WO2018202623A1 - Matériau composite de stockage d'eau et/ou de chaleur - Google Patents

Matériau composite de stockage d'eau et/ou de chaleur Download PDF

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Publication number
WO2018202623A1
WO2018202623A1 PCT/EP2018/061036 EP2018061036W WO2018202623A1 WO 2018202623 A1 WO2018202623 A1 WO 2018202623A1 EP 2018061036 W EP2018061036 W EP 2018061036W WO 2018202623 A1 WO2018202623 A1 WO 2018202623A1
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WO
WIPO (PCT)
Prior art keywords
composite material
salt
salts
hydrogel
active
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Application number
PCT/EP2018/061036
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German (de)
English (en)
Inventor
Paul Kallenberger
Michael FRÖBA
Michael Steiger
Felix BRIELER
Konrad POSERN
Original Assignee
Universität Hamburg
Bauhaus-Universität Weimar
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Application filed by Universität Hamburg, Bauhaus-Universität Weimar filed Critical Universität Hamburg
Priority to EP18724491.8A priority Critical patent/EP3619277A1/fr
Publication of WO2018202623A1 publication Critical patent/WO2018202623A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K5/00—Heat-transfer, heat-exchange or heat-storage materials, e.g. refrigerants; Materials for the production of heat or cold by chemical reactions other than by combustion
    • C09K5/02—Materials undergoing a change of physical state when used
    • C09K5/06—Materials undergoing a change of physical state when used the change of state being from liquid to solid or vice versa
    • C09K5/063—Materials absorbing or liberating heat during crystallisation; Heat storage materials
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F28—HEAT EXCHANGE IN GENERAL
    • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
    • F28D20/00—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00
    • F28D20/003—Heat storage plants or apparatus in general; Regenerative heat-exchange apparatus not covered by groups F28D17/00 or F28D19/00 using thermochemical reactions
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/14—Thermal energy storage

Definitions

  • the invention relates to a composite material for reversible water absorption and / or heat storage.
  • the invention applies a composite material that combines a host structural ⁇ structure based on polysaccharide acids or salts thereof and one or more introduced into the host structure active salts environmentally which can take up water by hydration and dehydration and deliver or store heat and release can.
  • Materials with the capability of reversible absorption of water, especially of water vapor from the air, are widely used, for example as building materials or to be conditioned ⁇ discrimination of food. Materials that are able to absorb large amounts of water or even small amounts of water vapor from the air and selectively release the stored water, can serve the provision of useful or even drinking water in water-poor areas.
  • the reversible water storage is usually accompanied by a reversible heat storage.
  • Sensitive heat storage involves the storage of heat by increasing the temperature of a storage medium.
  • the heat absorption causes a phase transition, in the reverse direction, the heat is released again.
  • a third possibility is the heat storage ⁇ by chemical reaction, this method in principle has the largest heat storage density compared to the two aforementioned possibilities.
  • thermochemical reaction In the heat storage by chemical reaction can be distinguished between heat storage by adsorption and heat storage by thermochemical reaction.
  • the adsorption of water or other adsorptive agents on the surface of, for example, zeolites or silicas is known and already commercially used.
  • thermochemical reaction The storage of heat by a thermochemical reaction can be achieved in various ways.
  • ⁇ play as naten by reversible decomposition reactions of carbonyl, oxides, hydroxides and hydrates.
  • phases of heat surplus eg due to high solar radiation or heat-releasing processes, the excess heat can be stored by the reversible decomposition reaction, eg the dehydration of a hydrate, and released again at a later time if necessary.
  • the individual materials differ in their heat storage density and the mögli ⁇ chen temperature range in which take place the reversible reactions and thus comes for the application as a heat storage in question.
  • Niedrigtemperaturbe ⁇ range of below 150 ° C play an important role salt hydrates.
  • the use of pure salts in powder form results in the aggregation of the individual particles, which ⁇ continuous reaction to give the corresponding hydrates or of incomplete dehydration leads to incomplete to the anhydrates.
  • WO 2014/104886 A1 describes, for example, a composite for heat storage, which comprises a thermochemical material which is enclosed in a water vapor-permeable, porous polymer material.
  • a composite for heat storage which comprises a thermochemical material which is enclosed in a water vapor-permeable, porous polymer material.
  • salt hydrates such as CaCl 2
  • porous polymer materials such as cellulose or ethyl cellulose and Verwen ⁇ tion
  • Kallenberger et al. discloses a composite material of a polymer and MgSC.
  • hydromagnesite particles are embedded in a polymer matrix of phenol-formaldehyde resin and poloxamers and converted into MgSC ⁇ by treatment with sulfuric acid.
  • a composite material is obtained having a volumetric thermal storage ⁇ cherêt of 0.93 kJ / cm 3 and may undergo up to 40 cycles of Hydratation- and dehydration.
  • the invention is therefore based on the object to provide a material which is suitable for storing water or for storing heat on the basis of salt hydrates and in particular a reversible heat absorption and Abgäbe he ⁇ allows, has a high permeability to water vapor and a high Has heat storage density.
  • the material through a high cycle stability be gekennzeich ⁇ net and be easy to manufacture and flexible in use.
  • This object is achieved by the composite material according to one of claims 1 to 8.
  • the invention also relates to the method according to any one of claims 9 to 13 and the use of the composite material according to claim 14 or 15.
  • the composite material according to the invention for storing water and / or heat is characterized in that it comprises a host structure based on polysaccharide acids or salts thereof and one or more active salts introduced into the host structure which store heat by hydration and dehydration. can give.
  • the composite material according to the invention has outstanding properties in order to be used as a water reservoir and / or a thermochemical heat store.
  • the invention compo ⁇ sitmaterial the high heat storage density, high Wasserspei ⁇ cherêt and high cycle stability of the water absorption and -abgäbe on.
  • the high cycle stability is achieved in particular by the fact that its incorporation into the dimensionally stable host structure can avoid or at least reduce agglomeration of active salt or washing out of active salt under hydration conditions.
  • composite material according to the invention is characterized particularly by the fact that the stored via thermochemical reaction heat not only completely but also partially released again can be .
  • the composite material is therefore characterized in particular by the fact that the host structure and thus the composite material itself is present as a solid under standard conditions, ie at 25 ° C. and 1.0 bar. Furthermore, the composite material characterized in particular in that the one or more active salts are incorporated as solid ⁇ material into the host structure. Preferably, the active salt is also present at a temperature of 28 ° C and a water vapor pressure of less than 10 mbar as a solid.
  • the composite material is preferably in the form of particles having a mean diameter (number average) of 0.1 to 10 mm, in particular 0.2 to 8 mm, preferably 0.5 to 6 mm, be ⁇ Sonders preferably 1.0 to 5.0 mm ago.
  • the particle size can be determined by a light microscope or a micrometer.
  • the particles are preferably present in spherical form.
  • the particle size depends on the conditions in the synthesis of the composite material. In particular, the particle size depends on the size of the drops of polysaccharide salt solution added to an active salt or gelling salt solution. Large drops lead to large particles, small drops lead to small particles.
  • the droplet size can be influenced by the flow rate of the polysaccharide salt solution and the size of the outlet nozzle.
  • special equipment can be used, such as a Büchi Encapsulator B390, which is manufactured in are able to generate small drops from a fluid flow via a vibrating membrane.
  • particles having a particle size as described above are particularly advantageous, since the composite material having such a particle size has both a high bulk density and a good wettability with water vapor.
  • Particles of the composite material according to the invention with a diameter of less than 0.1 mm can not flow sufficiently well, since the pressure loss during flow through the bed can be too high, so that good accessibility of the stored salt is not guaranteed safe for water vapor.
  • a diameter of more than 10 mm leads to a reduced bulk density of the composite material, which basically reduces the volumetric storage density and consequently increases the space requirement of the water and / or heat storage, which in turn does not make the composite material as broad as possible Scope is made available.
  • the diffusion pathways within the particle lengthen so that the rate of hydration and dehydration can be slowed.
  • mixtures of small and larger particles within the range described above are advantageous because they positively influence the bulk density and thus increase the storage density of the composite material.
  • the host structure of the composite material according to the invention preferably has an average pore size as determined by scanning electron microscopy ⁇ , in the range from 1 to more than 10 ym, the ⁇ particular 1 to 10 ym, on.
  • the host structure of the composite material according to the invention serves as a matrix or carrier structure for the one or more active ingredients. salts.
  • the host structure comprises one or more polysaccharide acids or a salt thereof.
  • Polysaccharide acids are polysaccharides having carboxy groups in their structural formula. It is believed that the carboxyl groups of the deprotonated Polysaccharidklare occur in aqueous solution with the cations of the active salt or other salt such as the below be ⁇ signed Geliersalzen, complex-like interact so as a hydrogel, ie, a three-dimensional network structure, form.
  • the host structure of the composite material according to the invention comprises one or more poly ⁇ saccharidklaridklaren selected from the group consisting of halides Polyuro-, ronsäure alginic, pectic acids, carboxymethyl cellulose, hyaluronic, and mixtures or salts thereof.
  • ei ⁇ ne host structure is based on sodium or potassium, Nat ⁇ rium- or Kaliumpektinat or sodium or Kaliumcarboxyme- methylcellulose preferred. More preferably a host Struk ⁇ ture is based on sodium alginate.
  • Alginates, in particular sodium alginates, are commercially available. They are harmless as toxico ⁇ cally.
  • Alginates are extracted from algae and therefore do not require a chemical synthesis process. They find a variety of applications in food and biotechnology. It is possible that the host structure changes during the synthesis of the composite material, during the drying, the exchange of salts or during the subsequent use of the composite material in the hydration or dehydration, so that, for example, no sodium alginate per se, but reaction or decomposition products thereof form the host structure.
  • the active salt is selected from the group consisting of chlorides, bromides, sulfates, sulfites, phosphates, hydrates of these salts or combinations thereof. Specifically, it is selected from the group consisting of LiCl, MgCl 2, CaCl 2, SrCl 2, Li 2 S0 4, Na 2 S0 4, MgS0 4, CaS0 4, SrS0 4, A ⁇ 2 (S0 4 ) 3, a 2 S, LiBr, SrBr 2 , hydrates of these salts, such as MgS0 4 * H 2 O, MgS0 4 * 6 H 2 0, MgS0 4 * 7 H 2 0, Al 2 (S0 4) 3 * 18 H 2 0, MgCl 2 * 6H 2 0, CaCl 2 * 2 H 2 0, CaCl 2 * 6 H 2 0, Na 2 S * 5 H 2 0, SrCl 2 * 6H 2 0, SrBr 2 * H 2 O, SrBr 2 * 6 H 2 O and CaS
  • the active salt is particularly preferably selected from the group consisting of MgS0 4 , MgCl 2 , CaCl 2 , SrCl 2 and mixtures thereof, in particular for applications as heat storage.
  • the active salt is particularly preferably CaCl 2 .
  • the active salt is incorporated in the host structure as a solid and is used for reversible water and / or heat storage. It can be hydrated and dehydrated depending on temperature and water vapor pressure.
  • the active salt preferably ⁇ its solid form, ie even at a hydration at a temperature of 28 ° C and a water vapor pressure of up to 10 mbar occurs essentially no phase transition of the active salt in the liquid state or no dissolution of the salt.
  • the active salts are dehydrated and charged the heat storage. If the charged composite material brought into contact with moist air, so it comes in from ⁇ sufficiently high water vapor pressure in an exothermic hydration and the composite material is the reaction enthalpy in the form of heat.
  • heat which is provided eg by solar thermal energy, for charging (dehydration) and thus to store it thermochemically in the composite material and to release it again during hydration, eg in times of low solar irradiation.
  • heat provided by, for example, solar thermal energy can be used to deliver water (dehydration) from the composite material, and in times of low heat input, the composite material can resume water, for example from atmospheric moisture (hydration).
  • the one or more active salts are capable of storing and releasing heat through hydration and dehydration.
  • the one or more solid active salts are in the La ⁇ ge, by chemical reaction with a gaseous reactant, in particular water vapor, to store heat or deliver.
  • a gaseous reactant in particular water vapor
  • latent heat storage it is possible to release the amount of heat only partially, and the release is not only at a material-dependent solid phase transition temperature.
  • the presence of the one or more active salts in the host structure can be demonstrated by X-ray diffraction or by energy dispersive X-ray spectroscopy.
  • inventive compos ⁇ TERIAL two or more different active salts.
  • Ver ⁇ application of two or more different active salts various temperature ranges for the activation (Dehydrata- tion) and water vapor pressures for the heat release (of hydration on) can be exploited.
  • a very flexible one ⁇ settable water and / or heat storage is obtained.
  • a composite material according to the invention is preferred wherein the active salt comprises at least 30 wt .-%, preferably at least 50 wt .-%, in particular at least 70 wt .-% and particularly be ⁇ vorzugt at least 80 wt .-% of the composite material, be ⁇ attracted to the dehydrated form of the active salt and Ge ⁇ fels the composite material.
  • a high proportion by weight of active salt in the composite material contributes to high water or heat storage density, which is generally desirable for a platzspa ⁇ -saving application of water or heat storage.
  • the amount of active salt in the composite material can be determined at ⁇ example by ICP-OES (with ⁇ means of inductively coupled plasma optical emission). For this purpose, the composite material is ground, dried at 130 ° C, with water extracted and filtered, and the filtrate Siert by ICP-OES analy ⁇ siert.
  • a composite material which particularly preferably has a cycle stabilizer ⁇ formality of hydration and dehydration of at least 10 cycles, preferably 20 cycles, and at least 30 cycles.
  • the cycling stability is measured by the composite material stored in a climate chamber and abwech ⁇ nately heated (dehydrated), and then loaded with moisture- ⁇ speed (hydrated) is. Cycle stability exists when no weight loss is recorded in each hydrated state after a certain number of cycles and after the letz ⁇ th cycle the calorimetrically determined heat release of the composite material corresponds to at least the heat release in the out put ⁇ stand or is greater than this.
  • the composite material according to the invention also has a heat storage density of at least 1.0 KJ / cm 3 , in particular at least 1.2 KJ / cm 3 and particularly preferably ⁇ at least 1.5 KJ / cm 3 .
  • the storage density is determined by calorimetric measurements.
  • Preferably used is a Setaram C80 calorimeter with a humidity generator.
  • the composite material is dehydrated in an oven and then placed in a measuring cell. It is passed a stream of dry air over the sample and introduced the measuring cell in the Kalo ⁇ rimeter. The temperature of the sample is determined continuously and heat flow is recorded. The air ⁇ current is converted to a moist air stream and released from the material by hydration heat quantity will be ⁇ distinguished. From the bulk density of the material and heat control ⁇ setting the storage densities can be calculated.
  • composite material according to the invention before ⁇ a water absorption of at least 0.2 g (H 2 O) per g (composite material), particularly at least 0.5 g (H 2 O) per g (composite material), more preferably at least 0.6 g (H 2 O) per g (composite material), such as 0.8 or 0.9 g (H 2 O) per g (composite material), wherein the water uptake determined by exposing samples dehydrated at 130 ° C for 12 hours for 12 hours to a stream of air at 30 ° C and at least 30% relative humidity. Specifically, the samples are placed an air stream at 30 ° C and 30%, 60% or 84% relative humidity from ⁇ .
  • samples containing CaCl 2 or MgCl 2 as the active salt are exposed to a 30% relative humidity air stream, SrCl 2 as the active salt to a 60% RH air stream, and MgSC as the active salt to 84% RH air stream.
  • the active salt is also at the end of Hydrati ⁇ onsrepress usually as a solid. Only when using very hygroscopic active salts, such as CaCl 2 and MgCl 2 , is it possible to rule out the onset of solution formation. However, such dissolution does not occur, if at all, until the end of the hydration reaction, so that the vast majority of water retention occurs as a gas-solid reaction.
  • the Kom ⁇ positmaterial (a water absorption capacity of at least 300 kg (H 2 0) per m 3 (composite material), particularly at least 400 kg (H 2 0) per m 3 (composite material), more preferably at least 500 kilograms H 2 0) per m 3 (composite material), most preferably at least 600 kg (H 2 O) per m 3 (composite material), the water absorption capacity being determined by dehydrated samples at 130 ° C for 12 hours 12 hours of air flow at 30 ° C and at least 30% relative humidity, as described above ⁇ be exposed.
  • the heat storage densities obtained in accordance with the invention are in some cases several times greater than the theoretical values for the sensible heat storage density of water in the temperature range from 20 ° C. to 70 ° C., the latent heat storage density of the phase transition of water at 0 ° C. and the heat storage density of the adjusttant. Sorption on commercially used zeolites, as shown in Table 1.
  • the present invention also relates to processes for the preparation of the composite material according to the invention.
  • the invention relates to a method for the manufacture ⁇ development of the composite material according to the invention, in which a) an aqueous mixture of Polysaccharidklare or a salt thereof and one or more Geliersalzen provides vicege- is to form a hydrogel, wherein the or the
  • the Polysaccharidklare or a salt thereof and / or one or more gelling salts can thereby be solved, especially in what ⁇ ser.
  • the polysaccharide acid solution may be added dropwise to the solution of the gelling salt or vice versa.
  • the interactions of the functional groups of the polysaccharide acid with the cations of the gelling salt form a hydrogel. More befindliches in the solution gelling ⁇ salt can diffuse into the hydrogel and thus becomes incorporated into the hydrochloride ⁇ gel.
  • the solid composite material according to the invention is obtained, which consists of a host structure based on polysaccharide acid and gelling salt. It is preferred that the hydrogel in getrockne ⁇ th state contains at least 30 wt .-% gelling salt, based on the total weight of the dried hydrogel.
  • the gelling salt or at least one of the plurality of gelling salts is an active salt, whereby the composite material is obtained after step b).
  • the hydrogel is treated before drying with the solution of one or more active salts in order to introduce the active salt (s) into the hydrogel and optionally gelling salt from the Displace hydrogel.
  • one or more gelling salts can be exchanged for the one or more active salts introduced or if the gelling salt is already active salt comprising one or more active salts is additionally introduced into the hydrogel ⁇ the.
  • this comprises that
  • the mixture in step a) additionally contains at least one undissolved precursor salt, which is formed in step a) a hydrogel, wherein the at least one precursor salt is turned ⁇ introduced into the hydrogel, and the obtained according to step b) of dried hydro ⁇ gel is treated with an acid to at least one pre ⁇ convert the salt into a run active salt.
  • the Polysaccharidklare or a salt thereof and / or one or more gelling salts can thereby be solved, especially in what ⁇ ser.
  • a suspension of the one or more precursor salts in the polysaccharide acid solution may be added dropwise to the solution of the one or more gelling salts, or conversely, a suspension of the one or more precursor salts in the solution of the one or more gelling salts of the polysaccharide acid solution may be added dropwise.
  • the interaction of the functional groups of the polysaccharide acid with the cations of the one or more gelling salts forms the hydrogel.
  • More befindliches in the solution may diffuse into the Ge liersalz ⁇ hydrogel and falls arrival at the closing the drying process, so that a composite material is obtained which comprises a host structure based on polysaccharide acid and one or more gelling salts introduced therein and one or more precursor salts incorporated therein.
  • the particles formed of the host structure for a certain time such as at least 2 hours or about 12 hours, immersed in the Geliersalzates to ermögli ⁇ chen a particularly suitable diffusion of the Geliersalzes in the hydrogel.
  • the composite material may be washed with water such that the one or more water-soluble gelling salts are removed and the composite material comprises only one polysaccharide acid host structure and the one or more precursor salts incorporated therein.
  • Subsequent acid treatment converts one or more precursor salts to active salt, ie, a salt that can store and / or release water and / or heat through hydration and dehydration.
  • active salt ie, a salt that can store and / or release water and / or heat through hydration and dehydration.
  • active salt ie, a salt that can store and / or release water and / or heat through hydration and dehydration.
  • the composite material comprises the polysaccharide acid host structure and at least one active salt embedded therein.
  • a) particles of a precursor salt are suspended in a solution of a polysaccharide acid or a salt thereof to form a suspension
  • the suspension is mixed with a solution of a Geliersalzes to form a hydrogel, wherein the particles of the pre ⁇ and the gelling salt are introduced into the hydrogel runner salt, c) drying the resulting hydrogel to obtain a compos ⁇ TERIAL,
  • the composite material is washed with water to remove the gelling salt from the composite material
  • the composite material is treated with an acid to convert the precursor salt into an active salt
  • the gelling salt may be an active salt.
  • the precursor salt is selected from the group consisting of Mg 5 (CO 3 ) 4 (OH) 2 .4H 2 O, SrC0 3 , CaC0 3 , MgC0 3 , Ca (OH) 2 , Mg (OH) 2 , Sr (OH) 2 , CaMg (CO 3 ) 2 , MgO, CaO and mixtures and double salts thereof.
  • Mg 5 (CO 3 ) 4 (OH) 2 .4H 2 O, MgC0 3 and CaCO 3 are preferred precursor salts.
  • salts are suitable which are water-insoluble even ⁇ substantially and by chemical reaction, for example with an acid can be converted into an active salt.
  • the precursor salt is provided as particles having a diameter of 3 to 100 ⁇ m, preferably 5 to 20 ⁇ m.
  • the particles of the precursor salt preferably have a defined shape and size. In particular, a spherical shape and a Pelleg ⁇ ize of about 10 .mu.m are preferred.
  • the particle size of the precursor ⁇ salt remains in the conversion in the active salt he prefers keeping ⁇ . In this manner, the morphology of the active ⁇ salt on the morphology of the precursor salt can be controlled advertising to.
  • a suitable method for determining the particle size of the precursor salt is scanning electron microscopy.
  • the gelling salt is selected from the group consisting of CaCl 2 , calcium lactate, SrCl 2 , calcium gluconate, strontium lactate, strontium gluconate, barium chloride - IS
  • Suitable salts are also salts which can form a hydrogel with polysaccharide acids, for example the abovementioned active salts.
  • water-soluble salts are suitable which contain Ca 2+ , Sr 2+ or Ba 2+ ions.
  • the acid is selected from the group consisting of sulfuric acid, hydrochloric acid, hydrobromic acid, sulfurous acid, phosphoric acid and mixtures thereof.
  • the acid may be present as a liquid, gas or solution thereof.
  • the reaction with the acid converts the precursor salt into an active salt containing as anion the anion corresponding to the acid.
  • a Kompositmate ⁇ rial which holds an active salt corresponds in addition to the gelling, which itself can not be used as gelling. If the gelling ent ⁇ removed by washing from the composite material, it is possible to obtain a composite material, which eventually contains an active salt from ⁇ , which itself can not be used as a gelling salt.
  • one or more fillers are further added to the solution of the polysaccharide acid or a salt thereof or the suspension of the one or more precursor salts in the polysaccharide acid solution.
  • the one or more fillers are selected from the group consisting of water-insoluble salts, such as CaC0 3 , carbon particles, such as activated carbon, silica gel, and mixtures thereof.
  • water-insoluble salts such as CaC0 3
  • carbon particles such as activated carbon, silica gel, and mixtures thereof.
  • CaCO 3 and activated carbon are preferred fillers.
  • fillers are suitable which are essentially water-insoluble and are not suitable for water absorption and / or heat storage. can. It is believed that the fillers increase the mechanical stability of the composite material.
  • the particle size depends on the conditions in the synthesis of the composite material, in particular the drop size of the solutions. Nonetheless, if desired, the composite material can also be comminuted to particles of a certain diameter after synthesis , in particular to particles with an average diameter of 0.1 to 5.0 mm, preferably 0.5 to 3.0 mm are processed.
  • the abovementioned processes according to the invention are particularly suitable for providing a composite material with a relatively high amount of active salt, so that a high water and / or heat storage density can be obtained. Furthermore, two or more different active salts can easily be introduced into the host structure by the processes according to the invention.
  • the composite material according to the invention is particularly suitable as a heat storage, which is used for example in homes or in the industrial waste heat recovery application.
  • the invention is therefore also the use of the composite material as a thermo-chemical heat storage material, in particular for re-fetched ⁇ heat storage and -abgäbe.
  • the composite material according to the invention is particularly suitable for storing water, for example, to extract water from the air and recover it later.
  • the invention is therefore also the use of the composite material for repeated water storage and -abgäbe and thus for the production of drinking or utility water from ambient air.
  • the embedded into the solid host structure fixed Ak ⁇ tivsalz a gas stream, for example a stream of air, exposed to a temperature which is sufficient to maintain the active salt at ⁇ least is for use of the composite material as a heat reservoir, partially dehydrate.
  • the liberated crystal ⁇ water is delivered to the gas stream in the form of water vapor.
  • the composite material is now at least partially gela ⁇ the. If the charged composite material is brought into contact with a moist gas stream, eg humid air, then sufficiently high water vapor pressure results in an exothermic hydration, ie a chemical reaction without a physical phase transition of the solid active salt, in particular without a change in the physical state of the active salt. and the composite material releases the reaction enthalpy in the form of heat.
  • the embedded into the solid host structure solid active salt to a moist gas stream for example a moist air stream, be exposed at a water vapor pressure sufficient to hydrate the active salt.
  • Water Discharge from the composite material is again heat, for example, is provided by solar thermal energy, fed and given ⁇ if the released gaseous water introduced ⁇ condensation ge.
  • FIG. 3 of FIG. 1 corresponds to a composite synthesized according to Examples 1, 2 or 6 and analyzed according to Examples 7 and 10.
  • Composite 2 corresponds to a composite synthesized according to Example 3.
  • Composite 1 corresponds to a composite synthesized according to Examples 4 and 5 and analyzed according to Examples 8 and 9.
  • the particle sizes of the composite materials were using a light microscope SZ-60 from Olympus and ei ⁇ ner Micrometer 0-25mm Hellios Preisser be ⁇ agrees.
  • the dried Kom ⁇ positmaterial was gela Gert ⁇ for 11 days more than 37 wt .-% hydrochloric acid.
  • Spherical Kompositmaterialp were obtained with an average diameter of 4 mm, which consist of a skeleton structure based on alginate, to magnesium chloride were converted ⁇ urea precursor salt and calcium chloride intercalated.
  • the Kompositmate- rial was stored for 48 hours at 70 ° C in demineralized water, then filtered and dried at 130 ° C getrock ⁇ net.
  • the dried composite material was stored for 14 days over 37 wt .-% hydrochloric acid.
  • spherical Kompositma ⁇ terialp with a mean diameter of 2 mm, which consisted of a framework structure based on alginate and converted to magnesium chloride precursor salt.
  • Example 5 (synthesis) 4.00 g of sodium alginate were dissolved in 200 ml demineralized What ⁇ ser. There were spherical hydromagnesite Parti ⁇ kel added with a mean diameter of 10 ym 16.00 g. A homogeneous suspension of Hydromagnesitparti ⁇ kel was prepared in the sodium alginate solution by stirring. The resulting suspension was dropwise added dropwise into 400 ml of a 0.2 molar calcium lactate solution to form spherical hydrogel particles with intercalated hydromagnesite. The Hydrogelparti ⁇ kel were stored for 15 hours in the calcium lactate solution, then briefly rinsed with demineralized water and dried at 140 ° C for 24 hours.
  • the resulting composite material rial was stored for 72 hours at 70 ° C in demineralized water, then filtered and dried at 130 ° C.
  • the dried composite material was stored for 11 days in sulfuric acid diluted with diethyl ether.
  • spherical composite material particles with a mean diameter of 4 mm which consisted of a framework structure based on alginate and converted to magnesium sulfate precursor salt.
  • Example 2 calorimetric investigations on a composite prepared according to Example 1 are described.
  • the composite was stored at 130 ° C for 7 days and about 300 mg was weighed into a gas flow cell of a Setaram C80 calorimeter.
  • the measuring cell was introduced into the measuring chamber of the calorimeter and a dry gas stream was passed through the measuring cell at 30 ° C. and a maximum of 5% relative humidity at a flow rate of 50 ml / min. passes.
  • the relative Feuch ⁇ ACTION of the gas stream was increased to 30% and thus induces Hydratati ⁇ on the active salt in the composite material.
  • the liberated during the hydration heat was determined using the Kalorime ⁇ ters and recorded.
  • the composite ⁇ material was weighed and water uptake from the difference of the initial and final weight Conference calculated. It was possible to determine a gravimetric storage density of 1239 KJ / g, based on the hydrated material, and a water absorption of 0.89 g / g, based on the dehydrated composite material. From the bulk density of the material and the total amount of heat liberated, a storage density of the compo ⁇ sitmaterials of 1.52 KJ / cm 3, based on the hydrated Ma ⁇ TERIAL calculated.
  • Example 5 calorimetric investigations on a composite prepared according to Example 5 are described.
  • the composite was stored at 130 ° C for 7 days and about 300 mg was weighed into a gas flow cell of a Setaram C80 calorimeter.
  • the measuring cell was introduced into the measuring chamber of the calorimeter, and it was a dry gas stream at 30 ° C and a maximum of 5% relative humidity at a flow rate of 50 ml / min through the measuring cell ge ⁇ passes.
  • the relative Feuch ⁇ ACTION of the gas stream was increased to 84% and thus induces Hydratati ⁇ on the active salt in the composite material.
  • the at the Hydration released heat was determined with the help of Kalorime ⁇ ters and recorded.
  • the composite was stored at 130 ° C for 7 days and about 300 mg was weighed into a gas flow cell of a Setaram C80 calorimeter.
  • the measuring cell was introduced into the measuring chamber of the calorimeter, and it was a dry gas stream at 30 ° C and a maximum of 5% relative humidity at a flow rate of 50 ml / min through the measuring cell ge ⁇ passes.
  • the relative Feuch ⁇ ACTION of the gas stream was increased to 30% and thus induces the hydration of the active salt in the composite material.
  • the liberated during the hydration heat was determined using the Kalorime ⁇ ters and recorded.
  • Example 11 Water Storage and Recovery / CaCl 2 composite

Abstract

L'invention concerne un matériau composite pour le stockage d'eau et/ou de chaleur. L'invention concerne plus spécifiquement un matériau composite comprenant une structure hôte à base d'acides polysaccharidiques ou de sels de ceux-ci, et un ou plusieurs sels actifs introduits dans la structure hôte, aptes à accumuler ou à libérer de la chaleur par hydratation et déshydratation.
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