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    • 专利摘要:
    The present invention relates to a trithermal cold adsorption cooling / heating method or method, based on MOF as the solid adsorbent, in certain specific operating ranges, depending on the MOF used. The invention also relates to air conditioning systems with fan coil or floor or cooling ceiling, as well as dehumidification systems, implementing the method or comprising the system according to the present invention.
    公开号:FR3026163A1
    申请号:FR1461273
    申请日:2014-11-20
    公开日:2016-03-25
    发明作者:Sonia Sierra Aguado；Bernd Wiskemann
    申请人:Mof Applic Services；
    IPC主号:
    专利说明:

    [0001] FIELD OF THE INVENTION The present invention relates to a trithermal cold adsorption cooling / heating method or process, based on MOF as a solid adsorbent, in certain ranges. depending on the MOF used. The invention also relates to air conditioning systems with fan coil or floor or ceiling cooling, and dehumidification 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 adsorbates 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 To the internal evaporation temperature at which cold Qo is produced, Tc the intermediate temperature of thermal rejection of Q (condensation and adsorption) and finally TA the internal temperature of the hot source that provides Qg for 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 adsorption time (power specific cooling: "SCP" or "specific cooling power". See Figure 1. Thus, the efficiency of the thermal transformation process is expressed: (i) By the coefficient of performance (COP) COP = 0,10 -s ,, - -s_g = QEvaporation / QDsorption The 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 short alcohols (methanol, ethanol) and in particular water. (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 Qdt or SCP 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 the heat transfer (time 1 0 necessary for the transfer of heat amounts of an element to a other, whose rate of conduction / convection of heat is an element). The performance (SCP) of a cold machine may be limited either by: - 1) the small amount of coolant cycled in a cycle (eg, silica gel) as adsorbent) = the COP - 2) the low rate of adsorption / desorption of the refrigerant in the adsorbent (eg silica gel ("silica gel" in English)) - transport of material - 3) the low transfer rate thermal = heat conduction of the adsorbent and the adsorber and its interface. In order to minimize the thermal loads or the size of the cold-machine devices, adsorbents with high adsorption capacity under the 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. 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 adsorption 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 [ 19]. 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 (isothermal profile according to IUPAC classification), 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 cycled refrigerant in a cycle (COP) - 2) adsorption / desorption rate of the refrigerant in the adsorbent - 3) thermal transfer rate = heat conduction between the adsorbent and the adsorber. DESCRIPTION OF THE INVENTION 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. A. Closed System According to the Invention - General Description In one aspect, the present invention relates to a closed cold adsorption cooling / heating trithermal method or system comprising: a. a refrigerant fluid (F) selected from water, alcohols and hydrocarbons; b. a condensation module (C) of said refrigerant (F), in thermal connection with a water circuit (CWTmoyen) whose water temperature at the outlet of the circuit is Tc; c. an evaporation module (E) of said refrigerant fluid (F), in thermal connection with a water circuit (CWTbasse) whose water temperature at the outlet of the circuit is Te; d. at least one adsorption / desorption module (AD) containing a solid adsorbent (A) consisting of a porous hybrid metallo-organic metallo-organic material (MOF), the adsorption / desorption module (AD) being alternately in connection fluid 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 (E) and condensation (C) module, respectively, and according to the temperature Tmcw to which the MOF material is subjected. Advantageously, the system is implemented so that the AD module is alternately put in adsorption then desorption mode.
    [0002] Advantageously, the system contains 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) then (AD ') is in fluid connection with the evaporation module (E), and vice versa. An exemplary configuration of such a system is shown in Figure 2. Advantageously, the refrigerant fluid (F) may be water, an alcohol or a hydrocarbon; preferably water or an alcohol. The alcohol may be methanol or ethanol. Advantageously, the refrigerant fluid (F) may be water. Advantageously, the refrigerant fluid (F) may be methanol or ethanol. 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 water circuit (CWT medium) or between evaporation module (E) and the circuit (CWTbasse) - For example, the thermal connection can be made via a heat exchanger. Alternatively, the thermal connection can be made by passing the water 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 water circuit passing through it, or conversely allowing the transfer of the adsorbed heat into the evaporation module (E) in the water circuit passing through it. The term "fluidly connected" as used herein refers to a connection means for the transfer of refrigerant vapor between the elements to which it 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 may 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. 2. Advantageously, this fluid connection may be controlled by a valve, which can be either in the closed position (no refrigerant vapor transfer from one module to another), or in the open position. It will be said that one module is in fluid connection with another when the valve connecting them is open.
    [0003] Advantageously, when the system has two modules (AD) and (AD '), the two adsorption / desorption modules contain the same solid adsorbent MOF, and are not in fluid connection with the condensation module (C) or the evaporation module (E) simultaneously. Advantageously, in the desorption mode, the adsorbent MOF is subjected to a temperature Tmcw such that Tmax> T-MOF> Tc, in which Tc represents the temperature of the water at the outlet of the water circuit (CWTmoyen), and Tmax represents the high range of the temperature at which the MOF is regenerated (ie it desorbs the refrigerant molecules). Of course, Tmax will be lower than the temperature at which the MOF is likely to decompose or degrade. The value of Tmax depends on the MOF used. Typically, a temperature Tmax of at least 85 ° C will regenerate the MOFs that may be used in the context of the present invention. Advantageously, Tmax may be between 60 ° C and 120 ° C, preferably between 60 ° C and 100 ° C, more preferably between 70 ° C and 90 ° C. An advantage of MOFs over conventionally used adsorbents is that they can be regenerated at lower temperatures. Advantageously, when the adsorption / desorption module (AD) or (AD ') is in desorption mode, the heat source for heating the MOF material at the temperature Tmax> Tmcw> Te is chosen from among the solar panels, the burners such as natural gas boilers, geothermal energy, fatal heats. Advantageously, the thermal connection between the refrigerant fluid (F) and the water circuits (CW, ..., .. Tmoyen) and (CWTbasse) of the condensation and evaporation modules, respectively, is ensured by an exchanger thermal (ET). In what follows, the elements described above in the "general description" part (F, C, CWT average, Tc, CWTbass, AD, A, E, AD ', etc.) are repeated in embodiments 1 to 3 which follow, adding an index (eg F1) to designate the embodiment concerned. Embodiment 1: For all the variants described in part A above for the closed system (general description), the solid adsorbent (A1) may consist of a porous hybrid organic-metal material (MOF) selected from zirconium fumarates, such as MOF-801, and aluminum aminoterephthalates, such as Al-CAU-10, and the adsorption / desorption operating parameters may be as follows: in adsorption mode: adsorption / desorption (AD1) is in fluid connection with evaporation module (El); the 25 - the MOF material is subjected to a Typcm temperature. = Tel; wherein Tel represents 45 ° C ± 4 ° C or 50 ° C ± 5 ° C, for use of the system as a fan coil or cooling surface, respectively; - 0.0 <Pe / Psat (e) 0.2; preferably / Pe. Psat (e) -0.1; and - Tel represents 5 ° C ± 2 ° C or 12 ° C ± 3 ° C, for use of the system as a fan coil or cooling surface, respectively; wherein: Pe / Psat (e) represents the partial vapor pressure value of the coolant (or relative humidity value when the coolant is water) in the evaporation module (El); pe represents the pressure of the refrigerant fluid (F1) in the gas phase in the evaporation module (E 1); and Psat (e) represents the saturating vapor pressure of the refrigerant fluid (F1) at the adsorption temperature thereof by the porous hybrid organic-metal material; in desorption mode: the adsorption / desorption module (AD1) is in fluid connection with the condensation module (C 1); the MOF material is subjected to a temperature Tmcw, such that Tmax> T -MOF> Tel; in which Tel is as defined above and Tma, is between 60-100 ° C; 0.0 <pc / Psat (c) 0.1; and Tel represents 45 ° C ± 4 ° C or 50 ° C ± 5 ° C, for use of the system as a fan coil or cooling surface, respectively; wherein: PciPsat (e) represents the partial vapor pressure value of the coolant (or relative humidity value when the coolant is water) in the condensing module (Cl); FI, represents the pressure of the refrigerant fluid (F1) in the gas phase in the condensation module (Cl); and Psat (c) represents the saturating vapor pressure of the refrigerant fluid (F1) at the desorption temperature thereof of the porous hybrid organic-metal material.
    [0004] Advantageously, Ti represents 5 ° C. ± 2 ° C. in adsorption mode, and Ti represents 45 ° C. ± 4 ° C. in the desorption mode. In this mode of operation, the method or system may be suitable for a fan coil air-conditioning system. Thus, the invention also provides a fan coil air conditioning system implementing this mode of operation. Advantageously, Tel represents 12 ° C. ± 3 ° C. in adsorption mode, and Tel represents 50 ° C. ± 5 ° C. in the desorption mode. In this mode of operation, the method or system may be suitable for an air conditioning system with floor or cooling ceiling. Thus, the invention also provides a floor cooling system or cooling ceiling implementing this mode of operation. Embodiment 2: For all the variants described in Part A above for the closed system (general description), the solid adsorbent (A2) may be made of a porous hybridized metallo-organic material (MOF) selected Among the aluminum aminoterephthalates, such as Al-CAU-10, and the adsorption / desorption operating parameters may be as follows: in adsorption mode: the adsorption / desorption module (AD2) is in fluid connection with the module evaporation (E2); the MOF material is subjected to a temperature Tmcw = Tc2; wherein Tc2 is 35 ° C ± 4 ° C or 45 ° C ± 4 ° C, for use of the system as a fan coil or a cooling surface, respectively; 0.05 pe / psat (e) 0.25; preferably pelpsate (e) = 0.15; and Te 2 represents 5 ° C ± 2 ° C or 12 ° C ± 3 ° C, for use of the system as a fan coil or cooling surface, respectively; wherein: Pe / Psat (e) represents the partial vapor pressure value of the coolant (or relative humidity value when the coolant is water) in the evaporation module (E2); pe represents the pressure of the refrigerant fluid (F2) in the gas phase in the evaporation module (E2); Psat (e) represents the saturation vapor pressure of the refrigerant fluid (F2) at the adsorption temperature thereof by the porous hybrid organic-metal material; in desorption mode: the adsorption / desorption module (AD2) is in fluid connection with the condensation module (C2); the MOF material is subjected to a temperature Tmcw, such that Tmax> T - MOF> Tc2; in which Tc2 is as defined above and Tma, is between 60-100 ° C; 0.05 171c / Psat (c) 0.15; and Tc2 represents 35 ° C ± 4 ° C or 45 ° C ± 4 ° C, for use of the system as a fan coil or a cooling surface, respectively; wherein: Pc / Psat (c) represents the partial vapor pressure value of the coolant (or relative humidity value when the coolant is water) in the condensation module (C2); FI, represents the pressure of the refrigerant fluid (F2) in the gas phase in the condensation module (C2); Psat (c) represents the saturating vapor pressure of the refrigerant fluid (F2) at the desorption temperature thereof of the porous hybrid organic-metal material. Advantageously, Te 2 represents 5 ° C. ± 2 ° C. in adsorption mode, and Tc 2 represents 35 ° C. ± 4 ° C. in the desorption mode. In this mode of operation, the method or system may be suitable for a fan coil air-conditioning system. Thus, the invention also provides a fan coil air conditioning system implementing this mode of operation. Advantageously, Te 2 represents 12 ° C. ± 3 ° C. in adsorption mode, and Tc 2 represents 45 ° C. ± 5 ° C. in the desorption mode. In this mode of operation, the method or system may be suitable for an air conditioning system with floor or cooling ceiling. Thus, the invention also provides a cooling system floor or ceiling refreshing implementing this mode of operation. Embodiment 3: For all the variants described in Part A above for the closed system (general description), the solid adsorbent (A3) may be made of a porous hybrid organic-metal material (MOF) selected from zirconium aminoterephthalates, such as Zr-UiO-66-NH2, zirconium methanetetrabenzoates, such as Zr-UiO-MTB (MOF-814), and aluminum fumarates, such as Basolite A520, and the 10 parameters. The adsorption / desorption operating mode can be as follows: in adsorption mode: the adsorption / desorption module (AD3) is in fluid connection with the evaporation module (E3); the MOF material is subjected to a temperature Tmcw = Tc3 in which Tc3 represents 25 ° C ± 4 ° C or 30 ° C ± 4 ° C for use of the system as a fan coil, or 35 ° C ± 4 ° C or 40 ° C ° C ± 4 ° C, for use of the system as a cooling surface; 0.10 Pe / Psat (e) 0.35; preferably JPsat (e) = 0.20 or 0.25; and Te3 represents 5 ° C ± 2 ° C or 12 ° C ± 3 ° C, for use of the system as a fan coil or cooling surface, respectively; wherein: Pe / Psat (e) represents the partial vapor pressure value of the coolant (or relative humidity value when the coolant is water) in the evaporation module (E3); 25 pe represents the pressure of the refrigerant fluid (F3) in the gas phase in the evaporation module (E3); Psat (e) represents the saturating vapor pressure of the refrigerant fluid (F3) at the adsorption temperature thereof by the porous hybrid organic-metal material; In desorption mode: the adsorption / desorption module (AD3) is in fluid connection with the condensation module (C3); the MOF material is subjected to a temperature TmoF, such that Tmax> TMOF> r1 ', 3; wherein Tc3 is as defined above and Tn, is between 60-100 ° C; 0.10 Pc / Psat (c) 0.20 or 0.15 pc / Psat (c) 0.25; and Tc3 is 25 ° C ± 4 ° C, 30 ° C ± 4 ° C, 35 ° C ± 4 ° C or 40 ° C ± 4 ° C, for use of the system as a fan coil or a cooling surface, respectively; wherein: PciPsat (e) represents the partial vapor pressure value of the coolant (or relative humidity value when the coolant is water) in the condensation module (C3); FI, represents the pressure of the refrigerant fluid (F3) in the gas phase in the condensation module (C3); Psat (c) represents the saturating vapor pressure of the refrigerant fluid (F3) at the desorption temperature thereof of the porous hybrid organic-metal material. Embodiment 3a: Advantageously, the solid adsorbent (A3) may consist of a porous hybrid organic-organic material (MOF) selected from zirconium aminoterephthalates, such as Zr-UiO-66-NH2, and Adsorption / desorption operating parameters are as follows: in adsorption mode: the MOF material is subjected to a temperature TmoF = Tc3 in which Tc3 represents 30 ° C ± 4 ° C or 40 ° C ± 4 ° C, for use of the system as a fan coil or cooling surface, respectively; 0.10 Pe / Psat (e) 0.30; preferably P - / Psat (e) = 0.20; and Te3 represents 5 ° C ± 2 ° C or 12 ° C ± 3 ° C, for use of the system as a fan coil or cooling surface, respectively; in desorption mode: the MOF material is subjected to a temperature TmoF, such that Tma, s> TMOF> Tc3; wherein Tc3 is as defined above and Tn, is between 60-100 ° C; 0.10 171c / Psat (c) 0.20; and Tc3 represents 30 ° C ± 4 ° C or 40 ° C ± 4 ° C, for use of the system as a fan coil or cooling surface, respectively. Advantageously, Te3 represents 5 ° C. ± 2 ° C. in adsorption mode, and Tc3 represents 30 ° C. ± 4 ° C. in the desorption mode. In this mode of operation, the method or system may be suitable for a fan coil air-conditioning system. Thus, the invention also provides a fan coil air conditioning system implementing this mode of operation. Advantageously, Te3 represents 12 ° C. ± 3 ° C. in adsorption mode, and Tc3 represents 40 ° C. ± 4 ° C. in the desorption mode. In this mode of operation, the method or system may be suitable for an air conditioning system with floor or cooling ceiling. Thus, the invention also provides a cooling system floor or ceiling refreshing implementing this mode of operation. Embodiment 3b: Advantageously, the solid adsorbent (A3) may consist of a porous hybrid organic-organic material (MOF) chosen from zirconium aminoterephthalates, such as Zr-UiO-66-NH2, zirconium methanetetrabenzoates , such as Zr-UiO-MTB (MOF-814), and aluminum fumarates, such as Basolite A520, and the adsorption / desorption operating parameters are as follows: in adsorption mode: the MOF material is subjected to a temperature TmoF = Tc3 wherein Tc3 represents 25 ° C ± 4 ° C or 35 ° C ± 4 ° C, for use of the system as a fan coil or cooling surface, respectively; 0.15 pe / Psat (e) 0.35; preferably PciPsat (e) = 0.25; and Te3 represents 5 ° C ± 2 ° C or 12 ° C ± 3 ° C, for use of the system as a fan coil or a cooling surface, respectively; in desorption mode: the MOF material is subjected to a temperature TmoF, such that Tmax> TMOF> 1 - ', 3; wherein Tc3 is as defined above and Tn, is between 60-100 ° C; 0.15 pc / Psat (c) 0.25; and Tc3 represents 25 ° C ± 4 ° C or 35 ° C ± 4 ° C, for use of the system as a fan coil or a cooling surface, respectively. Advantageously, Te3 represents 5 ° C. ± 2 ° C. in adsorption mode, and Tc3 represents 25 ° C. ± 4 ° C. in the desorption mode. In this mode of operation, the method or system may be suitable for a fan coil air-conditioning system. Thus, the invention also provides a fan coil air conditioning system implementing this mode of operation. Advantageously, Te3 represents 12 ° C. ± 3 ° C. in adsorption mode, and Tc3 represents 35 ° C. ± 4 ° C. in the desorption mode. In this mode of operation, the method or system may be suitable for a cooling floor or ceiling cooling system. Thus, the invention also provides a cooling system floor or ceiling refreshing implementing this mode of operation. In each of Embodiments 1 to 3, the cooling surface may be a cooling floor and / or ceiling. In each of Embodiments 1 to 3, the MOF adsorbent may be shaped by any method known in the art of cold-adsorption cooling / heating trithermal systems (eg stationary bed, adhesive coating or composite). Advantageously, the MOF adsorbent can be formed on a metal heat exchanger according to a method allowing the growth of MOF directly on the surface of a metal support (i.e., without binder, adhesive or composite). This may be, for example, a method of 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 an oxide layer metallic; (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 zu2 + ion, Ti3 +, Ti4 +, zr2 +, zr4 +, ±, ±, ca2 cu2 metal selected from Al3 ±, Fe2 +, Fe3 +, Gd3 +, mg2 +, mu2 +, mu3 +, mu4 + or if, - 4+; preferably Zr4 + or A13 +; and (b) at least one ligand L selected from a di-, tri- or tetracarboxylate ligand selected from: C2H2 (CO2) 2 (fumarate), C2114 (CO2) 2 (succinate), C3116 (CO2) 2 (glutarate), C4H4 (CO2) 2 (muconate), C4H8 (CO2) 2 (adipate), C71114 (CO2) 2 (azelate), C5H3S (CO2-) 2 (2,5-thiophene dicarboxylate), C6H4 (CO2) 2 (terephthalate), C6114 (CO2) 2 (isoterephthalate), C6H2N2 (CO2) 2 (2,5-pyrazine dicarboxylate), C10H6 (CO2-) 2 (naphthalene-2,6-dicarboxylate), C12H8 (CO2) 2 (biphenyl) -4,4'-dicarboxylate), C12H8N2 (CO2) 2 (azobenzenedicarboxylate), C6H3 (CO2-) 3 (benzene-1,2,4-tricarboxylate), C6H3 (CO2) 3 (1,3,5-benzene), 1 5 tricarboxylate), C24H15 (CO2) 3 (benzene-1,3,5-tribenzoate), C6H2 (CO2) 4 (1,2,4,5-benzene-tetracarboxylate, C10H4 (CO2) 4 C10H4 (CO2) 4 (naphthalene-2,3,6,7-tetracarboxylate), (naphthalene-1,4,5,8-tetracarboxylate), C12H6 (CO2-) 4 (biphenyl-3,5,5 ', 5'-tetracarboxylate) , 2-aminoterephthalate, 2-nitroterephthalate, 2-methylterephthalate, 2-chloroterephthalate, 2- Bromoterephthalate, 2,5-dihydroxterephthalate, tetrafluoroterephthalate, tetramethylterephthalate, dimethyl-4,4'-biphenydicarboxylate, tetramethyl-4,4'-biphenydicarboxylate, dicarboxy-4,4'-biphenydicarboxylate, or 2,5-dihydroxterephthalate; 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 48-36 hours, preferably at least 48-36 hours, hours; (v) Remove the metal support from the MOF material precursor solution / suspension, (vi) Rinse the support with a suitable solvent (vii) Dry in air at 40-60 ° C, preferably 45-55 ° C preferably at 50 ° C.
    [0005] In step (ii), the ligand L may also represent 2,5 diperfluoroterephthalate, azobenzene 4,4'-dicarboxylate, 3,3'-dichloro azobenzene 4,4'-dicarboxylate, 3,3'-dihydroxo azobenzene 4 , 4'-dicarboxylate, 3,3'-diperfluoroazobenzene 4,4'-dicarboxylate, 3,5,3 ', 5'-azobenzene tetracarboxylate, 2,5-dimethyl terephthalate, perfluorosuccinate, perfluoromuconate, perfluoro glutarate, 3,5 , 3 ', 5' perfluoro-4,4'-azobenzene dicarboxylate, 3,3'-diperfluoro azobenzene 4,4'-dicarboxylate. Advantageously, the ligand L may represent C2H2 (CO2-) 2 (fumarate), C6H4 (CO2) 2 10 (terephthalate), C6H4 (CO2-) 2 (isoterephthalate), 2-aminoterephthalate, MTB (methanetetrabenzoate), or 1,4-benzenedicarboxylate. Advantageously, the metal support may be copper or aluminum, and may be in the form of a plate, a honeycomb shape ("honeycomb shape" in English), or any form used in heat exchangers, for example a flat tube with fins. Advantageously, step (i) may be carried out by any means known to those skilled in the art, for example by a thermal or chemical treatment of the surface of the adsorber, and which is specific and adapted to the material of the adsorber and adsorbent. 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 period of time sufficient to effect the oxidation of the surface of the copper. copper support. 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 the aluminum), 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, such as for example hydrothermal or solvothermal conditions, but also by microwaves, by ultrasound, by grinding, by a process involving a supercritical fluid, etc. 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.
    [0006] Byrapsa, et al. "Handbook of Hydrothermal Technology," Noyes Publications, Parkridge, NJ, William Andrew Publishing, LLC, Norwich NY USA, 2001 [14]. For microwave synthesis, nonlimiting examples of usable protocols are described for example in G. Tompsett, et al. ChemPhysChem. 2006, 7, 296 [15]; in S.-E. Park, et al. Catal. Survey Asia 2004, 8, 91 [16]; in C. S. Cundy, Collect. Czech. Chem. Commom. 1998, 63, 1699 [17]; or in S. H. Jhung, et al. Bull. Kor. Chem. Soc. 2005, 26, 880 [18]. 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 [14]. 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 dimethylformamide (DMF). 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 chosen from HF, HCl, HNO 3, H 2 O 4, NaOH, KOH, lutidine, ethylamine, methylamine, ammonia, urea, EDTA, tripropylamine, pyridine, etc. . Advantageously, HC1 can 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, cold machines), this MOF shaping in a layer directly on the metal support makes it possible to optimize the heat transfer rate, and to reduce the 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 reduction of 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.
    [0007] The above method has the advantage of allowing the deposition of an MOF adsorbent 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 lead to a two-fold reduction in sensible heat 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.
    [0008] According to another aspect, in each of the embodiments 1 to 3, the invention also relates to a use of the method or system according to the invention as described above in any of the embodiments 1 to 3 for cooling or heating in a fan coil air conditioning system, or a cooling floor or ceiling. B. Open System According to the Invention Desiccant cooling systems are open cycle systems using refrigerant in direct contact with air. The cooling cycle consists of a combination of evaporative cooling and dehumidification of the air using a desiccant material. The term "open" indicates that the refrigerant can not be reused after providing the desired cooling, so new refrigerant must be re-injected into the system. Under these conditions, the only refrigerant that can be used is water because it will be in contact with the air supplied to the building. Usually, this technology uses rotating desiccant wheels as desiccant material. Apparatuses and methods for the exchange of heat and moisture between two drafts are known (see for example EP-0846923-A). Such apparatus and methods are used for improving ambient air, for example, small houses and buildings, ie for cooling and drying outdoor air that is introduced into a building in summer and for heat and humidify the air during the winter before the air is transferred into the building. However, there is a problem when the outside air is hot and humid, ie when the temperature is higher than 35 ° C and the external relative humidity p / psat is greater than 0.25, since the known devices are not suitable for treating this air. A particular design of these systems is required for use in extreme climates such as for Asian coastal regions. Indeed, due to the high humidity of the ambient air, the standard configuration of this system is not sufficient to reduce the humidity to a sufficient level to then use a direct evaporative cooling. Thus, there are other methods adapted to a specific climate that are either already used on installations or still in the development stage. Silica gel type adsorbents are most often used in the desiccating wheels of open cycles. OEMs have selected specific adsorbents for their wheels. Overall, we can say that for temperate climates, the wheels are very efficient and give excellent results. Nevertheless, this is not the case for humid tropical climates where the wheels are absolutely not adapted. Thus, an open cycle is shown in Figure 4 corresponding to typical humid tropical climate conditions. Consider air at 34 ° C and 80% relative humidity, point 1 (a content of 27.5g of water per kg of dry air), a fairly common situation in agglomerations in humid tropical zones (Figure 4). ). Point 2, at the wheel outlet, corresponds to a content of 20.5 g of water per kg of dry air (ie a loss of 7 g / kg of dry air) and a relative humidity of approximately 27% at 50 ° C. . Dehumidification is therefore insufficient to allow entering the comfort zone in the subsequent operations. Hence the need to use a chiller to cool from point 3 to point 4. The present invention addresses this technical problem by eliminating the aforementioned problems and by providing a method and apparatus that functions effectively in the conditions of high humidity above. Thus, according to another aspect, the present invention relates to an adsorption dehumidification process comprising the combination of a desiccant drying system with a solid (A5) consisting of a porous hybrid organic-metal material (MOF). ) selected from aluminum carboxylates, such as Al-MIL-100, zirconium fumarates, such as MOF-801, or MOF-841 (Zr-UiO-MTB), as the desiccant adsorbent. The adsorbent (A5) disposed on the desiccant wheel makes it possible to dehumidify and cool a first flow of air supplied from the ambient air (outside) to the interior of a building, and to restore a second flow of hot air and moist from the interior of said building bers the ambient air (outside). Indeed, the MOF-801 which has a high adsorption capacity up to 20% H.R. (relative humidity) looks promising and be suitable for such an application. Similarly MOF-841 which has a very high adsorption capacity for a H.R. between 100 and 25% can be interesting. An example of a device adapted to the implementation of this dehumidification process is illustrated in FIG. 3.
    [0009] Principle of operation, as shown in Figure 3: In summer (heater 4-5 is not used) In (1) the hot and humid outside air enters the system and passes through the desiccant wheel which is in slow rotation. While passing through this wheel (1-2), the air is dehumidified by the adsorption of the water. This phenomenon also implies an increase in the temperature of the air due to the heat of adsorption. Then the air passes through another wheel that is in fact a heat exchanger (2-3). The air is therefore cooled significantly. Finally, the air passes through a humidifier (3-4) in which its humidity is increased to its setpoint, and its temperature is further reduced. So we get in (5) fresh and dry air. In (6), a warmer and moister air is recovered than the distributed air. It will still be humidified in another humidifier (6-7) to arrive close to its saturation point. Then, the air passes through the heat exchanger (7-8), so this wheel will be cooled as the air warms up. This phenomenon has the effect of "regenerating" the properties of the heat exchanger wheel. Then, the air is still warmed thanks to the solar energy via the heater (8-9). Lastly, the desiccant wheel is regenerated (9-10) thanks to the hot air. In other words, as hot air passes, the humidity in the wheel decreases as the humidity in the warm air increases. In winter the heater (4-5) is used to heat the air entering the building. In order to operate, the system needs a relatively low sensor temperature (50 ° C to 75 ° C) so planar sensors are sufficient, and air sensors can sometimes be used. A storage tank can also be used to extend the use of the system. Thus, according to one aspect of the invention, an air conditioning method is proposed by exchange of heat and moisture between two air streams, one of the two being hot and humid, at least during a first part of the year, in which a first air flow is brought from the ambient air to the interior of a building and a second of said air flows is brought from inside said building to the ambient air, whereby said first air stream is transferred through a dehumidifier (a) and then transferred through a heat exchanger (b) before being transferred inside said building, while said second air stream is cooled and then transferred through said heat exchanger (b) after which it is transferred through said dehumidifier (a) characterized in that the first air stream has a relative humidity (RH) of 0.15 <HR <0.60; preferably 0.25 <HR <0.50, and the dehumidifier is an adsorption dehumidifier comprising a solid absorbent (A5) made of a porous hybrid organic-metal material (MOF) selected from aluminum carboxylates, such as Al-MIL-100, zirconium fumarates, such as MOF-801, or MOF-841 (Zr-UiO-MTB). According to another variant, said first air flow is, at least during a second part of the year, colder and less humid in absolute terms than the second air flow.
    [0010] Advantageously, the dehumidifier is a desiccant wheel. For example, a Munters type desiccant wheel can be used. Advantageously, the first air flow can be humidified by passing through a humidifier (cl) after passing through the heat exchanger (b). This step makes it possible to adjust the humidity of the first air flow to a set value before it is transferred to the building. Advantageously, the first air stream can be heated by passing through a heater (d1) after passing through the heat exchanger (b), and possibly into the humidifier (c1). This step makes it possible to adjust the temperature of the first air flow to a set value before it is transferred to the building. Preferably, the heating system (dl) will be used during the cold months of the year (eg during the winter), and will not be used during the summer months. Advantageously, the second air stream may be humidified by passing through a humidifier (c2) after passing through the heat exchanger (b). This step makes it possible to adjust the humidity of the second air flow to a value close to its saturation point before it is transferred to the ambient air (outside the building). Advantageously, the second air flow can be heated by passing through a heater (d2) after passing through the heat exchanger (b), and possibly into the humidifier (c2). This step makes it possible to adjust the temperature of the second air flow to a set value before it is transferred into the dehumidifier. The hot air flow can "regenerate the adsorbent dehumidifier: the passage of hot air, moisture in the dehumidifier decreases as the moisture in the second flow of air to the outside increases Advantageously, the heating systems (d1) and (d2) can be powered by solar panels. The system can be equipped with a storage tank (buffer tank) containing hot water (see Figure 3). According to another aspect, there is provided a dehumidification system implementing an air conditioning method by exchange of heat and moisture between two air flows according to the invention. For example, a system as shown in Figure 3 can be used. According to another aspect, it is proposed to use a dehumidification method or system according to the invention for the dehumidification of the ambient air.
    [0011] The MOF materials mentioned in the various embodiments described in the context of the present invention are known, and their synthesis and characterization have been reported in the literature: 1) Zr-Ui0-66: Cavka et al., J. Am. Chem. Soc., 2008, 130, 13850 [7] 2) Zr-U10-66-NH2: Kandiah et al J. Mater. Chem., 2010,20, 9848-9851 [9] 3) Zr-fumarate (MOF-801): ref [6] and Wifmann et al., Microporous mesoporous mater., 2012, 152, 64 [8] 4) MOF -841: ref [6] 5) Al-CAU-10: Reinsch et al, Chem. Mater. 2013, 25, 17-26 [10] 6) Al-fumarate (Basolite A520): EP2230288 7) Al-MIL 100: Volkringer, tChem. Mater. 2009, 21, 5695-5697 [11] Brief Description of the Figures - Figure 1 schematizes the principle of operation of cold machines using solid adsorbates in a trithermal (closed) system. FIG. 2 represents an exemplary configuration of a trithermal cooling / heating system with adsorption for a cold machine, with two adsorption / desorption modules operating in phase opposition. FIG. 3 represents an example of an air conditioning device by exchange of heat and humidity between two air flows according to the invention (open system). - Figure 4: Representation, in a psychometric diagram, of the open cycle supplemented by a LRG (evolution 3-4) in humid tropical climate (the reader can refer to "Solar air conditioning", FM and D. Mugnier, Dunod for further teaching) - Figure 5 represents a comparison of isothermal adsorption profiles of water MOFs Zr-Ui0-66 and Zr-Ui0-66-NH2 with various other solid adsorbents (MCM-41, silica gel Fuji RD , SAPO-34, and 13X). The two identified operating modes (dashed areas) correspond to two examples of potential operating modes for a closed trithermal cooling / adsorption heating system equivalent to that of FIG. 2, using MOF Zr-UiO-66-NH2. and MOF Zr-U10-66, respectively. The two operating modes were defined from the isothermal adsorption profiles of these MOFs, in particular as a function of / around the point of inflection of the Zr-UiO-66-NH2 MOF isotherm and that of the MOF. Zr-Ui0-66. "Te" corresponds to the temperature of the water at the outlet of the water circuit in thermal connection with the evaporation module (internal temperature of evaporation of the refrigerant), "Te" corresponds to the temperature of the water in output of the water circuit in thermal connection with the condensation module (intermediate temperature of thermal rejection), and "T'g" corresponds to the regeneration temperature to which the adsorbent is subjected in desorption mode (equivalent to "TMOF" in Figure 2). FIG. 6 represents an image of the section of a copper foil coated with MOF Zr-Ui0-66 according to Example 2a, using an electron microscope. FIG. 7 represents an image of the section of a copper foil 30 coated with MOF Zr-UiO-66 composite according to example 2b, using an electron microscope. FIG. 8 represents an image of the section of an aluminum foil coated with MOF Zr-fumarate according to Example 2e, using an electron microscope. Table 1 lists a comparison of the amounts of adsorbed water (in% of the anhydrous adsorbent mass) of different adsorbents relative to Fuji silica gel. Table 2 lists the comparative results of Example 1 EXAMPLES Some MOF solids which are porous coordination polymers exhibit adsorption-desorption capacities of interest for certain adsorptions and disorptions conditions, in particular at low vapor pressure. 'water. These performances come from the particular isothermal profile called "S" (type V by the IUPAC nomenclature). MOF adsorption isotherms advantageously used in the context of the present invention have been reported in the literature: Water adsorption isotherms of MOF Zr-UiO-66: [3] MOF water adsorption isotherm Zr-UiO-66-NH2: [4] Water adsorption isotherm of MOF Zr-UiO-66-NH2: [5] Water adsorption isotherms of MOF Zr-UiO-fumarate (MOF-801) : [6].
    [0012] Water adsorption isotherm of MOF Zr-Ui0-MTB (MOF-841): [6] Water adsorption isotherm of MOF Al-CAU-10: [6]. Water adsorption isotherm of MOF Basolite A520 [2] In summary, the MOFs mentioned are characterized by: - Large adsorptions of water at low relative pressure of water vapor (HR <40%) - A adsorption profile in "S" more or less marked which gives them a high capacity for cycling in a narrow window of pressure. However, the "S" adsorption character implies that an adsorbent performs only in a narrow range of partial pressure. Thus, Zr-terephthalate (Ui066) only makes it possible to cycle a quantity of water of less than 5% between an H.R between 10 and 30% whereas Fuji silica can cycle a quantity of water greater than 10%. Reference for Ui0-66 = D. Wiersum,. Asian J. 2011, 6, 3270-3280). Example 1 - Comparative Performance The performance of several adsorbents was compared in different modes of operation. These comparative results are listed in Table 1.
    [0013] In this study, 4 operating modes P / P't were considered where P / P't (or relative humidity, HR or RH) is the ratio between the pressure in the evaporator (or the condenser) and P't is the saturated vapor pressure corresponding to the adsorption temperature-which will be assumed equal to the condensation-(or desorption) temperature. The temperature of the thermal rejection depends on the type of cooling: water (in which case 25 ° C is possibly possible) or air and in the latter case, the temperature depends on the quality of cooling (cooling tower or simple refrigerant). In Table 1 is presented a comparison, for the 5 P / P't conditions studied, with respect to the Fuji silica gel (Fuji Davison RD silica gel) amounts of water adsorbed by the various adsorbents whose properties were provided . When the amount adsorbed by the 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 and about 3 times better, we use the +++ symbol. The absorbents mentioned in Table 1 and in FIG. 5 are known: they are either commercially available or their synthesis and characterization have been published: Silica gel: Fuji Davison RD silica gel Al-CAU-10: Reinsch et al, Chem . Mater. 2013, 25, 17-26 [10] MCM-41: reference 643645 Aldrich Silica, Mesostructured Cr-MIL-101-NH 2: Modrow et al, Dalton Trans., 2012, 41, 8690-8696 [12] Ti-MIL- 125: Dan-Hardi, et al J. Am. Chem. Soc. 2009, 131, 10857. [13] SAPO-34: The synthesis is described on the website of the IZA (International Zeolite Association) with the appropriate references. http: // www .iz a-online.org/synthesis/Recipes/SAP0-34.html Zr-UiO-66-NH2: The synthesis is described in Kandiah et al J. Mater. Chem., 2010,20, 9848-9851 [9] Zeolite 13X: 283592 Sigma-Aldrich, Molecular sieves, 13X The analysis of these comparative results made it possible to select the trinomials (relative humidity) / (Te / Tc) / MOF most suitable for optimal operation in various applications of cold adsorbent machines. The results of this analysis are listed in Table 2 (Te = evaporator temperature, Tc = condenser temperature). The adsorption properties of MOF Zr-UiO-66-NH2 make it a good candidate for cooling air conditioning applications (operating mode 3a and 3b). In addition, its desorption properties as a function of temperature demonstrate that its desorption is very effective between 60 and 70 ° C, making it an excellent candidate in terms of cyclic amount. The result is that the amount cyclized by UiO66-NH2 is 3 times that of silica gel. Example 2 Synthesis and Characterization of Coatings ("Coatings" in English) of MOF Example 2a: Cu / Ui0-66 Sheet A copper foil (50 × 50 mm) was sandblasted on both sides, treated ("etched" and English) in a solution of sodium hydroxide (pH> 12), deoxidized in dilute nitric acid (4 <pH <6), and air dried at 60 ° C. A solution containing 15.12 g (64.0 mmol) of ZrCl4, 10.8 g (65.2 mmol) of benzene-1,4-dicarboxylic acid, 11.44 mL of HCl in 200 mL of dimethylformamide (DMF) until the solution is completely transparent. The copper foil is then immersed in the solution in a Teflon coated stainless steel autoclave ("Teflonlined" in English). The mixture is heated to 120-160 ° C (preferably) for 48 hours. After cooling, the Cu sheet was carefully removed, rinsed three times in DMF and twice in EtOH and finally air-dried at 50 ° C. Example 2b: Composite UiO-66 / Polymer 1 UI0-66 powder was synthesized by successively adding 3.78 g of ZrC14 (16.2 mmol), 2.86 ml of 35% HCl (32.4 mmol), and 2.70 g of 1,4-benzene. dicarboxylic acid (16.3 mmol) to 100 ml of N, N'-dimethylformamide. The mixture was stirred until the solution was completely transparent, before being transferred and sealed in a Teflon-coated stainless steel autoclave ("Teflonlined" in English) where the mixture was heated to 220 °. C for 20 hours. The resulting microcrystalline powder was separated from the solvent by centrifugation and dried overnight in an oven set at 60 ° C. The UI0-66 powder was dispersed in DMF to form a homogeneous and white dispersion (15 mg m1-1) under ultrasound for 2 h. Then, 1270 μl of UI0-66 dispersion was added to a poly (MAA-co-EDMA) precursor containing 35 μl of MAA (methyl methacrylate) monomer, 400 μl of EDMA crosslinking agent and 400 mg of porogenic PEG 6000. After the above mixture was sonicated for 0.5 h, 10 mg AIBN initiator was added, and another 5 min sonication was required to dissolve the AIBN.
    [0014] A copper foil (50x50mm) was covered with the polymerization mixture using a syringe. After polymerization at 60 ° C for 24 h, the whole was washed with methanol to remove porogen and unreacted monomer.
    [0015] EXAMPLE 2c Composite Ui0-66 / Polymer 2 The crude UI0-66 samples were synthesized by successively adding 3.78 g of ZrC14 (16.2 mmol), 2.86 ml of 35% HCl (32.4 mmol). ) and 2.70 g of benzene-1,4-dicarboxylic acid (16.3 mmol) to 100 ml of N, N'-dimethylformamide. The mixture was stirred until the solution was completely transparent, before being transferred and sealed in a Teflon-coated stainless steel autoclave ("Teflonlined" in English) where the mixture was heated to 220 °. C for 20 hours. The resulting microcrystalline powder was separated from the solvent by centrifugation and dried overnight in an oven set at 60 ° C. The coating was prepared by a strip casting process. 0.3 g of 6FDA-ODA was dissolved in 10 ml of chloroform and the solution was filtered to remove undissolved materials and dust particles. Evaporation of the solvent was carried out to obtain a polymer solution of 10 to 12% by weight. The U10-66 powder was added to 5 ml of chloroform and sonicated for 1-2 minutes. About 10% of the polymer solution was then added to the MOF suspension U10-66. The suspension was stirred for 6 h. After good homogenization, the remaining amount of the polymer solution was added to the suspension and the final suspension was stirred again for 1 day. The suspension was then transferred to a vacuum oven for 30 minutes. to degass, then poured on a copper plate and covered to delay the evaporation of the solvent. After 48 h, the lid was removed to evaporate the residual chloroform for 24 h. The supported layers were then placed in a vacuum oven at 230 ° C for a 15 hour anneal, and the resulting membranes were finally slowly cooled to room temperature in the oven and stored in dryers.
    [0016] Example 2d: Cu / UiO-66-NH2 foil A copper foil (50x50 mm) was washed with ethanol for 30 minutes and then five times with water under ultrasound to clean the surface, and then placed in an oven at 100 ° C for oxidation. A solution containing 15.12 g (64.0 mmol) of ZrCl4, 11.81 g (65.2 mmol) of 2-amino-benzene-1,4-dicarboxylic acid, 11.44 ml of HCl was stirred. in 200 ml of dimethylformamide (DMF) until the solution is completely transparent. The copper 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.
    [0017] After cooling, the Cu sheet was carefully removed, rinsed five times in DMF and finally air-dried at 50 ° C.
    [0018] Example 2e: Al / Zr-fumarate 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.
    [0019] 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. D. Wiersum, Asian J. 2011, 6, 3270-3280. 4. Schoenecker, Ind. Eng. Chem. Res., 2012, 51, 6513. 5. Cmarik, Langmuir, 2012, 28, 15606. 6. Furukawa, J. Am. Chem. Soc., 2014, 136, 4369-4381. 7. Cavka et al., J. Am. Chem. Soc., 2008, 130, 13850 8. Wifmann et al., Microporous mesoporous mater., 2012, 152, 64. Kandiah et al J. Mater. Chem., 2010,20, 9848-9851. 10. Reinsch et al, Chem. Mater. 2013, 25, 17-26 11. Volkringer, t Chem. Mater. 2009, 21, 5695-5697 12. Modrow et al., Dalton Trans., 2012, 41, 8690-8696. 13. Dan-Hardi, et al J. Am. Chem. Soc. 2009, 131, 10857 14. K. Byrapsa, et al. Handbook of hydrothermal technology, Noyes Publications, Parkridge, NJ, William Andrew Publishing, LLC, Norwich, NY USA, 2001 15. G. Tompsett, et al. ChemPhysChem. 2006, 7, 296 16. S.-E. Park, et al. Catal. Survey Asia 2004, 8.91 17. C. S. Cundy, Collect. Czech. Chem. Commom. 1998, 63, 1699 18. S. H. Jhung, et al. Bull. Kor. Chem. Soc. 2005, 26, 880 19. EP204954925
    权利要求:
    Claims (12)
    [0001]
    REVENDICATIONS1. A trithermal cold adsorption cooling / heating method or system comprising: a. a refrigerant fluid (F3) selected from water and alcohols; b. a condensation module (C3) of said refrigerant fluid (F3), in thermal connection with a water circuit (CW3Tmoyen) whose water temperature at the outlet of the circuit is T3; c. an evaporation module (E3) of said refrigerant fluid (F3), in thermal connection with a water circuit (CW3Tbasse) whose water temperature at the outlet of the circuit is T3; d. at least one adsorption / desorption module (AD3) containing a solid adsorbent (A3) consisting of a porous hybrid organic-organic material (MOF) selected from zirconium aminoterephthalates, such as Zr-UiO-66-NH2, zirconium methanetetrabenzoates, such as Zr-UiO-MTB (MOF-814), and aluminum fumarates, such as Basolite A520, the adsorption / desorption module (AD3) alternately in fluid connection with said condensation module ( C3) and then said evaporation module (E3), which MOF material can adsorb or desorb the refrigerant (F3) depending on whether the adsorption / desorption module (AD3) is in fluid connection with the evaporation module ( E3) and of condensation (C3), respectively, and according to the temperature Tmcw 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 (AD3) is in fluid connection with the evaporation module (E3 ); the MOF material is subjected to a temperature Tmcw = Tc3 in which Tc3 represents 25 ° C ± 4 ° C or 30 ° C ± 4 ° C for use of the system as a convection heater, or 35 ° C ± 4 ° C or 40 ° C ± 4 ° C, for use of the system as a cooling surface; 0.10 Pe / Psat (e) 0.35; preferably17). - / Psat (e) -0.20 or 0.25; and Te3 represents 5 ° C ± 2 ° C or 12 ° C ± 3 ° C, for use of the system as a fan coil or a cooling surface, respectively; wherein: Pe / Psat (e) represents the relative humidity value in the evaporation module (E3); pe represents the pressure of the refrigerant fluid (F3) in the gas phase in the evaporation module (E3); Psat (e) represents the saturating vapor pressure of the refrigerant fluid (F3) at the adsorption temperature thereof by the porous hybrid organic-metal material; in desorption mode: the adsorption / desorption module (AD3) is in fluid connection with the condensation module (C3); the MOF material is subjected to a temperature Tmcw, such that Tinax> T - MOF> Te3; in which Tma is between 60-100 ° C; 0.10 nr Psat (c) 0.20 or 0.15 Pc / Psat (c) 0.25; and Te3 represents 25 ° C ± 4 ° C, 30 ° C ± 4 ° C, 35 ° C ± 4 ° C or 40 ° C ± 4 ° C, for use of the system as a fan coil or cooling surface, respectively; wherein: PciPsat (e) represents the partial vapor pressure value of the coolant (or relative humidity value when the coolant is water) in the condensation module (C3); FI, represents the pressure of the refrigerant fluid (F3) in the gas phase in the condensation module (C3); Psat (c) represents the saturating vapor pressure of the refrigerant (F3) at the desorption temperature thereof of the porous hybrid organic-metal material.
    [0002]
    A process or system according to claim 1, wherein the solid adsorbent (A3) consisting of a porous hybrid organic-organic material (MOF) selected from zirconium aminoterephthalates, such as Zr-UiO-66-NH2, and the adsorption / desorption operating parameters are as follows: in adsorption mode: the MOF material is subjected to a temperature Tmcw = Tc3 in which Tc3 represents 30 ° C ± 4 ° C or 40 ° C ± 4 ° C, for use of the system as a fan coil or cooling surface, respectively; 0.10 pe / Psat (e) 0.30; preferably 1 :), - / Psat (e) = 0.20; and Te3 represents 5 ° C ± 2 ° C or 12 ° C ± 3 ° C, for use of the system as a fan coil or a cooling surface, respectively; in desorption mode: the MOF material is subjected to a temperature TMOF, such that Tmax> TMOF> Tc3; wherein Tmax is from 60-100 ° C; 0.10 171c / Psat (c) 0.20; and Tc3 represents 30 ° C ± 4 ° C or 40 ° C ± 4 ° C, for use of the system as a fan coil or cooling surface, respectively.
    [0003]
    A process or system according to claim 1, wherein the solid adsorbent (A3) consisting of a porous hybrid organic metal-organic material (MOF) selected from zirconium aminoterephthalates, such as Zr-UiO-66-NH2, zirconium methanetetrabenzoates, such as Zr-UiO-MTB (MOF-814), and aluminum fumarates, such as Basolite A520, and the adsorption / desorption operating parameters are as follows: in adsorption mode: the MOF material is subjected at a temperature Tmcw = Tc3 in which Tc3 represents 25 ° C ± 4 ° C or 35 ° C ± 4 ° C, for use of the system as fan coil or cooling surface, respectively: 0.15 pe / Psat (e) 0 , 35; preferably pJpsat (e) = 0.25; and Te3 represents 5 ° C ± 2 ° C or 12 ° C ± 3 ° C, for use of the system as a fan coil or a cooling surface, respectively; in desorption mode: the MOF material is subjected to a temperature TmoF, such that Tmax> TMOF> Tc3; in which Tma is between 60-100 ° C; 0.15 171c / Psat (c) 0.25; and Tc3 represents 25 ° C ± 4 ° C or 35 ° C ± 4 ° C, for use of the system as a fan coil or a cooling surface, respectively.
    [0004]
    4. Method or system according to any one of claims 1 to 3, wherein the system contains two adsorption / desorption modules (AD3) and (AD3 '), each alternately in fluid connection with the condensation modules (C3). and evaporation (E3), so that when (AD3) is in fluid connection with the condensation module (C3) then (AD3 ') is in fluid connection with the evaporation module (E3), and vice versa.
    [0005]
    The method or system of claim 4, wherein the two adsorption / desorption modules contain the same solid adsorbent.
    [0006]
    The method or system of any one of claims 1 to 5, wherein when the adsorption / desorption module (AD3) or (AD3 ') is in desorption mode, the heat source for heating the MOF material to the temperature Tmax> 25 TmOF> Tc3 is chosen from solar panels, atmospheric burners such as natural gas boilers, geothermal energy, fatal heats.
    [0007]
    7. Method or system according to any one of claims 1 to 6, wherein the thermal connection between the refrigerant fluid (F3) and the water circuits (CW3 Tmoyen) and (CW3Tbasse) condensation and evaporation modules , respectively, is provided by a heat exchanger (ET3).
    [0008]
    The process or system of any one of claims 1 to 7, wherein Te3 is 5 ° C ± 2 ° C in adsorption mode, and Tc3 is 25 ° C ± 4 ° C or 30 ° C ± 4 ° C in desorption mode.
    [0009]
    The process or system of any one of claims 1 to 7, wherein Te3 is 12 ° C ± 3 ° C in adsorption mode, and Tc3 is 35 ° C ± 4 ° C or 40 ° C ± 4 ° C in desorption mode.
    [0010]
    Fan coil air-conditioning system embodying a method or comprising a system according to claim 8.
    [0011]
    11. Cooling floor or ceiling air conditioning system employing a method or comprising a system according to claim 9.
    [0012]
    12. Use of a method or system according to any one of claims 1 to 9 for cooling or heating in a fan-coil air conditioning system, or floor or ceiling cooling.
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    同族专利:
    公开号 | 公开日
    US20160084541A1|2016-03-24|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    EP3825627A1|2019-11-22|2021-05-26|Elektron Gri|System for cooling/heating by cascading adsorption/desorption|GB0808930D0|2008-05-16|2008-06-25|Sunamp Ltd|Energy Storage system|
    US8425674B2|2008-10-24|2013-04-23|Exxonmobil Research And Engineering Company|System using unutilized heat for cooling and/or power generation|
    MX368981B|2012-08-15|2019-10-23|Arkema Inc|Adsorption systems using metal-organic frameworks.|EP3504277B1|2016-08-23|2020-10-07|Basf Se|Composite materials|
    FR3063804B1|2017-03-10|2019-09-06|Mof Apps As|USE OF HYBRID METAL-ORGANIC MATERIAL IN AN ADSORPTION COOLING / HEATING SYSTEM FOR THERMAL BATTERY|
    JP2019171316A|2018-03-29|2019-10-10|大阪瓦斯株式会社|Humidity conditioning element and using method of the same|
    CN110396395A|2019-06-28|2019-11-01|湖北英特吉新能源科技有限公司|A kind of function reinforced metal organic frame base composite phase-change material and preparation method thereof|
    DE102019134587A1|2019-12-16|2021-06-17|Fahrenheit Gmbh|Heat exchanger and adsorption machine|
    法律状态:
    2015-11-25| PLFP| Fee payment|Year of fee payment: 2 |
    2016-09-09| PLFP| Fee payment|Year of fee payment: 3 |
    2017-09-11| PLFP| Fee payment|Year of fee payment: 4 |
    优先权:
    申请号 | 申请日 | 专利标题
    EP14290281|2014-09-18|EP15185194.6A| EP2998377A1|2014-09-18|2015-09-15|Uses of mof in an adsorption cooling/heating system|
    US14/858,949| US20160084541A1|2014-09-18|2015-09-18|Uses of mof in an adsorption cooling/heating system|
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