invention can advantageously be adapted to suit this use.

 Advantageously, the method or system according to the invention can be used in a thermal battery for example for:

Thermal automotive air conditioning Electric car air conditioning

 Hybrid automotive air conditioning (electric / thermal)

 Air conditioning of all types of mobile machinery.

 Air conditioning of boating cabins

 - Temperature controlled storage of products (perishable food, food, pharmaceuticals, vaccines, liquids and biological products, blood, ..) transported by light vehicles or heavy vehicles or by air or water.

By way of example, the following operating modes can be used: - cold battery to pre-cool / pre-condition a space, a place, a cabin, a cabin before use

 - cold battery to condition a space / place / cabin / cabin at startup, typically because of a strong demand for cooling / conditioning power during a "cold start" of a thermal vehicle and / or electric)

 - cold battery in addition to a compression / expansion air conditioning system, particularly when using vehicles in an urban environment, or when using boats at the dock or stationed in a port

- Continuous cooling with a system with 2 or more adsorbers; working in alternating phase.

Brief description of the figures

 FIG. 1 schematizes the principle of operation of cold machines using solid adsorbents in a trithermal (closed) system.

 - Figure 2 A shows an isothermal profile of water adsorption-desorption of MOF-801 at 30 ° C (empty squares: desorption branch, solid diamonds: adsorption branch). The vertical arrow indicates the maximum slope of the isotherm (relative humidity p / psat = 0.08).

Figure 2B shows an isothermal water adsorption profile of MOF MIL-160 at 25 ° C. It is observed that the point of maximum slope of the isotherm is at relative humidity w / w _the t = 0.08. FIG. 3 illustrates the operating principle of a trithermal cooling / heating system with adsorption for a thermal battery according to the invention, comprising a single module alternately serving as a condensation module (C) and an evaporation module (E). , and in particular the two modes of operation: adsorption mode and desorption mode. In desorption mode: (1) the adsorbent is heated by a heat source (eg, fatal heats of different origins such as thermal battery, solar panels, electrical circuit, etc.). (2) the water vapor is released by the adsorbent and condenses in the condensation module. (3) The water vapor is condensed and the heat released can be exploited p. ex. to cool a space or to heat domestic hot water. In adsorption mode: (1) the water is evaporated at low temperature in the evaporation module. Evaporation generates cold which cools either the water circuit passing through the evaporator (2) or a flow of air outside the evaporator. The water vapor is adsorbed by the adsorbent in the adsorption module. (3) The exothermic adsorption reaction releases heat that can be upgraded to heat domestic hot water or to be discharged into the environment.

 FIG. 4 represents an exemplary configuration of a trithermal cooling / heating system with adsorption for a thermal battery according to the invention, with an adsorption / desorption module and separate condensing and evaporation modules. 1 = adsorption / desorption module; 2 = condensation module: 3 evaporation module; 4 = "all or nothing" valve, the inlet valve in the evaporator between 1 and 3 may be a variable flow valve to control the flow rate to ensure the stability of the temperature of the evaporator; 6 = refrigerant tank.

 FIG. 5 represents an exemplary configuration of a closed trithermal cooling / heating system with adsorption for a thermal battery according to the invention, with two adsorption / desorption modules operating in phase opposition.

FIG. 6 represents an image of the section of an aluminum foil coated with MOF Zr-fumarate according to Example 2, using an electron microscope. EXAMPLES

Example 1 - Comparative Performance The performance of several adsorbents conventionally used in adsorption / desorption systems for a cold machine was compared to that of MOFs MIL-160 and MOF-801 in different modes of operation. These comparative results are listed in Table 1.

Table 1:

In this study, 5 operating modes Te / Tc / Tr (where Tr represents the regeneration temperature of the adsorbent) were considered.

In Table 1 is presented a comparison, for the 5 Te / Tc / Tr conditions studied, with respect to the Fuji silica gel (Fuji Davison RD silica gel) amounts of water adsorbed by the various adsorbents whose properties have been provided. . When the amount cyclized by the adsorbent (indicated in parentheses in g / kg of adsorbent) is close to that of Fuji silica gel, the sign = is used, when it is less good, the minus sign (-) is then retained and when it is a little better the sign + is used and if it is about double, ++ is used, about 3 times better, we use the +++ symbol, 4 times better, we use the symbol + +++, and finally 5 times better or more, we use the +++++ symbol. The absorbents mentioned in Table 1 are known: they are either commercially available, or their synthesis and characterization have been published:

Silica gel: Fuji Davison RD silica gel

 SAPO-34: The synthesis is described on the site of ΓΙΖΑ (International Zeolite Association) with the appropriate references. http://www.iza-online.org/synthesis/Recipes/SAPO- 34.html

 Al-CAU-10: Reinsch et al, Chem. Mater. 2013, 25, 17-26 [6]

Basolite A520: EP2230288 [2] The analysis of these comparative results reveals that:

 (i) The performance of MOFs MIL-160 and MOF-801 is significantly higher in a certain Te / Tc / Tr operating range (ie 0 ° C≤Te <15 ° C, Te = Te + 35 ° C ± 5 ° C, and TMOF = Tr = Tc + (Tc-Te + 10 ° C) ± 5 ° C. Outside this range, the performance of the aforementioned MOFs drops.

(ii) The performance of MOFs MIL-160 and MOF-801 is significantly higher than that of conventional silica gel adsorbents, SAPO-34, Al-CAU-10 and Basolite A520, in the same Te / Tc / Tr operating range identified above (ie 0 ° C≤Te <15 ° C, Te = Te + 35 ° C ± 5 ° C, and T _M OF = Tr = Tc + (Tc-Te + 10 ° C) ± 5 ° C Conventional adsorbents do not work or much less well.

Table 1 demonstrates the superior efficiency of aluminum or zirconium di-, tri- or tetracarboxylate MOFs, such as MOF-801 and MIL-160 in the particular mode of operation according to the present invention, by compared to conventionally used adsorbents, such as SAPO-34, Al-CAU-10, Basolite A520 or Fuji silica. It is recalled that the MOF-801 and MIL-160 having an S-shaped water adsorption isotherm, characterized in that the adsorption isotherm has the greatest slope at the relative humidity value p / p _its t = 0.08 ± 0.03 (see Figures 2 and 3).

Example 2 Synthesis and Characterization of a Coating of MOF-801 (Zr-fumarate) on an Aluminum Foil An aluminum foil (50x50 mm) was treated in a solution of sodium hydroxide (pH> 12), deoxidized in dilute nitric acid (4 <pH <6), then air-dried at 60 ° C. ° C.

 A solution containing 4.82 g (20.7 mmol) ZrC14, 10.29 g (62 mmol) fumaric acid in 200 ml dimethylformamide (DMF) was stirred until the solution was completely transparent.

 The aluminum foil is immersed in the solution in a Teflon coated stainless steel autoclave ("Teflonlined" in English). The mixture is heated at 120 ° C for 48 hours.

After cooling, the aluminum foil was carefully removed, rinsed five times in DMF and EtOH and finally air dried at 50 ° C.

REFERENCE LIST

 1. J. Bauer et al. Int. J. Energy Res. 2009; 33.1233-1249

 2. EP2230288

 3. EP2049549

4. Furukawa, J. Am. Chem. Soc., 2014, 136, 4369-4381.

 5. Wi mann et al, Microporous mesoporous mater., 2012, 152, 64

 6. Reinsch et al., Chem. Mater. 2013, 25, 17-26

 7. K. Byrapsa, et al. "Handbook of hydrothermal technology", Noyes

 Publications, Parkridge, New Jersey USA, William Andrew Publishing, LLC, Norwich NY USA, 2001

 8. G. Tompsett, et al. ChemPhysChem. 2006, 7, 296

 9. S.-E. Park, et al. Catal. Survey Asia 2004, 8, 91

 10. C. S. Cundy, Collect. Czech. Chem. Commom. 1998, 63, 1699

 11. S. H. Jhung, et al. Bull. Kor. Chem. Soc. 2005, 26, 880

12. Cadiau et al, Advanced Materials, 2015, 27, pp. 4775-4780

 13. D. Bazer-Bachi, Towards industrial use of metal-organic framework: Powder Technology Volume 255, March 2014, Pages 52-59

 14. S. Kaskel, Ed Book: Wiley-VCH, The Chemistry of Metal-Organic

 Frameworks: Synthesis, Characterization, and Applications lst Edition - ISBN-

13: 978-3527338740, ISBN-10: 3527338748

 15. WO2009 / 077670

 16. WO2009 / 077671

 17. K. S. Sing, Physisorption Data for Gas / Solid Systems Reporting, Pure & Appl. Chem., Vol. 57, No. 4, 603-619, 1985

Claims

 A thermal trithermal adsorption cooling / heating method or system comprising:

 at. a refrigerant (F) consisting of water;

b. a condensation module (C) of said refrigerant (F), in thermal connection with a coolant circuit (CWi-medium) whose temperature of the coolant at the output of the circuit is T _C ^EXT ;

vs. an evaporation module (E) of said refrigerant (F), in thermal connection with a coolant circuit (CWi-low) whose temperature of the coolant at the output of the circuit is T _E ^EXT ;

d. at least one adsorption / desorption module (AD) containing a solid adsorbent (A) consisting of a porous hybrid metallo-organic material (MOF) selected from di-, tri- or tetracarboxylate MOFs having an isotherm of S-shaped water adsorption characterized in that the adsorption isotherm exhibits the greatest slope at the relative humidity value p / p _its t 0.05 0, 1 1, preferably 0.08 , the adsorption / desorption module (AD) being alternately in fluid connection with said condensation module (C) and then said evaporation module (E), which MOF material can adsorb or desorb the refrigerant (F) depending on whether the adsorption / desorption module (AD) is in fluid connection with the evaporation module (E) or condensation module (C), respectively, and according to the temperature TMOF to which the MOF material is subjected; characterized in that the system is operated alternately in adsorption / desorption mode according to the following operating parameters: in adsorption mode: the adsorption / desorption module (AD) is in fluid connection with the evaporation module (E) at an internal evaporation temperature T _E ;

- 0 ° C <T _E <15 ° C;

the MOF material is subjected to a temperature TMOF = T _C where T _C = T _E + 35 ° C ± 5 ° C; and 0.05 <pe / _her p t (e) ≤ 0, 1 1; more preferably pe / p _its t (e) = 0.08;

 in which :

Pe / p _its t (e) represents the ratio between the evaporation pressure of the refrigerant fluid (F) in the evaporation unit (E) and the saturation pressure in the refrigerant adsorption temperature (F) by the porous hybrid metallo-organic material;

p _e represents the pressure of the refrigerant (F) in the gas phase in the evaporation module (E);

and psat (e) represents the saturating vapor pressure of the refrigerant (F) at the adsorption temperature thereof by the porous hybrid metallo-organic material; in desorption mode: the adsorption / desorption module (AD) is in fluid connection with the condensation module (C) at an internal condensing temperature T _c ;

 the MOF material is subjected to a temperature TMOF = Tr = Tc + (Tc-Te + 10 ° C) ± 5 ° C;

0,05 <pe / _her p t (e) ≤ 0, 1 1; more preferably pe / p _its t (e) = 0.08; and

in which :

Pc / p _sa t (c) represents the ratio of the condensing pressure of the refrigerant (F) in the condensing module (C) and the saturation pressure of the refrigerant (F) to the desorption temperature of the metallo material - porous hybrid organic;

p _c represents the pressure of the refrigerant (F) in the gas phase in the condensation module (C);

and psat (c) represents the saturating vapor pressure of the refrigerant (F) at the desorption temperature thereof of the porous hybrid metallo-organic material.

2. Trithermal method or trithermal system for adsorption cooling / heating for a thermal battery comprising: at. a refrigerant (F) selected from water and alcohols;

b. a condensation module (C) of said refrigerant (F), in thermal connection with a coolant circuit (CWi-medium) whose temperature of the coolant at the outlet of the circuit is T _c ^ext ;

vs. an evaporation module (E) of said refrigerant (F), in thermal connection with a coolant circuit (CWi-low) whose temperature of the coolant at the outlet of the circuit is T _e ^ext ;

d. at least one adsorption / desorption module (AD) containing a solid adsorbent (A) consisting of a porous hybrid metallo-organic material (MOF) chosen from di-, tri- or tetra-carboxylate MOFs characterized by a diameter of pores between 0.4 and 0.7 nm, preferably between 0.5 and 0.6 nm, and a microporous volume of between 0.2 and 0.5 cm ³ / g, preferably between 0.3 and 0 , 45 cm ³ / g, the adsorption / desorption module (AD) being alternately in fluid connection with said condensation module (C) and then said evaporation module (E), which MOF material can adsorb or desorb the refrigerant (F) according to whether the adsorption / desorption module (AD) is in fluid connection with the evaporation (E) or condensation (C) module, respectively, and according to the TMOF temperature to which the MOF material is subjected;

characterized in that the system is operated alternately in adsorption / desorption mode according to the following operating parameters: in adsorption mode: the adsorption / desorption module (AD) is in fluid connection with the evaporation module (E) at an internal evaporation temperature T _e ;

- 0 ° C <T _E <15 ° C;

the MOF material is subjected to a temperature TMOF = T _C where T _C = T _E + 35 ° C ± 5 ° C; and

0.05 <pe / _her p t (e) ≤ 0, 1 1; more preferably pe / p _its t (e) = 0.08;

in which :

p _e / p _S at (e) represents the ratio between the evaporation pressure of the refrigerant (F) in the evaporation module (E) and the saturation pressure at the adsorption temperature refrigerant (F) by the porous hybrid metallo-organic material (or the relative humidity value);

p _e represents the pressure of the refrigerant (F) in the gas phase in the evaporation module (E);

psat (e) represents the saturating vapor pressure of the refrigerant (F) at the adsorption temperature thereof by the porous hybrid metallo-organic material; in desorption mode: the adsorption / desorption module (AD) is in fluid connection with the condensation module (C) at an internal condensing temperature T _c ;

 the MOF material is subjected to a temperature TMOF = Tr = Tc + (Tc-Te + 10 ° C) ± 5 ° C;

0.05 <pe / p _its t (e) ≤ 0, 1 1; more preferably pe / p _its t (e) = 0.08; and

in which :

p _c / p _S at (c) represents the ratio between the condensing pressure of the refrigerant (F) in the condensing module (C) and the saturation pressure of the refrigerant (F) at the desorption temperature of the metallic material - porous hybrid organic (or relative humidity);

p _c represents the pressure of the refrigerant (F) in the gas phase in the condensation module (C);

Psat (c) represents the saturation vapor pressure of the refrigerant (F) at the desorption temperature thereof of the porous hybrid metallo-organic material.

3. Method or system according to claim 1 or 2, wherein the solid adsorbent (A) consisting of a porous hybrid metallo-organic material (MOF) is chosen from di, tri- or tetracarboxylate MOFs. aluminum or zirconium.

4. Method or system according to claim 1, 2 or 3, wherein the di-, tri- or tetracarboxylate ligands constituting the MOF material have a molar mass <260 g / mol, preferably <21 1 g / mol, more preferably <160 g / mol.

The method or system of any one of claims 1 to 4, wherein the adsorption / desorption operating parameters are as follows:

in adsorption mode: the adsorption / desorption module (AD) is in fluid connection with the evaporation module (E) in the absence of any non-adsorbable inert gas by the porous hybrid metallo-organic material;

- 0 ° C <T _E <15 ° C;

the MOF material is subjected to a temperature TMOF = T _C where T _C = T _E + 35 ° C ± 5 ° C; and

0.05 <pe / _her p t (e) ≤ 0, 1 1; more preferably pe / p _its t (e) = 0.08; in desorption mode: the adsorption / desorption module (AD) is in fluid connection with the condensation module (C) in the absence of any non-adsorbable inert gas by the porous hybrid metallo-organic material;

 the MOF material is subjected to a temperature TMOF = Tr = Tc + (Tc-Te + 10 ° C) ± 5 ° C;

0.05 <pe / _her p t (e) ≤ 0, 1 1; more preferably pe / p _its t (e) = 0.08; and

Tc = T _e + 35 ° C ± 5 ° C.

6. A process or system according to any one of claims 1 to 5, wherein the solid adsorbent (A) consisting of a porous hybrid metallo-organic material (MOF) is selected from zirconium fumarates, such as MOF. -801.

A method or system according to any one of claims 1 to 5, wherein the solid adsorbent (A) consisting of a porous hybrid metallo-organic material (MOF) is selected from aluminum furanedicarboxylates, such as MIL - 160.

8. Method or system according to any one of claims 1 to 7, wherein the system contains a single module alternately serving condensation module

(C) and evaporation module (E).

The method or system of any one of claims 1 to 7, wherein the system contains a separate condensing module (C) and evaporation module (E).

The method or system according to any one of claims 1 to 7, wherein the system contains two adsorption / desorption modules (AD) and (AD '), each alternately in fluid connection with the condensation modules (C). and evaporation (E), so that when (AD) is in fluid connection with the condensation module (C) then (AD ') is in fluid connection with the evaporation module (E), and vice versa.

The method or system of claim 10, wherein the two adsorption / desorption modules contain the same solid adsorbent.

A method or system according to any one of claims 1 to 11, wherein when the adsorption / desorption module (AD) or (AD ') is in desorption mode, the heat source for heating the MOF material at the temperature TMOF is chosen from fatal heats on heat engines, independent electric heating, and / or solar panels.

Method or system according to any of claims 1 to 12, wherein the thermal connection between the refrigerant (F) and the coolant circuits (CWi-medium) and (CWTbasse) of the condensation modules and evaporation, respectively, is provided by a heat exchanger (ET).

14. Method or system according to any one of claims 1 to 13, wherein the thermal connection between the refrigerant (F) and the outside is provided by a heat transfer fluid selected from a water flow or a ventilation of air.

15. An air conditioning or refrigeration system implementing a method or comprising a system according to any one of claims 1 to 14.

16. Use of a method or system according to any one of claims 1 to 14 in an air conditioning system for cabin or passenger compartment of a motor vehicle (light vehicle, utility, or heavy weight) or nautical.