EP3073212A1 - Protection system of a reactive solid medium for a thermochemical reactor - Google Patents
Protection system of a reactive solid medium for a thermochemical reactor Download PDFInfo
- Publication number
- EP3073212A1 EP3073212A1 EP16162489.5A EP16162489A EP3073212A1 EP 3073212 A1 EP3073212 A1 EP 3073212A1 EP 16162489 A EP16162489 A EP 16162489A EP 3073212 A1 EP3073212 A1 EP 3073212A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- reactive medium
- assembly
- protective envelope
- solid reactive
- solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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Images
Classifications
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B35/00—Boiler-absorbers, i.e. boilers usable for absorption or adsorption
- F25B35/04—Boiler-absorbers, i.e. boilers usable for absorption or adsorption using a solid as sorbent
-
- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F25—REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
- F25B—REFRIGERATION MACHINES, PLANTS OR SYSTEMS; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS
- F25B17/00—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type
- F25B17/08—Sorption machines, plants or systems, operating intermittently, e.g. absorption or adsorption type the absorbent or adsorbent being a solid, e.g. salt
Definitions
- the present invention is in the field of apparatus for the transfer and storage of thermal energy, more particularly the field of thermochemical reactors.
- the present invention provides an assembly comprising a solid reactive medium intended to be placed in a thermochemical reactor.
- the present invention also relates to a thermochemical reactor comprising such a set and a method of manufacturing such a set and use thereof.
- thermochemical systems for the production of cold and / or heat. These systems are based on the thermal variations resulting from physico-chemical transformations of a pair of compounds capable of interacting with each other.
- one of the compounds is a fluid
- the other compound is a reactive salt associating with the fluid when they are contacted at a given temperature, but dissociating when the temperature increases.
- the fluid may be in gaseous form or in liquid form depending on the temperature and pressure conditions to which it is subjected. In some systems, it is stored in a liquid state in a tank which is separated by a valve from the reactor containing the reactive salt. At the opening of the valve, the fluid expands during which it vaporizes and will react chemically with the reactive salt. The change in state of the fluid (from liquid to gas) consumes energy and therefore induces a drop in temperature at the reservoir or evaporator if a fluid expansion valve is placed between the reservoir and the reactor . On the contrary, the chemical reaction between the gaseous compound and the reactive salt is exothermic and causes a release of heat at the reactor. At equilibrium, after total vaporization of the fluid or when the reactive salt is saturated, the chemical reaction stops as well as the production of cold and heat.
- the solid reactive medium present in the reactor is commonly constituted of an expanded natural graphite matrix (GNE) into which a reactive salt is inserted.
- GNE expanded natural graphite matrix
- the GNE / reactive salt composite medium a mixture of GNE granules and a reactive salt is compressed in a mold, which guides the graphite sheets in a plane perpendicular to the direction of compression, the reactive salt interspersed in the space left between these sheets.
- the layers thus formed in the block of solid reactive medium thus formed are found oriented in planes perpendicular to the longitudinal axis of the cylindrical reactor, which will promote the radial thermal conductivity.
- the reactive salt is thus first dried in an oven set between 150 ° C and 200 ° C for several hours, then ground to reach a particle size of about 100 microns. , or inserted into a primary layered matrix. It is then maintained in temperature to avoid any absorption of moisture.
- the salt is mixed with the GNE, then the whole is compressed as described above.
- the third step of the procedure consists in assembling, in the open reactor, the previously formed blocks, then closing the reactor by welding or gluing / molding in the case of a thermosetting material. This step must be carried out quickly after the production of reactive medium blocks, and in the same workshop, or in a workshop geographically close to the place of manufacture. Indeed, it is classically observed a rapid degradation of reactive medium blocks after their manufacture, by friction / abrasion during handling.
- the present invention aims to allow such a dissociation of the preparation operations of the reactive medium blocks and integration of these blocks in the thermochemical reactor, ensuring that these blocks can be stored, handled and even easily transported, this without significant degradation of reactive medium.
- the present invention provides an assembly intended to be put into place in a thermochemical reactor, for the production of thermal energy, comprising at least one block of solid reactive medium capable of reacting with a fluid for produce heat. Said block is contained in a thermally conductive protective envelope comprising a microporous membrane impermeable to liquids and permeable to gases.
- This protective casing has the advantage of protecting the solid reactive medium from degradation associated with transport, storage and handling, while allowing for easy subsequent integration into the reactor.
- this protective envelope protects the solid reagent medium that it contains by preventing, or at least decreasing, the direct contact of the solid reactive medium with the manipulators of the solid reactive medium and, in general, with any element contained in the medium. outside the protective envelope and with which it is likely to be brought into contact.
- This protective envelope also advantageously facilitates the handling of the solid reactive medium, because it is more easily grasped and manipulated.
- the assembly is thus easier to handle and insert in a thermochemical reactor.
- solid reactive medium a solid reactive medium, composite or not, capable of absorbing by chemical combination a reactive fluid and to desorb the reactive fluid by reverse chemical reaction, under the effect of a temperature rise. Contacting the solid reactive medium with the fluid causes a release of heat.
- thermally conductive protective envelope means that this protective envelope does not constitute a thermal barrier, so that the assembly according to the invention can be put into place as such in the thermochemical reactor. , without separating the solid reactive medium from the protective envelope, and that the protective envelope then does not affect the heat exchange occurring in the thermochemical reactor.
- thermally conductive protective envelope includes, in particular, the protective shells formed in a thermally conductive material.
- the protective envelope may consist of the microporous membrane or be of the multilayer type, a layer of which is constituted by such a microporous membrane.
- Multilayer envelope is understood to mean an envelope comprising at least two layers, each layer being able to be added at different times during the manufacture of the assembly according to the invention. All layers are not necessarily positioned at the same time around the solid reactive medium.
- microporous membrane means that this membrane is pierced with micropores, preferably many micropores per square centimeter, for example with a diameter of between 0.02 micrometers and 40 micrometers.
- a liquid for example a drop of water
- a gas consisting of molecules that are far apart from one another (for example water vapor), is able to cross the membrane .
- the microporous membrane is preferably hermetically sealed around the solid reactive medium.
- Such a membrane is particularly advantageous in that it provides a high degree of protection of the solid reactive medium, particularly with respect to moisture-related degradations.
- thermochemical systems use a gas (ammonia, methylamine, etc.) and a solid reactive medium comprising in particular chloride ions which under certain conditions, in particular residual moisture, are chemically aggressive.
- This reaction is non-reversible and causes a significant degradation of the performance of the thermochemical reactor.
- the protective envelope of the reactive medium comprises a microporous membrane
- a degradation of the reactive medium is greatly reduced because it prevents water in liquid form from entering the envelope, contact of the solid reactive medium.
- the temperature maintenance step to prevent moisture absorption of the reactive medium after its compression and insertion into the protective envelope remains necessary but can be shortened.
- the fact that such a membrane is permeable to gases allows that under the effect of heat, for example during a temperature maintenance, water in the form of vapor from the reactive medium can pass through the membrane to the external environment .
- the membrane allows the evacuation of the water in gaseous form from the solid reactive medium to the external medium and thus maintains a low humidity atmosphere for the solid reactive medium contained in the membrane and thus makes it possible to preserve this reactive medium from degradation related to humidity.
- Such a membrane impervious to liquids in particular to water in liquid form, can be formed in breathable materials within the meaning of the international standard ISO 11092 related to textiles (for example Gore-Tex ® ).
- the solid reactive medium comprises expanded natural graphite (GNE) and a reactive salt.
- the reactive salt is preferably chosen from ammoniacal chlorides, for example CaCl 2 , LiCl, CuCl 2 , SrCl 2 , ZnCl 2 , etc.
- Reactive media comprising such reactive salts are particularly likely to expand on absorbing the reactive fluid and retracting during the desorption of the reactive fluid.
- the solid reactive medium contained in the thermally conductive protective envelope is in the form of a plurality of blocks in the same protective envelope. It must be understood by "block", a compact piece of solid reactive medium. In the case of a plurality of blocks, these are preferably of complementary geometry to conform, once associated, to the geometry of the receiving housing of the solid reactive medium in the thermochemical reactor.
- the microporous membrane is formed so that its Thermal Evaporative Resistance (RET) is between 6 and 12 m 2 .Pa / W.
- RET Thermal Evaporative Resistance
- the RET (Thermal Evaporative Resistance) test conventionally quantifies in itself the resistance of a membrane to the transmission of water vapor, that is to say its ability to limit the passage of a molecule of water. water vapor from a very humid area to a less humid area. The lower the resistance to the transmission of water vapor (the RET value), the more breathable the membrane.
- the measuring apparatus for performing the RET test is commonly called the "skin model".
- a porous metal plate of 20cm side is heated at 35 ° C by internal electrical resistances and its surface is kept saturated with moisture by an auxiliary feeder, which compensates for the evaporation occurring on the surface of the plate.
- a test piece is placed on the measuring plate, its upper face being scanned by a parallel air flow of 1 m / s.
- the ambient conditions during the test are 35 ° C and 40% relative humidity. Due to the difference in humidity between the saturated plate (35 ° C, 100% RH) and the drier ambient air (35 ° C, 40% RH), a transfer of water vapor occurs. through the test tube.
- the evaporation which occurs on the surface of the transpirant plate cools the latter, and the electrical energy supplied to the plate is measured to maintain its initial temperature of 35 ° C.
- the thermally conductive protective envelope is of multilayer type and has an outer layer perforated so that it forms a mesh.
- "External" means that said layer is not included in the microporous membrane with the solid reactive medium.
- the outer layer is around the microporous membrane, so it is less close to the solid reactive medium than the membrane and is visible when the microporous membrane is closed around the solid reactive medium.
- This outer layer is then advantageously configured so as not to create a thermal resistance between the solid reactive medium that it contains and the internal wall of the thermochemical reactor.
- the protective envelope therefore does not affect the thermochemical operation of the reactor and does not affect the heat exchange in the reactor.
- the empty space occupied by the perforations represents 60% to 95% of the surface of the outer layer of the protective envelope.
- the protective envelope is preferably closed around the solid reactive medium, for example by a link forming a ligature.
- the perforated outer layer is made of an extensible material or assembly of materials.
- the present invention is directed to a thermochemical reactor containing at least one assembly which is the subject of the present invention.
- the thermochemical reactor contains several sets according to the invention, each set may contain one or more blocks of reactive medium.
- the thermochemical reactor contains a plurality of protective shells, each containing a block of solid reactive medium, said blocks preferably being of complementary geometry to conform, once associated, with the geometry of the receiving housing of the solid reactive medium in the thermochemical reactor.
- the assembly obtained by this method comprises a protective envelope preventing or at least decreasing the contacting the solid reactive medium that it contains, with the manipulators of the solid reactive medium and in general, with any element contained in the environment outside the protective envelope and with which it is likely to be brought into contact. The risk of degradation of the solid reactive medium is thus reduced.
- the closure of the protective envelope can be made by a link or several links forming ligature (s).
- the present invention aims at the use of an assembly that is the subject of the present invention for producing thermal energy, according to which said assembly is placed in a thermochemical reactor then placed in the presence of a gaseous compound capable of react with said solid reactive medium to produce heat.
- An advantage of this use is the easier handling of the solid reagent medium due to its presence in a protective envelope. Indeed, it is easier for a person to grasp the protective envelope comprising the solid reactive medium with a closed end, than directly the solid reactive medium without a protective envelope. It is therefore easier to set up the assembly in the receiving housing of the solid reactive medium in the thermochemical reactor.
- thermochemical reactor The set-up of the assembly that is the subject of the present invention in a thermochemical reactor is typically carried out in such a way that the volume occupied by the solid reactive medium in the reactor is smaller than the volume of the receptacle for receiving the solid reactive medium in this reactor. reactor to allow swelling of the solid reactive medium as it absorbs the reactive fluid. This feature is used to accommodate the irregular geometry of a closed end of the protective envelope, for example by a link forming a ligature.
- the subject of the present invention is a set 50 ( figure 5 ) for a thermochemical reactor whose alternating phases of absorption and heat generation are used to produce a heating and / or cooling apparatus, said assembly 50 comprising at least one block 51 ( Figures 2 and 3 ) a solid reactive medium capable of reacting with a fluid to produce heat, included in a thermally conductive protective envelope 52 having a microporous membrane 57 impervious to liquids and permeable to gases.
- This protective envelope 52 may be multilayer and comprise in addition to the microporous membrane 57 an outer layer 58 perforated so that it forms a mesh.
- the microporous membrane 57 represents an inner layer of the protective envelope 52.
- the outer layer 58 is preferably made of an extensible material or assembly of materials.
- thermally conductive protective envelope 52 means that this protective envelope 52 does not constitute a thermal barrier, so that the assembly 50 according to the invention can be put into place as such in the thermochemical reactor, without separating the reactive medium from the protective envelope 52, and that the protective envelope 52 does not advantageously affect the heat exchange occurring in the thermochemical reactors.
- Protective wraps 52 formed in a thermally conductive material include, in particular, in the expression.
- this protective envelope 52 is formed of a material conferring on the protective envelope 52 the ability to be elastically deformed.
- the first step 41 of process 40 consists of the synthesis of the solid reactive medium.
- This synthesis can be carried out according to one of the procedures known from the prior art for the synthesis of a solid reactive medium for thermochemical reactors.
- this synthesis may comprise the prior drying of a reactive salt followed by grinding of the salt to reach a desired particle size, the salt being subsequently inserted into a matrix based on GNE while maintaining a temperature permitting avoid moisture absorption.
- the resulting mixture undergoes in a final step a compression in a mold adapted to the shape of the thermochemical reactor for which the synthesized solid reactive medium is intended.
- the block 51 of solid reactive medium thus obtained is in the cylindrical form when it is intended for a thermochemical reactor whose shape of the receptacle for receiving the solid reactive medium is cylindrical, and in the spherical form when it is intended for a thermochemical reactor whose receiving housing of the solid reactive medium is spherical, etc.
- the solid reactive medium is produced in the form of of one or more blocks 51. In the case of several blocks ( figure 4 ), these are complementary geometries to comply, once associated, with the geometry of the receiving housing of the solid reactive medium in the reactor.
- a block 51 resulting from the first step 41 of the method 40, and being intended for a cylindrical receiving housing of a thermochemical reactor, is for example in the form of a cylinder wafer, commonly called “wafer” as shown in FIG. figure 3 or in the form of a cylinder quarter (not shown in the figures), intended to be juxtaposed with other cylinder-shaped blocks to reconstitute a cylinder.
- the blocks 51 are for example in the form of sphere boundaries when the solid reactive medium is intended to be put in place in a thermochemical reactor whose shape of the receiving housing of the solid reactive medium is spherical.
- the block (s) 51 of solid reactive medium is inserted into the protective envelope 52.
- the technique of placing the solid reactive medium in a protective envelope 52 depends on the general shape receiving housing of the thermochemical reactor for which it is intended.
- the protective envelope 52 may comprise only the microporous membrane 57.
- the block (s) 51 are then inserted into the microporous membrane 57.
- the outer layer 58 can be added thereafter.
- the protective envelope 52 may already comprise the microporous membrane 57 and the outer layer 58.
- the block (s) 51 are then inserted in the microporous membrane 57 and consequently in the outer layer 58 located over the membrane 57 on the opposite side to that of the solid reactive medium relative to the latter.
- the protective casing 52 is placed around a tube of diameter equal to or slightly smaller than the diameter of said receptacle housing. reactor, containing the blocks, using the elastic deformation of the material constituting the protective envelope 52. In an advantageous embodiment, this tube was used as a template for the uniaxial compression of the solid reactive medium.
- a first end of the protective envelope 52 is closed (for example by ligation) and then the reactive medium solid in the form of at least one block 51, is pushed into the protective casing 52 by a piston effect before separating the protective casing 52 from the tube.
- step 42 is carried out using a device allowing the direct embossing of a solid reactive medium in a protective envelope 52. Then, the mixture containing the GNE and the reactive salt is directly inserted into an embossing device at the output of which is disposed a protective envelope 52 receiving at least one block of reactive medium.
- This embodiment has the advantage of saving time in the industrial production of the thermochemical reactors, but also a better homogeneity of the matrix mixture of GNE with the reactive salt and a suppression of the step of forming the blocks 51 of reactive medium. solid.
- the protective envelope 52 comprising the solid reactive medium is closed around the solid reactive medium that it contains.
- the protective casing 52 does not have an outer layer 58.
- the protective casing 52 illustrated on these figures 6 and 7 consists of a microporous membrane 57 having an inner face vis-à-vis the solid reactive medium and an opposite outer face.
- the assembly 50 comprises the outer layer 58, it is said outer face of the microporous membrane 57 which is opposite the outer layer 58.
- the microporous membrane 57 is thermally conductive.
- the membrane 57 does not create a thermal resistance detrimental to the performance of the reactor 54 in its thermochemical operation and does not affect the heat exchange, material or diffusion of gas bound to the reactor 54. Indeed, this membrane 57 may be made of a thermally conductive material.
- microporous membrane 57 means that this membrane 57 is pierced with micropores, preferably many micropores per square centimeter, for example with a diameter of between 0.02 micrometers and 40 micrometers.
- a liquid for example a drop of water
- a gas consisting of molecules that are far apart from one another (for example water vapor)
- membrane 57 is able to pass through the membrane 57.
- membrane 57 may be made of a breathable material according to ISO 11092. These materials, such as Gore-Tex ® , allow gas exchange through them but are impervious to liquids.
- the membrane 57 is formed so that its Thermal Evaporative Resistance (RET) is between 0 and 20 m 2 .Pa / W, preferably between 0 and 12 m 2 .Pa / W, plus preferably between 0 and 6 m 2 .Pa / W. In a particular embodiment, its Thermal Evaporative Resistance (RET) is between 6 and 12 m 2 .Pa / W.
- RET Thermal Evaporative Resistance
- the membrane 57 is hermetically closed around the solid reactive medium.
- thermochemical reactor 54 An advantage of this manufacturing process is that the final product obtained from this process, the assembly 50, can pass through a storage step 44, before being inserted into a thermochemical reactor 54. Optimally, this storage is carried out in a closed place in slight overpressure with respect to atmospheric pressure, under an inert atmosphere (nitrogen or equivalent) and dry to avoid hydration of the solid reactive medium. In particular embodiments, storage is performed at a temperature above 25 ° C.
- the microporous membrane 57 is hermetically closed on the solid reactive medium, however, the reactive fluid capable of reacting with the solid reactive medium must be able to reach the solid reactive medium.
- the prior art teaches that in a GNE-based composite solid reactive medium and a reactive salt, the mass and thermal transfers are preferably carried out in a radial and non-longitudinal orientation and this because of the structure in GNE leaflets. It is therefore advantageous for an overflow element 56 of the reactive fluid supply device (for example ammonia) of the thermochemical reactor 54 to be positioned in a central lumen 53 of the solid reactive medium so that the heat flows start radially from the reactor. central lumen 53 to the inner wall of the reactor 54. In the embodiments illustrated by the figures 6 and 7 , the discharge element 56 is located in the central lumen 53 of the solid reactive medium at the longitudinal axis of the cylinder formed by the solid reactive medium.
- the membrane 57 is hermetically sealed around the discharge member 56 of the fluid supply device (for example ammonia) reactive of the thermochemical reactor 54.
- the discharge element 56 can be dissociated from the feed device in fluid and thus be stored with the assembly 50 while being in the central lumen 53 of the reactive medium and hermetically attached to the membrane. This discharging element 56, when stored with the assembly 50 while in the central lumen 53 of the reactive medium and hermetically attached to the membrane 57, must not be opened in order to maintain the impermeability of the membrane 57.
- the membrane 57 is hermetically sealed around the discharge member 56 of the feed device of the thermochemical reactor 54 by a link 55.
- the membrane 57 is hermetically sealed around the discharge element 56 by screwing means (not shown in the figures). In other particular embodiments, the membrane 57 is hermetically closed by a sealing device capable of being pierced by the discharge element 56 of the supply device of the thermochemical reactor 54.
- the assembly 50 is stored vertically suspended by the protective envelope 52.
- This suspension can be performed for example by a link 55 used to close one end of the envelope of protection 52 on the horizontal rods in height.
- FIG. 5 a particular embodiment of an assembly 50 comprising a block 51 of cylindrical solid reactive medium and a protective envelope 52 whose ends are not yet closed.
- the protective envelope 52 comprises an outer layer 58 perforated so that it forms a mesh, preferably whose empty space due to perforation represents between 60% and 95% of the surface area. of the outer layer 58 of the protective envelope 52.
- the center distance of the meshes of the mesh is preferably between 0.5 and 30 millimeters (mm), preferably between 1 and 20 mm, preferably between 1 and 10 mm. preferably between 2 and 3 mm.
- This protective envelope 52 allows heat exchanges between the solid reactive medium and the inner wall of the thermochemical reactor 54 through the thermally conductive material of the membrane 57 and through the perforations of the outer layer 58.
- thermochemical reactor 54 of an assembly 50 is illustrated in FIG. figure 8 .
- the figure 8 presents a cylindrical thermochemical reactor 54 into which is inserted a unit 50 comprising a thermally conductive protective envelope 52 containing a block 51 of cylindrical solid reactive medium.
- the protective envelope 52 is closed around the block 51 of reactive medium with a link 55 forming a ligature.
- the link 55 closes the microporous membrane 57 and the outer layer 58.
- the volume occupied by the solid reactive medium in the reactor 54 is typically less than the volume of the receiving receptacle of the solid reactive medium in this reactor 54 to allow the swelling of the solid reactive medium as it absorbs the reactive fluid. This feature is used to accommodate the irregular geometry of a closed end, for example by a link 55, of the protective envelope 52.
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Abstract
La présente invention vise un ensemble (50) destiné à être mis en place dans un réacteur thermochimique (54), pour la production d'énergie thermique, comportant au moins un bloc (51) de milieu réactif solide apte à réagir avec un fluide pour produire de la chaleur. Ce bloc (51) est contenu dans une enveloppe de protection (52) thermiquement conductrice comportant une membrane microporeuse (57) imperméable aux liquides et perméable aux gaz.The present invention relates to an assembly (50) intended to be set up in a thermochemical reactor (54), for the production of thermal energy, comprising at least one block (51) of solid reactive medium capable of reacting with a fluid for produce heat. The block (51) is contained in a thermally conductive shield (52) having a microporous membrane (57) impermeable to liquids and permeable to gases.
Description
La présente invention s'inscrit dans le domaine des appareils de transfert et stockage de l'énergie thermique, plus particulièrement le domaine des réacteurs thermochimiques.The present invention is in the field of apparatus for the transfer and storage of thermal energy, more particularly the field of thermochemical reactors.
Plus particulièrement, la présente invention vise un ensemble comprenant un milieu réactif solide destiné à être mis en place dans un réacteur thermochimique. La présente invention vise aussi un réacteur thermochimique comportant un tel ensemble ainsi qu'un procédé de fabrication d'un tel ensemble et une utilisation de ce dernier.More particularly, the present invention provides an assembly comprising a solid reactive medium intended to be placed in a thermochemical reactor. The present invention also relates to a thermochemical reactor comprising such a set and a method of manufacturing such a set and use thereof.
Il est connu d'utiliser des systèmes thermochimiques pour la production de froid et/ou de chaleur. Ces systèmes sont fondés sur les variations thermiques résultant de transformations physico-chimiques d'un couple de composés aptes à interagir l'un avec l'autre. Typiquement, l'un des composés est un fluide, et l'autre composé est un sel réactif s'associant avec le fluide quand ils sont mis en contact à une température donnée, mais se dissociant lorsque la température augmente.It is known to use thermochemical systems for the production of cold and / or heat. These systems are based on the thermal variations resulting from physico-chemical transformations of a pair of compounds capable of interacting with each other. Typically, one of the compounds is a fluid, and the other compound is a reactive salt associating with the fluid when they are contacted at a given temperature, but dissociating when the temperature increases.
Le fluide peut être sous forme gazeuse ou sous forme liquide selon les conditions de température et de pression auxquelles il est soumis. Dans certains systèmes, il est conservé à l'état liquide dans un réservoir qui est séparé par une vanne du réacteur contenant le sel réactif. A l'ouverture de la vanne, le fluide subit une expansion au cours de laquelle il se vaporise et va réagir chimiquement avec le sel réactif. Le changement d'état du fluide (de liquide à gazeux) consomme de l'énergie et induit par conséquent une baisse de température au niveau du réservoir ou de l'évaporateur si une vanne de détente du fluide est placée entre le réservoir et le réacteur. Au contraire, la réaction chimique entre le composé gazeux et le sel réactif est exothermique et provoque un dégagement de chaleur au niveau du réacteur. A l'équilibre, après vaporisation totale du fluide ou lorsque le sel réactif est saturé, la réaction chimique s'arrête ainsi que la production de froid et de chaleur.The fluid may be in gaseous form or in liquid form depending on the temperature and pressure conditions to which it is subjected. In some systems, it is stored in a liquid state in a tank which is separated by a valve from the reactor containing the reactive salt. At the opening of the valve, the fluid expands during which it vaporizes and will react chemically with the reactive salt. The change in state of the fluid (from liquid to gas) consumes energy and therefore induces a drop in temperature at the reservoir or evaporator if a fluid expansion valve is placed between the reservoir and the reactor . On the contrary, the chemical reaction between the gaseous compound and the reactive salt is exothermic and causes a release of heat at the reactor. At equilibrium, after total vaporization of the fluid or when the reactive salt is saturated, the chemical reaction stops as well as the production of cold and heat.
Il est ensuite possible de régénérer le système en chauffant le sel réactif, ce qui provoque la séparation du sel réactif et du composé gazeux. De ce fait, on observe une montée de la pression dans le système et une condensation du gaz qui se retrouve à l'état liquide dans le réservoir. Le sel réactif ainsi régénéré est apte à réagir dans un nouveau cycle de réfrigération-chauffage.It is then possible to regenerate the system by heating the reactive salt, which causes the separation of the reactive salt and the gaseous compound. As a result, there is an increase in the pressure in the system and a condensation of the gas which is found in the liquid state in the tank. The reactive salt thus regenerated is able to react in a new refrigeration-heating cycle.
Il est connu de mettre à profit les phases alternées de production et d'absorption de chaleur d'un tel système, selon les besoins pour chauffer ou refroidir un compartiment auquel on l'associe par l'intermédiaire d'un dispositif thermiquement conducteur.It is known to take advantage of the alternating phases of production and heat absorption of such a system, as needed to heat or cool a compartment which is associated through a thermally conductive device.
Un tel procédé est divulgué par le Brevet Français n°
Le milieu réactif solide présent dans le réacteur est communément constitué d'une matrice en graphite naturel expansé (GNE) dans laquelle un sel réactif est inséré.The solid reactive medium present in the reactor is commonly constituted of an expanded natural graphite matrix (GNE) into which a reactive salt is inserted.
Dans un milieu réactif solide composite à base de GNE et d'un sel réactif, les transferts massiques (en gaz) et thermiques (refroidissement du milieu réactif solide en phase d'absorption et chauffage en phase de régénération) s'effectuent de manière privilégiée selon une orientation radiale et non longitudinale. Ce phénomène bien connu s'explique par la structure en feuillets du graphite qui est responsable de l'anisotropie de toutes les propriétés physiques du graphite. En particulier, sa conductivité thermique est très différente dans le plan des feuillets et dans la direction perpendiculaire.In a GNE-based composite solid reactive medium and a reactive salt, the mass (gas) and thermal transfers (cooling of the solid reactive medium in the absorption phase and heating in the regeneration phase) are carried out in a privileged manner. in a radial orientation and not longitudinal. This well-known phenomenon is explained by the graphite structure of graphite which is responsible for the anisotropy of all the physical properties of graphite. In particular, its thermal conductivity is very different in the plane of the sheets and in the perpendicular direction.
Lors de la fabrication du milieu composite GNE/sel réactif, un mélange de granulats de GNE et d'un sel réactif est comprimé dans un moule, ce qui oriente les feuillets de graphite selon un plan perpendiculaire au sens de la compression, le sel réactif venant s'intercaler dans l'espace laissé entre ces feuillets. Les couches ainsi formées dans le bloc de milieu réactif solide ainsi formé se retrouvent orientées selon des plans perpendiculaires à l'axe longitudinal du réacteur cylindrique, ce qui va favoriser la conductivité thermique radiale.During the manufacture of the GNE / reactive salt composite medium, a mixture of GNE granules and a reactive salt is compressed in a mold, which guides the graphite sheets in a plane perpendicular to the direction of compression, the reactive salt interspersed in the space left between these sheets. The layers thus formed in the block of solid reactive medium thus formed are found oriented in planes perpendicular to the longitudinal axis of the cylindrical reactor, which will promote the radial thermal conductivity.
La fabrication de ce bloc de milieu composite GNE/sel réactif est assez délicate à réaliser, et de nombreuses difficultés de mise en oeuvre apparaissent, en particulier en raison de la friabilité du produit solide obtenu et du caractère fortement hydrophile du sel utilisé (chlorure de calcium CaCl2 par exemple), provoquant un phénomène d'absorption d'humidité, d'exsudation du bloc de milieu réactif et de gonflement associé.The manufacture of this block of composite GNE / reactive salt medium is quite difficult to achieve, and many implementation difficulties arise, in particular because of the friability of the solid product obtained and the highly hydrophilic nature of the salt used (sodium chloride). calcium CaCl 2 for example), causing a phenomenon of moisture absorption, exudation of the reactive medium block and associated swelling.
Suivant un protocole de fabrication courant du milieu réactif solide, le sel réactif est ainsi d'abord séché dans une étuve réglée entre 150°C et 200°C environ pendant plusieurs heures, puis broyé pour atteindre une granulométrie de l'ordre de 100 µm, ou inséré dans une matrice feuilletée primaire. Il est alors maintenu en température pour éviter toute absorption d'humidité. Dans une seconde étape du mode opératoire, le sel est mélangé au GNE, puis l'ensemble est comprimé comme décrit précédemment.According to a standard manufacturing protocol of the solid reactive medium, the reactive salt is thus first dried in an oven set between 150 ° C and 200 ° C for several hours, then ground to reach a particle size of about 100 microns. , or inserted into a primary layered matrix. It is then maintained in temperature to avoid any absorption of moisture. In a second step of the procedure, the salt is mixed with the GNE, then the whole is compressed as described above.
Il peut ainsi être réalisé plusieurs blocs (ou morceaux) de milieu réactif de géométrie complémentaire pour se conformer, une fois associés, à la géométrie du logement de réception du réacteur thermochimique dans lequel ce milieu réactif est destiné à être mis en oeuvre.It can thus be achieved several blocks (or pieces) of reactive medium of complementary geometry to comply, once associated with the geometry of the receiving housing of the thermochemical reactor in which the reactive medium is intended to be implemented.
Ces morceaux sont ensuite classiquement maintenus en température pour les protéger le mieux possible d'une reprise d'humidité ambiante. La troisième étape du mode opératoire consiste à assembler, dans le réacteur ouvert, les blocs préalablement formés, puis de fermer le réacteur par soudure ou collage/moulage dans le cas d'un matériau thermodurcissable. Cette étape doit être réalisée rapidement après la fabrication des blocs de milieu réactif, et dans le même atelier, ou dans un atelier géographiquement proche du lieu de fabrication. En effet, on observe classiquement une dégradation rapide des blocs de milieu réactif après leur fabrication, par frottement/abrasion lors de leur manipulation.These pieces are then conventionally maintained in temperature to protect them as much as possible from a recovery of ambient humidity. The third step of the procedure consists in assembling, in the open reactor, the previously formed blocks, then closing the reactor by welding or gluing / molding in the case of a thermosetting material. This step must be carried out quickly after the production of reactive medium blocks, and in the same workshop, or in a workshop geographically close to the place of manufacture. Indeed, it is classically observed a rapid degradation of reactive medium blocks after their manufacture, by friction / abrasion during handling.
Or dans le cadre d'un processus industriel, il pourrait être avantageux de pouvoir préparer par avance des blocs de milieu réactif solide, bien avant l'opération d'intégration finale dans le réacteur, ceci afin de permettre une diminution des coûts de production. De même, il pourrait s'avérer intéressant de dissocier géographiquement l'atelier de fabrication du milieu réactif de l'atelier de soudure ou de fabrication de la paroi du réacteur (par exemple dans le cas d'une paroi en matériau composite thermodurcissable).However, in the context of an industrial process, it may be advantageous to be able to prepare blocks of solid reactive medium in advance, well before the final integration operation in the reactor, in order to allow a reduction in production costs. Similarly, it may be advantageous to geographically separate the manufacturing workshop of the reactive medium of the welding shop or manufacture of the reactor wall (for example in the case of a wall of thermosetting composite material).
La présente invention vise à permettre une telle dissociation des opérations de préparation des blocs de milieu réactif et d'intégration de ces blocs dans le réacteur thermochimique, en assurant que ces blocs puissent être stockés, manipulés et même transportés facilement, ceci sans dégradation importante du milieu réactif.The present invention aims to allow such a dissociation of the preparation operations of the reactive medium blocks and integration of these blocks in the thermochemical reactor, ensuring that these blocks can be stored, handled and even easily transported, this without significant degradation of reactive medium.
À cet effet, selon un premier aspect, la présente invention vise un ensemble destiné à être mis en place dans un réacteur thermochimique, pour la production d'énergie thermique, comportant au moins un bloc de milieu réactif solide apte à réagir avec un fluide pour produire de la chaleur. Ledit bloc est contenu dans une enveloppe de protection thermiquement conductrice comprenant une membrane microporeuse imperméable aux liquides et perméable aux gaz.For this purpose, according to a first aspect, the present invention provides an assembly intended to be put into place in a thermochemical reactor, for the production of thermal energy, comprising at least one block of solid reactive medium capable of reacting with a fluid for produce heat. Said block is contained in a thermally conductive protective envelope comprising a microporous membrane impermeable to liquids and permeable to gases.
Cette enveloppe de protection a pour avantage de protéger le milieu réactif solide des dégradations liées au transport, au stockage et à la manutention, tout en permettant une intégration aisée ultérieure dans le réacteur. En effet, cette enveloppe de protection protège le milieu réactif solide qu'elle contient en empêchant, ou au moins diminuant, le contact direct du milieu réactif solide avec les manipulateurs du milieu réactif solide et de manière générale, avec tout élément contenu dans le milieu extérieur à l'enveloppe de protection et avec lequel elle est susceptible d'être mise en contact.This protective casing has the advantage of protecting the solid reactive medium from degradation associated with transport, storage and handling, while allowing for easy subsequent integration into the reactor. Indeed, this protective envelope protects the solid reagent medium that it contains by preventing, or at least decreasing, the direct contact of the solid reactive medium with the manipulators of the solid reactive medium and, in general, with any element contained in the medium. outside the protective envelope and with which it is likely to be brought into contact.
Cette enveloppe de protection facilite également avantageusement la manipulation du milieu réactif solide, car elle est plus facilement saisissable et manipulable. L'ensemble est ainsi plus facile à manipuler et à insérer dans un réacteur thermochimique.This protective envelope also advantageously facilitates the handling of the solid reactive medium, because it is more easily grasped and manipulated. The assembly is thus easier to handle and insert in a thermochemical reactor.
Il doit être compris par milieu réactif solide, un milieu réactif solide, composite ou non, apte à absorber par combinaison chimique un fluide réactif et à désorber ce fluide réactif par réaction chimique inverse, sous l'effet d'une élévation de température. La mise en contact du milieu réactif solide avec le fluide provoque un dégagement de chaleur.It must be understood by solid reactive medium, a solid reactive medium, composite or not, capable of absorbing by chemical combination a reactive fluid and to desorb the reactive fluid by reverse chemical reaction, under the effect of a temperature rise. Contacting the solid reactive medium with the fluid causes a release of heat.
On entend dans la présente description par « enveloppe de protection thermiquement conductrice », le fait que cette enveloppe de protection ne constitue pas une barrière thermique, si bien que l'ensemble selon l'invention peut être mis en place tel quel dans le réacteur thermochimique, sans séparer le milieu réactif solide de l'enveloppe de protection, et que l'enveloppe de protection n'influe alors pas sur les échanges de chaleur se produisant dans le réacteur thermochimique. On englobe notamment, dans l'expression « enveloppe de protection thermiquement conductrice », les enveloppes de protection formées dans un matériau thermiquement conducteur.In the present description, the term "thermally conductive protective envelope" means that this protective envelope does not constitute a thermal barrier, so that the assembly according to the invention can be put into place as such in the thermochemical reactor. , without separating the solid reactive medium from the protective envelope, and that the protective envelope then does not affect the heat exchange occurring in the thermochemical reactor. The expression "thermally conductive protective envelope" includes, in particular, the protective shells formed in a thermally conductive material.
L'enveloppe de protection peut consister en la membrane microporeuse ou être du type multicouches, dont une couche est constituée par une telle membrane microporeuse. On entend par enveloppe multicouches, une enveloppe comportant au moins deux couches, chaque couche pouvant être ajoutée à des moments différents lors de la fabrication de l'ensemble selon l'invention. Toutes les couches ne sont pas forcément positionnées en même temps autour du milieu réactif solide.The protective envelope may consist of the microporous membrane or be of the multilayer type, a layer of which is constituted by such a microporous membrane. Multilayer envelope is understood to mean an envelope comprising at least two layers, each layer being able to be added at different times during the manufacture of the assembly according to the invention. All layers are not necessarily positioned at the same time around the solid reactive medium.
On entend dans la présente description, par « membrane microporeuse » le fait que cette membrane est percée de micropores, de préférence de nombreux micropores au centimètre carré, par exemple d'un diamètre compris entre 0,02 micromètres et 40 micromètres. Un liquide (par exemple une goutte d'eau) ne peut pas traverser cette membrane, tandis qu'un gaz, étant constitué de molécules fortement distantes les unes des autres (par exemple la vapeur d'eau), est apte à traverser la membrane.In the present description, the term "microporous membrane" means that this membrane is pierced with micropores, preferably many micropores per square centimeter, for example with a diameter of between 0.02 micrometers and 40 micrometers. A liquid (for example a drop of water) can not pass through this membrane, whereas a gas, consisting of molecules that are far apart from one another (for example water vapor), is able to cross the membrane .
La membrane microporeuse est de préférence fermée de façon hermétique autour du milieu réactif solide.The microporous membrane is preferably hermetically sealed around the solid reactive medium.
Une telle membrane s'avère particulièrement avantageuse en ce qu'elle assure un haut degré de protection du milieu réactif solide, notamment vis-à-vis des dégradations liées à l'humidité.Such a membrane is particularly advantageous in that it provides a high degree of protection of the solid reactive medium, particularly with respect to moisture-related degradations.
En effet, la reprise d'humidité par le milieu réactif solide est un problème récurrent tout au long de la mise en oeuvre de ce dernier.Indeed, the recovery of moisture by the solid reactive medium is a recurring problem throughout the implementation of the latter.
On sait que les systèmes thermochimiques mettent en oeuvre un gaz (ammoniac, méthylamine,...) et un milieu réactif solide comprenant en particulier des ions chlorure qui dans certaines conditions, en particulier d'humidité résiduelle, sont chimiquement agressifs.It is known that thermochemical systems use a gas (ammonia, methylamine, etc.) and a solid reactive medium comprising in particular chloride ions which under certain conditions, in particular residual moisture, are chemically aggressive.
En prenant l'exemple du chlorure de calcium, un sel réactif couramment utilisé dans les systèmes thermochimiques concernés, la littérature scientifique montre, que le chlorure de calcium pur forme quatre complexes différents en réagissant avec l'ammoniac sec. Les réactions réversibles sont les suivantes :
CaCl2 + NH3(g) ⇄ CaCl2(NH3)(s) Réaction I
CaCl2(NH3)(s) + NH3(g) ⇄ CaCl2(NH3)2(s) Réaction II
CaCl2(NH3)2(s) + 2 NH3(g) ⇄ CaCl2NH3)4(s) Réaction III
CaCl2(NH3)4(s) + 4 NH3(g) ⇄ CaCl2(NH3)8(s) Réaction IV
Taking the example of calcium chloride, a reactive salt commonly used in the relevant thermochemical systems, the scientific literature shows that pure calcium chloride forms four different complexes by reacting with dry ammonia. The reversible reactions are as follows:
CaCl 2 + NH 3 (g) ⇄ CaCl 2 (NH 3 ) (s) Reaction I
CaCl 2 (NH 3 ) (s) + NH 3 (g) ⇄ CaCl 2 (NH 3 ) 2 (s) Reaction II
CaCl 2 (NH 3 ) 2 (s) + 2 NH 3 (g) ⇄ CaCl 2 NH 3 ) 4 (s) Reaction III
CaCl 2 (NH 3 ) 4 (s) + 4 NH 3 (g) ⇄CaCl 2 (NH 3 ) 8 (s) Reaction IV
L'étude bibliographique montre que l'octo- et le tétraammoniacate sont peu stables, ce qui fait que ces composés d'addition sont à la base des réacteurs thermochimiques. Par contre, le chlorure de calcium est un produit très hygroscopique et même déliquescent s'il est exposé assez longtemps à l'air, et le composé CaCl2(H2O)(s) est quant à lui très stable avec une liaison CaCl2 - H2O très difficile à rompre : pour dessécher complètement 500g de CaCl2, il faut maintenir une température de 170°C sous un vide primaire pendant 48 heures. Ces précautions sont essentielles sinon la non-réversibilité des réactions I à IV apparaît. Si le chlorure n'est pas complètement déshydraté avant l'absorption d'ammoniac, il se produit une décomposition des produits de départ suivant la réaction suivante :
CaCl2(H2O)(s) + NH3(g) → CaCl2OH(s) + NH4Cl(s)
The literature review shows that octo- and tetraammoniacate are unstable, so that these adducts are the basis of thermochemical reactors. On the other hand, calcium chloride is a very hygroscopic and even deliquescent product if it is exposed to air long enough, and the CaCl 2 (H 2 O) (s) compound is very stable with a
CaCl 2 (H 2 O) (s) + NH 3 (g) → CaCl 2 OH (s) + NH 4 Cl (s)
Cette réaction est non-réversible et entraine une dégradation importante des performances du réacteur thermochimique.This reaction is non-reversible and causes a significant degradation of the performance of the thermochemical reactor.
De manière tout à fait avantageuse, grâce au fait que l'enveloppe de protection du milieu réactif comprend une membrane microporeuse, une telle dégradation du milieu réactif est fortement diminuée car elle empêche l'eau sous forme liquide de pénétrer dans l'enveloppe, au contact du milieu réactif solide. De plus, lors du protocole de fabrication, l'étape de maintien à température pour éviter la reprise d'humidité du milieu réactif après sa compression et insertion dans l'enveloppe de protection reste nécessaire mais peut être raccourcie. Le fait qu'une telle membrane soit perméable aux gaz permet que sous l'effet de la chaleur, par exemple lors d'un maintien en température, l'eau sous forme de vapeur provenant du milieu réactif puisse traverser la membrane vers le milieu extérieur. Ainsi, la membrane permet l'évacuation de l'eau sous forme gazeuse depuis le milieu réactif solide vers le milieu extérieur et maintien ainsi une atmosphère faible en humidité pour le milieu réactif solide contenu dans la membrane et donc permet de préserver ce milieu réactif de la dégradation liée à l'humidité.Advantageously, thanks to the fact that the protective envelope of the reactive medium comprises a microporous membrane, such a degradation of the reactive medium is greatly reduced because it prevents water in liquid form from entering the envelope, contact of the solid reactive medium. In addition, during the manufacturing protocol, the temperature maintenance step to prevent moisture absorption of the reactive medium after its compression and insertion into the protective envelope remains necessary but can be shortened. The fact that such a membrane is permeable to gases allows that under the effect of heat, for example during a temperature maintenance, water in the form of vapor from the reactive medium can pass through the membrane to the external environment . Thus, the membrane allows the evacuation of the water in gaseous form from the solid reactive medium to the external medium and thus maintains a low humidity atmosphere for the solid reactive medium contained in the membrane and thus makes it possible to preserve this reactive medium from degradation related to humidity.
Une telle membrane imperméable aux liquides, en particulier à l'eau sous forme liquide, peut être formée dans des matériaux respirant au sens de la norme internationale ISO 11092 liée aux textiles (par exemple le Gore-Tex®).Such a membrane impervious to liquids, in particular to water in liquid form, can be formed in breathable materials within the meaning of the international standard ISO 11092 related to textiles (for example Gore-Tex ® ).
Dans des modes de réalisation particuliers de l'invention, le milieu réactif solide comprend du graphite naturel expansé (GNE) et un sel réactif. Le sel réactif est choisi de préférence parmi les chlorures ammoniacates, par exemple, CaCl2, LiCl, CuCl2, SrCl2, ZnCl2,... Des milieux réactifs comportant de tels sels réactifs sont en particulier susceptibles de s'expanser lors de l'absorption du fluide réactif et de se rétracter lors de la désorption du fluide réactif.In particular embodiments of the invention, the solid reactive medium comprises expanded natural graphite (GNE) and a reactive salt. The reactive salt is preferably chosen from ammoniacal chlorides, for example CaCl 2 , LiCl, CuCl 2 , SrCl 2 , ZnCl 2 , etc. Reactive media comprising such reactive salts are particularly likely to expand on absorbing the reactive fluid and retracting during the desorption of the reactive fluid.
Dans des modes de réalisation particuliers de l'invention, le milieu réactif solide contenu dans l'enveloppe de protection thermiquement conductrice est sous forme d'une pluralité de blocs dans une même enveloppe de protection. Il doit être compris par « bloc », un morceau compact de milieu réactif solide. Dans le cas d'une pluralité de blocs, ceux-ci sont de préférence de géométrie complémentaire pour se conformer, une fois associés, à la géométrie du logement de réception du milieu réactif solide dans le réacteur thermochimique.In particular embodiments of the invention, the solid reactive medium contained in the thermally conductive protective envelope is in the form of a plurality of blocks in the same protective envelope. It must be understood by "block", a compact piece of solid reactive medium. In the case of a plurality of blocks, these are preferably of complementary geometry to conform, once associated, to the geometry of the receiving housing of the solid reactive medium in the thermochemical reactor.
Dans des modes de réalisation particuliers de l'invention, la membrane microporeuse est formée de sorte à ce que sa Résistance Evaporative Thermique (RET) soit comprise entre 6 et 12 m2.Pa/W. Le test RET (Résistance Evaporative Thermique) quantifie de manière classique en elle-même la résistance d'une membrane à la transmission de la vapeur d'eau, c'est-à-dire sa capacité à limiter le passage d'une molécule de vapeur d'eau d'une zone très humide à une zone moins humide. Plus la résistance à la transmission de la vapeur d'eau (la valeur RET) est faible, plus la membrane est respirante. L'appareil de mesure permettant de réaliser le test RET est couramment appelé « skin model ». Comme décrit dans le brevet français
Dans des modes de réalisation particuliers de l'invention, l'enveloppe de protection thermiquement conductrice est de type multicouche et comporte une couche externe perforée de sorte qu'elle forme un maillage. On entend par « externe » le fait que ladite couche n'est pas comprise dans la membrane microporeuse avec le milieu réactif solide. La couche externe est autour de la membrane microporeuse, elle est donc moins proche du milieu réactif solide que la membrane et elle est visible lorsque la membrane microporeuse est fermée autour du milieu réactif solide. Cette couche externe est alors avantageusement configurée de sorte à ne pas créer une résistance thermique entre le milieu réactif solide qu'elle contient et la paroi interne du réacteur thermochimique. L'enveloppe de protection n'influe donc pas sur le fonctionnement thermochimique du réacteur et elle n'influe pas sur les échanges de chaleur dans le réacteur. De préférence, l'espace vide occupé par les perforations représente 60% à 95% de la surface de la couche externe de l'enveloppe de protection.In particular embodiments of the invention, the thermally conductive protective envelope is of multilayer type and has an outer layer perforated so that it forms a mesh. "External" means that said layer is not included in the microporous membrane with the solid reactive medium. The outer layer is around the microporous membrane, so it is less close to the solid reactive medium than the membrane and is visible when the microporous membrane is closed around the solid reactive medium. This outer layer is then advantageously configured so as not to create a thermal resistance between the solid reactive medium that it contains and the internal wall of the thermochemical reactor. The protective envelope therefore does not affect the thermochemical operation of the reactor and does not affect the heat exchange in the reactor. Preferably, the empty space occupied by the perforations represents 60% to 95% of the surface of the outer layer of the protective envelope.
L'enveloppe de protection est de préférence fermée autour du milieu réactif solide, par exemple par un lien formant une ligature.The protective envelope is preferably closed around the solid reactive medium, for example by a link forming a ligature.
Dans des modes de réalisation particuliers de l'invention, la couche externe perforée est constituée en un matériau ou un assemblage de matériaux extensible.In particular embodiments of the invention, the perforated outer layer is made of an extensible material or assembly of materials.
Selon un deuxième aspect, la présente invention vise un réacteur thermochimique contenant au moins un ensemble objet de la présente invention. Il est possible, dans des modes de réalisations particuliers, que le réacteur thermochimique contienne plusieurs ensembles selon l'invention, chaque ensemble pouvant contenir un ou plusieurs blocs de milieu réactif. Par exemple, dans des modes de réalisation particuliers de l'invention, le réacteur thermochimique contient plusieurs enveloppes de protection, chacune contenant un bloc de milieu réactif solide, lesdits blocs étant de préférence de géométrie complémentaire pour se conformer, une fois associés, à la géométrie du logement de réception du milieu réactif solide dans le réacteur thermochimique.According to a second aspect, the present invention is directed to a thermochemical reactor containing at least one assembly which is the subject of the present invention. It is possible, in particular embodiments, that the thermochemical reactor contains several sets according to the invention, each set may contain one or more blocks of reactive medium. For example, in particular embodiments of the invention, the thermochemical reactor contains a plurality of protective shells, each containing a block of solid reactive medium, said blocks preferably being of complementary geometry to conform, once associated, with the geometry of the receiving housing of the solid reactive medium in the thermochemical reactor.
Selon un autre aspect, la présente invention vise un procédé de fabrication d'un ensemble objet de la présente invention, comportant les étapes suivantes :
- insertion d'au moins un bloc de milieu réactif solide dans l'enveloppe de protection thermiquement conductrice et;
- fermeture de l'enveloppe de protection comportant le milieu réactif solide.
- inserting at least one block of solid reactive medium into the thermally conductive shield and;
- closing the protective envelope comprising the solid reactive medium.
Ce procédé de fabrication engendre un produit final qui peut être stocké dans des conditions avantageuses. En effet, l'ensemble obtenu par ce procédé comprend une enveloppe de protection empêchant ou au moins diminuant le contact du milieu réactif solide qu'elle contient, avec les manipulateurs du milieu réactif solide et de manière générale, avec tout élément contenu dans le milieu extérieur à l'enveloppe de protection et avec lequel elle est susceptible d'être mise en contact. Le risque de dégradation du milieu réactif solide est ainsi diminué.This manufacturing process produces a final product that can be stored under advantageous conditions. Indeed, the assembly obtained by this method comprises a protective envelope preventing or at least decreasing the contacting the solid reactive medium that it contains, with the manipulators of the solid reactive medium and in general, with any element contained in the environment outside the protective envelope and with which it is likely to be brought into contact. The risk of degradation of the solid reactive medium is thus reduced.
La fermeture de l'enveloppe de protection peut être effectuée par un lien ou plusieurs liens formant ligature(s).The closure of the protective envelope can be made by a link or several links forming ligature (s).
Selon un autre aspect, la présente invention vise l'utilisation d'un ensemble objet de la présente invention pour produire de l'énergie thermique, selon laquelle ledit ensemble est disposé dans un réacteur thermochimique puis mis en présence d'un composé gazeux apte à réagir avec ledit milieu réactif solide pour produire de la chaleur.According to another aspect, the present invention aims at the use of an assembly that is the subject of the present invention for producing thermal energy, according to which said assembly is placed in a thermochemical reactor then placed in the presence of a gaseous compound capable of react with said solid reactive medium to produce heat.
Un avantage de cette utilisation est la manipulation plus aisée du milieu réactif solide due à sa présence au sein d'une enveloppe de protection. En effet, il est plus facile pour une personne de saisir l'enveloppe de protection comprenant le milieu réactif solide par une extrémité fermée, que directement le milieu réactif solide sans enveloppe de protection. Il est donc plus aisé de mettre en place l'ensemble dans le logement de réception du milieu réactif solide dans le réacteur thermochimique.An advantage of this use is the easier handling of the solid reagent medium due to its presence in a protective envelope. Indeed, it is easier for a person to grasp the protective envelope comprising the solid reactive medium with a closed end, than directly the solid reactive medium without a protective envelope. It is therefore easier to set up the assembly in the receiving housing of the solid reactive medium in the thermochemical reactor.
La mise en place de l'ensemble objet de la présente invention dans un réacteur thermochimique est typiquement réalisée de façon à ce que le volume occupé par le milieu réactif solide dans le réacteur soit inférieur au volume du logement de réception du milieu réactif solide dans ce réacteur pour permettre le gonflement du milieu réactif solide lorsqu'il absorbe le fluide réactif. Cette particularité est mise à profit pour loger la géométrie irrégulière d'une extrémité fermée de l'enveloppe de protection, par exemple par un lien formant une ligature.The set-up of the assembly that is the subject of the present invention in a thermochemical reactor is typically carried out in such a way that the volume occupied by the solid reactive medium in the reactor is smaller than the volume of the receptacle for receiving the solid reactive medium in this reactor. reactor to allow swelling of the solid reactive medium as it absorbs the reactive fluid. This feature is used to accommodate the irregular geometry of a closed end of the protective envelope, for example by a link forming a ligature.
D'autres avantages, buts et caractéristiques particuliers de l'invention ressortiront de la description non-limitative qui suit d'au moins un mode de réalisation particulier d'un ensemble et d'un procédé, en regard des dessins annexés, dans lesquels :
- la
figure 1 représente, un mode de mise en oeuvre particulier d'un procédé de fabrication d'un ensemble destiné à être mis en place dans un réacteur thermochimique, pour la production d'énergie thermique, comportant au moins un bloc de milieu réactif solide apte à réagir avec un fluide pour produire de la chaleur, ledit bloc étant contenu dans une enveloppe de protection thermiquement conductrice. - la
figure 2 représente, selon un mode de réalisation de l'invention, un bloc de milieu réactif solide de forme cylindrique destiné à être mis en place dans un réacteur thermochimique dont le logement de réception du milieu réactif solide est de forme cylindrique. - la
figure 3 représente, selon un mode de réalisation de l'invention, un bloc de milieu réactif solide de forme cylindrique, communément appelé « galette », destiné à être mis en place dans un réacteur thermochimique dont le logement de réception du milieu réactif solide est de forme cylindrique. - la
figure 4 représente, selon un mode de réalisation de l'invention, un milieu réactif solide de forme cylindrique sous forme de blocs assemblés ou empilés les uns sur les autres, destiné à être mis en place dans un réacteur thermochimique dont le logement de réception du milieu réactif solide est de forme cylindrique. - la
figure 5 représente, selon un mode de réalisation de l'invention, un ensemble comportant un bloc de milieu réactif solide de forme cylindrique contenu dans une enveloppe de protection comprenant une membrane microporeuse imperméable aux liquides et perméable aux gaz, recouverte d'une couche externe perforée de sorte qu'elle forme un maillage, et les extrémités de l'enveloppe n'étant pas fermées. - la
figure 6 représente, selon un mode de réalisation de l'invention, une vue en coupe longitudinale d'un réacteur thermochimique de forme cylindrique comportant un ensemble comprenant un bloc de milieu réactif solide contenu dans une enveloppe de protection, ladite enveloppe de protection étant constituée d'une membrane microporeuse imperméable aux liquides et perméable aux gaz. - la
figure 7 représente, selon un mode de réalisation de l'invention, un ensemble selon l'invention comportant au moins un bloc de milieu réactif solide de forme cylindrique compris dans une enveloppe de protection, ladite enveloppe de protection étant constituée d'une membrane microporeuse imperméable aux liquides et perméable aux gaz. - la
figure 8 représente, selon un mode de réalisation particulier, une étape d'introduction d'un ensemble selon l'invention dans un réacteur thermochimique.
- the
figure 1 represents a particular embodiment of a method of manufacturing an assembly intended to be set up in a thermochemical reactor, for the production of thermal energy, comprising at least one block of reactive solid medium capable of reacting with a fluid for producing heat, said block being contained in a thermally conductive protective envelope. - the
figure 2 represents, according to one embodiment of the invention, a block of solid reactive medium of cylindrical form intended to be put in place in a thermochemical reactor whose receiving housing of the solid reactive medium is of cylindrical shape. - the
figure 3 represents, according to one embodiment of the invention, a block of solid reactive medium of cylindrical shape, commonly called "slab", intended to be set up in a thermochemical reactor whose receiving housing of the solid reactive medium is shaped cylindrical. - the
figure 4 represents, according to one embodiment of the invention, a solid reactive medium of cylindrical form in the form of blocks assembled or stacked on each other, intended to be put in place in a thermochemical reactor whose receiving housing of the reactive medium solid is cylindrical in shape. - the
figure 5 represents, according to one embodiment of the invention, an assembly comprising a block of solid reactive medium of cylindrical shape contained in a protective envelope comprising a microporous membrane impermeable to liquids and permeable to gas, covered with a perforated outer layer of so that it forms a mesh, and the ends of the envelope are not closed. - the
figure 6 represents, according to one embodiment of the invention, a longitudinal sectional view of a cylindrical thermochemical reactor comprising an assembly comprising a block of solid reactive medium contained in a protective envelope, said protective envelope consisting of a microporous membrane impervious to liquids and permeable to gases. - the
figure 7 represents, according to one embodiment of the invention, an assembly according to the invention comprising at least one block of solid reactive medium of cylindrical form included in a protective envelope, said protective envelope consisting of a microporous membrane impervious to liquid and permeable to gases. - the
figure 8 represents, according to a particular embodiment, a step of introducing an assembly according to the invention into a thermochemical reactor.
On note dès à présent que les figures ne sont pas à l'échelle.It is already noted that the figures are not to scale.
La présente description est donnée à titre non limitatif, chaque caractéristique d'un mode de réalisation pouvant être mise en oeuvre isolément ou combinée à toute autre caractéristique de tout autre mode de réalisation de manière avantageuse.This description is given in a nonlimiting manner, each feature of an embodiment can be implemented in isolation or combined with any other feature of any other embodiment advantageously.
On note que le terme « un » est utilisé au sens « au moins un ».It is noted that the term "one" is used in the sense of "at least one".
La présente invention a pour objet un ensemble 50 (
On entend dans la présente description par « enveloppe de protection 52 thermiquement conductrice », le fait que cette enveloppe de protection 52 ne constitue pas une barrière thermique si bien que l'ensemble 50 selon l'invention peut être mis en place tel quel dans le réacteur thermochimique, sans séparer le milieu réactif de l'enveloppe de protection 52, et que l'enveloppe de protection 52 n'influe alors avantageusement pas sur les échanges de chaleur se produisant dans les réacteurs thermochimiques. On englobe notamment, dans l'expression, les enveloppes de protection 52 formées dans un matériau thermiquement conducteur.In the present description, the term "thermally conductive
Dans des modes de réalisation, cette enveloppe de protection 52 est formée en un matériau conférant à l'enveloppe de protection 52 l'aptitude d'être déformée élastiquement.In embodiments, this
Un procédé 40 de fabrication d'un ensemble 50 destiné à être mis en place dans un réacteur thermochimique, pour la production d'énergie thermique, comportant au moins un bloc 51 de milieu réactif solide apte à réagir avec un fluide pour produire de la chaleur, dans lequel ledit bloc 51 est contenu dans une enveloppe de protection 52 thermiquement conductrice, est illustré en
Dans une deuxième étape, 42, le ou les bloc(s) 51 de milieu réactif solide est inséré dans l'enveloppe de protection 52. La technique de mise en place du milieu réactif solide dans une enveloppe de protection 52 dépend de la forme générale du logement de réception du réacteur thermochimique auquel il est destiné. A cette étape, l'enveloppe de protection 52 peut ne comporter que la membrane microporeuse 57. Le ou les bloc(s) 51 sont alors insérés dans la membrane microporeuse 57. La couche externe 58 peut être rajoutée par la suite. Ou bien, l'enveloppe de protection 52 peut déjà comporter la membrane microporeuse 57 et la couche externe 58. Le ou les bloc(s) 51 sont alors insérés dans la membrane microporeuse 57 et par conséquent dans la couche externe 58 située par dessus la membrane 57 du côté opposé à celui du milieu réactif solide par rapport à cette dernière.In a second step, 42, the block (s) 51 of solid reactive medium is inserted into the
Dans des modes de réalisation particuliers où le logement de réception du milieu réactif solide dans le réacteur est de forme cylindrique, on place l'enveloppe de protection 52 autour d'un tube, de diamètre égal ou légèrement inférieur au diamètre dudit logement de réception du réacteur, contenant les blocs, en utilisant la déformation élastique du matériau constitutif de l'enveloppe de protection 52. Dans un mode de réalisation avantageux, ce tube a servi de gabarit pour la compression uniaxiale du milieu réactif solide.In particular embodiments in which the receptacle for receiving the solid reactive medium in the reactor is of cylindrical shape, the
Dans le cas de blocs 51 d'un milieu réactif solide, sous forme de quartiers de cylindre, géométrie avantageuse pour constituer un réacteur cylindrique de fort diamètre résistant à la pression des systèmes thermochimiques sans mettre en oeuvre un milieu réactif solide présentant un volume difficile à manipuler et à comprimer, ce tube à la forme du quartier de cylindre ayant servi à la compression uniaxiale de chaque quartier.In the case of
Après avoir positionné l'enveloppe de protection 52 autour du tube, dans le cas où l'enveloppe de protection 52 possède deux extrémités ouvertes, une première extrémité de l'enveloppe de protection 52 est fermée (par exemple par ligature) puis le milieu réactif solide sous forme d'au moins un bloc 51, est poussé dans l'enveloppe de protection 52 par un effet de piston avant de désolidariser l'enveloppe de protection 52 du tube.After positioning the
Dans un mode de réalisation particulier, l'étape 42 est réalisée en utilisant un dispositif permettant l'embossage direct d'un milieu réactif solide dans une enveloppe de protection 52. Alors, le mélange comportant le GNE et le sel réactif est directement inséré dans un dispositif d'embossage à la sortie duquel est disposée une enveloppe de protection 52 réceptionnant au moins un bloc de milieu réactif. Ce mode de réalisation a pour avantage un gain de temps au niveau de la réalisation industrielle des réacteurs thermochimiques mais aussi une meilleure homogénéité du mélange de matrice de GNE avec le sel réactif et une suppression de l'étape de formage des blocs 51 de milieu réactif solide.In a particular embodiment,
Dans une troisième étape, 43, l'enveloppe de protection 52 comportant le milieu réactif solide est fermée autour du milieu réactif solide qu'elle contient.In a third step, 43, the
Dans un mode de réalisation particulier, comme illustré en
On entend dans la présente description par « membrane microporeuse 57 » le fait que cette membrane 57 est percée de micropores, de préférence de nombreux micropores au centimètre carré, par exemple d'un diamètre compris entre 0,02 micromètres et 40 micromètres. Un liquide (par exemple une goutte d'eau) ne peut pas traverser cette membrane 57, tandis qu'un gaz, étant constitué de molécules fortement distantes les unes des autres (par exemple la vapeur d'eau), est apte à traverser la membrane 57. Une telle membrane microporeuse 57 peut être constituée en un matériau respirant au sens de la norme ISO 11092. Ces matériaux, comme le Gore-Tex®, permettent des échanges gazeux à travers eux mais sont imperméables aux liquides. Selon un mode de réalisation particulier, la membrane 57 est formée de sorte à ce que sa Résistance Evaporative Thermique (RET) soit comprise entre 0 et 20 m2.Pa/W, préférentiellement entre 0 et 12 m2.Pa/W, plus préférentiellement entre 0 et 6 m2.Pa/W. Dans un mode de réalisation particulier, sa Résistance Evaporative Thermique (RET) est comprise entre 6 et 12 m2.Pa/W.In the present description, the term "
La membrane 57 est fermée de façon hermétique autour du milieu réactif solide.The
Un avantage de ce procédé de fabrication est que le produit final obtenu de ce procédé, l'ensemble 50, peut passer par une étape de stockage 44, avant d'être inséré dans un réacteur thermochimique 54. De façon optimale, ce stockage est réalisé dans un lieu fermé en légère surpression par rapport à la pression atmosphérique, sous atmosphère inerte (azote ou équivalent) et sec pour éviter l'hydratation du milieu réactif solide. Dans des modes de réalisation particuliers, le stockage est effectué à une température supérieure à 25°C.An advantage of this manufacturing process is that the final product obtained from this process, the
La membrane microporeuse 57 est hermétiquement fermée sur le milieu réactif solide cependant, le fluide réactif apte à réagir avec le milieu réactif solide doit pouvoir atteindre le milieu réactif solide. L'art antérieur enseigne que dans un milieu réactif solide composite à base de GNE et d'un sel réactif, les transferts massiques et thermiques s'effectuent de manière privilégiée selon une orientation radiale et non longitudinale et cela à cause de la structure en feuillets du GNE. Il est donc avantageux qu'un élément déverseur 56 du dispositif d'alimentation en fluide réactif (par exemple amoniac) du réacteur thermochimique 54, soit positionné dans une lumière centrale 53 du milieu réactif solide pour que les flux thermiques partent de manière radiale de la lumière centrale 53 vers la paroi interne du réacteur 54. Dans les modes de réalisation illustrés par les
Dans des modes de réalisation, la membrane 57 est fermée hermétiquement autour de l'élément déverseur 56 du dispositif d'alimentation en fluide (par exemple ammoniac) réactif du réacteur thermochimique 54. L'élément déverseur 56 peut être dissocié du dispositif d'alimentation en fluide et ainsi être stocké avec l'ensemble 50 tout en étant dans la lumière centrale 53 du milieu réactif et hermétiquement attaché à la membrane. Cet élément déverseur 56, lorsqu'il est stocké avec l'ensemble 50 tout en étant dans la lumière centrale 53 du milieu réactif et hermétiquement attaché à la membrane 57, ne doit pas être ouvert afin de conservée l'imperméabilité de la membrane 57. Dans des modes de réalisation particuliers, la membrane 57 est fermée hermétiquement autour de l'élément déverseur 56 du dispositif d'alimentation du réacteur thermochimique 54 par un lien 55. Dans d'autres modes de réalisation la membrane 57 est fermée hermétiquement autour de l'élément déverseur 56 par des moyens de vissage (non représentés sur les figures). Dans d'autres modes de réalisation particuliers la membrane 57 est fermée hermétiquement par un dispositif d'opercule apte à être percé par l'élément déverseur 56 du dispositif d'alimentation du réacteur thermochimique 54.In embodiments, the
Dans des modes de réalisation particuliers, l'ensemble 50 est stocké de façon suspendu verticalement par l'enveloppe de protection 52. Cette suspension peut être effectuée par exemple par un lien 55 ayant servi à la fermeture d'une extrémité de l'enveloppe de protection 52 sur les tiges horizontales en hauteur. Ce dernier mode de réalisation apporte un avantage par gain de place et absence de contact avec des surfaces dures pouvant déformer ou dégrader le milieu réactif solide réactif.In particular embodiments, the
On observe sur la
Comme illustré sur la
La mise en place dans un réacteur thermochimique 54, d'un ensemble 50 selon un mode de réalisation de l'invention, est illustré en
Claims (9)
Applications Claiming Priority (1)
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FR1552592A FR3034029B1 (en) | 2015-03-27 | 2015-03-27 | SYSTEM FOR PROTECTING A SOLID REACTIVE MEDIUM FOR THERMOCHEMICAL REACTOR |
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2455713A1 (en) * | 1979-04-30 | 1980-11-28 | Wallsten Hans | DEVICE CONTAINING SORTING BODY AND MANUFACTURING METHOD THEREOF |
FR2873793A1 (en) | 2004-07-30 | 2006-02-03 | Alcali Ind Sa | THERMOCHEMICAL REACTOR FOR REFRIGERATION AND / OR HEATING APPARATUS |
WO2012052633A2 (en) * | 2010-10-20 | 2012-04-26 | Coldway | Thermochemical system having a housing made of a composite material |
-
2015
- 2015-03-27 FR FR1552592A patent/FR3034029B1/en active Active
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2016
- 2016-03-25 EP EP16162489.5A patent/EP3073212B1/en active Active
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2455713A1 (en) * | 1979-04-30 | 1980-11-28 | Wallsten Hans | DEVICE CONTAINING SORTING BODY AND MANUFACTURING METHOD THEREOF |
FR2873793A1 (en) | 2004-07-30 | 2006-02-03 | Alcali Ind Sa | THERMOCHEMICAL REACTOR FOR REFRIGERATION AND / OR HEATING APPARATUS |
WO2012052633A2 (en) * | 2010-10-20 | 2012-04-26 | Coldway | Thermochemical system having a housing made of a composite material |
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FR3034029B1 (en) | 2019-11-22 |
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