KR20170040646A - Organic-inorganic nanoporous materials and metal halide hybrid adsorbent, and manufacturing method of the same, and application of the same - Google Patents
Organic-inorganic nanoporous materials and metal halide hybrid adsorbent, and manufacturing method of the same, and application of the same Download PDFInfo
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/32—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating
- B01J20/3231—Impregnating or coating ; Solid sorbent compositions obtained from processes involving impregnating or coating characterised by the coating or impregnating layer
- B01J20/3242—Layers with a functional group, e.g. an affinity material, a ligand, a reactant or a complexing group
- B01J20/3244—Non-macromolecular compounds
- B01J20/3265—Non-macromolecular compounds with an organic functional group containing a metal, e.g. a metal affinity ligand
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
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- F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
- F24—HEATING; RANGES; VENTILATING
- F24F—AIR-CONDITIONING; AIR-HUMIDIFICATION; VENTILATION; USE OF AIR CURRENTS FOR SCREENING
- F24F5/00—Air-conditioning systems or apparatus not covered by F24F1/00 or F24F3/00, e.g. using solar heat or combined with household units such as an oven or water heater
- F24F5/0007—Air-conditioning systems or apparatus not covered by F24F1/00 or F24F3/00, e.g. using solar heat or combined with household units such as an oven or water heater cooling apparatus specially adapted for use in air-conditioning
- F24F5/0014—Air-conditioning systems or apparatus not covered by F24F1/00 or F24F3/00, e.g. using solar heat or combined with household units such as an oven or water heater cooling apparatus specially adapted for use in air-conditioning using absorption or desorption
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- 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
Abstract
The present invention relates to a process for preparing a water-based nanoporous material and a metal chloride hybrid water-absorbing composition and a water-absorbing composition prepared thereby. More specifically, the present invention relates to a process for producing an aluminum- A step of synthesizing an organic nanoporous material, a step of heat-treating the organic nanoporous material to remove unreacted organic material, mixing the nanoporous material with a metal chloride solution to impregnate the inorganic nanoporous material particles with a metal chloride, Drying the resultant to remove the solvent, pulverizing the dried product to obtain a powder, and vacuum-drying the powder to remove excess moisture. The present invention also provides a process for producing a water- The water-absorbing composition according to the embodiment has a pore size distribution in the range of 0.2 to 0 in the range of the driving pressure P / P0 = 0.1 to 0.3. (Absorption amount of water per unit weight of adsorbent) of 9 g / g, so that it can be applied to an air conditioner, an adsorption refrigerator, a dehumidifier, and a cooling and heating apparatus.
Description
The present invention relates to a water-absorbing composition, and more particularly, to a method for producing a water-based nano-porous body-metal chloride hybrid water adsorption composition formed by impregnating a surface of an organic nanoporous material with a metal chloride, To an adsorbent composition and uses thereof.
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 to 90 ℃ in various forms such as medium and low temperature water and saturated water vapor, but is mostly discarded without being reused.
Adsorption - type refrigeration systems have attracted great interest as a way to effectively utilize these waste heat energy. From the early 1980s, adsorption systems such as water, alcohols, ammonia and natural refrigerants, silica gel, zeolite, and activated carbon were used in the absorption system. In Japan, in 1986, 17kW Adsorption type refrigerators have been commercialized. At present, Nishiyodo and Mayekawa in Japan are commercializing 70 to 500 kW absorption chillers and SorTech in Germany has 7.5 kW and 15 kW solar heating systems. Developed and sold.
The adsorption refrigeration system can use waste heat from each process as a driving source and it is an environmentally friendly system that is not related to ozone layer destruction by using water as a refrigerant. In the conventional commercialized adsorption refrigeration system, silica gel and water are used, but the silica gel has a tendency to start adsorption at a low water vapor partial pressure due to strong hydrophilicity. In addition, the adsorption rate at the operating pressure range (P / P 0 = 0.1 to 0.3) on the adsorption refrigeration system is slow and the desorption is not easy and the amount of water adsorbed per unit adsorbent is 0.1 g-water / g-sorbent / g-sorbent: the number of water adsorbed per g of adsorbent). In addition, the moisture adsorbent used in commercialized desiccant type dehumidifiers, adsorption heat pumps, dehumidification rotors, air conditioners and the like mainly includes porous silica and zeolite. In the case of the moisture adsorbent having such a structure, the adsorption rate of water is low and the adsorption It is necessary to research and develop new porous water adsorbent which can reach the limit of the amount of water absorbing agent and replace it. That is, in order to improve the performance of the apparatus including the adsorption type refrigeration system, the desiccant type dehumidifier, the adsorption type heat pump and the like, and to reduce the maintenance cost, a new moisture adsorption composition having a higher water adsorption amount within the driving pressure range is developed This is a reality.
On the other hand, organic nanoporous materials attract attention as materials that can replace silica gel and zeolite, which are porous structures. In general, metals easily form coordination compounds at room temperature with organic ligands having non-covalent electron pairs. Such coordination compounds are polymerized to form a three-dimensional skeleton structure in water or an organic solvent. Such compounds are generally referred to as " Metal-Organic Frameworks (MOF) ", and some compounds are also referred to as" inorganic nanoporous materials "because they have nano-sized pores while forming a three-dimensional framework structure. In addition, the organic nanoporous material has various structures depending on the number of coordination metal ions and the type of organic ligand compound, and can be applied to various fields, and it has been reported that the surface area of zeolite is 3 to 15 times larger than that of zeolite . In addition, there is an advantage that zeolite composed of an inorganic metal exists in an unsaturated metal ion site which is not present, so that it is easy to impart reactivity and adsorption selectivity.
In this connection, Korean Patent No. 10-0803945 (entitled "Porous organic or nonaqueous adsorbent for adsorbing moisture, hereinafter referred to as
The organic or inorganic porous adsorbent according to
SUMMARY OF THE INVENTION Accordingly, the present invention has been made in view of the above problems, and it is an object of the present invention to provide an organic nanoporous material-metal chloride hybrid water adsorption composition which is impregnated with metal chloride on the surface of an inorganic nanoporous material and has improved water adsorption characteristics. It is another object of the present invention to provide a moisture adsorption composition and a method for producing the same that exhibit more effective water adsorption characteristics in a driving pressure range of an adsorption refrigerator, a cooling / heating apparatus, a dehumidifier, and the like in order to enable industrial application of the water adsorption composition. The purpose.
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 method for preparing a water-based nanoporous-metal chloride hybrid water-absorbing composition. In an embodiment of the present invention, a method for producing a water-absorbing composition comprises the steps of: i) synthesizing an organic nanoporous material, ii) preparing a metal chloride solution by dissolving the metal chloride in water, iii) Iv) impregnating the surface of the organic / inorganic nanoporous material with metal chloride, iv) drying the mixture of step iii), v) crushing the dried product in step iv) , vi) crushing, and vacuum-drying the powder to produce a water-absorbing composition.
Also, in one embodiment of the present invention, the method may further include a step of heat-treating the organic nanoporous material formed from step ii) between step i) and step ii), wherein the step of heat- At a temperature of 30 to 360 minutes.
In an embodiment of the present invention, the organic nanoporous material may be prepared by ia) mixing a solvent, a dicarboxylic acid organic ligand and an aluminum precursor in a predetermined ratio, ib) stirring the mixture of ia) Performing a crystallization reaction of the aluminum precursor and the organic ligand in step ib), i) filtering the product, which has been reacted in step ib), and dispersing it in water to ultrasonify the solution, ii) , I.e., drying the filtrate obtained through the second filtration to obtain an inorganic or organic nano-porous body in powder form.
In one embodiment of the present invention, the solvent in step ia) is at least one selected from the group consisting of water, an alcohol solvent, dimethylformamide, diethylformamide, N, N-dimethylformamide, acetonitrile, , N-methylpyrrolidone, and tetrahydrofuran, or a mixture of two or more solvents. The aluminum precursor may be selected from aluminum nitrate, aluminum chloride, aluminum sulfate, and alumina And may be at least one compound, and the dicarboxylic acid organic ligand may be isophthalic acid.
In one embodiment of the present invention, the metal chloride of step ii) is selected from the group consisting of calcium chloride (CaCl 2 ), magnesium chloride (MgCl 2 ), lithium chloride (LiCl), zinc chloride (ZnCl 2 ), potassium chloride (NaCl). In step iii), the organic nanoporous material may be mixed in an amount of 5 to 50 wt% with respect to 100 wt% of the metal chloride solution, , iv) may be characterized by drying in an oven at 100 to 200 ° C for a predetermined period of time.
According to another aspect of the present invention, there is provided a water-absorbing composition prepared by the above-described method. In the embodiment of the present invention, the moisture adsorption composition has a maximum moisture adsorption amount (amount of water adsorbed per unit weight of the adsorbent) of 0.2 to 0.9 g / g at a driving pressure P / P0 of 0.1 to 0.3 .
In one embodiment of the present invention, the water adsorbing composition is formed by impregnating a surface of an organic nanoporous material with a metal chloride, wherein the organic nanoporous material has an aluminum ion and a dicarboxylic acid organic ligand coordinated to the aluminum ion Wherein the organic nanoporous material has an average particle diameter of 100 to 2000 nm and an average particle size of 0.6 to 1.7 nm in the particles.
In order to accomplish the above object, another embodiment of the present invention provides an air conditioning apparatus or an adsorption refrigerator including the moisture adsorption composition.
The process for preparing a water-absorbing composition according to an embodiment of the present invention is a first effect that the preparation of the water-absorbing composition including the porous zeolite is easy compared to the conventional method. The water- The third effect is that the second effect that the maximum moisture adsorption amount is in a range of P0 = 0.1 to 0.3 and that it has industrially useful moisture adsorption characteristics and that it is easy to manufacture and that the process efficiency can be shortened and the manufacturing cost can be reduced.
With regard to the first effect, it may be possible to use an organic or inorganic nano-porous material having a moisture adsorption property equal to or higher than that of zeolite mainly used as a moisture adsorbent, as the moisture adsorbent composition. The organic nanoporous material forms a porous structure similar to that of zeolite. The porous nanoporous material has a small number of kinds of raw materials to be used in manufacturing the nanoporous material, and the manufacturing time is short, thereby improving the efficiency of the manufacturing process of the moisture adsorbent composition.
With regard to the second effect, impregnation of the surface of the organic / inorganic nanoporous material having moisture adsorption properties with metal chloride having hygroscopicity maximizes the water adsorption characteristic, and the device including the adsorbent refrigerator, the dehumidifier, It is possible to have a high rate of moisture adsorption and a high moisture adsorption amount in the pressure range.
In relation to the third effect, the manufacturing process can be shortened as in the first effect, the process efficiency can be improved, and the manufacturing cost can be reduced.
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.
FIG. 1 is a flow chart showing a method of manufacturing an organic nanoporous material-metal chloride hybrid water adsorption composition according to an embodiment of the present invention.
2 is an X-ray diffraction spectrum of an organic nanoporous material (Al-MOF-300C) prepared according to an embodiment of the present invention.
3 is a view showing a lattice structure of an organic nanoporous material according to the present invention of the present invention.
4 is a TGA and DTG graph of an organic-inorganic nanoporous material (Al-MOF) prepared according to an embodiment of the present invention.
5 is a TGA and DTG graph of an organic / inorganic nanoporous material (Al-MOF-300C) prepared according to another embodiment.
FIG. 6 is a graph showing changes in moisture adsorption amount of the water-absorbing composition according to the present invention and the conventional water-absorbing composition according to the driving pressure.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. In order to clearly illustrate the present invention, parts not related to the description are omitted, and similar parts are denoted by like reference characters throughout the specification.
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, embodiments of the present invention will be described in detail with reference to the accompanying drawings. FIG. 1 is a flow chart showing a method of manufacturing an organic nanoporous material-metal chloride hybrid water adsorption composition according to an embodiment of the present invention.
The present invention relates to a method for preparing a metal chloride solution, comprising the steps of: i) synthesizing an organic nanoporous material, ii) preparing a metal chloride solution by dissolving a metal chloride in water, iii) mixing the organic nanoporous material with a metal chloride solution, Impregnating the surface of the workpiece with a metal chloride, iv) drying the mixture of iii), v) crushing the dried product in iv), vi) vacuum drying the powder after crushing And a step of preparing a water-absorbing composition for a water-based nano-porous body-metal chloride hybrid adsorbent composition.
Hereinafter, the present invention will be described in the above-described manner for each manufacturing step.
Step i) of the present invention is a step of synthesizing an organic nanoporous material. In one embodiment of the present invention, the organic nanoporous material comprises ia) mixing a solvent, a dicarboxylic acid organic ligand and an aluminum precursor at a predetermined ratio, ib) stirring the mixture of ia) I) performing the crystallization reaction of the aluminum precursor and the organic ligand, ic) first filtering the reaction product in the step ib), and ultrasonically dispersing the filtered product in water, id) dispersing the dispersion of ic) Filtration step, i.e., drying the filtrate obtained through the second filtration step to obtain an inorganic or organic nano-porous body in powder form.
In one embodiment of the present invention, the solvent in step ia) is at least one selected from the group consisting of water, an alcohol solvent, dimethylformamide, diethylformamide, N, N-dimethylformamide, acetonitrile, , N-methylpyrrolidone, and tetrahydrofuran, or a mixture of two or more solvents selected from the group consisting of water, dimethylformamide, N , N-dimethylformamide, tetrahydrofuran, and the like.
Also, in one embodiment of the present invention, the aluminum precursor in step ia) may comprise at least one compound selected from aluminum nitrate, aluminum chloride, aluminum sulphate and alumina, and the aluminum hydrate of aluminum nitrate, aluminum chloride and aluminum sulphate It is specified that the form may be possible.
In an embodiment of the present invention, the dicarboxylic acid organic ligand in step ia) may be isophthalic acid. Organic ligands linker (linker), also called, -CO 2 acting as a chelate to the metal ion -, CS 2 -, -SO 3 - , and which is an organic compound that has a binding site that can be coordinated to it such as -N It may be preferable to use an organic ligand having two or more bonding sites to induce a stable metal-organic skeleton. In the present invention, a dicarboxylic acid organic ligand having excellent bonding stability is used. More preferably, the dicarboxylic acid organic ligand may be isophthalic acid, which has a structure in which a carboxylic acid is bonded to the 1,3-position of the benzene ring and is coordinated to the aluminum ion by a carboxylic acid, It may be preferable as an organic ligand because it is coordinated to aluminum ions to form a stable porous structure. The isophthalic acid is bonded to the aluminum ion of the aluminum precursor through the crystallization reaction, and forms a metal-organic skeleton having a high surface area and a very high regularity and thus has excellent properties as a moisture adsorbent.
In addition, step (i-b) of the present invention may be performed for a predetermined time at a temperature range of 100 to 150 ° C, but it is not limited thereto. However, when the crystallization temperature is less than 100 ° C, the reaction rate is slow and the reaction time is long to lower the efficiency of the low-temperature process. When the crystallization temperature exceeds 150 ° C, a material free from pores can be formed , There is a problem that the reaction speed is fast and the incorporation of impurities is short. In addition, the step ib) may be performed by hydrothermal synthesis through heating, solvent synthesis, or microwave irradiation. When the crystallization reaction is performed using a microwave synthesizer, heat is uniformly transferred into the reactant, Can be synthesized and the synthesis time can be greatly shortened.
In the present invention, step ic) is a step of uniformly dispersing the aluminum precursor and the organic ligand-binding structure formed in step ib) in water by injecting ultrasonic waves into the water. In this step, the metal nanoporous material This is to evenly impregnate the chloride. In the present invention, the steps i-d) and i-e) are carried out in order to increase the purity by removing unreacted materials or solvents.
Next, step ii) of the present invention is a step of completely dissolving a metal chloride in water to prepare a metal chloride solution. It may be desirable to heat with stirring or stirring at a predetermined rate to completely dissolve the metal chloride in a short period of time. At this time, if the metal chloride is not completely dissolved in water and the next step is carried out, it may be difficult to produce a moisture adsorption composition having a low impregnation efficiency of metal chloride and excellent moisture adsorption characteristics. Also, in one embodiment of the present invention, the method may further include the step of heat-treating the organic or inorganic nanoporous material formed from step i) between step i) and step ii). The heat treatment may be performed at a temperature of 200 to 400 DEG C for 30 to 360 minutes. This is to remove unreacted unreacted materials (such as organic ligands), side reaction products and solvent components through drying and filtration processes to obtain highly purified organic or inorganic nanoporous materials.
Next, in step iii) of the present invention, metal chloride is impregnated on the surface of the organic nanoporous material by mixing the organic nanoporous material with the metal chloride solution. The moisture adsorbent according to the present invention can be expected to have an effect of maximizing the water adsorbability by composing the adsorbability and hygroscopicity by impregnating the surface of the organic / inorganic nanoporous material having excellent adsorption characteristics with metal chloride having deliquescence. In the present invention, the metal chloride is at least one selected from the group consisting of calcium chloride (CaCl 2 ), magnesium chloride (MgCl 2 ), lithium chloride (LiCl), zinc chloride (ZnCl 2 ), potassium chloride (KCl) and sodium chloride It may contain an inert compound.
Next, step iv) of the present invention is a step of drying the mixture of step iii) at a predetermined temperature condition. In one embodiment of the present invention, step iv) may be carried out in an oven at 100-200 [deg.] C for a predetermined time, and the solvent water may be removed by performing oven drying. If the drying temperature is less than 100 ° C, the evaporation time of the solvent may be prolonged and the process efficiency may be deteriorated. If the drying temperature exceeds 200 ° C, the stability of the organic nanoporous material and metal chloride may be impaired Which may be undesirable.
Next, step v) of the present invention is a step of disrupting the dried product in step iv). Generally, a moisture adsorbent exhibits a tendency to adsorb more gas as the surface area increases. Therefore, in order to maximize the moisture adsorption characteristic, it is preferable to carry out the step of pulverizing the product using a crusher for a predetermined time.
Next, step vi) of the present invention is a step of vacuum-drying the pulverized powder to prepare a moisture adsorbent. In this step, the excess moisture contained in the moisture adsorbent is completely removed through the vacuum drier, thereby improving the moisture adsorption characteristics.
Hereinafter, the compounding ratio of the substances constituting the moisture adsorption composition will be described.
The organic or inorganic nanoporous material according to the present invention can be prepared by mixing an aluminum precursor and a dicarboxylic acid organic ligand in a solvent. Preferably, the organic nanoporous material may be prepared by incorporating 4 to 40 wt% of an aluminum precursor and 1 to 10 wt% of a dicarboxylic acid organic ligand to 100 wt% of a solvent.
In addition, the water absorption composition according to the present invention may be characterized in that the organic or inorganic nanoporous material is mixed in an amount of 5 to 50 wt% with respect to 100 parts by weight of the metal chloride solution, but the present invention is not limited thereto. However, since the amount of the metal chloride that can be impregnated in the organic nanoporous material is limited, when the metal chloride solution is excessively added in the production of the moisture adsorbent, the effect of increasing the moisture adsorption characteristic that can be obtained relative to the addition amount may be insufficient There may be a problem. When the content of the metal chloride solution is smaller than that of the organic nanoporous material, the effect of increasing the moisture adsorption characteristics induced by complexing the organic nanoporous material having adsorption characteristics with the metal chloride having hygroscopicity can not be sufficiently secured This can be.
In addition, the water-absorbing composition prepared through the above-described method has a maximum moisture adsorption amount (an amount of water adsorbed per unit weight of the adsorbent) of 0.2 to 0.9 g / g at a driving pressure P / P0 of 0.1 to 0.3 . This is a driving pressure range suitable for the adsorbing part of adsorption type refrigerator, air conditioner, radiator, dehumidifier and air conditioner. Therefore, the moisture adsorption composition according to the present invention can be provided in the adsorbing portion of the apparatus to improve the moisture adsorption property.
In addition, the water-absorbing composition prepared according to the present invention is formed by impregnating a surface of an organic nanoporous material with a metal chloride, and the organic nanoporous material includes an aluminum ion and a dicarboxylic acid organic ligand coordinated to the aluminum ion Is a metal-organic skeleton. Also, the organic nanoporous material may have an average particle diameter of 100 to 2000 nm and an average particle size of 0.6 to 1.7 nm.
The smaller the particle size of the porous organic / inorganic nanoporous material to be applied to the moisture adsorbing composition, the larger the specific surface area and the moisture adsorption amount per unit weight of the moisture adsorbent is increased. However, when the particle size is less than 100 nm, It may be difficult to uniformly disperse it on the metal chloride aqueous solution, and the coagulation effect between the particles may be increased, which may cause the efficiency of the manufacturing process to be lowered. When the particle size of the organic nanoporous material exceeds 2000 nm, it may be difficult to maximize the water adsorption performance in a desired driving pressure range since the specific surface area is small.
The size of pores provided in the organic nanoporous material may be preferably 0.6 to 1.7 nm, but is not limited thereto. The organic nanoporous material has many nano-scale pores due to the regular combination of the metal ion and the organic ligand, and is capable of adsorbing gaseous molecules containing moisture in nanoporous pores. Therefore, as the specific surface area of the moisture adsorbent increases as the size of the pores formed in the organic nanoporous material becomes smaller, the moisture adsorption amount per unit weight of the water adsorbent and the moisture adsorption rate can be maximized. Therefore, the smaller the size of the pores provided in the organic nanoporous material particles, the more favorable characteristics are exhibited as a moisture adsorbent. However, when the pore size is less than 0.6 nm, the pore size may be too small to lower the permeability of water, which may lower the water adsorption performance. If the pore size exceeds 1.7 nm, To achieve moisture adsorption performance.
Hereinafter, examples and experimental examples of the present invention will be described.
[Example 1]
10 ml of dimethylformamide (DMF) and 40 ml of distilled water as a solvent were mixed, 2.0 g of isophthalic acid was added, and the mixture was stirred at 1000 rpm for 30 minutes. Next, the aluminum sulfate hydrate (Al 2 (SO 4) 3 · 18H 2 O) After mixing 8.0g, was prepared and the reaction stirred for 30 minutes at 1000rpm. The reaction vessel containing the reaction product was placed in an oven and subjected to a crystallization reaction at 135 ° C for 12 hours. After the reaction was completed, it was cooled to room temperature and then filtered to obtain the product. The product was placed in distilled water, stirred vigorously for 30 minutes, and then ultrasonically dispersed for 30 minutes to disperse evenly. The aqueous dispersion was filtered and the filtrate was dried at 100 ° C for 1 hour to prepare an organic nano-porous body (hereinafter referred to as Al-MOF) powder.
[Example 2]
The method according to
[Experimental Example 1]
X-ray diffraction analysis was performed to analyze the crystal structure of the organic or inorganic nanoporous material prepared according to Example 2, and x-ray diffraction analysis was performed using an X-ray diffractometer of Rigaku in the room temperature atmosphere. The results are shown in Fig. 2 shows the peak intensity for the diffraction angle (2 &thetas;). Through the X-ray diffraction analysis, the lattice constants and the axial angles of the organic or inorganic nanoporous material according to the present invention were respectively derived as follows.
- lattice constant: a = b = 21.547, c = 10.3780
-Axial angle:? =? =? = 90?
(The symbols a, b and c derived from the X-ray diffraction analysis mean the x, y and z axial lengths of the unit cell, and α, β and γ mean the angles between the x, y and z axes .)
The results of the X-ray diffraction analysis show that the organic / inorganic nanoporous material according to the present invention is a tetragonal structure, and its lattice structure is shown in FIG.
[Experimental Example 2]
Thermogravimetric analysis (TGA) and derivative thermogravimetry (DTG) were performed to analyze the thermal behavior of the organic and inorganic nanoporous materials prepared according to Examples 1 and 2. The measurement was carried out at a heating rate of 10 DEG C / min in a nitrogen atmosphere. The results are shown in FIG. 4 and FIG. FIG. 4 is a thermogravimetric analysis result of the organic or inorganic nanoporous material according to Example 1, and FIG. 5 is a result of thermogravimetric analysis of the organic nanoporous material according to Example 2. FIG.
As a result, according to TGA / DTG analysis, the mass of the organic / inorganic nanoporous material (Al-MOF) according to Example 1 tends to decrease from the initial temperature rise, and a mass loss of about 20% Can be seen. On the other hand, as a result of TGA / DTG analysis of the organic-inorganic nanoporous material (Al-MOF-300C) according to Example 2, it was found that mass loss hardly occurred up to 400 DEG C, It can be confirmed that a mass loss of about 50% occurs at a high rate. The difference in pyrolysis behavior of the organic or inorganic nanoporous material according to Example 1 and Example 2 can be more specifically confirmed by the DTG curve shown in FIG. 4 and FIG.
Thus, the difference in thermal decomposition behavior between Example 1 and Example 2 can be seen as a result of the presence or absence of a high-temperature heat treatment process after the organic nanoporous material is synthesized. Since the unreacted organic material (mainly organic ligand component) and other impurities which have not participated in the crystallization reaction are thermally decomposed when a separate heat treatment step is performed after synthesizing the organic nanoporous material, As shown in the TGA / DTG analysis results of the porous body, no mass loss occurs at the initial temperature rise. In addition, unnecessary organic substances contained in the organic nanoporous material can be removed through the heat treatment process, thereby improving the moisture adsorption rate and the moisture adsorption amount. Also, it can be understood that the heat treatment temperature of the organic / inorganic nanoporous material according to the present invention through TGA / DTG analysis is preferably not higher than 400 ° C considering the decomposition temperature of the organic nanoporous material.
[Example 3]
≪ Production of organic / inorganic nanoporous material &
An organic nanoporous material (Al-MOF-300C) was prepared under the same conditions and in the same manner as in Example 2.
≪ Preparation of organic nano-porous body-metal chloride hybrid water adsorption composition >
250 g of metal chloride, CaCl 2, was added to 500 ml of distilled water and thoroughly stirred to prepare a metal chloride aqueous solution. 250 g of the organic nanoporous material (Al-MOF-300C) and 500 ml of distilled water were mixed with the aqueous metal chloride solution, followed by vigorous stirring for 30 minutes. In order to evaporate the moisture in the mixture, it was dried in a drying oven set at 150 DEG C for 24 hours. After the drying was completed, the product was ground in a powder form using a crusher, and then vacuum dried for 24 hours to prepare a moisture adsorption composition in which excess water was completely removed.
[Comparative Example 1]
As a comparative example, AQSOA Z01, a commercial moisture adsorbent, was used.
[Experimental Example 3]
The moisture adsorption isotherms of the organic and inorganic nanoporous materials and the water adsorbing compositions prepared according to Examples 1 to 3 and Comparative Example 1 were evaluated at 25 ° C. The results are shown in FIGS. Respectively. Fig. 6 shows the amount of water adsorption according to the driving pressure, and Table 1 shows the maximum moisture adsorption amount at the driving pressure P / Po = 0.1 to 0.3.
division
Maximum moisture adsorption amount [mg / g]
Example 3
432
Example 2
228
Example 1
152
Comparative Example 1
182
The moisture adsorption composition according to Example 3 prepared by impregnating the surface of the organic nanoporous material with a metal chloride impregnated with the metal nanoporous material had a significantly higher moisture adsorption characteristic at a driving pressure range of P / P0 = 0.1 to 0.3 . It can be seen that the adsorption property of the organic nanoporous material and the hygroscopic property of the metal chloride are combined and the moisture adsorption characteristic is improved.
With continued reference to the drawings, it was confirmed that the moisture adsorption amounts of Example 2 and Example 1 were higher than that of the organic nanoporous material of Example 1, which was manufactured by further including the heat treatment step have. In the case of the organic nanoporous material according to Example 2, the unnecessary organic substances contained in the particles were decomposed through the heat treatment process and the amount of water adsorption was improved compared with the organic nanoporous material of Example 1 which was not subjected to the heat treatment process .
In addition, it can be confirmed that the moisture adsorption characteristics of Comparative Example 1 using commercially available zeolite are significantly lower than those of the moisture adsorption materials of Examples 2 and 3. The AQSOA Z01 used in Comparative Example 1 is a porous zeolite moisture adsorbent. The organic nanoporous material and the porous zeolite have a crystalline structure in common. However, the organic nanoporous material having coordination of metal ions and organic ligands , It is known that the surface area and pore volume of zeolite are 3 to 15 times larger than those of zeolite.
According to the experimental examples, the organic nanoporous material according to the present invention is superior in moisture adsorption characteristics to the conventional zeolite moisture adsorbent, and further comprises a step of heat-treating the nanoporous material at a temperature of 200 ° C to 400 ° C , It is possible to further improve the moisture adsorption property. In addition, by impregnating metal chloride having hygroscopicity in the organic / inorganic nanoporous particles having enhanced water adsorption characteristics, the adsorption property and the hygroscopic property can be combined to maximize the water adsorption property. Particularly, the organic nanoporous material-metal chloride hybrid water adsorption composition according to the present invention has a maximum moisture adsorption amount in a driving pressure range of a dehumidifier, an air conditioner, an adsorption refrigerator, and an air conditioner, which are application fields of a moisture adsorbent, It can be expected to act as an effective moisture adsorbent when applied to a device.
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 (18)
i) synthesizing an organic or inorganic nanoporous material;
ii) dissolving the metal chloride in water to produce a metal chloride solution;
iii) impregnating the surface of the organic nanoporous material with the metal chloride by mixing the organic nanoporous material with the metal chloride solution;
iv) drying the mixture of step iii);
v) crushing the dried product in step iv);
vi) after completion of the step v), vacuum drying the powder to prepare a water adsorption composition;
Wherein the water-based nano-porous body and the metal chloride hybrid water adsorbent composition are prepared by the method.
The method according to claim 1, further comprising the step of heat-treating the organic / inorganic hybrid nanoporous material produced from the step ii) between the step i) and the step ii) to form a hygroscopic nanoporous material- Way.
Wherein the heat-treating step is performed at a temperature of 200 to 400 ° C for 30 to 360 minutes.
The organic nanoporous material of step (i)
ia) mixing the solvent, the dicarboxylic acid organic ligand and the aluminum precursor in a predetermined ratio;
ib) stirring the mixture of step ia) and performing crystallization of the aluminum precursor and the organic ligand at a predetermined temperature;
ic) a step of first filtrating the reaction-completed product in the step ib), ultrasonifying the product by dispersing it in water;
id) second filtration of the dispersion of step ic);
i) drying the filtrate obtained through the second filtration to obtain a powdery organic or inorganic nano-porous body;
Wherein the water-based nanoporous material-metal chloride hybrid water-absorbing composition is prepared by including the water-based nanoporous material-metal chloride hybrid water-absorbing composition.
The solvent in step ia) is selected from the group consisting of water, an alcohol solvent, dimethylformamide, diethylformamide, N, N-dimethylformamide, acetonitrile, 1,4-dioxane, chlorobenzene, And tetrahydrofuran, or a mixed solvent comprising at least two kinds of solvents selected from the group consisting of hydrogen chloride, hydrogen chloride, and tetrahydrofuran.
Wherein the aluminum precursor in step ia) comprises at least one compound selected from aluminum nitrate, aluminum chloride, aluminum sulphate and alumina.
Wherein the dicarboxylic acid organic ligand in step ia) is isophthalic acid. The method of claim 1, wherein the dicarboxylic acid organic ligand is isophthalic acid.
Wherein the step ib) is carried out at a temperature of 100 to 150 ° C for a predetermined time.
Wherein the step ia) comprises adding 4 to 40 wt% of the aluminum precursor and 1 to 10 wt% of the organic dicarboxylic acid ligand to the solvent. Way.
The metal chloride of step ii) is selected from the group consisting of calcium chloride (CaCl 2 ), magnesium chloride (MgCl 2 ), lithium chloride (LiCl), zinc chloride (ZnCl 2 ), potassium chloride (KCl) and sodium chloride A method for producing an organic / inorganic hybrid nano-porous body-metal chloride hybrid water adsorption composition, which comprises at least one compound.
Wherein the organic nanoporous material is mixed in an amount of 5 to 50 wt% with respect to 100 wt% of the metal chloride solution, and the organic nanoporous material-metal chloride hybrid water absorption composition is mixed with the organic nanoporous material at a rate of 5 wt% to 50 wt%.
Wherein the step iv) is performed in an oven at 100 to 200 ° C for a predetermined period of time. The method for producing a water-based nanoporous-metal chloride hybrid water-absorbing composition according to claim 1,
Wherein the moisture adsorbent composition has a maximum moisture adsorption amount (amount of water adsorbed per unit weight of the adsorbent) of 0.2 to 0.9 g / g at a driving pressure P / P0 of 0.1 to 0.3. - metal chloride hybrid water adsorption composition.
Wherein the water adsorbing composition is formed by impregnating a surface of an organic nanoporous material with a metal chloride, wherein the inorganic nanoporous material is impregnated with a metal chloride.
Wherein the organic or inorganic nanoporous material comprises aluminum ion and a dicarboxylic acid organic ligand coordinated to the aluminum ion, wherein the organic nanoporous material has an average particle size of 100 to 2000 nm, an average size of 0.6 to 1.7 nm Wherein the method comprises the steps of: (a) preparing a water-based nano-porous body-metal chloride hybrid water-absorbing composition;
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| KR1020150139906A KR101728505B1 (en) | 2015-10-05 | 2015-10-05 | Organic-inorganic nanoporous materials and metal halide hybrid adsorbent, and manufacturing method of the same, and application of the same |
| US15/750,613 US11161089B2 (en) | 2015-10-05 | 2016-09-28 | Moisture adsorption composition, a method of preparing the same, and a surface coating including the same |
| PCT/KR2016/010844 WO2017061726A1 (en) | 2015-10-05 | 2016-09-28 | Method for preparing organic/inorganic nanoporous material-metal chloride hybrid water absorbent composition, water absorbent composition prepared thereby, and water absorbent composition for surface coating, containing same |
| CN201680046242.1A CN107921409B (en) | 2015-10-05 | 2016-09-28 | Method for preparing moisture-absorbing composition, moisture-absorbing composition prepared by the same and moisture-absorbing composition for surface coating |
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| KR20210048028A (en) * | 2019-10-22 | 2021-05-03 | 한국생산기술연구원 | Manufacturingmethod of organic-inorganic nanoporous material adsorbent and adsorbent produced by the same |
| CN115193228A (en) * | 2022-07-05 | 2022-10-18 | 中国制浆造纸研究院有限公司 | Preparation method of moisture absorption component |
| WO2023243772A1 (en) * | 2022-06-14 | 2023-12-21 | 창원대학교 산학협력단 | Dual metal-organic framework for carbon dioxide adsorption and manufacturing method therefor |
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| KR20240012080A (en) * | 2022-07-20 | 2024-01-29 | 한국생산기술연구원 | Inorganous organoporous adsorbent containing hydroxy ligand and method for producing the same |
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| KR20210048028A (en) * | 2019-10-22 | 2021-05-03 | 한국생산기술연구원 | Manufacturingmethod of organic-inorganic nanoporous material adsorbent and adsorbent produced by the same |
| WO2023243772A1 (en) * | 2022-06-14 | 2023-12-21 | 창원대학교 산학협력단 | Dual metal-organic framework for carbon dioxide adsorption and manufacturing method therefor |
| CN115193228A (en) * | 2022-07-05 | 2022-10-18 | 中国制浆造纸研究院有限公司 | Preparation method of moisture absorption component |
| CN115193228B (en) * | 2022-07-05 | 2024-04-30 | 中国制浆造纸研究院有限公司 | Preparation method of moisture absorption component |
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