KR101859112B1 - Thermochemical energy storage materials using zeolite-metallic salt composite and manufacturing method of the same - Google Patents

Thermochemical energy storage materials using zeolite-metallic salt composite and manufacturing method of the same Download PDF

Info

Publication number
KR101859112B1
KR101859112B1 KR1020160141093A KR20160141093A KR101859112B1 KR 101859112 B1 KR101859112 B1 KR 101859112B1 KR 1020160141093 A KR1020160141093 A KR 1020160141093A KR 20160141093 A KR20160141093 A KR 20160141093A KR 101859112 B1 KR101859112 B1 KR 101859112B1
Authority
KR
South Korea
Prior art keywords
metal salt
porous zeolite
metal
chloride
zeolite
Prior art date
Application number
KR1020160141093A
Other languages
Korean (ko)
Other versions
KR20180046170A (en
Inventor
박인
박제성
권오경
Original Assignee
한국생산기술연구원
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by 한국생산기술연구원 filed Critical 한국생산기술연구원
Priority to KR1020160141093A priority Critical patent/KR101859112B1/en
Publication of KR20180046170A publication Critical patent/KR20180046170A/en
Application granted granted Critical
Publication of KR101859112B1 publication Critical patent/KR101859112B1/en

Links

Images

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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B37/00—Compounds having molecular sieve properties but not having base-exchange properties
    • C01B37/06—Aluminophosphates containing other elements, e.g. metals, boron
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/02—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof; Direct preparation thereof; Preparation thereof starting from a reaction mixture containing a crystalline zeolite of another type, or from preformed reactants; After-treatment thereof
    • C01B39/026—After-treatment
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B39/00—Compounds having molecular sieve and base-exchange properties, e.g. crystalline zeolites; Their preparation; After-treatment, e.g. ion-exchange or dealumination
    • C01B39/54—Phosphates, e.g. APO or SAPO compounds
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/10—Process efficiency
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Combustion & Propulsion (AREA)
  • Thermal Sciences (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)

Abstract

One embodiment of the present invention provides a thermal storage material comprising a porous zeolite and a metal salt, wherein the metal salt is impregnated in the pores of the porous zeolite and between the porous zeolite particles to form a metal salt in the pores and between the porous zeolite particles Wherein the porous zeolite-metal salt complex has a volume change rate of 1 to 30% and an axial heat quantity of 300 J / g to 1200 J / g. A method for producing a porous zeolite-metal salt complex is provided.

Description

TECHNICAL FIELD [0001] The present invention relates to a thermal storage material using a porous zeolite-metal salt complex and a method for manufacturing the same,

The present invention relates to a thermal storage material, and more particularly, to a porous zeolite, especially an aluminophosphate porous zeolite, and a porous zeolite particle impregnated with a metal salt having a deliquescent property, To a thermal storage material using a porous zeolite-metal salt complex which is excellent in the degree of heat storage compared to a porous zeolite and can reduce a large volume change before and after the hydration reaction of a metal salt, and a manufacturing method thereof will be.

At present, efficient utilization of energy is becoming a big issue in the world, and researches on the application technology of various industrial waste heat generated in industrial sites are actively being actively carried out. The industrial waste heat is mostly in the range of 70 ° C to 90 ° C in various forms such as low and medium hot water and saturated water vapor, but is mostly discarded without being reused.

In order to convert and discard waste heat into high-quality energy, it is necessary to minimize the heat loss by densifying the waste heat. This technology is called a thermal energy storage (TES) system.

There are three known methods of heat storage: sensible heat storage, latent heat storage, and thermochemical storage. First, the sensible heat storage method is a method of storing heat energy while heating or cooling a liquid or solid storage medium (for example, water, sand, etc.), and is relatively inexpensive as compared with the thermal storage type. However, it is disadvantageous in that the energy density is small (about 1/3 level) and must be designed in a large volume. In addition, there has been a problem in that expensive heat insulation design is required to dissipate heat at a constant temperature.

Next, the latent heat storage method uses phase change materials such as paraffin and molten salt, and is a method of storing heat energy by using a material that releases or absorbs heat at the time of phase change. This is because the energy storage density is high compared to the sensible heat storage method, and the technical maturity is high and it is a practical storage method that is applied in the industrial application. In particular, it is advantageous in that it has a high energy density as well as a heat recovery property and a characteristic that maintains a constant heat temperature, so that the target release temperature can be adjusted and a daytime / quarterly heat storage is possible.

Next, the thermochemical storage method is to store heat energy by using the principle that the heat is released or absorbed during the reaction of the compound by using a material that stores or emits heat energy through chemical reaction. Compared to conventional sensible storage and latent heat storage methods, they have a high heat capacity and a high efficiency as a technology using chemical reaction and have a long storage period. With these advantages, the thermoelectric type heat storage system can be applied as a system for storing heat in a sub-scale or a heat delivery system (a system for storing waste heat and moving it to a necessary place and utilizing it). In other words, the thermo-accumulation method can contribute to solve the temporal and spatial load difference between the use-side (between the heat source and the customer).

However, in spite of the above advantages, the thermo-chemical heat storage system has recently been in increased interest, and thus has a difficulty in commercialization due to its low technical maturity compared to the other thermal storage system.

Currently, the most widely known thermochemical storage materials are zeolites or silica gels using adsorption, and thermochemical materials for hygroscopic metal compounds have also been disclosed.

Japanese Laid-Open Patent Application No. 2014-177619 (hereinafter referred to as "Prior Art 1") discloses a process for producing a composite containing a third anhydrous gypsum, a magnesium compound and a compound containing Ca x Mg 1 - x SO 4 , a hemihydrate gypsum, And a compound containing a hydrate of Ca x Mg 1 - x SO 4 , a reaction part provided with the reaction material, an evaporation condensing part for evaporating or condensing the water, And a chemical heat pump having a connection part for connecting the evaporation and condensation part and an opening and closing mechanism for controlling the opening and closing of the connection part.

However, the heat storage material of the prior art 1 is a metal sulfide having hygroscopicity, which is excellent in heat accumulation, but has a problem that the volume expands due to absorption of water, .

JP 2014-177619

As described above, the heat storage material of the conventional sensible heat storage method has a disadvantage that it is required to be designed with a large volume because of low energy density and can be used practically, and there is a problem that a heat insulation design is required. In addition, the heat storage material and system of the latent heat storage type have a high energy density, have heat recovery property and maintain a constant heat temperature, and are industrially applied, but the problem of low heat storage density compared with the thermal storage material there was. However, despite the advantages of excellent energy density and long storage time compared with other types of thermal storage systems, the thermal storage system has not yet achieved the commercialization performance and stability due to its low technical maturity.

Accordingly, another object of the present invention is to contribute to the construction of a thermal storage system having a high-density storage capacity by providing a technique relating to a thermal storage type composite storage material having excellent thermal storage characteristics.

Another object of the present invention is to provide a porous zeolite-metal salt composite material, which is different from a single material heat storage material which is conventionally composed of only a metal salt, prevents excessive volume expansion that may occur during a heat storage reaction, It is another object of the present invention.

It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory and are not intended to limit the invention to the precise form disclosed. There will be.

According to an aspect of the present invention, there is provided a porous zeolite which comprises a porous zeolite and a metal salt, wherein a metal salt is impregnated in the porous zeolite and between the porous zeolite particles to form a metal salt between the porous zeolite particles and the porous zeolite particles. Wherein the porous zeolite-metal salt complex is composed of a porous zeolite-metal complex.

In an embodiment of the present invention, the porous zeolite may be selected from the group consisting of aluminophosphate type zeolite, ferroaluminophosphate type zeolite, and silicoaluminophosphate type zeolite, Lt; RTI ID = 0.0 > zeolite < / RTI >

In an embodiment of the present invention, the thermal storage material using the porous zeolite-metal salt composite may have a volume change rate of 1% to 30% and an axial heat of 300 J / g to 1200 J / g.

In an embodiment of the present invention, the porous zeolite may comprise a void having an average size of the particles of 50 nm to 50000 nm and an average size of 0.05 nm to 2 nm in the particles.

In an embodiment of the present invention, the metal salt may include at least one selected from a metal chloride having a decomposition property, a metal sulfate, a metal hydroxide, and a metal oxide.

In one embodiment of the present invention, the metal chloride is selected from the group consisting of CaCl 2 , LiCl, ZnCl 2 , NaCl, KCl, MgCl 2 , And at least one metal chloride selected from manganese chloride (MnCl 2 ), iron chloride (FeCl 2 ), nickel chloride (NiCl 2 ), and strontium chloride (SrCl 2 ).

In another embodiment of the present invention, the metal sulfates may be at least one metal sulfide selected from magnesium sulfate (MgSO 4 ), calcium sulfate (CaSO 4 ), and zinc sulfate (ZnSO 4 ).

In another embodiment of the present invention, the metal hydroxide may be a metal hydroxide such as barium hydroxide (Ba (OH) 2 ) or sodium hydroxide (NaOH).

In another embodiment of the present invention, the metal oxides include at least one metal selected from among at least one metal oxides selected from calcium nitrate (CaNO 3 ), magnesium nitrate (MgNO 3 ), and zinc nitrate (ZnNO 3 ) Lt; / RTI >

However, the kind of the metal salt is not limited thereto. The metal salts described above are hygroscopic and can be used as a heat storage material by releasing or absorbing heat by a reversible chemical reaction between anhydride and hydrate.

According to another aspect of the present invention, there is provided a method for preparing a porous zeolite-metal salt complex for thermal storage material.

In a preferred embodiment of the present invention, a thermal storage material using a porous zeolite-metal salt complex is prepared by dissolving a metal salt in water to prepare an aqueous metal salt solution. The porous zeolite is dipped in a metal salt aqueous solution to form a porous zeolite, A second step of impregnating the porous zeolite particles with a metal salt, and a step of drying the porous zeolite impregnated with a metal salt in the pores and between the porous zeolite particles at a temperature of 100 ° C to 200 ° C to prepare a porous zeolite- Three steps can be included.

In an embodiment of the present invention, the porous zeolite in the second step is selected from the group consisting of aluminophosphate type zeolite, ferroaluminophosphate type zeolite, and silicoaluminophosphate type porous zeolite silicoaluminophosphate type zeolite).

In the embodiment of the present invention, the metal salt in the first step may include at least one selected from metal chloride, metal sulfide, metal hydroxide, and metal oxides having decomposition properties.

The composite thermal storage material according to an embodiment of the present invention includes a porous zeolite that is a thermal storage material based on chemical adsorption, and a metal salt having impairing properties between the porous zeolite particles and the porous zeolite particles are impregnated into the voids and between the porous zeolite particles And the metal salt is located in the region where the metal salt is located. As described above, the conventional metal salt-based thermal storage material has a high heat accumulation density (heat quantity), but the volume expands as moisture is absorbed. Due to the nature of the material having hygroscopicity when repeatedly used, Respectively. However, the thermal storage material according to the present invention is characterized in that the metal salt is impregnated in the pores of the porous zeolite and between the porous zeolite particles to form the metal salt in the pores and between the porous zeolite particles, It can be improved at the same time.

According to an embodiment of the present invention, a porous zeolite is used with a ferroaluminophosphate-based porous zeolite, which has a relatively small surface charge, thereby facilitating the impregnation of the metal salt into a salt state, The phenomenon of impregnation between the porous zeolite particles can be minimized.

In addition, the porous zeolite-metal salt composite thermal storage material according to an embodiment of the present invention has an excellent heat storage density of 300 J / g to 1200 J / g as compared to a single material.

In addition, the porous zeolite-metal salt composite thermal storage material according to the present invention can be used to supply process heat in the hot water supply and heating and industrial fields of a district or a building, As shown in FIG.

It should be understood that the effects of the present invention are not limited to the above effects and include all effects that can be deduced from the detailed description of the present invention or the configuration of the invention described in the claims.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a flow chart showing each step of the process for producing a porous zeolite-metal salt complex.
FIG. 2 is a schematic view showing a step of producing a porous zeolite-metal salt complex. FIG.
3 is a DSC curve according to CaCl 2 content of FAPO4-5 / CaCl 2 .
FIG. 4 is a DSC curve according to the MgSO 4 content of FAPO 4 - 5 / MgSO 4 .
5 is a photograph showing the after hydration of the resulting FAPO4-5 / MgSO 4 (adsorption) reaction.

Hereinafter, the present invention will be described with reference to specific examples. It will be apparent, however, to one skilled in the art that the present invention may be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Throughout the specification, when a part is referred to as being "connected" (connected, connected, coupled) with another part, it is not only the case where it is "directly connected" "Is included. Also, when an element is referred to as "comprising ", it means that it can include other elements, not excluding other elements unless specifically stated otherwise.

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In this specification, the terms "comprises" or "having" and the like refer to the presence of stated features, integers, steps, operations, elements, components, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

Hereinafter, the porous zeolite-metal salt complex will be described based on the following drawings.

FIG. 1 is a schematic view showing a step of preparing a porous zeolite-metal salt complex. In step (a), a porous zeolite is prepared. In step (b), a porous zeolite is impregnated into a metal salt aqueous solution. In step (c), the metal salt aqueous solution impregnated with the porous zeolite is dried to prepare a metal salt in the pores of the porous zeolite and between the porous zeolite particles. The final structure (c) Complex.

The present invention provides a technique for a thermal storage material using a porous zeolite-metal salt complex. The thermal storage material according to the present invention comprises a porous zeolite and a metal salt. The porous zeolite and metal salt are dispersed in the porous zeolite and between the porous zeolite particles (In the form of a composite salt in porous matrix (CSPM) in which a metal salt is impregnated with a metal salt in the pores and between porous zeolite particles. The porous zeolite-metal salt complex according to the present invention has a volume change ratio of 1% to 30% and an axial heat capacity of 300 J / g to 1200 J / g. May be a thermal storage material used. The porous zeolite itself has a relatively large surface area as compared with other materials used as a heat storage material as a porous material, and thus it is difficult to realize a desired heat storage density. However, the porous zeolite itself and the porous zeolite particles are filled with a metal salt In the case of a porous zeolite-metal salt complex, the surface area of the porous zeolite itself may be reduced.

Further, in the case of a single metal salt used as a heat storage material, the metal salt itself does not maintain the previous powder state in the process of adsorption (or hydration) and desorption (or dehydration) of water and coagulates to form a cluster (Or hydration), the volume thereof is expanded. As a result, a large volume change of the heat storage material itself causes a problem that the heat storage material can not be supplied to the system, Stability in the process may be a problem.

However, in the case of the porous zeolite-metal salt complex of the present invention, the metal salt itself exists in a form (CSPM form) in which the porous zeolite is located in the pores of the porous zeolite and between the porous zeolite particles, It is possible to prevent the volume from expanding at a rate of 1% to 30%, thereby preventing a large change in volume and reducing the heat storage capacity caused by aggregation of the salt, J / g can be provided. This can be explained in more detail through the following examples and experimental examples.

Hereinafter, the present invention will be described in detail with reference to the constituent components of the thermal storage material of the present invention in detail.

The porous zeolite of the present invention is a porous zeolite having at least one porous structure selected from aluminophosphate type zeolite, ferroaluminophosphate type zeolite, and silicoaluminophosphate type zeolite, Zeolite, the average size of the particles is 50 nm to 50000 nm, and the average size in the particles is 0.05 nm to 2 nm. When the average size of the porous zeolite particles exceeds 50,000 nm, the surface area becomes relatively small, which may be difficult to realize the desired heat storage density. When the average size of the porous zeolite particles is less than 50 nm, There is a problem that the particle size is excessively small and the aggregation property can be increased. In addition, when the average size of the voids formed in the porous zeolite is less than 0.05 nm, the impregnation of the metal salt may not be easy and may cause clogging of voids, which is not preferable.

The porous zeolite of the present invention can be easily impregnated with a metal salt, which is a thermal storage material, by having the particle size and the void as described above, and can be used as a storage material of a porous zeolite based on chemical adsorption, Can be expected to be synergistic.

In the present invention, the metal salt impregnated in the voids of the porous zeolite and between the porous zeolite particles may be at least one selected from metal chloride, metal sulfide, metal hydroxide and metal oxide having detachability.

More specifically, the metal chloride is selected from the group consisting of calcium chloride (CaCl 2 ), lithium chloride (LiCl), zinc chloride (ZnCl 2 ), sodium chloride (NaCl), potassium chloride (KCl), magnesium chloride (MgCl 2 ) 2 ), iron chloride (FeCl 2 ), nickel chloride (NiCl 2 ), and strontium chloride (SrCl 2 ).

In another embodiment of the present invention, the metal sulfates may be at least one metal sulfide selected from magnesium sulfate (MgSO 4 ), calcium sulfate (CaSO 4 ), and zinc sulfate (ZnSO 4 ).

In another embodiment of the present invention, the metal hydroxide may be a metal hydroxide such as barium hydroxide (Ba (OH) 2 ) or sodium hydroxide (NaOH).

In another embodiment of the present invention, the metal oxides include at least one metal selected from among at least one metal oxides selected from calcium nitrate (CaNO 3 ), magnesium nitrate (MgNO 3 ), and zinc nitrate (ZnNO 3 ) Lt; / RTI >

However, the kind of the metal salt is not limited thereto. The metal salts described above are hygroscopic and can be used as a heat storage material by releasing or absorbing heat by a reversible chemical reaction between anhydride and hydrate.

The porous zeolite according to the present invention has a structure in which a metal salt is impregnated in the pores of the porous zeolite and between the porous zeolite particles so that the metal salt is located in the pores and between the porous zeolite particles. And the heat is released at the time of adsorption of moisture. The metal salt impregnated in the pores of the porous zeolite and between the porous zeolite particles absorbs heat in the vicinity of the dehydration reaction in the hydrate state in the hydrate state, . Therefore, the heat storage characteristics by the chemical adsorption of the porous zeolite and the heat storage characteristics by the reversible chemical reaction between the anhydride and the hydrate of the metal salt are combined, and the high heat storage characteristic compared to the single material can be expected. (Comparison of the heat storage characteristics of a single material and a composite material will be described later in Examples and Experimental Examples.)

 Hereinafter, a method for producing a porous zeolite-metal salt composite for a thermal storage material according to the present invention will be described with reference to the following drawings.

FIG. 2 is a flow chart showing each step of the method for producing a porous zeolite-metal salt complex for thermal storage material.

2, the porous zeolite-metal salt complex for thermal storage material comprises a first step (S100) of preparing a metal salt aqueous solution by dissolving a metal salt in water, a step of immersing porous zeolite in a metal salt aqueous solution to form a porous zeolite- (S200) of impregnating the porous zeolite particles with a metal salt between the porous zeolite particles, and drying the porous zeolite impregnated with the metal salt in the pores and between the porous zeolite particles at a temperature of 100 ° C to 200 ° C to remove the porous zeolite- The porous zeolite-metal salt composite for thermal storage material according to the present invention is manufactured by including the third step (S300) of preparing the porous zeolite material and the third step (S300) , Wherein the volume change rate is 1% to 30% And an axial heat amount of 300 J / g to 1200 J / g. Hereinafter, a method of preparing the porous zeolite-metal salt composite for a thermal storage material will be described step by step. However, the description of the same parts as the porous zeolite-metal salt composite will be omitted.

The first step of the present invention is a step (S100) of producing an aqueous metal salt solution. In order to uniformly impregnate the metal salt in the pores of the porous zeolite and between the porous zeolite particles in a step to be described later, it may be preferable to dissolve the metal salt in water in the first step. In order to rapidly dissolve the metal salt according to the embodiment, it may be possible to heat at a predetermined temperature (less than 100 ° C, more preferably 60 ° C to 90 ° C) in the first step.

The second step of the present invention is a step (S200) of immersing a porous zeolite in a metal salt aqueous solution to impregnate a metal salt between the porous zeolite and the porous zeolite particles. In the present invention, the porous zeolite may be at least one selected from the group consisting of an aluminophosphate type zeolite, a ferroaluminophosphate type zeolite, and a silicoaluminophosphate type zeolite. Zeolite, and the production method thereof is as follows.

In the embodiment of the present invention, the ferroaluminophosphate-based porous zeolite has a neutral surface charge. The method for producing the same is to prepare an aqueous phosphoric acid solution, adding triethylamine to the aqueous phosphoric acid solution and stirring, (II) hydrate is added to the solution to which aluminum isopropoxide has been added, and the mixture is stirred for 1 to 2 hours, stirring is performed for 1 to 2 hours, Heating the completed solution to a temperature of 150 to 250 ° C. for 30 minutes to 2 hours, cooling the reaction solution to room temperature, cooling the solution at 100 ° C. to 200 ° C. for 30 minutes to 2 hours , And after the drying is completed, the temperature is raised to a temperature of 500 캜 to 700 캜 and firing is performed for 4 to 6 hours It can be referenced.

The ferroaluminophosphate-based porous zeolite prepared by such steps may be constituted in a weight ratio of Al 2 O 3 : P 2 O 5 : FeO: TEA: H 2 O = 1: 1.05: 0.1: have.

Also, in the second step of the present invention, the porous zeolite and the metal salt aqueous solution may be mixed in a weight ratio of 10: 2 to 10: 30. The higher the content of the metal salt, the more the heat storage efficiency can be increased. However, the higher the content of the metal salt, the more the metal salt may aggregate. Therefore, the porous zeolite is preferably impregnated with a metal salt to be used as the porous zeolite-metal salt composite structure, and is preferably mixed in the weight ratio as described above. Hereinafter, the present invention will be specifically described in the following examples and experimental examples.

The third step of the present invention is a step (S300) of drying the porous zeolite impregnated with the metal salt in the pores and between the porous zeolite particles at a temperature of 100 ° C to 200 ° C. The dryer used for the drying process may be a general drying oven or a spray drier. If a spray dryer is used, it may be dried and then powdered. In this case, the drying temperature may be preferably 100 ° C or higher in order to effectively remove water as a solvent component of the present manufacturing method, and when it is higher than 200 ° C, it may not be preferable due to problems such as using more energy than necessary.

The preparation of the porous zeolite-metal salt complex for thermal storage material according to the present invention will be described in detail in the following examples.

Hereinafter, the present invention will be described in more detail with reference to specific examples and experimental examples.

[ Example  One]

One. Ferroaluminophosphate-based  Porous zeolite production

A ferroaluminophosphate-based porous zeolite (FAPO 4 -5) having a weight ratio of Al 2 O 3 : P 2 O 5 : FeO: TEA: H 2 O = 1: 1.05: 0.1: 1.2: To a solution of 41.2 g of phosphoric acid in 76 g of water is added 24.2 g of triethylamine and the mixture is stirred vigorously for 30 minutes. The container of the stirred solution is immersed in ice water and the temperature is lowered. 81.8 g of aluminum isopropoxide is slowly added thereto while stirring vigorously. 1.6 g of iron chloride (II) · tetrahydrate (Iron chloride (II) · tetrahydrate), which is a precursor of Fe, was added to the well-mixed solution, stirred for 2 hours to allow iron to be dispersed well, transferred to an autoclave, Followed by hydrothermal synthesis for 7 hours. After 7 hours, the temperature was lowered to room temperature to terminate the reaction, and the product was washed several times with distilled water. The washed reactant is dried at 150 ° C for 1 hour, heated to 550 ° C and calcined for 5 hours. The final product is obtained in the form of a pale ocher powder.

2. Porous zeolite-metal salts ( FAPO 4 -5 - CaCl 2 ) Manufacture of composite heat storage material

Dissolve 250 g of CaCl 2 hydrate in 500 mL of water so that there is no precipitate, add 500 g of FAPO 4 -5 to this solution and mix well. If the amount of water is insufficient, mix a small amount of water. When the mixing is complete, the mixture is placed in an oven or spray dryer at 150 ° C to 200 ° C for 24 hours to evaporate water in the mixture. After drying was completed, a ferroaluminophosphate-based porous zeolite-calcium chloride composite heat storage material (hereinafter referred to as FAPO 4 -5 - CaCl 2 ) was completed.

[ Example  2]

One. Ferroaluminophosphate-based  Porous zeolite production

The same procedure as in Example 1 was followed.

2. Porous zeolite-metal salts ( FAPO 4 -5 - MgSO4 4 ) Manufacture of composite heat storage material

Dissolve 250 g of MgSO 4 hydrate in 500 mL of water without any precipitate, add 500 g of FAPO 4 -5 to this solution and mix well. If the amount of water is insufficient, mix a small amount of water. When mixing is complete, the mixture is placed in an oven at 150 ° C to 200 ° C for 24 hours to evaporate water in the mixture. After drying was completed, preparation of a ferroaluminophosphate-based porous zeolite-magnesium sulfate composite heat storage material (hereinafter referred to as FAPO 4 -5 - MgSO 4 ) was completed.

[Reaction Scheme 1]

The whole process: AH 2 O + heat ↔ A + H 2 O

Heat storage: AH 2 O + heat → A + H 2 O

Heat dissipation: A + H 2 O → AH 2 O + heat

[ Experimental Example 1] - ( FAPO 4 -5 - CaCl 2 ) hydration (adsorption) reaction calorimetry

As shown in Reaction Scheme 1, FAPO 4 -5 - CaCl 2 can be stored in an aqueous solution state according to a hydration reaction for adsorbing moisture, thereby releasing heat released. The amount of heat generated during the hydration reaction of FAPO 4 -5 - CaCl 2 prepared according to Example 1 was calculated by measuring the amount of heat generated at a temperature of 25 ° C. under a 30% Holed Pan) using a differential scanning calorimeter (DSC). Further, in order to compare the characteristics of a single material with a case where the porous zeolite is composed of a porous metal oxide impregnated with a metal salt (CSPM) in the pores and between the porous zeolite particles, FAPO 4 -5 - CaCl 2 the amount of the second water (moisture) absorption of emitted and yeolreul accordingly after each measurement, and the measurement axis yeolryangreul. The measurement results are also shown in Table 1 and Fig. 3 below.

CaCl 2 content in CSPM (wt%) Amount of water adsorbed (g / g) Calories (J / g) 0 (FAPO 4 -5) 0.178 395 3.8 0.204 437 7.7 0.222 535 15.9 0.303 633 33.3 0.387 770 100 (CaCl 2 ) 0.720 1223

As shown in Table 1, in the case of FAPO 4 -5-CaCl 2 composed of a form (CSPM) in which CaCl 2 is impregnated in the pores of the porous zeolite and between the porous zeolite particles at respective ratios, the amount of CaCl 2 It can be confirmed that the amount of heat increases sharply.

However, as mentioned above, when the amount of CaCl 2 is increased, CaCl 2 may agglomerate to form a lump, so that CaCl 2 may be added in order to minimize aggregation while maintaining a high endothermic value within a certain range. It is desirable to adjust the amount.

Thus, FAPO 4 The weight ratio of the contrast CaCl 2 is preferably 100: 2 to 100:40.

[ Experimental Example 2] - ( FAPO 4 -5 - MgSO 4 ) hydration (adsorption) reaction calorimetry

As described in Reaction Scheme 1, FAPO 4 -5 - MgSO 4 can be stored in an aqueous solution state according to a hydration reaction for adsorbing water (moisture), thereby releasing heat released. The amount of heat generated during the hydration reaction of FAPO 4 -5 - MgSO 4 prepared according to Example 2 was measured by measuring the amount of heat generated at a temperature of 25 ° C under a condition of 75% Holed Pan) using a differential scanning calorimeter (DSC). Further, in order to compare the characteristics of a single material with the case where the porous zeolite is composed of a porous metal oxide impregnated with a metal salt (CSPM) in the pores of the zeolite and the porous zeolite particles, FAPO 4 -5 - MgSO 4 4 was measured, and then the amount of heat absorbed was measured. The measurement results are shown in Table 2 and FIG.

MgSO 4 content (wt%) in CSPM Amount of water adsorbed (g / g) Calories (J / g) 0 (FAPO 4 -5) 0.178 471 5 0.242 515 10 0.201 547 15 0.262 557 25 0.294 657 40 0.348 716 100 0.982 1084

As shown in Table 2, in the case of FAPO 4 -5-MgSO 4 composed of CPSM in which MgSO 4 was impregnated in the pores of the porous zeolite and between the porous zeolite particles, the amount of MgSO 4 It can be confirmed that the amount of heat generated during the hydration reaction increases.

However, as mentioned above, as in the case of CaCl 2 , MgSO 4 may also aggregate to form a lump. As a result, the amount of MgSO 4 To minimize cross-agglomeration is preferred to control the amount of MgSO 4. Therefore, MgSO 4 vs. FAPO 4 -5 Is in the range of 100: 2 to 100: 60.

FIG. 5 is a photograph showing the FAPO 4 -5 - MgSO 4 after the hydration reaction. FIG. 5 (1) shows that FAPO 4 - 5 without addition of MgSO 4 itself does not cause aggregation. one, in the case of (4) of MgSO 4 is 5wt% in FIG. 5 (2), a 5 (3), a 5-containing 15wt% containing 10wt% contained both in the formation of a powder that mungchiji after hydration Can be confirmed.

[ Experimental Example 3] - ( FAPO 4 -5 - MgSO 4 ) Measurement of volume change according to hydration (adsorption) reaction

FAPO 4 -5 - MgSO4 4 (25%) MgSO4 4 Mass (g) before hydration (adsorption) reaction 49.94 44.89 Mass after hydration (adsorption) reaction (g) 62.08 90.06 Mass change ratio (%) 12.14 100.62 Volume (ml) before hydration (adsorption) reaction 54.4 60.5 Volume (mL) after hydration (adsorption) reaction 61.5 175 Volume change ratio (%) 13.05 189.5

In Table 3, when the hydration (adsorption) reaction was performed with MgSO 4 alone, the volume before and after moisture adsorption increased from 60.5 ml to 175 ml, indicating a volume change rate of 189.5%. This leads to an increase in the volume of the salt itself as the MgSO 4 becomes a 6- to 7-hydrate when it causes a hydration (adsorption) reaction.

On the other hand, more than the case of hydrated (adsorption) reaction for 4 FAPO -5- MgSO 4 consisting CPSM form (MgSO 4 containing 25wt%), hydrated volume before and after the (suction) in the reaction to 54.4ml with MgSO 4 danil 61.5ml And the volume change rate is 13.5%.

Which, if consisting of CPSM type, metal salt is the adsorption of moisture by the metal salt only between 4 -5 FAPO constant air gap within the porous zeolite particles and the bar, a certain air gap within the porous zeolite particles and which is located between the so made MgSO 4 is It can be confirmed that the volume change hardly occurs as compared with the case where it is present singly. Also, when it is constituted in the form of CPSM, the phenomenon of MgSO 4 aggregation is also less likely to occur. Based on these facts, it can be confirmed that the present invention can be utilized as a heat storage material having excellent efficiency while ensuring stability without degradation of performance due to material deformation during adsorption process.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

Claims (16)

In a thermal storage material,
Porous zeolites and metal salts,
Wherein the metal salt is impregnated in the pores of the porous zeolite and between the porous zeolite particles so that the metal salt is located in the pores and between the porous zeolite particles,
The porous zeolite and the metal salt are mixed at a weight ratio of 100: 2 to 100: 60,
Wherein the volume change rate is 1% to 30%, and the amount of heat of condensation is 300 J / g to 1200 J / g.
The method according to claim 1,
The porous zeolite may be at least one porous zeolite selected from the group consisting of aluminophosphate type zeolite, ferroaluminophosphate type zeolite, and silicoaluminophosphate type zeolite. Characterized in that the porous zeolite-metal salt complex is a thermal storage material.
The method according to claim 1,
Wherein the porous zeolite has a particle size of 50 nm to 50000 nm and a pore size of 0.05 nm to 2 nm in the particle, wherein the porous zeolite-metal salt composite comprises a porous zeolite-metal salt complex.
The method according to claim 1,
Wherein the metal salt is at least one selected from metal chloride, metal sulfide, metal hydroxide, and metal oxides having deliquescent properties, and a thermal storage material using the porous zeolite-metal salt complex.
5. The method of claim 4,
The metal chloride is calcium chloride (CaCl 2), lithium chloride (LiCl), zinc chloride (ZnCl 2), sodium chloride (NaCl), potassium chloride (KCl), Magnesium Chloride (MgCl 2), manganese chloride (MnCl 2), iron ( FeCl 2), nickel chloride (NiCl 2), and strontium chloride (SrCl 2) high porosity zeolite, characterized in that any one or more of the metal chloride is selected, heating the heat storage material with the general formula for a metal salt complex.
5. The method of claim 4,
Wherein the metal sulfates are at least one selected from the group consisting of magnesium sulfate (MgSO 4 ), calcium sulfate (CaSO 4 ), and zinc sulfate (ZnSO 4 ).
5. The method of claim 4,
Wherein the metal hydroxide is barium hydroxide (Ba (OH) 2 ) or sodium hydroxide (NaOH).
5. The method of claim 4,
Wherein the metal oxides are at least one selected from the group consisting of calcium nitrate (CaNO 3 ), magnesium nitrate (MgNO 3 ), and zinc nitrate (ZnNO 3 ). Thermal storage material used.
A first step of preparing a metal salt aqueous solution by dissolving a metal salt in water;
A second step of immersing the porous zeolite in the metal salt aqueous solution to impregnate the porous zeolite and the porous zeolite particles with a metal salt;
And a third step of drying the porous zeolite impregnated with the metal salt at a temperature of 100 ° C to 200 ° C to prepare a porous zeolite-metal salt complex,
Wherein the porous zeolite-metal salt complex is composed of a metal salt located in the pores of the porous zeolite and between the porous zeolite particles, the porous zeolite and the metal salt are mixed in a weight ratio of 100: 2 to 100: 60, Wherein the rate of change is 1% to 30%, and the amount of heat of crystallization is 300 J / g to 1200 J / g.
10. The method of claim 9,
The porous zeolite may be at least one porous zeolite selected from the group consisting of aluminophosphate type zeolite, ferroaluminophosphate type zeolite, and silicoaluminophosphate type zeolite. Wherein the porous zeolite-metal salt complex is a porous zeolite-metal complex.
11. The method of claim 10,
The ferroaluminophosphate-based porous zeolite may be prepared by,
a) preparing an aqueous phosphoric acid solution;
b) adding triethylamine to the phosphoric acid aqueous solution and stirring the mixture;
c) lowering the temperature of the solution from step b) and stirring while adding aluminum isopropoxide;
d) mixing the solution from step c) with the iron (II) chloride hydrate and stirring for 1 to 2 hours;
e) reacting the solution from step d) above at a temperature of 150 ° C to 250 ° C for 30 minutes to 2 hours;
f) cooling the solution from step e) to room temperature;
g) after cooling is completed, drying at a temperature of 100 to 200 DEG C for 30 minutes to 2 hours; And
h) after drying is completed, heating to a temperature of 500 ° C to 700 ° C and calcining for 4 hours to 6 hours;
Wherein the porous zeolite-metal salt complex is produced by a process comprising the steps of:
10. The method of claim 9,
Wherein the metal salt is at least one selected from metal chloride, metal sulfide, metal hydroxide, and metal oxides having deliquescent properties.
13. The method of claim 12,
The metal chloride is calcium chloride (CaCl 2), lithium chloride (LiCl), zinc chloride (ZnCl 2), sodium chloride (NaCl), potassium chloride (KCl), Magnesium Chloride (MgCl 2), manganese chloride (MnCl 2), iron ( method of producing a composite metal - FeCl 2), nickel chloride (NiCl 2), and strontium chloride (SrCl 2) heat formula heat storage material for the high porosity zeolite of choice characterized in that any one or more of the metal chloride is.
13. The method of claim 12,
Wherein the metal sulfates are at least one selected from the group consisting of magnesium sulfate (MgSO 4 ), calcium sulfate (CaSO 4 ) and zinc sulfate (ZnSO 4 ). .
13. The method of claim 12,
Wherein the metal hydroxide is barium hydroxide (Ba (OH) 2 ) or sodium hydroxide (NaOH).
13. The method of claim 12,
Wherein the metal oxides are at least one selected from the group consisting of calcium nitrate (CaNO 3 ), magnesium nitrate (MgNO 3 ), and zinc nitrate (ZnNO 3 ). Zeolite - metal salt complex.
KR1020160141093A 2016-10-27 2016-10-27 Thermochemical energy storage materials using zeolite-metallic salt composite and manufacturing method of the same KR101859112B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
KR1020160141093A KR101859112B1 (en) 2016-10-27 2016-10-27 Thermochemical energy storage materials using zeolite-metallic salt composite and manufacturing method of the same

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
KR1020160141093A KR101859112B1 (en) 2016-10-27 2016-10-27 Thermochemical energy storage materials using zeolite-metallic salt composite and manufacturing method of the same

Publications (2)

Publication Number Publication Date
KR20180046170A KR20180046170A (en) 2018-05-08
KR101859112B1 true KR101859112B1 (en) 2018-05-21

Family

ID=62187240

Family Applications (1)

Application Number Title Priority Date Filing Date
KR1020160141093A KR101859112B1 (en) 2016-10-27 2016-10-27 Thermochemical energy storage materials using zeolite-metallic salt composite and manufacturing method of the same

Country Status (1)

Country Link
KR (1) KR101859112B1 (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023166044A1 (en) * 2022-03-03 2023-09-07 Vital Energi Solutions Limited Energy storage
KR20240006995A (en) 2022-07-07 2024-01-16 한국에너지기술연구원 Development of high durable heat storage molding platform in repetitive hydration-dehydration cycles

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102147205B1 (en) * 2018-06-19 2020-08-25 한국생산기술연구원 Manufacturing Method of Latent Heat Storage Material Using Atmospheric Pressure Melting Impregnation Method
CN113606974B (en) * 2020-12-11 2022-10-28 浙江大学 Composite metal oxide thermochemical heat storage material, thermochemical heat storage module and preparation method

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2023166044A1 (en) * 2022-03-03 2023-09-07 Vital Energi Solutions Limited Energy storage
GB2618985A (en) * 2022-03-03 2023-11-29 Vital Energi Solutions Ltd Energy storage
KR20240006995A (en) 2022-07-07 2024-01-16 한국에너지기술연구원 Development of high durable heat storage molding platform in repetitive hydration-dehydration cycles

Also Published As

Publication number Publication date
KR20180046170A (en) 2018-05-08

Similar Documents

Publication Publication Date Title
KR101859112B1 (en) Thermochemical energy storage materials using zeolite-metallic salt composite and manufacturing method of the same
JP6248623B2 (en) Reaction material and chemical heat pump
Tang et al. Highly porous carbons derived from MOFs for shape-stabilized phase change materials with high storage capacity and thermal conductivity
Kubota et al. Enhancement of hydration rate of LiOH by combining with mesoporous carbon for Low-temperature chemical heat storage
US20230348772A1 (en) In-situ reactive absorption for equilibrium-shifting of non-condensable gases
US11560504B2 (en) Salt hydrate-based phase change thermal energy storage and encapsulation thereof
US11709023B2 (en) Enhanced TCM production and use
CN114214039A (en) Hydrated salt porous material composite phase-change plate and preparation method thereof
CN106221675A (en) A kind of phase-change and energy-storage medium
Yan et al. Experimental study of thermal performance on the adsorption of stearic acid into different morphology sepiolite
KR102599491B1 (en) Chemical heat storage material and its manufacturing method, and chemical heat pump and its operating method
CN110770523B (en) Chemical heat storage material and method for producing same, and chemical heat pump and method for operating same
JP6895108B2 (en) Moisture adsorbent
US20230417458A1 (en) Improved reagent for thermal machine
JP7332316B2 (en) Method for producing granules for chemical heat storage
Nguyen et al. MgSO4 composites in a ferroaluminophosphate for enhancement of volumetric heat storage capacity at a low charging temperature
Palacios et al. Water sorption-based thermochemical storage materials: A review from material candidates to manufacturing routes
JP2015232101A (en) Reaction material for chemical heat pump and chemical heat pump
RU2729004C1 (en) Material for heat accumulation, method of making material for heat accumulation and chemical heat pump
Clark et al. Salt hydrate-based composite materials for thermochemical energy storage
CN111684039B (en) Chemical heat storage material and preparation method thereof
WO2022071405A1 (en) Absorptive heat pump
KR20210127832A (en) Method of manufacturing thermo chemical energy storage mesoporous materials
JP7064179B2 (en) Moisture adsorbent
WO2021106881A1 (en) Chemical heat storage material and method for producing same, and chemical heat pump

Legal Events

Date Code Title Description
A201 Request for examination
E902 Notification of reason for refusal
E701 Decision to grant or registration of patent right