KR101105640B1 - Apparatus for treating air - Google Patents

Abstract

The present invention relates to an air treatment apparatus, and provides an air treatment apparatus including a porous organic-inorganic hybrid formed by combining a central metal ion with an organic ligand.

Air treatment unit, porous organic-inorganic hybrid, moisture adsorbent

Description

Air Handling Unit {APPARATUS FOR TREATING AIR}

The present invention relates to an air treatment apparatus.

In various fields, there is an increasing need for humidity and / or temperature control in air. Conventionally, a cooler has been used to regulate humidity and / or temperature. However, the greater the latent heat load of the total cooling load, the more dry air needs to be supplied to the air conditioning space. For this reason, the temperature of the evaporator or cooling coil should be kept lower. As a result, when the temperature of the supply air becomes lower than necessary, it may be necessary to reheat the supply air after cooling the supply air.As the temperature of the cooler decreases, the cooling efficiency decreases, and the energy efficiency of the overall air treatment system decreases. do. In addition, when the target humidity is very low, frost is generated in the evaporator coil, which makes it difficult to operate the system smoothly.

The desiccant / cooling system uses a desiccant to handle latent heat loads to compensate for this drawback. Previously, as a dehumidifying agent, activated carbon, activated alumina, silica gel, solid dehumidifying agents such as zeolites (molecular sieves), triethylene glycol, liquid dehumidifying agents such as lithium chloride, and the like have been used. However, conventional dehumidifiers are not satisfactory in terms of dehumidification efficiency, dehumidification amount, and the like, and need to be improved.

The present invention provides an air treatment apparatus comprising a porous organic-inorganic hybrid formed by combining a central metal ion with an organic ligand.

In one embodiment, the air treatment device comprises:

Intake passage through which air is sucked from the outside,

Dehumidifier including an adsorbent, for removing moisture from the air sucked through the intake passage,

Regeneration means for regenerating the adsorbent of the dehumidifying part, and

Exhaust passage for exhausting dehumidified air to the outside.

In one embodiment, the adsorbent comprises a porous organic-inorganic hybrid formed by combining a central metal ion with an organic ligand.

In one embodiment, the dehumidifying part of the air treatment apparatus includes an adsorption region which is a region through which air supplied through the intake passage passes, and a regeneration region which is a region through which air supplied through the regeneration passage passes. The regeneration means of the air treatment apparatus includes a regeneration passage for introducing the outside air of the air treatment apparatus and / or circulating air in the air treatment apparatus, and a heating portion connected to the regeneration passage. By heating the air moved through the regeneration passage and supplying it to the regeneration region of the dehumidification unit, moisture adsorbed to the adsorbent of the dehumidifying unit can be desorbed.

In one embodiment, the air treatment apparatus may further include a heat exchanger for performing heat exchange between the exhaust passage and the air in the regeneration passage.

In one embodiment, the air treatment apparatus may further include a cooling unit cooling the air dehumidified by the dehumidifying unit in the exhaust passage.

In one embodiment, the dehumidifying unit includes a dehumidifying rotor having a cylindrical shape including an adsorption region for adsorbing moisture as the air containing moisture passes therethrough, and a regeneration region for desorbing moisture while the heated air passes therethrough. As it rotates, the adsorption zone and the regeneration zone may continuously change.

In one embodiment, the air treatment device includes two portions of a two-bed dehumidifier, and two switch valves, and the two portions of the two-bed dehumidifier are provided by switching the flow direction of air. Alternately, dehumidification and regeneration can be performed.

In one embodiment, the porous organic-inorganic hybrid can adsorb at least 0.1 g of moisture per gram.

In one embodiment, the porous organic-inorganic hybrids are Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir , Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb and Bi It includes at least one metal element selected from the group.

In one embodiment, the porous organic-inorganic hybrid includes at least one metal element selected from the group consisting of Ag (I), Cu (II or I) and Ni (II), which are metals having antimicrobial activity.

In one embodiment, the porous organic-inorganic hybrid is copper terephthalate, iron terephthalate, manganese terephthalate, chromium terephthalate, vanadium terephthalate, aluminum terephthalate, titanium terephthalate, zirconium terephthalate, magnesium terephthalate, copper benzenetri Carboxylate, Iron Benzene Tricarboxylate, Manganese Benzene Tricarboxylate, Chromium Benzene Tricarboxylate, Vanadium Benzene Tricarboxylate, Aluminum Benzene Tricarboxylate, Titanium Benzene Tricarboxylate, Zirconium Benzentricar Carboxylate, magnesium benzenetricarboxylate, nickel dihydroxyterephthalate, cobalt dihydroxyterephthalate, magnesium dihydroxyterephthalate, manganese dihydroxyterephthalate, iron dihydroxyterephthalate, iron benzenetribenzo Ate, chromium benzenetribenzoate, aluminum benzenetribenzoate, derivatives thereof, solvates thereof, hydrates thereof or combinations thereof.

In one embodiment, the porous organic-inorganic hybrid is at least one compound selected from compounds represented by the formula: or hydrates thereof:

_{M 3 X (H 2 O)} 2 O [C 6 Z 4-y Z 'y (CO 2) 2] 3 (M = Cu, Fe, Mn, Cr, V, Al, Ti, Zr or Mg; X = Cl, Br, I, F or OH, Z or Z '= H, NH ₂ , Br, I, NO ₂ or OH; 0 ≦ y ≦ 4);

M ₃ O (H ₂ O) ₂ X [C ₆ Z _3-y Z ' _y- (CO ₂ ) ₃ ] ₂ (M = Cu, Fe, Mn, Cr, V, Al, Ti, Zr or Mg; X = Cl, Br, I, F or OH; Z or Z '= H, NH ₂ , Br, I, NO ₂ or OH; 0 <y <3);

M ₃ O (H ₂ O) ₂ X _1-y (OH) _y [C ₆ H _3- (CO ₂ ) ₃ ] ₂ (0 ≤ y ≤ 1; M = Cu, Fe, Mn, Cr, V, Al , Ti, Zr or Mg; X = Cl, Br, I or F); or

M ₃ X _1-y (OH) _y (H ₂ O) ₂ O [C ₆ H ₄ (CO ₂ ) ₂ ] ₃ (0 ≤ y ≤ 1; M = Cu, Fe, Mn, Cr, V, Al, Ti, Zr or Mg; X = Cl, Br, I or F).

In one embodiment, the porous organic-inorganic hybrid is at least one compound selected from compounds represented by the formula: or hydrates thereof:

_{M 6 O 4 (OH) 4} [C 6 Z 4-y Z 'y (CO 2) 2] 12 (M = Ti, Sn , or Zr; Z or _{Z' = H, NH 2,} Br, I, NO 2 Or OH, 0 ≦ y ≦ 4); or

M ₂ (dhtp) (H ₂ O) ₂ (M = Ni, Co, Mg, Mn and Fe; dhtp = 2,5-dihydroxyterephthalic acid).

), 아미드기 (-CONH₂), 술폰산기 (-SO₃H), 술폰산의 음이온기(-SO₃ ^-), 메탄디티오산기(-CS₂H), 메탄디티오산의 음이온기(-CS₂ ^-), 피리딘기 및 피라진기로 이루어지는 군으로부터 선택되는 하나 이상의 작용기를 갖는 화합물 또 는 이의 혼합물이다.In one embodiment, the organic compound that can act as the organic ligand is a carbonate group (-CO ₃ H), of the acid anion group (-CO ₃ ^-), a carboxyl group, a carboxylic anionic group of the acid, an amino group (-NH ₂₎ , Iminogi (

), Amide group (-CONH _2), a sulfonic acid group (-SO ₃ H), a sulfonic acid anion group (-SO ₃ ^-), methane dithiol Osan group (-CS ₂ H), methane dithiol Osan anion group (-CS of ₂ ^LUC), pyridine group, and a compound having at least one functional group selected from the group consisting of pyrazinyl group is a mixture thereof.

In one embodiment, the porous organic-inorganic hybrid has unsaturated metal sites, to which the surface functionalizing compound is bound.

In one embodiment, the porous organic-inorganic hybrid is a powder, thin film, membrane, pellet, ball, foam, slurry, paste, paint, honeycomb, bead, mesh, fiber, corrugated sheet or rotor It is prepared in the form of.

In one embodiment, the dehumidifying portion is at least one selected from the group consisting of platinum, silver, gold, palladium, ruthenium, rhodium, osmium, iridium, manganese, copper, cobalt, chromium, nickel, iron, zinc, or a combination thereof. It further comprises a metal catalyst.

In one embodiment, the air treatment device may remove hydrocarbons, NOx, CO or volatile organic compounds contained in air introduced from the outside.

In one embodiment, the dehumidifying portion further comprises at least one dehumidifying agent selected from the group consisting of zeolite, activated alumina, lithium chloride, activated carbon, aluminum silicate, calcium chloride and calcium carbonate.

In one embodiment, the cylindrical dehumidification rotor comprising an adsorption region for adsorbing moisture as the air containing moisture passes therethrough and a regeneration region for desorbing moisture as the heated air passes therethrough is absorbed as the dehumidification rotor rotates. The region and the regeneration region are constantly changing, and the adsorbent includes a porous organic-inorganic hybrid formed by binding a central metal ion with an organic ligand.

In one embodiment, the air treatment device comprises: a two-part adsorption section including an adsorbent and capable of alternately adsorbing or desorbing a refrigerant; A condenser capable of condensing the refrigerant desorbed from the adsorption unit; An evaporator capable of evaporating the refrigerant to provide a cooling effect; A refrigerant passage connecting the adsorption unit, the condenser and the evaporator, and through which the refrigerant can flow; And a valve provided on the refrigerant flow path, wherein the evaporator and the condenser are respectively installed between the two adsorption portions, and the adsorbent forms a porous organic-inorganic hybrid formed by combining a central metal ion with an organic ligand. Include.

The foregoing is provided to introduce a simplified form of excerpts from the concepts further described in the detailed description below. This disclosure is not intended to identify key features or essential features of the claimed subject matter, nor is it intended to be used to limit the scope of the claimed subject matter.

In the following detailed description, reference is made to the accompanying drawings, which form a part hereof. The illustrative embodiments described in the detailed description, drawings, and claims are not meant to be limiting. Other embodiments may be utilized, and other changes may be made, without departing from the spirit or scope of the subject matter presented herein. As described herein throughout and illustrated in the figures, the disclosure herein may be arranged, substituted, combined, and designed in a very wide variety of different configurations, all of which are expressly contemplated and form part of the present disclosure. The point will be easily understood.

1 is a schematic drawing of an apparatus for treating air according to one illustrative embodiment.

In one embodiment, the apparatus for treating air comprises a case (1) attached to the outside, a dehumidifying unit (2) installed in the case (1) and containing an adsorbent, and a dehumidifying unit (2) containing moisture from the outside. And an exhaust passage 5 for discharging air from which moisture has been removed by the dehumidifying unit 2.

In one embodiment, in the case 1 of the air treatment device, outside air of the air treatment device and / or circulating air in the air treatment device are introduced to regenerate the adsorbent of the dehumidifying part 2 to which moisture has been adsorbed. A regeneration passage 6 is provided, and a heating part 3 is provided on the regeneration passage 6. In one embodiment, the heating section 3 may mean any heating source for supplying heat to the air passing through the regeneration passage 6. The heating section 3 may heat the air passing through the regeneration passage 6 in a manner of directly transferring thermal energy, and the regeneration passage 6 in a manner of supplying hot air heated outside the air treatment apparatus. The air passing through may be heated, but is not limited to any particular manner. In some embodiments, the heating section 3 may comprise a conventional heater, such as a heating coil.

In some embodiments, a blowing fan may be installed on the intake passage 4, the exhaust passage 5 and / or the regeneration passage 6 to advance air in the direction shown in FIG. 1 (not shown). . In another embodiment, the dehumidifying part 2 and / or the heating part 3 may further be provided with an air filter for removing dirt such as dust contained in the air (not shown).

In one embodiment, the dehumidifying part 2 can comprise a desiccant rotor in the form of a cylinder, as shown in FIG. 2, the dehumidifying rotor rotating at a constant speed about the central axis A. FIG. Is arranged to. The dehumidifying unit 2 including the dehumidifying rotor includes an adsorption region 11 which is a region through which air supplied through the intake passage 4 passes and a regeneration region 12 which is a region through which air supplied through the regeneration passage passes. Include. In one embodiment, the position of the adsorption zone 11 and the regeneration zone 12 is determined relative to the positions of the intake passage 4 and the regeneration passage 6, respectively, so that a drive motor connected to the dehumidification rotor (shown Rotation), the adsorption region 11 and the regeneration region 12 in the dehumidification rotor change continuously. For example, when the dehumidification rotor rotates, a part of the dehumidification rotor that was the adsorption region 11 becomes the regeneration region 12, and a part of the dehumidification rotor that was the regeneration region 12 becomes the adsorption region 11. This is done repeatedly. In some embodiments, the area ratio of the adsorption region 11 and the regeneration region 12 to the total area of the dehumidification rotor may be appropriately set according to the required dehumidification amount and the regeneration efficiency. In some embodiments, if desired, the air treatment device may include two or more dehumidification rotors, connected in series and / or in parallel, and when the dehumidification section 2 includes two or more dehumidification rotors, the dehumidification section The dehumidification efficiency per volume can be increased.

Referring to the operation of the air treatment device according to one embodiment, air supplied from the outside by the intake passage 4 is supplied to the adsorption region 11 of the dehumidification section 2, and the adsorbent in the adsorption region 11 is provided. Moisture in the air is removed. The air from which moisture has been removed through the adsorption region 11 of the dehumidifying unit 2 is discharged to the outside through the exhaust passage 5. The part of the dehumidification part 2 corresponding to the adsorption | suction area | region 11 which adsorb | sucked water moves to the area | region which contact | connects the regeneration path | path 6 by rotation of the dehumidification part 2, and turns into the regeneration area | region 12. As shown in FIG. Next, after the air moved through the regeneration passage 6 (external air and / or the circulating air in the air treatment apparatus) is heated by the heating section 3, the regeneration area 12 of the dehumidifying section 2 Will pass). When the heated air comes into contact with the adsorbent in the regeneration region 12 where moisture is adsorbed, the adsorbed moisture is desorbed. In one embodiment, as the dehumidifying unit 2 rotates, the water adsorbed in the adsorption region 11 is removed in the regeneration region 12, and the adsorbent regenerated in the regeneration region 12 in the adsorption region 11. In such a way that moisture in the air is removed, it is possible to continuously remove moisture from the outside air and supply the dehumidified air.

In some embodiments, some of the air supplied to the intake passage 4 and / or the regeneration passage 6 does not pass through the dehumidification section 2 but by-passes the other passing through the dehumidification section 2. Can join air. In another embodiment, a part of the air supplied to the intake passage 4 passes through a purge region (not shown) designated at the portion of the dehumidifying rotor that changes from the regeneration region 12 to the adsorption region 11, so that the adsorption region ( It is possible to lower the temperature of the dehumidifying rotor moving to 11 and to supply it to the heating part 3. In the case where a purge zone is provided between the adsorption zone 11 and the regeneration zone 12, the movement of sensible heat can be suppressed, and the adsorption can be performed at a lower temperature, so that adsorption in the adsorption zone 12 is achieved. The efficiency can be improved.

3 is a schematic illustration of an air treatment apparatus further comprising a heat exchanger 7 according to an exemplary embodiment. The air treatment apparatus disclosed in FIG. 3 further comprises a heat exchanger 7 for performing heat exchange between the exhaust passage 5 and the air in the regeneration passage 6, except for the air treatment according to FIG. 1. Same as the device. Therefore, description is abbreviate | omitted about the structure common to FIG.

In one embodiment, the process of adsorbing moisture to the adsorbent of the dehumidifying unit 2 in the dehumidification step is an exothermic process, and diluted heat is generated, and in the regeneration step, the process of desorbing water from the adsorbent is an endothermic process. Reaction heat is needed. The heat exchanger 7 performs heat exchange between the air before passing through the heating unit 3 in the regeneration passage 6 and the air that has passed through the adsorption region 11 of the dehumidifying unit 2. Cooling of the air from which water has been removed through the heat exchange unit 7 through the adsorption region 11 and air moving through the regeneration passage 6 (external air and / or circulating air in the air treatment apparatus) Preheating (heat recovery) can be achieved simultaneously. When the heat exchanger 7 is further used, the efficiency of the energy required to operate the air treatment apparatus can be increased.

In some embodiments, the heat exchanger 7 may comprise a cylindrical rotor having a honeycomb structure. A plurality of passages are formed along the axial term of the rotary rotor, and the passage inner surface may be treated with a material that is well-transmitted, such as a metal such as aluminum. The rotary rotor is divided into a heating zone and a cooling zone, and the heating zone and the cooling zone may be continuously changed by the rotation of the drive motor connected to the rotary rotor.

The dehumidification and cooling actions of the air treatment device according to one embodiment will be described. The air (outdoor, high temperature) supplied from the intake passage 4 removes moisture while passing through the adsorption region 11 of the dehumidifying unit 2, and the temperature may increase somewhat by the heat of adsorption. The dry air is cooled while passing through the heat exchange part 7 (for example, the cooling area of the rotary rotor), and the dry air is supplied to the room through the exhaust passage 5. On the other hand, the air (indoor, low temperature) supplied from the regeneration passage 6 is heated up while passing through the heat exchanger 7 (for example, the heating region of the rotary rotor). The heated air is heated by the heating unit 3 and then passes through the regeneration region 12 of the dehumidifying unit 2. When the heated air comes into contact with the adsorbent in the regeneration region 12 where moisture is adsorbed, the adsorbed moisture is desorbed. In the above air treatment device, the latent heat load can be processed by the dehumidifying unit 2 and the sensible heat load can be processed by the heat exchanger 7, so that the energy efficiency is higher than that of the condensation type cooling device. . In addition, it is possible to efficiently achieve dehumidification and cooling of air at the same time.

4 is a schematic illustration of an air treatment apparatus further comprising a cooling section 8 according to one exemplary embodiment. The air treatment apparatus disclosed in FIG. 4 is the same as the air treatment apparatus according to FIG. 3 except that a cooling unit 8 is additionally provided in the exhaust passage 5. Therefore, description is abbreviate | omitted about the structure common to FIG.

In one embodiment, the cooling section 8 may include conventional cooling coils, condensation cooling devices, evaporative cooling devices, combinations thereof, and the like, but is not limited to a specific cooling scheme. Moisture is removed by the dehumidifying part 2, and the air cooled by the heat exchange part 7 can be further lowered while passing through the cooling part 8. The latent heat load can be processed by the dehumidifying part 2 and the sensible heat load can be further processed by the cooling part 8, so that the humidity and temperature of the supply air can be controlled independently.

5 is a schematic drawing of the apparatus for treating air according to one illustrative embodiment. In this embodiment, the air treatment apparatus is shown in FIG. 1 except that the regeneration passage 6 is installed to circulate the heating section 3, the adsorption region 11 of the dehumidifying section 2 and the condenser 9. The same as the air treatment device according to. Therefore, description is abbreviate | omitted about the structure common to FIG.

In one embodiment, the moisture contained in the air passing through the regeneration zone 12 of the dehumidifying section 2 is liquefied into water in the condenser 9, and the liquefied water is discharged through the drainage passage 13 to an external or separate storage section. do. The air from which moisture is removed by the condenser 9 moves to the heating part 3 again. In some embodiments, some of the air circulating in the regeneration passage 6 may be discharged to the outside through appropriate means, and some of the air entering from the outside into the air treatment apparatus is included in the circulating air of the regeneration passage 6. Can be. In some embodiments, the air treatment device may further include a heat exchanger 7 in the exhaust passage 5 and a regeneration passage 6 and / or further include a cooling unit 8 in the exhaust passage 5. (Not shown).

6 is a schematic drawing of the apparatus for treating air according to one illustrative embodiment. In the above embodiment, the air treatment apparatus is provided so that the regeneration passage 6 is installed to circulate the heating section 3, the adsorption region 11 of the dehumidifying section 2, and the heat exchange section 7 ′, Same as the air treatment device according to FIG. 1. Therefore, description is abbreviate | omitted about the structure common to FIG.

In one embodiment, the air in the intake passage 4 passes through the heat exchanger 7 ′ before being supplied to the dehumidification section 2, and the air in the regeneration passage 6 passes through the regeneration region 12 of the dehumidification section 2. After passing through), it passes through heat exchanger (7 ') before being fed back to heating unit (3). The heat exchange part 7 'exchanges heat between the air of the regeneration passage 6 which adsorbed moisture in the dehumidification part 2 and the air on the intake passage 4 supplied from the outside, and regenerates the dehumidification part 2. Moisture contained in the air passing through the region 12 is liquefied into water in the heat exchanger 7 ', and the liquefied water is discharged through the drainage passage 13 to an external or separate reservoir. Air dehumidified in the heat exchanger 7 'moves to the heating unit again. In some embodiments, some of the air circulating in the regeneration passage 6 may be discharged to the outside through appropriate means, and some of the air entering from the outside into the air treatment apparatus is included in the circulating air of the regeneration passage 6. Can be. In some embodiments, the air treatment device may further include a heat exchanger 7 in the exhaust passage 5 and the regeneration passage 6 and / or further include a cooling unit 8 in the exhaust passage 5. (Not shown).

In one embodiment, the air treatment apparatus including the dehumidifying unit 2 may be classified into an total external air type, a total circulation type, or an external air mixing type according to the introduction method of the external air. The external air system can be used when it is difficult to recycle dry air due to dust or the like generated in the air treatment target space. The pre-circulation method may be used when it does not require the introduction of external air, such as storage warehouses, indoors that do not install outdoor units. The outdoor air mixing method is a method of mixing return air and may be used when high temperature and moisture control are required.

7 is a schematic drawing of the apparatus for treating air according to one illustrative embodiment. The air treatment device according to this embodiment is a 2-bed type having two parts of a dehumidifying part. As shown in FIGS. 7A and 7B, the two-bed type air treatment device includes two parts of the dehumidifying parts 2a and 2b and two switch valves 14 and 15, and the switch valves 14 and 15. By changing the flow direction of the air, the dehumidifying parts 2a and 2b of the two parts can alternately perform the dehumidifying action and the regenerating action.

Specifically, in FIG. 7A, the switch valve 15 supplies the humid air introduced through the intake passage 4 to the dehumidifying unit 2b through the path 4b, whereby the dehumidifying unit 2b performs the dehumidifying action. And dehumidified air is discharged through the path (5b), the switch valve (14). Further, dry air for regeneration is introduced through the path 6a and heated by the heating section 3, and then supplied to the switch valve 14, and the switch valve 14 supplies the heated air to the path 5a. The dehumidifying unit 2a is supplied to the dehumidifying unit 2a so that a regeneration action is performed in the dehumidifying unit 2a. Air which absorbed moisture from the dehumidifying part 2a passes through the path 4a and the switch valve 15, and then is discharged to the outside through the path 6b.

By the above operation, when the adsorbent of the dehumidifying part 2b approaches the saturation state and the regeneration is required, the switch valves 14 and 15 are switched to change the flow direction of the wet air and the regeneration air. Specifically, as shown in FIG. 7B, the humid air introduced through the intake passage 4 is sent to the path 4a by the switch valve 15 to be supplied to the dehumidifying unit 2a where the regeneration is completed. The regeneration air introduced through the path 6a is sent to the path 5b by the switch valve 14 to be supplied to the dehumidifying part 2b which needs to be regenerated. Air dried by the dehumidifying part 2a is discharged through the path 5a and the switch valve 14, and air which absorbs moisture from the dehumidifying part 2b is externally supplied through the path 4b and the path 6b. Is discharged.

As described above, the switch valves 14 and 15 change the flow direction of air, so that the two dehumidifying parts 2a and 2b can be used continuously.

8 is a schematic drawing of the apparatus for treating air according to one illustrative embodiment. An apparatus for treating air according to one embodiment includes two portions of adsorption portions 23 and 24 including an adsorbent and capable of alternately adsorbing or desorbing refrigerant; A condenser 21 capable of condensing the refrigerant desorbed from the adsorption unit; An evaporator 22 capable of evaporating the refrigerant to provide a cooling effect to the outside; A refrigerant passage connecting the adsorption unit 21, the condenser 21, and the evaporator 22, through which the refrigerant can flow; Four flow control valves (V1, V2, V3, and V4) provided on the refrigerant passage are provided, and an evaporator and a condenser are respectively installed between the two portions of the adsorption portions 23 and 24.

As shown in FIG. 8, of the four flow control valves, the valve V1 is disposed between the condenser 21 and the adsorption part 23, and the valve V2 is the adsorption part 23 and the evaporator 22. Disposed between, the valve V3 is disposed between the evaporator 22 and the adsorption part 24, and the valve V4 is disposed between the adsorption part 24 and the condenser 21. By opening or closing the valves V1, V2, V3 and V4, the flow direction on the refrigerant passage is determined.

In some embodiments, the flow of the coolant in the coolant flow path may be made by the pressure difference between each component, and a predetermined pump (not shown) may be installed on the coolant flow path to smooth the flow.

In one embodiment. The air treatment device may include a predetermined control device (not shown), which controls the adsorption portions 23 and 24, the condenser 21 and the like, the evaporator 22, the valves V1, V2, By controlling the opening and closing of V3 and V4 and the like, the flow direction of the refrigerant can be controlled.

In one embodiment, heat is released when adsorbed to the adsorption units 23 and 24 or condensed in the condenser 21 and absorbs heat when desorbed in the adsorption units 23 and 24 or evaporated in the evaporator 21. Refrigerant can be used. As the refrigerant, water may be used in terms of cost, environment, and the like, but is not limited thereto, and alcohols (eg, methanol, ethanol), ammonia, and the like may be used.

Referring to Fig. 8, the specific operation of the air treatment device following the operation modes [A] to [D] will be described. The air treatment apparatus according to the present embodiment operates with a closed refrigerant flow path through which a refrigerant is circulated (closed cycle). In some embodiments, the air treatment device can be operated in a vacuum or in proximity to the vacuum, thereby reducing the diffusion resistance of the refrigerant. See Table 1 below for the open / close mode of the valves V1, V2, V3 and V4 according to the operating modes [A] to [D] and the operation of the adsorption sections 23 and 24.

[Table 1]

Operating mode [A] [B] [C] [D] valve V1 X X O X V2 O X X X V3 O X X X V4 X X O X Adsorption part 23 Cooling heating heating Cooling 24 heating Cooling Cooling heating O: open X: closed

In the operation mode [A], the valves V2 and V3 are opened and the valves V1 and V4 are closed. Heat is supplied to the adsorption part 24 from any heating source (for example, supply of heating fluid H, such as hot water), and the refrigerant adsorbed to the adsorption part 24 is desorbed. Heat is removed from the adsorption section 23 through any cooling means (for example, supply of a cooling fluid C such as cooling water), and the incoming refrigerant is adsorbed to the adsorption section 23. Heat is removed from the condenser 21 through any cooling means (for example, supply of a cooling fluid C such as cooling water), and the refrigerant desorbed from the adsorption portion 24 is condensed in the condenser 21. The refrigerant condensed in the evaporator 22 absorbs heat while evaporating, and a cooling effect can be obtained. This cooling effect allows to obtain a chilled fluid F (eg, cooled water), which can be supplied and cooled where desired.

When desorption in the adsorption part 24 and adsorption in the adsorption part 23 advance and reach equilibrium state, the adsorption / desorption action in the adsorption part 24 and the adsorption part 23 is switched. In preparation for such a conversion, in the operation mode [B], all the valves V1, V2, V3 and V4 are closed to stop heat and mass transfer by adsorption / desorption, and then heat is supplied to the adsorption section 24. It supplies and removes heat from the adsorption part 23.

In the operation mode [C], the valves V1 and V4 are opened and the valves V2 and V3 are closed. Cooling by the evaporator 22 similar to in operation mode [A], except that heat is removed from the adsorption section 24 and the refrigerant is adsorbed, heat is supplied to the adsorption section 23 and the refrigerant is desorbed. The effect can be obtained.

Similar to the operation mode [B], in operation [D], all the valves V1, V2, V3 and V4 are closed to prepare for switching of the adsorption / desorption action, and then operation mode [A] is made again.

In this way, by allowing adsorption and desorption to occur alternately in the adsorption section 24 and the adsorption section 23, the cooling effect by evaporation can be continuously provided.

Such an adsorption type air treatment device has a small driving portion, thus low vibration and noise, and can provide a cooling effect without using a freon refrigerant that causes ozone layer destruction, and when water is used as the refrigerant, the stability is high (toxic , In terms of corrosiveness, flammability, etc.), there is no disadvantage of solution crystallization as in the absorption type, and there is little possibility of generating non-condensable gas (hydrogen, etc.) (no further operation is necessary and advantageous for vacuum maintenance). In addition, since the adsorbent containing the porous organic-inorganic hybrid in the adsorption part 23 and 24 can desorb a refrigerant | coolant even at comparatively low temperature, it is low as a heating source of the adsorption parts 23 and 24 for desorption. Waste heat at a temperature (eg, approximately 50-90 ° C.) can be used. The heating source may be heat discharged from cooling water or equipment in various factory production processes; It may be derived from heat emitted from an engine or a generator of a vehicle such as a ship, a train, a car, but is not limited thereto.

9 is a schematic drawing of the apparatus for treating air according to one illustrative embodiment. The air treatment device according to the present embodiment is a two-stage (4 bed) air treatment device, and as shown in FIG. 9, adsorption portions 23, 24, 25, and 26 and valves V1, V2, V3, V4, and V5. And V6), but similar to the air treatment device according to FIG. 8. As shown, by allowing the adsorption and desorption to take place alternately in the adsorption sections 23, 24, 25 and 26, the cooling effect by evaporation can be continuously provided. The description common to FIG. 1 is omitted.

10 is a schematic drawing of the apparatus for treating air according to one illustrative embodiment. The air treatment device according to the present embodiment is a three-stage (6 bed) air treatment device, and as shown in FIG. 9, adsorption portions 23, 24, 25, 26, 27, and 28 and valves V1, V2, and V3. V4, V5, V6, V7 and V8), except that it is similar to the air treatment apparatus according to FIG. As shown, by allowing the adsorption and desorption to take place alternately in the adsorption units 23, 24, 25, 26, 27 and 28, the cooling effect by evaporation can be continuously provided. The description common to FIG. 1 is omitted.

In one embodiment, in a multi-stage air treatment apparatus such as a two-stage or three-stage system, a cooling effect can be obtained even if the temperature of the heating source of the adsorption unit is lower (for example, 40 to 50 ° C.), which is discarded in large quantities. Low temperature waste heat can be recovered and used.

11 is a schematic drawing of the apparatus for treating air according to one illustrative embodiment. The air treatment apparatus according to the present embodiment is similar to the air treatment apparatus according to FIG. 8 except that it further includes a refrigerant passage and a valve V5 connecting the adsorption portion 23 and the adsorption portion 24. Do. The pressure difference in the adsorption | suction part 23 and the adsorption | suction part 24 can be used, and the freezing capacity can be improved. By controlling the valve V5 between the adsorption section 23 and the adsorption section 24, the latent heat of the refrigerant vapor is exchanged to increase the adsorption / desorption amount, and the difference in concentration during the adsorption / desorption at the adsorption section increases, resulting in a freezing capacity. Is increased. In this embodiment, as in operating modes [B] and [E], valve V5 can be opened so that latent heat of refrigerant vapor can be exchanged between adsorption section 23 and adsorption section 24.

In one embodiment, an additional booster pump or compressor may be installed between the adsorption section and the condenser 21. In this embodiment, the refrigerant vapor can be condensed by compressing the refrigerant vapor desorbed from the adsorption unit to a high pressure even at a normal environmental temperature without removing heat from the condenser 21 through separate cooling means.

In one embodiment, the dehumidifying part (2), (2a) and (2b) and the adsorption part (23), (24), (25), (26), (27) and (28) are moisture adsorbents as adsorbents. Can be used. The adsorbent may include a porous organic-inorganic polymer compound (or porous organic-inorganic hybrid) formed by combining a central metal ion with an organic ligand. The porous organic-inorganic hybrid may include both organic and inorganic substances in the framework structure, and may be a crystalline compound having a pore structure of molecular size or nano size. The porous organic-inorganic hybrids are porous coordination polymers [Angew. Chem. Intl. Ed., 43, 2334, 2004], or metal-organic frameworks (MOF) [Chem. Soc. Rev., 32, 276, 2003].

In another embodiment, the adsorbent may further include a dehumidifying agent, such as silica gel, zeolite, activated alumina, lithium chloride, activated carbon, aluminum silicate, calcium chloride, calcium carbonate, etc., if necessary, one of them. Alternatively, two or more species and a porous organic-inorganic hybrid may be mixed and used as an adsorbent.

In one embodiment, the porous organic-inorganic hybrids have pores of molecular size or several nm in size. In some embodiments, the pore size of the porous organic-inorganic hybrid can be from about 0.3 to about 10 nm. In some embodiments, the average particle diameter of the porous organic-inorganic hybrid is 100 μm or less.

In one embodiment, the larger the surface area and / or pore volume of the porous organic-inorganic hybrid, the better the adsorption effect. In some embodiments, the surface area of the porous organic-inorganic hybrid may be at least 300 m ² / g. In other embodiments the surface area of the porous organic-inorganic hybrid is at least 500 m ² / g, at least 700 m ² / g, at least 1,000 m ² / g, at least 1,200 m ² / g, at least 1,500 m ² / g or at 1,700 m ² / g or more, but is not limited thereto. In some embodiments, the surface area of the porous organic-inorganic hybrid may be up to 10,000 m ² / g. In one embodiment, the pore volume of the porous organic-inorganic hybrid may be at least 0.1 mL / g, or at least 0.4 mL / g. In other embodiments, the pore volume of the porous organic-inorganic hybrid can be 10 mL / g or less.

In one embodiment, the porous organic-inorganic hybrid may comprise a metal element. In some embodiments, the porous organic-inorganic hybrid is, for example, Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os , Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As It may include one or more of, Sb, Bi. In some embodiments, the porous organic-inorganic hybrid may include one cycle transition metal such as Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga; Bicycle transition metals such as Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd; Such as Lu, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg It may comprise one or more of three cycle transition metals. In one exemplary embodiment, when the transition metal is chromium, vanadium, iron, nickel, cobalt, copper, titanium, manganese, it may be easy to prepare a coordination compound. In another embodiment, the porous organic-inorganic hybrid is a typical element such as magnesium, aluminum, silicon, or a lanthanoid series such as cerium, yttrium, terbium, europium, or lanthanum, from which coordination compounds can be prepared. ) May comprise a metal. In another embodiment, the porous organic-inorganic hybrid may be formed by coordinating bonds with divalent to hexavalent metal ions. In one exemplary embodiment, the divalent metal ion is Ni ³⁺ , Cu ²⁺ , Co ²⁺ , Mg ²⁺ , Ca ²⁺ , Fe ²⁺ , Mn ²⁺ , Zn ^2+, etc. The metal ion may be Fe ³⁺ , Cr ³⁺ , Al ³⁺ , Mn ³⁺ . In another embodiment, the porous organic-inorganic hybrid may be formed by coordinating with tetravalent, pentavalent or hexavalent metal ions of Zr, Ti, Sn, V, W, Mo or Nb.

In one embodiment, the porous organic-inorganic hybrid may be substituted with a metal component having antibacterial activity against various bacteria. Examples of the metal component having the antimicrobial activity include Ag (I), Cu (II or I), Ni (II) and the like, but is not limited thereto.

), 아미드기 (-CONH₂), 술폰산기 (-SO₃H), 술폰산의 음이온기(-SO₃ ^-), 메탄디티오산기(-CS₂H), 메탄디티오산의 음이온기(-CS₂ ^-), 피리딘기, 피라진기 등을 포함할 수 있으나 이에 제한되는 것은 아니다.Organic compounds that can act as organic ligands in porous organic-inorganic hybrids are also referred to as linkers. In one embodiment, the organic ligands include organic compounds having functional groups that can be coordinated. In some embodiments, the example of the functional groups can be coordinated to the acid group (-CO ₃ H), of the acid anion group (-CO ₃ ^-), a carboxyl group, a carboxylic acid anion group, an amino group (-NH _2), Iminogi (

), Amide group (-CONH _2), a sulfonic acid group (-SO ₃ H), a sulfonic acid anion group (-SO ₃ ^-), methane dithiol Osan group (-CS ₂ H), methane dithiol Osan anion group (-CS of ₂ ^-), but it may comprise a pyridine group, a pyrazine group or the like without being limited thereto.

In one embodiment, examples of organic ligands include compounds having two or more coordinating sites, for example, polydentate organic compounds such as bidentate, tridentate, and the like. can do. Examples of such organic ligands are, if there is a position to coordinate, neutral organic compounds such as bipyridine, pyrazine, anionic organic compounds such as terephthalate, naphthalenedicarboxylate, benzenetricarboxylate, benzenetribenzo Anionic compounds of carboxylic acids such as ates, pyridinedicarboxylates, bipyridyldicarboxylates, and the like, as well as cationic materials. In another embodiment, as the anionic organic ligand of the carboxylic acid, in addition to the anion having an aromatic ring such as terephthalate, for example, formate, oxalate, malonate, succinate, glutamate, hexyndioate, heptanedio Anions of linear carboxylic acids such as ions, anions having non-aromatic rings such as cyclohexyl dicarboxylate, and the like may be used, but are not limited thereto.

In other embodiments, the organic ligand can be dihydroxyterephthalate, or a derivative thereof. In some exemplary embodiments, 2,5-dihydroxyterephthalate or derivative thereof can be included as an organic ligand. In one embodiment, dihydroxyterephthalate containing Cl, Br, I, NO ₃ , NH ₂ , COOH, SO ₃ H and the like in the benzene ring may be used as the dihydroxyterephthalate derivative.

In one embodiment, the porous organic-inorganic hybrid is copper terephthalate, iron terephthalate, manganese terephthalate, chromium terephthalate, vanadium terephthalate, aluminum terephthalate, titanium terephthalate, zirconium terephthalate, magnesium terephthalate, copper benzenetri Carboxylate, Iron Benzene Tricarboxylate, Manganese Benzene Tricarboxylate, Chromium Benzene Tricarboxylate, Vanadium Benzene Tricarboxylate, Aluminum Benzene Tricarboxylate, Titanium Benzene Tricarboxylate, Zirconium Benzentricar But may include, but are not limited to, carboxylates, magnesium benzenetricarboxylates, derivatives thereof, solvates thereof, hydrates thereof, or combinations thereof. In one embodiment, carboxylates containing Cl, Br, I, NO ₃ , NH ₂ , COOH, SO ₃ H and the like may be used as the carboxylate derivative.

In other embodiments, the porous organic-inorganic hybrid is nickel dihydroxyterephthalate, cobalt dihydroxyterephthalate, magnesium dihydroxyterephthalate, manganese dihydroxyterephthalate or iron dihydroxyterephthalate, derivatives thereof, Solvates thereof, hydrates thereof or combinations thereof.

In one embodiment, the crystalline porous organic-inorganic hybrid may comprise at least two ligands and metal elements of terephthalate, benzenetribenzoate or benzenetricarboxylate.

In one embodiment, the porous organic-inorganic hybrid is a compound of formula M ₃ X (H ₂ O) ₂ O [C ₆ Z _4-y Z ' _y (CO ₂ ) ₂ ] ₃ (M = Cu, Fe, Mn, Cr, V, Al, Ti, Zr or Mg; X = Cl, Br, I, F or OH; Z or Z '= H, NH ₂ , Br, I, NO ₂ or OH; 0 <y <4) or Hydrates thereof, and in other embodiments, the porous organic-inorganic hybrid may be selected from the formula M ₃ O (H ₂ O) ₂ X [C ₆ Z _3-y Z ' _y- (CO ₂ ) ₃ ] ₂ (M = Cu, Fe, Mn, Cr, V, Al, Ti, Zr or Mg; X = Cl, Br, I, F or OH; Z or Z '= H, NH ₂ , Br, I, NO ₂ or OH; 0 ≤ y ≤ 3) or a hydrate thereof, but is not limited thereto. In some embodiments, the hydrate is represented by the formula M ₃ X (H ₂ O) ₂ O [C ₆ Z _4-y Z ' _y (CO ₂ ) ₂ ] ₃ nH ₂ O (M = Cu, Fe, Mn, Cr). , V, Al, Ti, Zr or Mg; X = Cl, Br, I, F or OH; Z or Z '= H, NH ₂ , Br, I, NO ₂ or OH; 0 ≤ y ≤ 4; 0.1 ≤ n ≦ 50) or M ₃ O (H ₂ O) ₂ X [C ₆ Z _3-y Z ' _y- (CO ₂ ) ₃ ] ₂ nH ₂ O (M = Cu, Fe, Mn, Cr, V, Al, Ti, Zr or Mg; X = Cl, Br, I, F or OH; Z or Z '= H, NH ₂ , Br, I, NO ₂ or OH; 0 ≤ y ≤ 3; 0.1 ≤ n ≤ 50 )

In another exemplary embodiment, the porous organic-inorganic hybrid is of formula M ₃ O (H ₂ O) ₂ X _1-y (OH) _y [C ₆ H _3- (CO ₂ ) ₃ ] ₂ (0 ≦ y ≦ 1; M = Cu, Fe, Mn, Cr, V, Al, Ti, Zr or Mg; X = Cl, Br, I or F) or M ₃ X _1-y (OH) _y (H ₂ O) ₂ O Of [C ₆ H ₄ (CO ₂ ) ₂ ] ₃ (0 ≦ y ≦ 1; M = Cu, Fe, Mn, Cr, V, Al, Ti, Zr or Mg; X = Cl, Br, I or F) Compounds, or hydrates thereof. In one embodiment, the hydrate is of formula

M ₃ O (H ₂ O) ₂ X _1-y (OH) _y [C ₆ H _3- (CO ₂ ) ₃ ] ₂ nH ₂ O (0 ≤ y ≤ 1; M = Cu, Fe, Mn, Cr , V, Al, Ti, Zr or Mg; X = Cl, Br, I or F; 0.1 <n <50) or

M ₃ X _1-y (OH) _y (H ₂ O) ₂ O [C ₆ H ₄ (CO ₂ ) ₂ ] ₃ nH ₂ O (0 ≤ y ≤ 1; M = Cu, Fe, Mn, Cr, V, Al, Ti, Zr or Mg; X = Cl, Br, I or F; 0.1 ≦ n ≦ 50). In some embodiments, -OH may be partially substituted for X in the above formula. In one exemplary embodiment, a porous organic-inorganic hybrid comprising a halogen element can be prepared using metal halides or hydrates thereof as metal precursors.

In one embodiment, the porous organic-inorganic hybrid can be prepared by reacting a metal precursor with an organic compound that can act as an organic ligand. In some embodiments, the porous organic-inorganic hybrid can be prepared by a method comprising heating a reaction mixture comprising a metal precursor, an organic compound that can act as an organic ligand, and a solvent.

In some embodiments, a method of making a porous organic-inorganic hybrid may comprise a step comprising:

Preparing a reactant mixture containing a metal precursor, an organic compound capable of acting as an organic ligand, and a solvent; And

Heating the reactant mixture.

In one embodiment, examples of metal precursors are Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb, Bi, etc. The metal itself or the compound containing these metal elements can be included. In some embodiments, the metal precursor may be a transition metal itself or a compound comprising a transition metal element, and in one exemplary embodiment, the transition metal is chromium, vanadium, iron, nickel, cobalt, copper, titanium, manganese In this case, the preparation of the coordination compound may be easy. In other embodiments, the metal precursor may comprise typical elements such as magnesium, calcium, aluminum, silicon, or lanthanoid series metals such as cerium and lanthanum, from which coordinating compounds can be prepared.

In some embodiments, examples of compounds comprising metal elements used as metal precursors include metal halides, metal nitrates, metal sulfates, metal acetates, metal carbonyls, metal alkoxides Metal salts, or hydrates thereof. Halogen may refer to F, Cl, Br, or I. In some embodiments, examples of metal precursors include copper chloride (eg, CuCl ₂ ), iron chloride (eg, FeCl ₃ ) manganese chloride (eg, MnCl ₂ ), chromium chloride (eg, CrCl ₃ ), vanadium chloride (eg, VCl) ₃ ), titanium chloride (eg, TiCl ₄ ) or hydrates thereof, and the like. In other embodiments, examples of metal precursors may include, but are not limited to, copper nitrate, iron nitrate, manganese nitrate, chromium nitrate, vanadium nitrate, zinc nitrate or hydrates thereof.

), 아미드기 (-CONH₂), 술폰산기 (-SO₃H), 술폰산의 음이온기(-SO₃ ^-), 메탄디티오산기(-CS₂H), 메탄디티오산의 음이온기(-CS₂ ^-), 피리딘기, 피라진기 등을 포함할 수 있으나 이에 제한되는 것은 아니다.In one embodiment, organic compounds capable of acting as organic ligands include organic compounds having functional groups that can coordinate. In some embodiments, examples of functional groups capable of coordinating acid group (-CO _3), of the acid anion group (-CO ₂ ^-), a carboxyl group, a carboxylic anionic group of the acid, an amino group (-NH _2), imino group (

), Amide group (-CONH _2), a sulfonic acid group (-SO ₃ H), a sulfonic acid anion group (-SO ₃ ^-), methane dithiol Osan group (-CS ₂ H), methane dithiol Osan anion group (-CS of ₂ ^-), but it may comprise a pyridine group, a pyrazine group or the like without being limited thereto.

In one embodiment, examples of organic compounds capable of acting as organic ligands include those compounds having two or more coordinating sites, for example, organic compounds that are bidentate or tridentate. Can be. In some embodiments, compounds having two or more coordinating sites can induce a stable porous organic-inorganic hybrid. In one embodiment, examples of organic compounds that can act as organic ligands are, if there is a position to coordinate, neutral organic compounds such as bipyridine, pyrazine, etc., anionic organic compounds such as terephthalate, naphthalenedicarboxylate And anionic compounds of carboxylic acids such as benzenetricarboxylate, benzenetribenzoate, pyridinedicarboxylate, bipyridyldicarboxylate, and the like, as well as cationic materials. In another embodiment, as the anionic organic compound of the carboxylic acid, in addition to the anion having an aromatic ring such as terephthalate, for example, formate, oxalate, malonate, succinate, glutamate, hexyndioate, heptanedio Anions of linear carboxylic acids such as ions, anions having non-aromatic rings such as cyclohexyl dicarboxylate, and the like may be used, but are not limited thereto.

In another embodiment, organic compounds capable of acting as organic ligands include organic compounds with coordinating sites, as well as organic compounds with potentially coordinating sites, which are capable of coordinating under reaction conditions. Can be used. For example, in the case of using an organic acid such as terephthalic acid, it may be converted to terephthalate and then combined with a metal component after the reaction. In some embodiments, examples of such organic compounds include benzenedicarboxylic acid, naphthalenedicarboxylic acid, benzenetricarboxylic acid, benzenetribenzoic acid, naphthalenetricarboxylic acid, pyridinedicarboxylic acid, bipyridyldicarboxylic acid. Organic acids such as acids, formic acid, oxalic acid, malonic acid, succinic acid, glutamic acid, hexanedioic acid, heptanedioic acid, cyclohexyldicarboxylic acid and their anions, pyrazine, bipyridine, dihydroxyterephthalic acid and the like. In some embodiments, one or more organic organics may be used in combination.

In one embodiment, a solvent capable of dissolving both a metal precursor and an organic compound that can act as an organic ligand can be used. In some embodiments, examples of solvents are water, alcohols, ketones, hydrocarbons, N, N-dimethylformamide (DMF), N, N-diethylformamide (DEF), N, N-dimethylacetamide (DMAc ), Acetonitrile, dioxane, chlorobenzene, pyridine, N-methyl pyrrolidone (NMP), sulfolane, tetrahydrofuran (THF), gamma-butyrolactone, cycloaliphatic alcohols such as cyclohexanol and the like However, it is not limited thereto. In other embodiments, two or more solvents may be used in combination. In another embodiment, as the solvent, water; Mono or polyalcohols having 1 to 10 carbon atoms, such as methanol, ethanol, propanol, alkylene polyols such as EG (ethylene glycol, glycerol; polyalkylene polyols such as polyethylene glycol; ketones having 2 to 10 carbon atoms, such as One or two or more selected from acetone, methyl ethyl ketone, acetylacetone, and the like, and hydrocarbons having 4 to 20 carbon atoms (e.g., linear and cyclic alkanes having 4 to 10 carbon atoms, such as hexane, heptane, octane, toluene, etc.) Mixtures may be used In some exemplary embodiments, water, EG, DMF, THF may be used as the solvent.

The molar ratio of the organic compound which can act as the metal precursor and the organic ligand can be appropriately adjusted according to the kind of the metal component and the organic compound used. In one embodiment, the molar ratio of the metal precursor and the organic compound that can act as the organic ligand may be 1: 0.1 to 500, but is not limited thereto. In other embodiments, the molar ratio of the metal precursor and the organic compound that can act as the organic ligand can be from 1: 0.1 to 100 or from 1: 0.1 to 10.

The heating temperature of the reactant mixture is not substantially limited. In some embodiments, the heating temperature of the reactant mixture may be at least room temperature. In other embodiments, the heating temperature of the reactant mixture may be at least 20 ° C., and in another embodiment, the heating temperature of the reactant mixture may be at least 50 ° C., at least 60 ° C., at least 80 ° C., or at least 100 ° C. In some embodiments, the heating temperature can be up to 250 ° C.

In the heating step of the reactant mixture, the reaction pressure is not substantially limited. In one embodiment, the reaction can be carried out by setting the reaction pressure to the autogeneous pressure of the reactants at the reaction temperature in the reactor. In another embodiment, the reaction can be carried out under high pressure by adding an inert gas such as nitrogen, helium.

In another embodiment, the porous organic-inorganic hybrid may comprise preparing a reactant mixture containing one or more inorganic metal precursors, organic compounds that can act as one or more ligands, and a solvent; And forming a crystalline porous organic-inorganic hybrid through the reaction from the reactant mixture, and the reaction may be performed at a pressure of 3 atm or less. The crystalline porous organic-inorganic hybrid may be synthesized by any conventionally known method, and the preparation method may include hydrothermal synthesis, solvothermal synthesis, microwave irradiation, and sono synthesis. In one embodiment, the crystalline porous organic-inorganic hybrid can be prepared by hydrothermal synthesis by reaction at high temperature using solvent diffusion at room temperature or using water as a solvent. In another embodiment, crystalline porous organic-inorganic hybrids can be prepared via solvothermal synthesis using organics as a solvent [Microporous Mesoporous Mater., Vol 73, p. 15 (2004)]. In another embodiment, the crystalline porous organic-inorganic hybrid is prepared by boiling water or a suitable organic solvent, similar to the process for preparing other inorganic porous materials such as zeolites or mesoporous compounds, to form boiling point synthesis temperatures of solvents or mixed solutions. It is generally prepared by crystallization process under the condition of autogeneous pressure. In some embodiments, a metal ion or a compound thereof and an organic ligand are stirred or ultrasonically irradiated for a predetermined time in the presence of a solvent to allow organic substances to be coordinated with a metal to form crystal nuclei, and to form a crystal nucleus in the reaction solution in which the nucleus is formed. May be irradiated to perform a crystallization reaction.

In some exemplary embodiments, the reaction may be carried out at low pressure up to 3 atmospheres to dramatically increase the rate of crystallization at high concentrations of synthesis and to control the rate of crystallization and solvent autoadsorption during the reaction. In other embodiments, the reaction can be carried out at 2.5 atm or less, or at 2 atm or less. Although not bound by theory, it is thought that the porous organic-inorganic hybrid crystals formed during the reaction rapidly adsorb the solvent and the pressure does not rise even when a solvent having a break point lower than the reaction temperature is used. According to one embodiment, when the reaction is carried out at low pressure conditions, various kinds of inexpensive reactors may be used instead of expensive high pressure reactors, thereby reducing the investment cost for the preparation of crystalline porous organic-inorganic hybrids. In addition, when the crystalline porous organic-inorganic hybrid is produced by the production method performed at a low pressure of 3 atm or less, despite the low pressure conditions, regardless of the presence or absence of a crystallization aid (for example, hydrofluoric acid), it has a high crystallinity A crystalline porous organic-inorganic hybrid having a uniform particle size distribution can be provided.

In one embodiment, the low pressure reaction is carried out under high concentration of metal precursor in the reactant mixture. For example, the molar ratio of the solvent to the inorganic metal precursor in the reactant mixture is 100 or less. In other embodiments, the molar ratio of solvent to inorganic metal precursor in the reactant mixture is at most 60, at most 50, or at most 25. When the reaction proceeds at high concentration, the crystallization rate of the porous organic-inorganic hybrid and / or the yield per unit volume of the reactor of the crystalline porous organic-inorganic hybrid obtained can be increased.

In the method for producing a crystalline porous organic-inorganic hybrid according to another embodiment, the obtained porous organic-inorganic hybrid may further comprise the step of purifying by treating with the inorganic salt, acidity regulator, solvent or a mixture thereof. have. In order to remove the metal or organic ligand present in the pores of the crystalline porous organic-inorganic hybrid, a solvent-inorganic salt, an acidity regulator, or a mixture thereof is used to remove the organic or inorganic impurities chelated in the pores to form a porous organic-inorganic hybrid. This can be done further by increasing the surface area of the sieve.

Inorganic salts according to one embodiment include monovalent or divalent cations selected from the group consisting of ammonium ions (NH ₄ ⁺ ), alkali metals and alkaline earth metals, halogen anions, carbonate ions (CO ₃ ^2- ), nitrate ions And monovalent or divalent anions selected from the group consisting of sulfate ions. In some embodiments, examples of inorganic salts are salts comprising Ca ²⁺ or Mg ²⁺ as divalent cations, in other embodiments salts comprising F ⁻ , I ⁻ or Br ⁻ as monovalent anions, another embodiment In an aspect, salts comprising monovalent cations and divalent anions, in one exemplary embodiment may comprise NH ₄ F, KF, KI, KBr.

By using an acidity regulator, an economical purification process can be realized by shortening the purification time of the crystalline porous organic-inorganic hybrid. In one embodiment, basic compounds may be used as pH adjusting agents, preferably ammonia or potassium chloride (KOH).

In one embodiment, the surface functionalized compound having various functional groups can be bonded to unsaturated metal sites of the porous organic-inorganic hybrid to modify or functionalize the surface of the porous organic-inorganic hybrid. Unsaturated metal sites are coordinated sites in the metal from which water or organic solvent has been removed from the porous organic-inorganic hybrid, and means a position where a compound having a functional group can form a covalent bond or a coordinating bond. Such surface functionalization may be performed as disclosed in Korean Patent Publication Nos. 10-0864313, 10-0816538, and the like, which are incorporated herein by reference.

In one embodiment, one or more selected from organic, inorganic, ionic liquids or organic-inorganic hybrids may be used as the surface functionalizing compound capable of binding to unsaturated metal sites.

In one embodiment, one or more selected from the compounds represented by the following Chemical Formulas 1 to 3 may be used as the organic material:

[Formula 1]

H ₂ NM-R1

[Formula 2]

HS-M-R2

(3)

(OH) ₂ OP-M-R3

Wherein M is a C ₁ to C ₂₀ alkylene or aralkylene group, with or without unsaturated hydrocarbons; R 1, R 2 or R 3 are independently a halogen, vinyl group (—C═CH ₂ ), amino group ( -NH ₂ ), imino group (-NHR ¹⁴ ), mercapto group (-SH), hydroxy group (-OH), carboxyl group (-COOH), sulfonic acid group (-SO ₃ H), alkoxy group (-OR) or force C ₁ -C ₂₀ alkylene or aralkylene group which is unsubstituted or substituted with one or more selected from a poly group (-PO (OH) ₂ ).

In one embodiment, a polyoxometalate such as [AlO ₄ Al ₁₂ (OH) ₂₄ (H ₂ O) ₁₂ ] ⁷⁺ or [PW ₁₂ O ₄₀ ] ^4- may be used as the inorganic material. Examples of the polyoxometallate compound include anion [(XM ₁₂ O ₄₀ ) ^n- of a Keggin structure; n = 1 to 10; X = P, Si, H, Ga, Ge, V, Cr, Me or Fe; One or more of M = W, Mo, and Co], an anion of the Lindqvist structure [(M ₆ O ₁₉ ) ^n- ; n = 1 to 10; M = W, Mo, Ta, V or W], anion of Anderson-Evans structure [(M _x (OH) ₆ M ₆ O ₁₈ ) ^n- ; n = 1 to 10; M _x = Cr, Ni, Fe or Mn; M = Mo, W] or [(M ₄ (H ₂ O) ₄ (P ₂ W ₁₅ O ₅₆ ) ₂ ) ^n- ; n = 1 to 10; One or more transition metals or transition metal clusters selected from M = Cu, Zn, Ni, Mn, and the like, or (P ₂ W ₁₅ O ₅₆ ) ₂ of the Dawson-Wells structure.

In one embodiment, the ionic liquid is ammonium, phosphonium, sulfonium, pyrrolididinum, imidazolium, thiazonium, pyridinium (Pyridium), triazonium (Triazolium) salts can be used to select one or more.

In one embodiment, an organometallic compound may be used as the organic-inorganic hybrid. In some embodiments, it is possible to use compounds containing organosilicon as organosilane compounds among organometallic compounds, examples of which include silylating agents, silane coupling agents, silane polymers or mixtures thereof. Among the surface functionalized compounds, the organosilane compound may not only be easily bonded to the unsaturated metal site of the porous organic-inorganic hybrid but also may be stably present after the bonding. In some embodiments, when one of the organosilane compounds has an alkyl, alkenyl, alkynyl group having an alkoxy group on one side and an amino group or a mercapto group on the other side, it forms a stable bond with the porous organic-inorganic hybrid. And / or have high activity as a catalyst.

In one embodiment, as the organic-inorganic hybrid, one kind selected from the compounds represented by the following Chemical Formulas 4 to 11 may be used.

[Formula 4]

Si (OR ¹ ) _4-x R _x (1≤x≤3)

[Chemical Formula 5]

Si (OR ³ ) _{4- (y + z)} R ² _y Z _z (1≤y + z≤3)

[Formula 6]

Si (OR ⁴ ) _4-a R ⁵ _a Si (1≤a≤3)

[Formula 7]

Z ¹ _b (OR ⁶ ) _3-b Si-A-Si (OR ⁷ ) _3-C Z ² _C (0≤b≤2, 0≤c≤2)

[Formula 8]

R ⁸ _e M ¹ (OR ⁹ ) _4-e (1≤e≤3)

[Formula 9]

R ¹⁰ _g M ² Z ³ _f (OR ¹¹ ) _{4- (f + g)} (1≤f + g≤3)

[Formula 10]

M ³ (OR ¹² ) _h (1≤h≤2)

[Formula 11]

M ⁴ (OR ¹³ ) _i Z ⁴ _j (1≤i + j≤2)

Wherein A is a C ₁ to C ₂₀ alkylene or aralkylene group with or without unsaturated hydrocarbons; Z ¹ to Z ⁴ are independently selected from halogen elements; M ¹ and M ² are independently At least one element selected from transition metals, lanthanide series and actinium series metals; M ³ and M ⁴ are independently at least one element selected from alkaline earth metals or alkali metals; R and R ¹ to R ¹³ are independently halogen At least one selected from an element, a vinyl group (-C = CH ₂ ), an amino group (-NH ₂ ), an imino group (-NHR ¹⁴ ), a mercapto group (-SH), a hydroxy group (-OH) or a carboxyl group (COOH) C ₁ to C ₂₀ alkyl group, alkenyl group or alkynyl group substituted or unsubstituted with a vinyl group (-C = CH), amino group (-NH ₂ ), or No group (-NHR ¹⁴ ), mercapto group (-SH), hydroxy group (-OH) or carboxyl group ( CO ¹⁴ ), wherein R ¹⁴ is a C ₁ to C ₁₀ alkyl group, alkenyl group or alkynyl group which is unsubstituted or substituted with a halogen, amino group, mercapto group or hydroxy group)

In one embodiment, when functionalizing the porous organic-inorganic hybrids by selecting two or more from organic, inorganic, ionic liquids and organic-inorganic hybrids, two or more substances may be mixed and used sequentially. It is also possible to use a method of first functionalizing a species of substance and then later functionalizing another species of substance. In some embodiments, the surface functionalization of two or more materials by primary reaction with an organic or organometallic compound followed by secondary reaction with an ionic liquid or an inorganic polyoxometallate, a noble metal, a transition metal, a typical metal or a lanthanide metal. Porous organic-inorganic hybrids can be prepared. This method has the advantage of inhibiting the dissolution of the metal when the active material is secondly supported on the functional group.

In one embodiment, the porous organic-inorganic hybrid is powder, thin film, membrane, pellet, ball, foam, slurry, paste, paint, honeycomb, beads, mesh, fiber, corrugated sheet, rotor It may be provided in the form of, but is not limited to a specific form. For example, the porous organic-inorganic hybrid in the form of a thin film or membrane may be prepared by immersing a predetermined substrate in a reactant mixture and then heating. In other embodiments, shaped bodies such as pellets, beads, honeycombs, meshes, membranes, fibers, corrugated cardboard can be prepared using suitable organic or inorganic binders.

In some embodiments, the added organic and inorganic binder does not exceed 50% of the weight of the porous organic-inorganic hybrid and the powder. In one exemplary embodiment, examples of inorganic binders include silica, alumina, boehmite, zeolites, mesoporous bodies, carbon, graphite, layered compounds, metal alkoxides, metal halides, and the like, and in other exemplary embodiments, Examples of organic binders include, but are not limited to, one or more alcohols and cellulose, polyvinyl alcohol, polyacrylates, and the like.

In one exemplary embodiment, after manufacturing a ceramic paper manufactured using inorganic fibers, the cylindrical paper may be rolled into a circular shape after polarization after the single side corrugated molding of the ceramic paper. The dehumidifying part including the porous organic-inorganic hybrid may be manufactured by using the ceramic paper, the polarized molded body or the cylindrical honeycomb as a substrate, and immersing them in the reactant mixture, followed by heating.

According to one embodiment, the porous organic-inorganic hybrid material disclosed above is useful as an adsorbent because of the large difference between the low temperature adsorption amount and the high temperature adsorption amount. In another embodiment, the porous organic-inorganic hybrids are characterized by easy desorption even at low temperatures (eg, below 100 ° C.), high water adsorption per unit weight of porous organic-inorganic hybrids, and / or high adsorption rates. Have

In one embodiment, the porous organic-inorganic hybrid may desorb more than 10% of the adsorbed moisture within 5 minutes at a water desorption temperature of 100 ° C. or less after moisture adsorption. In some embodiments, the porous organic-inorganic hybrid may desorb at least 20%, at least 40%, at least 60%, or at least 75% of the adsorbed moisture within 5 minutes at a water desorption temperature of 100 ° C. or less.

In one embodiment, the porous organic-inorganic hybrid can adsorb 0.1 g to 3 g of adsorbent per g. In some embodiments, the porous organic-inorganic hybrid is from 0.1 g to 2 g per g of porous organic-inorganic hybrid at 100 ° C. or less, and in other embodiments, the porous organic-inorganic hybrid is 0.1 to 1 g at 10 ° C. to 100 ° C. At least g, at least 0.2 g, at least 0.4 g or at least 0.5 g of the adsorbent may be adsorbed, and in yet another embodiment, the porous organic-inorganic hybrid is at most 1 g per g, at most 0.9 g at 10 ° C. to 100 ° C. Up to 0.8 g, or up to 0.7 g of adsorbent.

In other embodiments, porous organic-inorganic hybrids have high surface areas and molecular or nano-sized pores that can be used as adsorbents, gas storage, sensors, membranes, functional thin films, catalysts, catalyst carriers, and the like. In addition, porous organic-inorganic hybrids can be used to trap guest molecules smaller than the pore size, or to separate molecules according to their size using pores. In one exemplary embodiment, an adsorbent comprising a porous organic-inorganic hybrid, as well as moisture, hydrocarbons such as hydrogen, oxygen, nitrogen, methane, paraffin, olefins, carbon monoxide, carbon dioxide, odor causing compounds, for example, Various components such as nitrogen-containing compounds such as ammonia and trimethylamine, sulfur-containing compounds such as methyl sulfide, methyl mercaptan and hydrogen sulfide, and volatile organic compounds (VOC) such as formaldehyde and acetaldehyde can be adsorbed. Therefore, when using a porous organic-inorganic hybrid in the air treatment apparatus, it is possible to provide fresh air from which various odor causing components and the like are removed. In some embodiments, when the porous organic-inorganic hybrid is used in the air treatment apparatus, gas such as hydrocarbon, NOx, CO, VOC, etc. contained in the air introduced from the outside can be effectively adsorbed and removed, and in particular, The air from which NOx etc. were removed can be provided in a desired place.

In one embodiment, the dehumidifying unit 2 may further include a catalyst component capable of decomposing various volatile organic compounds and the like, but is not limited to a specific catalyst. When simultaneously using a catalyst component capable of decomposing volatile organic compounds and the like, the removal efficiency can be improved by decomposing contaminants contained in the air introduced from the outside.

For example, the catalyst may be a metal catalyst comprising platinum, silver, gold, palladium, ruthenium, rhodium, osmium, iridium, manganese, copper, cobalt, chromium, nickel, iron, zinc, or the like, or a combination of one or more thereof. Can be. The metal catalyst may be provided in various forms combined with a carrier such as alumina, silica, zeolite, zirconia, ceria-zirconia, porous organic-inorganic hybrid, and the like.

In one embodiment, the metal catalyst combined with the carrier can be obtained by preparing a catalyst powder by supporting a metal salt containing palladium ions and transition metal ions such as copper, manganese, nickel, chromium, cobalt, and the like on a porous carrier, an oxide carrier, or the like. have. In some embodiments, a catalyst slurry is prepared by combining an adsorbent such as the catalyst powder and a porous organic / inorganic hybrid, and a binder such as bentonite, silica colloid, and methyl cellulose, and honeycomb type by wet coating the catalyst slurry on the honeycomb carrier surface. Integrated catalysts can be prepared. Such metal catalysts may be prepared as disclosed in Korean Laid-Open Patent Publication No. 10-2001-0037883, which is incorporated herein by reference.

In another exemplary embodiment, the metal catalyst may be a metal supported organic-inorganic mesoporous catalyst in which the lipophilic group is included in the backbone of the mesoporous body, and the active metal is highly dispersed in the pore cavity. The organic-inorganic mesoporous body on which the metal component is supported is prepared by stirring a noble metal compound containing a metal ion such as platinum, silver, gold, palladium, ruthenium, rhodium, osmium and iridium, a chelating agent and an organosilane compound. step; Hydrothermally reacting the mixture to prepare an organic-inorganic silica mesoporous body in which metal components are dispersed; And it may be prepared by a method comprising the step of firing the organic-inorganic silica mesoporous body, but is not limited thereto. Such metal catalysts may be prepared as disclosed in Korean Patent Publication No. 10-0816485, which is incorporated herein by reference.

In another exemplary embodiment, the metal catalyst is a precious metal such as platinum, palladium, or a metal component of at least one metal of transition metals such as copper, cobalt, chromium, zinc, iron, silver, nickel, or the like, supported on alumina, hydrophobic zeolite, or the like. It may be a catalyst. Examples of hydrophobic zeolites include, but are not limited to, MFI (HZSM-5), FAU (HY), Mordenite (HMOR), Beta (H-Beta), and the like. The metal catalyst may be a pellet, honeycomb catalyst. For such a metal catalyst, reference may be made to the contents disclosed in Korean Patent Publication No. 10-0578106, which is incorporated herein by reference.

In one embodiment, when using an adsorbent comprising a porous organic-inorganic hybrid in the air treatment apparatus, since the dehumidifying portion is in a low humidity state, microorganisms can be reduced when passing through the dehumidifying portion, and mold or bacteria can be suppressed. They can also reduce airborne bacteria and fungi in the room. In some embodiments, when a metal component having antimicrobial activity against various bacteria is substituted in a porous organic-inorganic hybrid, clean air is removed by removing the bacteria and the like contained in the air introduced from the outside by the antimicrobial action. Can provide.

The air treatment device including the porous organic-inorganic hybrid is not only used in a general home but also in various industries such as chemical industry, food industry, electric / electronic industry, precision machinery industry, textile industry, printing industry, military industry, etc. which require dehumidification and / or cooling. It can be used in the industrial field.

The following examples are intended to further illustrate the features and advantages of the subject matter of the present invention, but are not limited to the following examples. The subject matter of the present invention should not be considered limited to the specific embodiments and examples described herein. In view of the present disclosure, in addition to various exemplary embodiments and embodiments, those skilled in the art will readily recognize that modifications, substitutions, additions, and combinations of some of the configurations disclosed herein are possible.

&Lt; Example 1 >

Cr (NO ₃ ) ₃ .9H ₂ O, and 1,4-benzenedicarboxylic acid (BDCA) were added to the Teflon reactor, followed by distilled water to add a final molar ratio of Cr: BDCA: H ₂ O = 1: 1: 272. The Teflon reactor containing the reactants was placed in a convection oven, reacted at 210 ° C. for 11 hours, cooled to room temperature, centrifuged, washed with distilled water and dried to obtain a porous organic-inorganic hybrid having a surface area of 3,300 m ² / g chromium terephthalate (Cr-BDC) was obtained. After 0.1 g of the obtained organic-inorganic hybrid Cr-BDC was vacuum dried at 70 ° C. for 30 minutes, adsorption experiments of water were carried out by gravimetric method. At 60% relative humidity, the water adsorption amount per adsorbent weight was 1.2 g / g (within 3 hours).

<Example 2>

1 mmol of iron salt (iron nitrate) and 0.67 mmol of 1,3,5-benzenetricarboxylic acid (BTCA) were added to the Teflon reactor, followed by addition of acid and distilled water. The final molar ratio of the reactants was Fe: HNO ₃ : BTCA. : H ₂ O = 1: 0.7: 0.67: 278. The Teflon reactor containing the reactants was placed in a Convection oven, held at 160 ° C. for 8 hours to conduct a crystallization reaction, and then cooled to room temperature, centrifuged, washed (distilled water) and dried to give a surface area of 2,200 m ² / g. Phosphorus porous organic-inorganic hybrid (Fe-BTC) was obtained. 0.1 g of the obtained organic-inorganic hybrid Fe-BTC was vacuum dried at 70 ° C. for 30 minutes, and then a water adsorption experiment was performed by gravimetric method. The moisture adsorption amount per weight of the adsorbent was 0.8 g / g even at a relative humidity of 60%. In this way, the porous organic-inorganic hybrid is easily adsorbed and desorbed even at 100 ℃ or less, it can be seen that the excellent performance, such as humidification, dehumidification.

<Example 3>

1 mmol of iron salt and 0.67 mmol of 1,3,5-benzenetricarboxylic acid (BTCA) were added to the Teflon reactor, followed by distilled water, and the final molar ratio of the reactants was Fe (NO ₃ ) ₃ .9H ₂ O: BTCA: H ₂ O = 1: 0.67: 278. The Teflon reactor containing the reactants was placed in a Convection oven, held at 160 ° C. for 8 hours to conduct a crystallization reaction, and then cooled to room temperature, centrifuged, washed (distilled water) and dried to obtain a surface area of 1,800 m ² / g. Phosphorus porous organic-inorganic hybrid (Fe-BTC) was obtained. 0.1 g of the obtained organic-inorganic hybrid Fe-BTC was vacuum dried at 70 ° C. for 30 minutes, and then a water adsorption experiment was performed by gravimetric method. The moisture adsorption amount per weight of the adsorbent was 0.6 g / g even at 60% relative humidity. In this way, the porous organic-inorganic hybrid is easily adsorbed and desorbed even at 100 ℃ or less, it can be seen that the excellent performance, such as humidification, dehumidification.

<Example 4>

An organic-inorganic hybrid was prepared using aluminum nitrate hydrate instead of the iron nitrate of Example 3. The surface area of Al-BTC having the same structure was 1,720 m ² / g.

Example 5

0.227 mmol of TiCl _{4 and} 0.227 mmol of 1,4-benzenedicarboxylate (H ₂ BDC) were added to the Teflon reactor, followed by addition of 340 mmol of N, N-dimethylformamide (DMF). The reaction was stirred at 50 rpm for 20 minutes at room temperature to prepare a mixed reaction. The Teflon reactor containing the reactant was mounted in a microwave reactor (Milestone), heated to 120 ° C by irradiation with microwaves, and maintained at 120 ° C for 1 hour to carry out a crystallization reaction, followed by cooling to room temperature and washing ( Distilled water) and dried to obtain a porous organic-inorganic hybrid (Ti-BDC).

<Example 6>

CrCl ₃ · 9H ₂ O, and 1,4-benzenedicarboxylic acid (BDCA) were added to the Teflon reactor and distilled water was added to mix the final molar ratio of the reactants to Cr: BDCA: H ₂ O = 1: 1: 272. It was. The Teflon reactor containing the reactant mixture was placed in an electric oven, reacted at 210 ° C. for 16 hours, cooled to room temperature, centrifuged, washed with distilled water and dried to form chromium terephthalate (Cr-) as a porous organic-inorganic hybrid. BDC) was formed.

It was confirmed that the XRD pattern of the chromium terephthalate crystals obtained in the above examples was consistent with the literature values [Science 23, 2040, 2005]. In addition, as a result of nitrogen adsorption and desorption, the adsorption amount was 1,200 ml / g at a relative pressure of 0.5, and it was confirmed that a high surface area was obtained at a surface area of 3,800 m ² / g. In addition, as a result of ICP analysis, the structure of the obtained porous organic-inorganic hybrid chromium terephthalate is the same as that of MIL-101, but does not contain fluorine in the structure: Cr ₃ (Cl _0.8 (OH) _0.2 ) (H ₂ O) It was confirmed that the material can be represented by ₂ O [C ₆ H ₄ (CO ₂ ) ₂ ] ₃ .

<Example 7>

40.8 mmol of metal iron chloride (FeCl ₃ ), and 26.8 mmol of 1,3,5-benzenetricarboxylic acid (BTCA) were added to the Teflon reactor, followed by distilled water, and the final molar ratio of the reactants was FeCl ₃ : BTCA: H ₂ O. = 1: 0.66: 54. The reaction was stirred at 500 rpm for 20 minutes at room temperature to give a homogeneous reaction. The Teflon reactor containing the pretreated reactant was maintained at a reaction temperature of 160 ° C. for 8 hours to perform a crystallization reaction, and then cooled, washed (distilled water) and dried to room temperature to form a porous organic-inorganic hybrid (Fe-BTC). .

It was confirmed that the shape of the X-ray diffraction spectrum was the same as that of the MIL-100 (Fe) structure, which is the crystal structure of [Chemical Communication 2820, 2007]. As a result of the ICP analysis, the structure of the obtained porous organic-inorganic hybrid iron terephthalate is the same as that of MIL-100, but does not include fluorine in the structure, and is represented by the formula: Fe ₃ O (H ₂ O) ₂ Cl [C ₆ H ₃ − (CO ₂ ) ₃ ] _{2 It} was confirmed that the material can be represented. As a result of nitrogen adsorption and desorption experiment, the surface area was 1500 m ² / g and the adsorption amount was 450 ml / g at P / Po = 0.5. Electron microscopic analysis confirmed that the particle size was ~ 500 nm.

<Example 8>

1 g of the porous organic-inorganic hybrid prepared in Example 7 was placed in 50 ml of 1M NH ₄ F, and stirred at a temperature of 70 ° C. to remove impurities present in the pores of the pores, thereby improving the specific surface area of the organic-inorganic hybrid. Was prepared. From the X-ray diffraction spectrum, it was confirmed that the crystallinity remained intact even after treatment with ammonium fluoride. In addition, the surface area of the porous organic-inorganic hybrid after the ammonium fluoride treatment was measured at 1,820 m ² / g, the adsorption amount was measured at 550 ml / g at P / Po = 0.5.

Example 9

In Example 7, a porous organic-inorganic hybrid was prepared in the same manner as in Example 7, except that the heating was performed by microwave heating instead of electric heating. In the microwave heating, the Teflon reactor containing the mixed solution prepared in Example 7 was mounted in a microwave reactor (CEM Co., Model Mars-5), heated to 180 ° C. after irradiation with microwaves (2.54 kV), and then heated to 180 ° C. After the crystallization reaction was carried out by maintaining for 30 minutes at room temperature, cooled to room temperature, centrifuged, washed (distilled water) and dried to prepare a porous organic-inorganic hybrid (Fe-BTC).

As a result of XRD analysis for the porous organic-inorganic hybrid prepared in this example, it was confirmed that the diffraction pattern was obtained at the same position as in Example 7, although the relative intensity of the peak was different. As a result of the surface area measurement, it was confirmed that 200 m ² / g higher than the electric heating method. As a result of analysis by electron microscope, the size of organic-inorganic hybrid particles was 1 μm and the crystal was relatively uniform.

<Example 10>

A porous organic-inorganic hybrid was prepared in the same manner as in Example 7, except that VCl ₃ was used instead of FeCl _{3 in} Example 7. From the X-ray diffraction spectrum, it was confirmed that a material having the same structure as in Example 7 was obtained. From the electron micrograph, it was confirmed that a porous organic-inorganic hybrid having a uniform particle size characteristic of about 100 nm was obtained.

<Example 11>

In Example 7, CuCl ₂ was used instead of FeCl ₃ , H ₂ O and ethanol mixed solution were added as a solvent, and the final molar ratio was Cu: BTCA: EtOH: H ₂ O = 1: 0.56: 14.4: 14.4. A reactant mixture was prepared. At this time, the reactant mixture prepared in Example 7 was irradiated with ultrasonic waves at room temperature and pretreated for 5 minutes to make the reactants as uniform as possible and to facilitate nucleation. The Teflon reactor containing the pretreated reactant was mounted in a microwave reactor (CEM, Model Mars-5) and heated to 140 ° C. over 2 minutes by irradiating a microwave at 2.45 GHz. Thereafter, the mixture was held at 140 ° C. for 30 minutes to react, and after cooling to room temperature, the powder was filtered using a paper filter. It was confirmed that the shape of the X-ray diffraction spectrum was the same as that of the HKUST-1 structure, which is the crystal structure of Science 283 (1999) 1148 in the literature.

<Example 12>

In Example 8, a porous organic-inorganic hybrid was prepared in the same manner as in Example 8 except that Fe was used instead of FeCl ₃ . From the X-ray diffraction pattern, it was confirmed that the material was the same as in Example 8, and the surface area of the prepared porous organic-inorganic hybrid was 1,300 m ² / g.

Example 13

Ni (CH ₃ COO) ₂ · 4H ₂ O, and 2,5-dihydroxyterephthalate (DHT) were added to the Teflon reactor, and distilled water and THF were added to give a final molar ratio of Ni: DHT: H ₂ O. : THF = 1: 0.5: 367: 140. The reaction was stirred at 50 rpm for 20 minutes at room temperature to prepare a mixed reaction. The Teflon reactor containing the reactant was mounted in a microwave reactor (CEM Co., Model Mars-5), irradiated with microwave (2.54 GHz), heated to 110 ° C., and then maintained at 110 ° C. for 10 minutes to perform a crystallization reaction. Then, cooled to room temperature, washed (distilled water) and dried to obtain a porous organic-inorganic hybrid (Ni-DHT). It was confirmed that the XRD pattern of the crystals obtained in this example is consistent with the literature values [J. AM. CHEM. SOC. 130, 10870, 2008]. It was confirmed that the particle size calculated from the half-width of the FWHM of the XRD pattern was 28 nm. In addition, as a result of electron microscope analysis, it was confirmed that the secondary particle size of Ni-DHT was 200 nm.

<Example 14>

To the Teflon reactor was added 1.85 mmol of Mg (NO ₃ ) ₂ .6H ₂ O, and 0.559 mmol of 2,5-dihydroxyterephthalate (DHT), followed by 15: 1: 1 (v / ethanol) in DMF-ethanol-water. 50 ml was added at the ratio of v / v). The reaction was stirred at 50 rpm for 20 minutes at room temperature to prepare a mixed reaction. The Teflon reactor containing the reactant was mounted in a microwave reactor (CEM Co., Model Mars-5), irradiated with microwave (2.54 GHz), heated to 125 ° C., and then maintained at 125 ° C. for 1 hour to perform a crystallization reaction. After cooling to room temperature, washing (distilled water) and drying gave a porous organic-inorganic hybrid (Mg-DHT). As a result of XRD analysis on the porous organic-inorganic hybrid prepared in this example, it was confirmed that the diffraction pattern was obtained at the same position as Example 13, although the relative intensity of the peak was different.

<Example 15>

8.67 mmol of Co (NO ₃ ) ₃ .6H ₂ O, and 2.43 mmol of 2,5-dihydroxyterephthalate (DHT) were added to the Teflon reactor, and then DMF-ethanol-water was 1: 1: 1 (v / v / v) to 50 ml. The reaction was stirred at 50 rpm for 20 minutes at room temperature to prepare a mixed reaction. The Teflon reactor containing the reactant was mounted in a microwave reactor (CEM Co., Model Mars-5), irradiated with microwave (2.54 GHz), heated to 100 ° C., and maintained at 100 ° C. for 1 hour to carry out a crystallization reaction. After performing, cooling to room temperature, washing (distilled water) and drying gave a porous organic-inorganic hybrid (Co-DHT). As a result of XRD analysis on the porous organic-inorganic hybrid prepared in this example, it was confirmed that the diffraction pattern was obtained at the same position as Example 13, although the relative intensity of the peak was different.

<Example 16>

ZrCl ₄ and 1,4-benzenedicarboxylate (H ₂ BDC) were added to the Teflon reactor, followed by addition of N, N-dimethylformamide (DMF) to give a final molar ratio of Zr: H ₂ BDC: DMF. = 1: 1: 497. The reaction was stirred at 50 rpm for 20 minutes at room temperature to prepare a mixed reaction. The Teflon reactor containing the reactant was mounted in a microwave reactor (Milestone), irradiated with microwave (2.54 GHz), heated to 120 ° C., maintained at 120 ° C. for 2 hours, and then subjected to crystallization at room temperature. Cooling, washing (distilled water) and drying gave a porous organic-inorganic hybrid (Zr-BDC). It was confirmed that the XRD pattern of the crystals obtained in this example is consistent with the literature values [J. AM. CHEM. SOC. 130, 13850, 2008]. As a result of analysis by electron microscope, the particle size was 200 nm, and it was confirmed that the crystal was relatively uniform.

<Example 17>

0.227 mmol of ZrCl _{4 and} 0.227 mmol of 1,4-benzenedicarboxylate (H ₂ BDC) were added to the Teflon reactor, and N, N-dimethylformamide (DMF) and 2-propanol were set at a molar ratio of 5: 5. Was added. The reaction was stirred at 50 rpm for 20 minutes at room temperature to prepare a mixed reaction. The Teflon reactor containing the reactant was mounted in a microwave reactor (Milestone), irradiated with microwave (2.54 GHz), heated to 120 ° C., maintained at 120 ° C. for 1 hour to carry out a crystallization reaction, and then returned to room temperature. Cooling, washing (distilled water) and drying gave a porous organic-inorganic hybrid (Zr-BDC). As a result of XRD analysis for the prepared porous organic-inorganic hybrid, it was confirmed that a diffraction pattern was obtained at the same position as in Example 16, although the relative intensities of the peaks were different.

&Lt; Example 18 >

1 g of Cr-BDC prepared in Example 1 was dried in a vacuum oven at 200 ° C. for 12 hours to dehydrate water coordinated to an unsaturated metal site. 1 g of the dehydrated Cr-BDC was added to 50 ml of a toluene solution containing 5.7 ml of 3-aminopropyltriethoxysilane (APS). The solution was refluxed at 110 ° C. for 12 hours to prepare a porous organic-inorganic hybrid having an ethoxy functional group coordinated at an unsaturated metal site. Infrared spectroscopy showed that the absorption peaks were detected at 2,800 to 3,000 cm ^-1 and 3,200 to 3,400 cm ^-1 corresponding to the amino group (-NH ₂ ) and ethyl group (-CH ₂ CH _2- ) of the APS. It was confirmed that is coordinated.

&Lt; Example 19 >

0.227 mmol of ZrCl _{4 and} 0.227 mmol of 1,4-benzenedicarboxylate (H ₂ BDC) were added to the Teflon reactor, and N, N-dimethylformamide (DMF) and ethanol were added at a molar ratio of 5: 5. . The reaction was stirred at 50 rpm for 20 minutes at room temperature to prepare a mixed reaction. The Teflon reactor containing the reactant was mounted in a microwave reactor (Milestone), and irradiated with microwave (2.54 GHz) to raise the temperature to 120 ° C., and then maintained at 120 ° C. for 1 hour to carry out a crystallization reaction, followed by room temperature. Cooling, washing (distilled water) and drying gave a porous organic-inorganic hybrid (Zr-BDC) having a surface area of 1320 m ² / g.

Example 20

A slurry solution was prepared by mixing 100 g of Fe-BDC powder obtained in Example 3 and 600 g of water. Cordierite honeycomb pretreated with the Fe-BDC slurry solution (Corning Korea, 200 cell, 15 × 15 × 5 cm) (Honeycomb pretreatment condition: treated with 1M-HNO ₃ at 70 ° C. for 5 hours, and distilled water Washed, dried in air at 600 ° C. for 5 hours), and a honeycomb coated with a Fe-BDC adsorbent was dried in an oven at 70 ° C. to support the Fe-BDC adsorbent on a honeycomb monolith support. The amount of supported Fe-BDC adsorbent was 30% by weight relative to the honeycomb support.

&Lt; Example 21 >

1 mmol of iron salt (iron nitrate) and 0.67 mmol of 1,3,5-benzenetricarboxylic acid (BTCA) were added to the Teflon reactor, followed by addition of acid and distilled water. The final molar ratio of the reactants was Fe: HNO ₃ : BTCA. : H ₂ O = 1: 0.7: 0.67: 278. The Teflon reactor containing the reactant was placed in a convection oven, maintained at 160 ° C. for 8 hours to conduct a crystallization reaction, and then cooled to room temperature, centrifuged and washed (distilled water) to form a slurry-containing porous organic-inorganic hybrid (Fe). -BTC) was obtained. The obtained Fe-BTC slurry was put into a cylindrical extruder, the inside of the extruder was kept in a vacuum state, and an extruded body was produced at a cylinder rotational speed of 50 rpm and a molding speed of 300 mm / min. The prepared extruded body was dried at 80 ° C. for 12 hours and then heat-treated at 120 ° C. for 2 hours using a calcination furnace. The BET surface area of the final extrusion molded body was 1750 m ² / g.

<Example 22>

67 mmol of iron nitrate (Fe (NO ₃ ) ₃ .6H ₂ O) and 44 mmol of 1,3,5-benzenetricarboxylic acid (BTCA) were added to the glass reactor, followed by distilled water, and the final molar ratio of the reactants. Was Fe (NO ₃ ) ₃ .6H ₂ O: BTCA: H ₂ O = 1: 0.66: 11.3. The reaction was stirred at 500 rpm for 20 minutes at room temperature to give a homogeneous reaction. The glass reactor containing the pretreated reactant was maintained at a reaction temperature of 120 ° C. for 8 hours to carry out a crystallization reaction, and then cooled to room temperature (distilled water) and dried to form a porous organic-inorganic hybrid (iron benzenetricarboxylate; Fe -BTC) was prepared. As a result of measuring the reaction pressure when preparing the porous organic-inorganic hybrid (Fe-BTC), the internal pressure at the reaction temperature of 120 ° C. was 1 bar. Without being bound by theory, it is believed that this low pressure synthesis process is due to the fact that Fe-BTC crystals rapidly absorb the solvent at the reaction temperature.

It was confirmed by electron microscopy that the particle size of the prepared porous organic-inorganic hybrid was formed into highly uniform nanoparticles of ~ 200 nm by controlling the nuclear growth rate. Although the X-ray diffraction spectrum has the same structure as Fe-BTC in the literature [Chemical Communication 2820, 2007] (FIG. 1), the porous organic-inorganic hybrid Fe-BTC iron terephthalate obtained from ICP analysis does not contain fluorine. It was confirmed that the material can be represented by the formula Fe ₃ O (H ₂ O) ₂ OH [C ₆ H _3- (CO ₂ ) ₃ ] ₂ nH ₂ O (0 <n <50). As a result of nitrogen adsorption and desorption experiments, the surface area was 1850 m ² / g, and the adsorption amount was 540 mL / g at P / P0 = 0.5 (FIG. 2). In particular, the yield of porous organic-inorganic hybrids was 150 g per 1 L of reactor.

<Example 23>

A porous organic-inorganic hybrid was prepared in the same manner as in Example 22 except that HF was added to prepare a mixture. The final molar ratio of reaction was Fe (NO ₃ ) ₃ .6H ₂ O: BTCA: H ₂ O: HF = 1: 0.66: 11.3: 0.15. The reaction was stirred at 500 rpm for 20 minutes at room temperature to give a homogeneous reaction. The taperon reactor containing the pretreated reactant was maintained at a reaction temperature of 120 ° C. for 12 hours to perform a crystallization reaction, and then cooled to room temperature (distilled water) and dried to prepare a porous organic-inorganic hybrid (Fe-BTC). As a result of measuring the reaction pressure when preparing the porous organic-inorganic hybrid (Fe-BTC), the internal pressure at the reaction temperature of 120 ° C. was 1 bar. Although not bound by theory, it is believed that this result is due to the fact that Fe-BTC crystals rapidly adsorb the solvent at 120 ° C.

It was confirmed that the shape of the X-ray diffraction spectrum was the same structure as Fe-BTC in Chemical Communication 2820, 2007. The porous organic-inorganic hybrid Fe-BTC iron terephthalate obtained as a result of ICP analysis is represented by the formula Fe ₃ O (H ₂ O) ₂ F _1-y OH _y [C ₆ H _3- (CO ₂ ) ₃ ] ₂ nH ₂ O ( 0 <y <1, 0 <n <50) it was confirmed that the material. 0.1 g of the obtained organic-inorganic hybrid Fe-BTC was vacuum dried at 70 ° C. for 30 minutes, and then a water adsorption experiment was performed by gravimetric method. Even at a relative humidity of 60%, the water adsorption amount per weight of the adsorbent was 0.8 g / g. In this way, the porous organic-inorganic hybrid is easily adsorbed and desorbed even at 100 ℃ or less, it can be seen that the excellent performance, such as humidification, dehumidification. The shape of the X-ray diffraction spectrum was confirmed to have the same structure as Fe-BTC in [Chemical Communication 2820, 2007].

<Example 24>

A porous organic-inorganic hybrid (Fe-BTC) was prepared by the same method as Example 22 using iron chloride (FeCl ₃ · 6H ₂ O) instead of iron nitrate as a metal salt. The form of the X-ray diffraction spectrum was confirmed to have the same structure as Fe-BTC in the literature [Chemical Communication 2820, 2007]. The porous organic-inorganic hybrid Fe-BTC iron terephthalate obtained as a result of ICP analysis was formulated without the fluorine formula Fe ₃ O (H ₂ O) ₂ Cl _1-y OH _y [C ₆ H _3- (CO ₂ ) ₃ ] ₂ It was confirmed that the substance could be represented by nH ₂ O (0 <y <1, 0 <n <50).

<Example 25>

A porous organic-inorganic hybrid (Fe-BTC) was prepared in the same manner as in Example 22 except that the reaction temperature was 100 ° C. The X-ray diffraction spectrum has the same structure as that of Fe-BTC in the literature [Chemical Communication 2820, 2007], but the porous organic-inorganic hybrid Fe-BTC iron terephthalate obtained by ICP analysis has the formula Fe ₃ O without fluorine. (H ₂ O) ₂ OH [C ₆ H _3- (CO ₂ ) ₃ ] ₂ · nH ₂ O (0 <n <50) It was confirmed that the material can be represented.

<Example 26>

An organic-inorganic hybrid was prepared using aluminum nitrate hydrate instead of the iron nitrate of Example 22. However, the specific surface area was 1,930 m ² / g as a result of measuring the adsorption amount of Al-BTC prepared by heat-treating in a nitrogen atmosphere at 300 ° C. to remove the remaining BTCA ligand.

Example 27

(1) Preparation of catalyst powder and slurry for wet coating

PdCl ₂ (6.10 g), CuCl ₂ · 2H ₂ O (18.80 g), and Cu (NO ₃ ) ₂ · 3H ₂ O (62.80 g) were added sequentially to 1 L of distilled water, and when the solution became a clear solution, the USY-zeolite was added thereto. (200 g; PQ, SiO ₂ / Al ₂ O ₃ = 80, S _BET = 780 m ² / g) was added thereto. The resultant mixture was stirred until the remaining moisture evaporated in a water bath at 70 ° C., and the obtained product was dried at 110 ° C. for 3 hours and calcined at 400 ° C. for 6 hours to give 1.6% by weight of Pd and 10.35% by weight of Cu. Phosphorus (Pd, Cu) / USY catalyst powder was prepared.

(Pd, Cu) / USY catalyst powder, bentonite (Junsei) and distilled water prepared above were mixed at a weight ratio of 12/3/35 and stirred for 30 minutes to sufficiently disperse, for wet coating having a solid content of 30% by weight. Catalyst slurry was prepared.

(2) Preparation of honeycomb integral catalyst

The honeycomb cordierite (Corning Korea Co., Ltd., 200 cell, 15 × 15 × 5 cm) obtained in Example 20 was soaked for 5 minutes in the wet slurry catalyst slurry, and the compressed air was blown out so that the honeycomb hole was not blocked. . And, it was dried for 3 hours at 100 ℃. The coating-drying process was repeated two more times and finally dried at 100 ° C. for 12 hours. The dried honeycomb integral catalyst was calcined at 500 ° C. for 6 hours to complete the wet coating process. In the wet coating process, the coating amount of the catalyst powder per honeycomb carrier volume was 42.7 g / L, the Pd content of the prepared monolithic catalyst was 0.67 g / L per catalyst volume, and the Cu content was 4.42 g / L per catalyst volume. .

The honeycomb integrated catalyst prepared above was reduced with 5% hydrogen at 300 ° C. for 3 hours before use, and then mounted on a catalytic combustion activity measuring apparatus for methyl ethyl ketone (MEK), which is a VOC material. The size of the catalyst used was Φ 4 cm × 5 cm, the temperature of the column attached to the gas comatography (GC) was 50 ℃, the temperature of the Flame Ionization Detector (FID) was 200 ℃. The experiment was carried out in a dry state, and the inlet concentration of the VOC was adjusted to 500 ppm and the gas flow velocity (GHSV) to 30,000 h ⁻¹ . In the case of (Pd, Cu) / USY catalyst, MEK was confirmed to be removed 95% at 210 ℃, 99% at 220 ℃.

<Example 28>

PdCl ₂ (0.38 g), CuCl ₂ · 2H ₂ O (18.80 g) and Cu (NO ₃ ) ₂ · 3H ₂ O (62.80 g) were sequentially added to 1 L of distilled water, and γ-Al was added to the transparent solution. ₂ O ₃ (200 g; Strem, S _BET = 150 m ² / g) was added. Then, in the same manner as in Example 27 (Pd, Cu) / Al ₂ O ₃ catalyst powder having a Pd content of 0.10% by weight, Cu content of 10.35% by weight and a catalyst slurry for wet coating having a solid content of 30% by weight Prepared. Further, by performing the same wet coating process as in Example 27, a honeycomb integral catalyst having a Pd content of 0.04 g / L per catalyst volume and a 4.42 g / L Cu content was prepared.

Comparative Example 1

Zeolite Y (Aldrich, Si / Al = 5.6, specific surface area = 827 m ² / g, pore volume = 0.35 ml / g) used as a commercial moisture adsorbent was prepared. The zeolite Y adsorbent was vacuum dried at 200 ° C. for 30 minutes, and a water adsorption experiment was conducted under the same conditions as in Example 2, and the water adsorption amount was 0.35 g / g. That is, although the adsorbent of Example 2 had a desorption temperature of 70 ° C., the adsorbent according to the present invention showed a water adsorption amount of 2.2 times or more.

Comparative Example 2

Carbon (Ecopro Carbon specific surface area = 665 m ² / g, pore volume = 0.39 ml / g) used as a commercial moisture adsorbent was prepared. After the carbon adsorbent was vacuum dried at 100 ° C. for 30 minutes, a water adsorption experiment was conducted under the same conditions as in Example 2, and the water adsorption amount was 0.36 g / g. That is, although the adsorbent of Example 2 had a desorption temperature of 70 ° C., the water adsorption amount of 2.2 times or more was compared with that of the carbon adsorbent.

Comparative Example 3

SAPO-34 (silicoaluminophosphate) was prepared by referring to US Patent 6773688. The ratio of starting material was Al: P: Si: TEAOH (tetraethylammonium hydroxide): H ₂ O = 1: 1: 0.3: 2: 52. The precursor solution was reacted at 190 ° C. for 2 days to prepare SAPO-34 having a surface area of 734 m ² / g and a pore volume of 0.57 ml / g. After the carbon adsorbent was vacuum dried at 100 ° C. for 30 minutes, a water adsorption experiment was conducted under the same conditions as in Example 2, and the water adsorption amount was 0.24 g / g.

Experimental Example 1 Measurement of Water Adsorption

0.1 g of each of the adsorbents (porous organic-inorganic hybrids [Fe-BTC]) obtained in Examples 8, 9, and 12 was vacuum dried at 150 ° C. for 30 minutes, and then adsorption experiments of water were carried out by gravimetric method. The result is shown in FIG.

As shown in FIG. 12, the moisture adsorption amount per weight of the adsorbent at 60% relative humidity was 0.28 g / g in Example 8, 0.31 g / g in Example 9, and 0.19 g / g in Example 12 within the initial 5 minutes. Was measured. In particular, it was confirmed that the water adsorption rate (initial water adsorption rate) in all areas from the initial stage of adsorption to 5 minutes was very fast. When the porous organic-inorganic hybrid is used as a low temperature moisture adsorbent, it exhibits easy desorption properties even at 100 ° C. or lower, and it can be seen that very excellent performance can be achieved by using such properties.

Experimental Example 2 Desorption Experiment

0.02 g each of the adsorbent (porous organic-inorganic hybrid [Fe-BTC]) obtained in Example 8 and SAPO-34 obtained in Comparative Example 3 was exposed to saturated NH ₄ Cl vapor to sufficiently adsorb moisture to the adsorbent, The temperature was changed to 70 ° C. (Fe-BTC) and 100 ° C. (SAPO-34), and the weight loss of the adsorbent over time was measured twice using thermogravimetric analysis (FIG. 13). Compared with SAPO-34, despite the desorption experiment at 70 ℃ for Fe-BTC, it was confirmed that the water desorption time of 80% by weight was reduced to 1/2 (Fig. 14 (A) SAPO-34 And Figure 14 (B) Fe-BTC). In addition, the maximum weight loss was 25% for SAPO-34 and 40% for Fe-BTC (Fig. 13 (A) SAPO-34 and Fig. 13 (B) Fe-BTC).

All publications, patent applications, registered patents, and other documents mentioned herein are incorporated herein by reference, with each publication, patent application, registered patent, or other document set forth in detail and individually as a whole. It is introduced by reference. Definitions included in documents incorporated by reference are excluded to the extent that they contradict definitions herein.

From the foregoing, it will be understood that various embodiments of the invention have been described herein for purposes of illustration, and that various modifications may be made without departing from the scope and spirit of the invention. Accordingly, the various embodiments disclosed herein are not intended to be limiting, the true scope and spirit of which are set forth in the following claims.

1 is a diagram of an apparatus for treating air according to one illustrative embodiment.

2 is a diagram of a dehumidifying unit according to an exemplary embodiment.

3 is a diagram of an apparatus for treating air according to one illustrative embodiment.

4 is a diagram of an apparatus for treating air according to one illustrative embodiment.

5 is a drawing of an apparatus for treating air according to one illustrative embodiment.

6 is a diagram of an apparatus for treating air according to one illustrative embodiment.

7 is a diagram of an apparatus for treating air according to one illustrative embodiment.

8 is a drawing of an apparatus for treating air according to one illustrative embodiment.

9 is a diagram of an apparatus for treating air according to one illustrative embodiment.

10 is a diagram of an apparatus for treating air according to one illustrative embodiment.

11 is a diagram of an apparatus for treating air according to one illustrative embodiment.

12 is a result of a water adsorption experiment according to one exemplary embodiment.

13 is a result of a desorption experiment according to one exemplary embodiment.

14 is a result of a desorption experiment according to one exemplary embodiment.

Claims (19)

Intake passage through which air is sucked from the outside, Dehumidifier including an adsorbent, for removing moisture from the air sucked through the intake passage, Regeneration means for regenerating the adsorbent of the dehumidifying part, and An air treatment apparatus including an exhaust passage for discharging air from which moisture is removed to the outside, The air treatment device includes two parts of a 2-bed type dehumidifier, and two switch valves, By switching the flow direction of the switch valve, the two-bed dehumidifying part of the two parts can alternately dehumidify and regenerate, And the adsorbent comprises a porous organic-inorganic hybrid formed by combining a central metal ion with an organic ligand. The method of claim 1, The regeneration means includes a regeneration passage for introducing external air of the air treatment device and / or circulating air in the air treatment device, and a heating portion connected to the regeneration passage, The dehumidifying unit includes an adsorption region, which is a region through which air supplied through the intake passage passes, and a regeneration region, which is a region through which air supplied through the regeneration passage passes, The air processing apparatus which desorbs the moisture adsorbed to the adsorbent of the dehumidification part by heating the air which the said heating part moves through a regeneration path, and supplies it to the regeneration area | region of the said dehumidification part. The method of claim 2, And an heat exchanger for performing heat exchange between the exhaust passage and the air in the regeneration passage. The method of claim 1, And an cooling section for cooling air dehumidified by the dehumidifying section in the exhaust passage. The method of claim 1, The dehumidification unit includes a dehumidification rotor having a cylindrical shape including an adsorption region for adsorbing moisture as the air containing moisture passes therethrough, and a regeneration region for desorbing moisture while the heated air passes therethrough, and the dehumidification rotor rotates as the dehumidification rotor rotates. An air treatment apparatus in which the region and the regeneration region are constantly changing. delete The air treatment device of claim 1 wherein the porous organic-inorganic hybrid is capable of adsorbing at least 0.1 g of moisture per gram. The method of claim 1, wherein the porous organic-inorganic hybrid is Sc, Y, Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Tc, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb and Bi An air treatment apparatus comprising at least one metal element selected from the group consisting of: The method of claim 1, wherein the porous organic-inorganic hybrid comprises at least one metal element selected from the group consisting of Ag (I), Cu (II or I) and Ni (II), which are metals having antimicrobial activity. Air treatment unit. The method of claim 1, wherein the porous organic-inorganic hybrid is copper terephthalate, iron terephthalate, manganese terephthalate, chromium terephthalate, vanadium terephthalate, aluminum terephthalate, titanium terephthalate, zirconium terephthalate, magnesium terephthalate, copper benzene Tricarboxylate, Iron Benzene Tricarboxylate, Manganese Benzene Tricarboxylate, Chromium Benzene Tricarboxylate, Vanadium Benzene Tricarboxylate, Aluminum Benzene Tricarboxylate, Titanium Benzene Tricarboxylate, Zirconium Benzene Tri Carboxylate, magnesium benzenetricarboxylate, nickel dihydroxyterephthalate, cobalt dihydroxyterephthalate, magnesium dihydroxyterephthalate, manganese dihydroxyterephthalate, iron dihydroxyterephthalate, iron benzene Benzoate, chromium benzenetricarboxylic benzoate, aluminum benzoate-benzenetricarboxylic, derivatives thereof, their solvates, hydrates thereof or the air treatment apparatus, comprising a combination of the two. The air treatment device according to claim 1, wherein the porous organic-inorganic hybrid is at least one compound selected from a compound represented by the following formula or a hydrate thereof: _{M 3 X (H 2 O)} 2 O [C 6 Z 4-y Z 'y (CO 2) 2] 3 (M = Cu, Fe, Mn, Cr, V, Al, Ti, Zr or Mg; X = Cl, Br, I, F or OH, Z or Z '= H, NH ₂ , Br, I, NO ₂ or OH; 0 ≦ y ≦ 4); M ₃ O (H ₂ O) ₂ X [C ₆ Z _3-y Z ' _y- (CO ₂ ) ₃ ] ₂ (M = Cu, Fe, Mn, Cr, V, Al, Ti, Zr or Mg; X = Cl, Br, I, F or OH; Z or Z '= H, NH ₂ , Br, I, NO ₂ or OH; 0 <y <3); M ₃ O (H ₂ O) ₂ X _1-y (OH) _y [C ₆ H _3- (CO ₂ ) ₃ ] ₂ (0 ≤ y ≤ 1; M = Cu, Fe, Mn, Cr, V, Al , Ti, Zr or Mg; X = Cl, Br, I or F); or M ₃ X _1-y (OH) _y (H ₂ O) ₂ O [C ₆ H ₄ (CO ₂ ) ₂ ] ₃ (0 ≤ y ≤ 1; M = Cu, Fe, Mn, Cr, V, Al, Ti, Zr or Mg; X = Cl, Br, I or F). The air treatment device according to claim 1, wherein the porous organic-inorganic hybrid is at least one compound selected from a compound represented by the following formula or a hydrate thereof: _{M 6 O 4 (OH) 4} [C 6 Z 4-y Z 'y (CO 2) 2] 12 (M = Ti, Sn , or Zr; Z or _{Z' = H, NH 2,} Br, I, NO 2 Or OH, 0 ≦ y ≦ 4); or M ₂ (dhtp) (H ₂ O) ₂ (M = Ni, Co, Mg, Mn and Fe; dhtp = 2,5-dihydroxyterephthalic acid). The method of claim 1, wherein the organic ligand is acid group (-CO ₃ H), of the acid anion group (-CO ₃ ^-), a carboxyl group, a carboxylic anionic group of the acid, an amino group (-NH _2), imino group (

), Amide group (-CONH _2), a sulfonic acid group (-SO ₃ H), a sulfonic acid anion group (-SO ₃ ^-), methane dithiol Osan group (-CS ₂ H), methane dithiol Osan anion group (-CS of ₂ ^-), pyridine group, and a pyrazinyl group which is a mixture compound having at least one functional group selected from the group consisting of or a air processing apparatus. The air treatment device according to claim 1, wherein the porous organic-inorganic hybrid has an unsaturated metal site and a surface functionalizing compound is bonded to the unsaturated metal site. The method of claim 1, wherein the porous organic-inorganic hybrid is powder, thin film, membrane, pellet, ball, foam, slurry, paste, paint, honeycomb, bead, mesh, fiber, corrugated sheet Or in the form of a rotor. The method of claim 1, wherein the dehumidifying unit is one selected from the group consisting of platinum, silver, gold, palladium, ruthenium, rhodium, osmium, iridium, manganese, copper, cobalt, chromium, nickel, iron, zinc and combinations thereof. An air treatment apparatus further comprising the above metal catalyst. The air treatment apparatus according to claim 1 or 16, which is capable of removing hydrocarbons, NOx, CO or volatile organic compounds contained in air introduced from the outside. The air treatment apparatus according to claim 1, wherein the dehumidifying unit further comprises at least one dehumidifying agent selected from the group consisting of zeolite, activated alumina, lithium chloride, activated carbon, aluminum silicate, calcium chloride and calcium carbonate. Air treatment device comprising: A two-part adsorption unit including an adsorbent, which can alternately adsorb or desorb the refrigerant, A condenser to condense the refrigerant desorbed from the adsorption unit, An evaporator capable of evaporating refrigerant to provide a cooling effect, A refrigerant passage connecting the adsorption unit, the condenser and the evaporator, and through which the refrigerant flows; A flow control valve installed on the refrigerant passage, Here, the evaporator and the condenser are respectively installed between the two portions of the adsorption unit, The adsorbent comprises a porous organic-inorganic hybrid formed by combining a central metal ion with an organic ligand.

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