CN111138672B - Metal organic framework material, preparation method thereof and adsorption device comprising metal organic framework material - Google Patents
Metal organic framework material, preparation method thereof and adsorption device comprising metal organic framework material Download PDFInfo
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- CN111138672B CN111138672B CN201910969688.7A CN201910969688A CN111138672B CN 111138672 B CN111138672 B CN 111138672B CN 201910969688 A CN201910969688 A CN 201910969688A CN 111138672 B CN111138672 B CN 111138672B
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- 239000000463 material Substances 0.000 title claims abstract description 147
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 124
- 238000002360 preparation method Methods 0.000 title claims abstract description 118
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 107
- MPFLRYZEEAQMLQ-UHFFFAOYSA-N dinicotinic acid Chemical compound OC(=O)C1=CN=CC(C(O)=O)=C1 MPFLRYZEEAQMLQ-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 19
- -1 aluminum ion Chemical class 0.000 claims abstract description 11
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 5
- 229910001430 chromium ion Inorganic materials 0.000 claims abstract description 5
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims description 74
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 69
- 238000000034 method Methods 0.000 claims description 54
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 33
- 150000002736 metal compounds Chemical class 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 23
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 19
- 239000003463 adsorbent Substances 0.000 claims description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- ANBBXQWFNXMHLD-UHFFFAOYSA-N aluminum;sodium;oxygen(2-) Chemical compound [O-2].[O-2].[Na+].[Al+3] ANBBXQWFNXMHLD-UHFFFAOYSA-N 0.000 claims description 14
- 229910001388 sodium aluminate Inorganic materials 0.000 claims description 14
- 150000004645 aluminates Chemical class 0.000 claims description 13
- 238000010438 heat treatment Methods 0.000 claims description 12
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 10
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 6
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 5
- CMOAHYOGLLEOGO-UHFFFAOYSA-N oxozirconium;dihydrochloride Chemical compound Cl.Cl.[Zr]=O CMOAHYOGLLEOGO-UHFFFAOYSA-N 0.000 claims description 4
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 claims description 4
- YQNQTEBHHUSESQ-UHFFFAOYSA-N lithium aluminate Chemical compound [Li+].[O-][Al]=O YQNQTEBHHUSESQ-UHFFFAOYSA-N 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- KVOIJEARBNBHHP-UHFFFAOYSA-N potassium;oxido(oxo)alumane Chemical compound [K+].[O-][Al]=O KVOIJEARBNBHHP-UHFFFAOYSA-N 0.000 claims description 3
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical class [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 claims description 2
- ILRRQNADMUWWFW-UHFFFAOYSA-K aluminium phosphate Chemical compound O1[Al]2OP1(=O)O2 ILRRQNADMUWWFW-UHFFFAOYSA-K 0.000 claims description 2
- XFWJKVMFIVXPKK-UHFFFAOYSA-N calcium;oxido(oxo)alumane Chemical compound [Ca+2].[O-][Al]=O.[O-][Al]=O XFWJKVMFIVXPKK-UHFFFAOYSA-N 0.000 claims description 2
- 150000001844 chromium Chemical class 0.000 claims description 2
- 229910000151 chromium(III) phosphate Inorganic materials 0.000 claims description 2
- IKZBVTPSNGOVRJ-UHFFFAOYSA-K chromium(iii) phosphate Chemical compound [Cr+3].[O-]P([O-])([O-])=O IKZBVTPSNGOVRJ-UHFFFAOYSA-K 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000003754 zirconium Chemical class 0.000 claims description 2
- 229910000166 zirconium phosphate Inorganic materials 0.000 claims description 2
- LEHFSLREWWMLPU-UHFFFAOYSA-B zirconium(4+);tetraphosphate Chemical compound [Zr+4].[Zr+4].[Zr+4].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O LEHFSLREWWMLPU-UHFFFAOYSA-B 0.000 claims description 2
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 34
- 230000000052 comparative effect Effects 0.000 description 21
- 238000010521 absorption reaction Methods 0.000 description 20
- 239000003960 organic solvent Substances 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 239000007787 solid Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000003795 desorption Methods 0.000 description 10
- 239000000843 powder Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 229910021536 Zeolite Inorganic materials 0.000 description 6
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 6
- 239000002244 precipitate Substances 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000010457 zeolite Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 238000002411 thermogravimetry Methods 0.000 description 4
- 239000006227 byproduct Substances 0.000 description 3
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical group OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 description 3
- 239000003446 ligand Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 2
- 238000005265 energy consumption Methods 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 208000016261 weight loss Diseases 0.000 description 2
- 230000004580 weight loss Effects 0.000 description 2
- CABMTIJINOIHOD-UHFFFAOYSA-N 2-[4-methyl-5-oxo-4-(propan-2-yl)-4,5-dihydro-1H-imidazol-2-yl]quinoline-3-carboxylic acid Chemical compound N1C(=O)C(C(C)C)(C)N=C1C1=NC2=CC=CC=C2C=C1C(O)=O CABMTIJINOIHOD-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- GISRWBROCYNDME-PELMWDNLSA-N F[C@H]1[C@H]([C@H](NC1=O)COC1=NC=CC2=CC(=C(C=C12)OC)C(=O)N)C Chemical compound F[C@H]1[C@H]([C@H](NC1=O)COC1=NC=CC2=CC(=C(C=C12)OC)C(=O)N)C GISRWBROCYNDME-PELMWDNLSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 239000013065 commercial product Substances 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 208000020442 loss of weight Diseases 0.000 description 1
- MJIVRKPEXXHNJT-UHFFFAOYSA-N lutidinic acid Chemical compound OC(=O)C1=CC=NC(C(O)=O)=C1 MJIVRKPEXXHNJT-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- WHQSYGRFZMUQGQ-UHFFFAOYSA-N n,n-dimethylformamide;hydrate Chemical compound O.CN(C)C=O WHQSYGRFZMUQGQ-UHFFFAOYSA-N 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/26—Drying gases or vapours
- B01D53/261—Drying gases or vapours by adsorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/80—Water
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a metal organic framework material, a preparation method thereof and an adsorption device containing the metal organic framework material. The metal-organic framework material comprises 3, 5-pyridinedicarboxylic acid; and a metal ion that is an aluminum ion, a chromium ion, or a zirconium ion, wherein the 3, 5-pyridinedicarboxylic acid is coordinated to the metal ion.
Description
Technical Field
The invention relates to a metal organic framework material and a preparation method thereof, in particular to a metal organic framework material with good adsorbability under low humidity.
Background
Water vapor adsorbents are currently widely used in adsorption dryers in compressed air systems. After passing through the air compressor, the outside air is in a state of humidity higher than 80% Relative Humidity (RH), and most of moisture in the compressed air needs to be removed by the freeze dryer, and then a small amount of residual moisture in the compressed air needs to be removed by the adsorption dryer. After the compressed air is processed by the freeze dryer, the humidity of the compressed air is reduced to below about 30% RH, and a small amount of residual moisture in the compressed air is removed by the adsorption dryer. Therefore, the adsorbent suitable for the aforementioned equipment must have high moisture adsorption rate in an extremely low relative humidity environment, which is very helpful for the volume, construction cost and operation efficiency of the equipment.
Although the traditional water-gas adsorbent 4A zeolite still has good water-gas adsorption rate in a low-humidity environment, the high hydrophilicity of the traditional water-gas adsorbent increases the difficulty of water-gas desorption. Generally, the 4A zeolite is required to be at a temperature of 140-160 ℃ or higher for moisture desorption. However, high temperature desorption not only causes a large amount of energy consumption in the regeneration of the adsorbent, but also increases inconvenience in use. In view of the above, there is a need for an adsorbent that can be desorbed at low temperatures and can adsorb moisture in a low humidity environment.
However, the current adsorbent is limited to the situation of small adsorption capacity under low humidity and desorption temperature higher than 140 ℃, which increases the cost of equipment construction and operation, and the energy consumption of the equipment is high.
Therefore, there is a need for a novel metal organic frame material to solve the problems encountered in the prior art.
Disclosure of Invention
According to one aspect of the present invention, there is provided a metal organic framework material comprising 3, 5-pyridinedicarboxylic acid; and a metal ion, wherein the metal ion is an aluminum ion, a chromium ion, or a zirconium ion, wherein the 3, 5-pyridinedicarboxylic acid is coordinated to the metal ion.
According to another aspect of the present invention, the present invention provides a method for preparing a metal organic framework material, which is used for preparing the metal organic framework material. The preparation method of the metal organic framework material comprises the following steps: providing a composition, wherein the composition comprises 3, 5-pyridinedicarboxylic acid, a metal compound, and a solvent; and heating the composition to react the 3, 5-pyridinedicarboxylic acid with the metal compound to obtain the metal-organic framework material. According to still another aspect of the present invention, the solvent includes at least one selected from the group consisting of an organic solvent, and water.
Drawings
FIG. 1 is a thermogravimetric analysis test chart of example 1 of the present invention.
FIG. 2 is a graph showing a test of an isothermal adsorption curve in example 1 of the present invention.
FIG. 3 shows examples 1,
Adsorption test patterns of product number a520, activated alumina and 4A zeolite powder under different humidity.
FIG. 4 shows examples 1 and 4 of the present invention
Adsorption test pattern of article No. a520 at 30% RH.
FIG. 5 is a graph of the adsorption test at 80% RH for example 1 of the present invention.
FIG. 6 is a schematic view of an adsorption apparatus according to the present invention.
Wherein the reference numerals are:
100 an adsorption device;
120 a carrier;
140 adsorbing the material.
Detailed Description
Embodiments of the present invention provide a metal organic framework material, a method for preparing the same, and an adsorption apparatus including the metal organic framework material. The metal organic framework material has a rapid moisture absorption effect under low humidity, and the low humidity condition is defined as that the relative humidity is below 30% RH at a temperature of 25 ℃. The metal organic framework material can be further configured on a carrier to be used as an adsorption device for an adsorption dryer to achieve the purpose of rapid moisture absorption in a low-humidity environment.
According to an embodiment of the present invention, there is provided a metal organic framework material. The metal-organic framework material comprises 3, 5-pyridinedicarboxylic acid; and a metal ion, wherein the metal ion is an aluminum ion, a chromium ion, or a zirconium ion, wherein the 3, 5-pyridinedicarboxylic acid is coordinated to the metal ion. The molar ratio of the 3, 5-pyridinedicarboxylic acid to the metal ion is between 3:1 and 1: 2. If the molar ratio of the 3, 5-pyridinedicarboxylic acid to the metal ions is less than 1:2, a porous material cannot be formed, so that the water absorption rate is too low; if the molar ratio of 3, 5-pyridinedicarboxylic acid to metal ion is higher than 3:1, a porous material is likewise not formed, and the water absorption rate is deteriorated.
According to an embodiment of the present invention, there is provided a method for preparing the metal organic framework material. First, a composition is provided, wherein the composition comprises 3, 5-pyridinedicarboxylic acid, a metal compound, and a solvent. Next, the composition is heated to react the 3, 5-pyridinedicarboxylic acid with the metal compound to obtain the metal-organic framework material.
According to an embodiment of the invention, wherein the molar ratio of the 3, 5-pyridinedicarboxylic acid to the metal compound is between 3:1 and 1:2, such as 2:1, or 1: 1.
According to an embodiment of the present invention, wherein the metal compound may be at least one selected from the group consisting of an aluminum salt, a chromium salt, and a zirconium salt. Wherein the metal compound may be at least one selected from the group consisting of aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum phosphate, chromium nitrate, chromium phosphate, zirconium nitrate, zirconium phosphate, and zirconium oxychloride.
According to an embodiment of the present invention, wherein the initial concentration of the metal compound in the composition may be between 0.15mol/L and 0.66mol/L, based on the volume of the composition.
According to embodiments of the invention, the temperature of the heating may be about 100 ℃ to 150 ℃, e.g., 110 ℃ to 140 ℃. Further, the heating time may be 1 to 66 hours.
According to an embodiment of the present invention, the solvent includes at least one selected from the group consisting of an organic solvent, and water. According to some embodiments of the invention, the solvent is an organic solvent. According to some embodiments of the invention, the solvent is water. According to some embodiments of the invention, the solvent may consist of water and an organic solvent, wherein the weight ratio of organic solvent to water may be between 1:99 and 99:1 (e.g., 1:99 to 1:29, 1:99 to 1:1, 10:90 to 2:1, or 1:1 to 99: 1). For example, the weight ratio of organic solvent to water can be 4:1, 2:1, 1:2, 1:4, or 1: 8. The organic solvent according to the present invention may be at least one selected from the group consisting of N, N-dimethylformamide, N-diethylformamide, and N, N-dimethylacetamide. According to some embodiments of the invention, the solvent is at least one selected from the group consisting of water, N-dimethylformamide, N-diethylformamide, and N, N-dimethylacetamide.
According to an embodiment of the present invention, the composition may be composed of 3, 5-pyridinedicarboxylic acid, a metal compound, and an organic solvent. When the composition consists of 3, 5-pyridinedicarboxylic acid, a metal compound, and an organic solvent, the temperature of heating may be about 100 ℃ to 150 ℃ (e.g., 120 ℃ to 140 ℃); the time of heating can be 12 to 66 hours, e.g., 12 to 48 hours, or 24 to 48 hours; and, the initial concentration of the metal compound in the composition may be between 0.15mol/L and 0.33mol/L, based on the volume of the composition.
According to an embodiment of the invention, when the solvent is water, the composition further comprises an alkali metal hydroxide. In other words, the composition may consist of 3, 5-pyridinedicarboxylic acid, a metal compound, water, and an alkali metal hydroxide. The alkali metal hydroxide includes at least one selected from the group consisting of lithium hydroxide (lithium hydroxide), sodium hydroxide (sodium hydroxide), and potassium hydroxide (potassium hydroxide).
According to an embodiment of the invention, when the solvent is water, the composition further comprises an alkali metal hydroxide and an aluminate. In other words, the composition may consist of 3, 5-pyridinedicarboxylic acid, a metal compound, water, an alkali metal hydroxide, and an aluminate. The aluminate includes at least one selected from the group consisting of lithium aluminate (lithium aluminate), sodium aluminate (sodium aluminate), potassium aluminate (potassium aluminate), magnesium aluminate (magnesium aluminate), and calcium aluminate. Further, the initial concentration of the aluminate in the composition is between 0.05mol/L and 0.20mol/L (e.g., between 0.05mol/L and 0.15mol/L), based on the volume of the composition.
According to an embodiment of the invention, the composition does not comprise alcohol. According to a certain embodiment of the invention, when the solvent is water, the composition does not comprise alcohol.
According to an embodiment of the invention, when the solvent is water, the alkali metal hydroxide is added in order to neutralize the 3, 5-pyridinedicarboxylic acid in the composition, so as to maintain the composition (aqueous solution) near neutral (i.e. the pH of the composition is between 6 and 8), forming a composition that is soluble in water. For the reasons mentioned above, the molar ratio of the alkali metal hydroxide to the 3, 5-pyridinedicarboxylic acid may be from 1.8 to 2.2, for example 2. Therefore, when the molar ratio of the alkali metal hydroxide to the 3, 5-pyridinedicarboxylic acid is too low or too high, or the alkali metal hydroxide cannot completely neutralize the 3, 5-pyridinedicarboxylic acid in the composition, or the alkali metal hydroxide is present in the composition in an excessive amount, both of them make it impossible to maintain the pH of the composition between 6 and 8, resulting in poor adsorption rate of moisture to the resulting metal-organic framework material, or even failure to obtain the metal-organic framework material.
According to an embodiment of the present invention, when the solvent is water, the addition of aluminate to the composition can inhibit the formation of crystalline by-products when the 3, 5-pyridinedicarboxylic acid reacts with the metal compound, so as to avoid the crystalline by-products from affecting the water absorption rate of the resulting metal organic framework material.
According to the embodiment of the present invention, when the solvent is water, the waste liquid generated after the reaction of the 3, 5-dipicolinic acid and the metal compound does not contain an organic solvent, so that the cost for treating the waste liquid can be reduced, and the environmental pollution can be reduced. On the other hand, when the composition consists of 3, 5-pyridinedicarboxylic acid, a metal compound, water, an alkali metal hydroxide, and an aluminate, the temperature of heating may be about 100 ℃ to 150 ℃ (e.g., 110 ℃ to 130 ℃); the heating time may be 2 to 3 hours; and, the initial concentration of the metal compound in the composition may be between 0.15mol/L and 0.66mol/L, based on the volume of the composition. Therefore, when the solvent is water, the preparation time of the metal organic framework material can be greatly shortened, and the production efficiency of the metal organic framework material is improved.
According to an embodiment of the present invention, when the solvent consists of water and an organic solvent, and the weight ratio of the organic solvent to the water is 1:29 to 1:99, the composition further comprises an alkali metal hydroxide and an aluminate. According to some embodiments of the present invention, when the weight ratio of the organic solvent to water is 1:29 to 1:99, if the composition does not include the alkali metal hydroxide and/or aluminate, the resulting metal-organic framework material has a poor adsorption rate of moisture, and even the metal-organic framework material cannot be obtained. In addition, the initial concentration of the aluminate in the composition is between 0.05mol/L and 0.20mol/L (e.g., between 0.05mol/L and 0.15mol/L), based on the volume of the composition.
According to an embodiment of the present invention, there is provided an adsorption apparatus (100). The adsorption device comprises a carrier (120), and an adsorption material (140). The adsorbent material (140) may be disposed on the carrier (120). The adsorbent material may include 3, 5-dipicolinic acid, and a metal ion, wherein the metal ion is an aluminum ion, a chromium ion, or a zirconium ion, wherein the 3, 5-dipicolinic acid is coordinated to the metal ion. According to the embodiment of the invention, the adsorption rate of the adsorption device on moisture can reach 18 wt% to 40 wt% after the adsorption device is placed in an environment with 30% RH (relative humidity) and 25 ℃ for 30 minutes. Here, the adsorption rate of moisture according to the present invention is determined by the following formula:
W1is the weight of the material after moisture absorption, W0The weight obtained after desorption of the water from the material at 80 ℃.
According to the embodiment of the invention, the adsorbing material can be applied to low-humidity environments, and can be used in adsorption dryers, such as high-pressure air dryers and plastic dryers. And the adsorbent material can also be used as an adsorbent for removing specific polar harmful small molecules or gases.
In order to make the aforementioned and other objects, features, and advantages of the present invention comprehensible, several embodiments accompanied with figures are described in detail below:
preparation example of Metal organic framework Material
Preparation example 1
First, aluminum nitrate (Al (NO)3)3·9H2O) (0.015mol), 3, 5-pyridinedicarboxylic acid (0.015mol), 72 ml of water were mixed with 18 ml of N, N-dimethylformamide, the molar ratio of 3, 5-pyridinedicarboxylic acid to aluminum nitrate being 1: 1. Subsequently, the resultant composition was reacted at 120 ℃ for 48 hours with uniform stirring. Subsequently, after allowing the reaction to cool to room temperature, a yellow precipitate was obtained. The yellow precipitate was washed with water and filtered to give a yellow solid. The resulting yellow solid was then dried in an oven overnight at a temperature of about 140 ℃. After drying, the yellow solid was ground to a powder. The powdery solid was then vacuum dried using a vacuum oven, wherein the temperature of the vacuum drying was about 140 ℃ for about 6 hours. After cooling to room temperature, the metal organic framework material (pale yellow powder) (1) was obtained. The specific surface area of the metal organic framework material measured by a specific surface area and porosity analyzer is 1133m2The water-gas adsorption rate was 34.48 wt%. The calculation method of the water-gas adsorption rate comprises the following steps:
W1w is the weight after 30 minutes in an environment of 30% RH (relative humidity) and 25 deg.C0The weight obtained after desorption of the water from the material at 80 ℃.
Preparation example 2
The procedure was carried out in the manner as described in preparation example 1, except that the molar ratio of 3, 5-pyridinedicarboxylic acid to aluminum nitrate was increased from 1:1 to 2:1 to obtain a metal-organic framework material (2) having a moisture adsorption rate of 34.96 wt%.
Preparation example 3
The procedure was carried out in the manner as described in preparation example 1, except that the molar ratio of 3, 5-pyridinedicarboxylic acid to aluminum nitrate was increased from 1:1 to 3:1 to obtain a metal-organic framework material (3) having a moisture adsorption rate of 33.81 wt%.
Preparation example 4
The procedure was carried out in the manner as described in preparation example 1, except that the molar ratio of 3, 5-pyridinedicarboxylic acid to aluminum nitrate was increased from 1:1 to 4:1 to obtain a metal-organic framework material (4) having a moisture adsorption rate of 13.4% by weight.
Preparation example 5
The procedure was carried out in the manner as described in preparation example 1, except that the molar ratio of 3, 5-pyridinedicarboxylic acid to aluminum nitrate was reduced from 1:1 to 1:2, to give a metal-organic framework material (5) having a moisture adsorption rate of 28.42% by weight.
Preparation example 6
The procedure was carried out as described in preparation example 1, except that the molar ratio of 3, 5-pyridinedicarboxylic acid to aluminum nitrate was reduced from 1:1 to 1:3, giving a metal-organic framework material (6) having a moisture adsorption rate of 17.85% by weight.
Preparation example 7
The procedure was carried out as described in preparation example 1, except that water was increased from 72 ml to 87 ml and N, N-dimethylformamide was decreased from 18 ml to 3ml, to give a metal-organic framework material (7) having a moisture adsorption of 34.90 wt%.
Preparation example 8
The procedure was carried out as described in preparation example 1, except that the addition volumes of water and N, N-dimethylformamide were adjusted from 72 ml and 18 ml to 81 ml and 9ml, to give a metal-organic framework material (8) having a moisture adsorption rate of 35.20% by weight.
Preparation example 9
The procedure was carried out as described in preparation example 1, except that water was increased from 72 ml to 76.5 ml and N, N-dimethylformamide was decreased from 18 ml to 13.5 ml, to give a metal-organic framework material (9) having a moisture adsorption rate of 34.30% by weight.
Preparation example 10
The procedure was carried out as described in preparation example 1, except that water was increased from 72 ml to 75 ml and dimethylformamide was decreased from 18 ml to 15 ml, to give a metal-organic framework material (10) having a moisture adsorption rate of 35.66 wt%.
Preparation example 11
The procedure was carried out as described in preparation example 1, except that water was reduced from 72 ml to 67.5 ml and dimethylformamide was increased from 18 ml to 22.5 ml, to give a metal-organic framework material (11) having a moisture adsorption rate of 34.99 wt%.
Preparation example 12
The procedure was carried out as described in preparation example 1, except that water was reduced from 72 ml to 54 ml and N, N-dimethylformamide was increased from 18 ml to 36 ml, to give a metal-organic framework material (12) having a moisture adsorption rate of 31.17% by weight.
Preparation example 13
The procedure was carried out as described in preparation example 1, except that water was reduced from 72 ml to 30 ml and N, N-dimethylformamide was increased from 18 ml to 60 ml, to give a metal-organic framework material (13) having a moisture adsorption rate of 29.61 wt%.
Preparation example 14
The procedure was carried out in the same manner as described in preparation example 1 except that 90 ml of dimethylformamide was substituted for 72 ml of water and 18 ml of N, N-dimethylformamide to give a metal-organic framework material (14) having a water-gas adsorption rate of 20.94% by weight.
Preparation example 15
The procedure was carried out as described in preparation example 1, except that aluminum nitrate was replaced by aluminum sulfate (Al)2(SO4)3·18H2O) and adjusting the molar ratio of 3, 5-pyridinedicarboxylic acid to aluminum sulfate to 2:1 to obtain a metal-organic framework material (15) having a moisture adsorption rate of 25.3 wt%.
Preparation example 16
The procedure was carried out as described in preparation example 1, except that aluminum nitrate was replaced by zirconium oxychloride (ZrOCl)2·8H2O) (molar ratio of 3, 5-pyridinedicarboxylic acid to zirconium oxychloride1:1) to obtain a metal organic framework material (16).
Preparation example 17
The procedure was carried out as described in preparation example 1, except that aluminum nitrate was replaced by chromium nitrate (Cr (NO)3)3·9H2O) (molar ratio of 3, 5-pyridinedicarboxylic acid to chromium nitrate 1:1) to obtain a metal-organic framework material (17) having a moisture adsorption rate of 22.05 wt%.
Comparative example 1
The procedure was carried out as described in preparation example 1, except that aluminum nitrate was replaced by iron nitrate (Fe (NO)3)3·9H2O) (molar ratio of 3, 5-pyridinedicarboxylic acid to ferric nitrate was 1:1), giving a metal-organic framework material (18) having a moisture adsorption rate of 0.79 wt%.
Comparative example 2
The procedure was carried out in the manner described in preparation example 1, except that aluminum nitrate was replaced by copper nitrate (Cu (NO)3)2·3H2O) (molar ratio of 3, 5-pyridinedicarboxylic acid to copper nitrate was 1:1), giving a metal-organic framework material (19) having a moisture adsorption rate of 0.66 wt%.
Comparative example 3
The procedure was carried out as described in preparation example 1, except that 3, 5-dipicolinic acid was replaced with 2, 6-dipicolinic acid (molar ratio of 2, 6-dipicolinic acid to aluminum nitrate was 1:1), to obtain a metal-organic framework material (20) having a moisture adsorption rate of 0 wt%.
Comparative example 4
The procedure was carried out in the manner as described in preparation example 1, except that 3, 5-dipicolinic acid was replaced with 2, 4-dipicolinic acid (molar ratio of 2, 4-dipicolinic acid to aluminum nitrate was 1:1), to obtain a metal-organic framework material (21) having a moisture adsorption rate of 9.8 wt%.
Comparative example 5
First, aluminum nitrate (0.015mol), 3, 5-dipicolinic acid (0.015mol) and 90 ml of water were mixed, wherein the molar ratio of 3, 5-dipicolinic acid to aluminum nitrate was 1: 1. Subsequently, the resultant composition was reacted at 120 ℃ for 48 hours with uniform stirring. Subsequently, after allowing the reaction to cool to room temperature, a yellow precipitate was obtained. The yellow precipitate was washed with water and filtered to give a yellow solid. The resulting yellow solid was then dried in an oven overnight at a temperature of about 140 ℃. After drying, the yellow solid was ground to a powder. The powdery solid was then vacuum dried using a vacuum oven, wherein the temperature of the vacuum drying was about 140 ℃ for about 6 hours. After cooling to room temperature, no metal-organic framework material could be obtained.
Table 1 shows the moisture adsorption rates of the metal organic framework materials described in preparation example 1 and comparative examples 1 to 5.
TABLE 1
| Water gas adsorption rate (wt%) | |
| Preparation example 1 | 34.48 |
| Comparative example 1 | 0.79 |
| Comparative example 2 | 0.66 |
| Comparative example 3 | 0 |
| Comparative example 4 | 9.8 |
| Comparative example 5 | The metal organic frame material cannot be obtained |
As can be seen from Table 1, the metal organic framework material of the present invention can achieve a moisture adsorption rate of about 35 wt% when using a specific ligand (e.g., 3, 5-pyridinedicarboxylic acid) and a suitable metal ion. On the contrary, even though ligands with similar structures (such as 2, 4-pyridinedicarboxylic acid or 2, 6-pyridinedicarboxylic acid) are selected, the effect of water vapor adsorption cannot be achieved (such as comparative examples 3 and 4). If an unsuitable metal ion (such as iron ion or copper ion) is used together with a specific ligand (such as 3, 5-pyridinedicarboxylic acid), the water vapor adsorption rate of the obtained metal-organic framework material is not good (the water vapor adsorption rate is also less than 1 wt%) (as in comparative examples 1 and 2). Furthermore, as can be seen from comparative example 5, if only water is used as a solvent (i.e., the organic solvent, the alkali metal hydroxide, and the aluminate are not included) in the composition for preparing the metal-organic framework material, the metal-organic framework material cannot be obtained.
Preparation example 18
First, 3, 5-pyridinedicarboxylic acid (9mmol), sodium hydroxide (18mmol) and 15.78 ml of water were mixed, followed by addition of an aqueous aluminum nitrate solution (Al (NO)3)3·9H2O) (1M, 6.75mmol) and aqueous sodium aluminate solution (NaAlO)2) (0.5M, 2.25mmol) to give a composition. Wherein in the composition, the molar ratio of 3, 5-dipicolinic acid to aluminum nitrate is 4:3, the initial concentration of aluminum nitrate in the composition is 0.28mol/L, and the initial concentration of sodium aluminate in the composition is 0.09 mol/L. Subsequently, the resultant composition was reacted at 130 ℃ for 3 hours with uniform stirring. Then, after allowing the reaction to cool to room temperature, a precipitate was obtained. The precipitate was washed with water and filtered to give a solid. The resulting solid was then dried in an oven overnight at a temperature of about 80 ℃. After drying, the solid was ground into a powder to obtain a metal organic framework material (22) having a moisture adsorption rate of 33.65 wt%.
Although preparation example 18 used water as a solvent as in comparative example 5, since the composition used in preparation example 18 to prepare a metal-organic framework material further contained an alkali metal hydroxide (i.e., sodium hydroxide), the composition (aqueous solution) could be maintained near neutral, resulting in a composition that was soluble in water. In contrast, the composition for preparing a metal-organic framework material of comparative example 5 does not contain an alkali metal hydroxide, and thus a metal-organic framework material cannot be obtained.
Preparation example 19
The procedure was carried out in the same manner as described in preparation example 18, except that the aqueous sodium aluminate solution was not added, to obtain a metal-organic framework material (23) having a moisture adsorption rate of 25.43% by weight.
Preparation example 20
The procedure was carried out in the same manner as described in preparation example 18, except that the initial concentration of sodium aluminate in the composition was adjusted from 0.09mol/L to 0.05mol/L, to obtain a metal-organic framework material (24) having a moisture adsorption rate of 32.13% by weight.
Preparation example 21
The procedure was carried out in the same manner as described in preparation example 18, except that the initial concentration of sodium aluminate in the composition was adjusted from 0.09mol/L to 0.07mol/L, to obtain a metal-organic framework material (25) having a moisture adsorption rate of 31.80% by weight.
Preparation example 22
The procedure was carried out in the same manner as described in preparation example 18, except that the initial concentration of sodium aluminate in the composition was adjusted from 0.09mol/L to 0.11mol/L, to obtain a metal-organic framework material (26) having a moisture adsorption rate of 33.47 wt%.
Preparation example 23
The procedure was carried out in the same manner as described in preparation example 18, except that the initial concentration of sodium aluminate in the composition was adjusted from 0.09mol/L to 0.15mol/L, to obtain a metal-organic framework material (27) having a moisture adsorption rate of 27.77% by weight.
Table 2 shows the water vapor adsorption rates of the metal-organic framework materials described in preparation examples 18 to 23.
TABLE 2
As can be seen from Table 2, when the solvent used to prepare the composition for a metal-organic framework material according to the present invention is water, the composition with sodium aluminate (the initial concentration of the aqueous sodium aluminate solution may be between 0.05mol/L and 0.15mol/L) can increase the moisture adsorption rate of the resulting metal-organic framework material, as compared to the composition without sodium aluminate. This is because sodium aluminate can act as an inhibitor in the composition, avoiding the formation of crystalline by-products when 3, 5-pyridinedicarboxylic acids react with metal compounds.
Preparation example 24
The procedure was carried out as described in preparation example 18, except that the reaction temperature of the composition was lowered from 130 ℃ to 110 ℃ to give a metal-organic framework material (28) having a moisture adsorption rate of 32.17% by weight.
Preparation example 25
The procedure was carried out as described in preparation example 18, except that the reaction temperature of the composition was lowered from 130 ℃ to 120 ℃ to obtain a metal-organic framework material (29) having a moisture adsorption rate of 32.67% by weight.
As can be seen from preparation examples 18, 24 and 25, when the composition for preparing a metal organic framework material has a solution of water, the reaction temperature of the composition may be 110 ℃ to 130 ℃.
Preparation example 26
The procedure was carried out as described in preparation example 18, except that the reaction time was reduced from 3 hours to 2 hours, to give a metal-organic framework material (30) having a moisture adsorption rate of 32.31% by weight.
As can be seen from preparation examples 18 and 26, when the composition for preparing a metal organic framework material has water as a solution, the reaction time of the composition may be 2 to 3 hours.
Preparation example 27
The procedure was carried out as described in preparation 18, except that aluminum nitrate was replaced by zirconium oxychloride (ZrOCl)2·8H2O) to obtain the metal-organic framework material (31).
Preparation example 28
The procedure was carried out as described in preparation 18, except that aluminum nitrate was replaced by chromium nitrate (Cr (NO)3)3·9H2O) to obtain the metal-organic framework material (32).
Preparation example 29
The procedure was carried out as described in preparation 18, except that aluminum nitrate was replaced by aluminum sulfate (Al)2(SO4)3·14H2O) to obtain a metal-organic framework material (33)) The water-gas adsorption rate was 30.85 wt%.
Preparation example 30
The procedure was carried out as described in preparation 18, except that aluminum nitrate was replaced by aluminum chloride (AlCl)3·6H2O) to obtain a metal-organic framework material (34) having a moisture adsorption rate of 33.25 wt%.
Preparation example 31
The procedure was carried out as described in preparation example 18, except that the molar ratio of 3, 5-pyridinedicarboxylic acid to aluminum nitrate was adjusted from 4:3 to 2:1, to obtain a metal-organic framework material (35) having a moisture adsorption rate of 31.86% by weight.
Preparation example 32
The procedure was carried out as described in preparation example 18, except that the molar ratio of 3, 5-pyridinedicarboxylic acid to aluminum nitrate was adjusted from 4:3 to 1:1, to obtain a metal-organic framework material (36) having a moisture adsorption rate of 30.68% by weight.
Preparation example 33
The procedure was carried out as described in preparation example 18, except that the molar ratio of 3, 5-pyridinedicarboxylic acid to aluminum nitrate was adjusted from 4:3 to 1:2, to obtain a metal-organic framework material (37) having a moisture adsorption rate of 30.67 wt%.
Preparation example 34
The procedure was followed as described in preparation 18, except that the initial concentration of aluminum nitrate was reduced from 0.28mol/L to 0.22mol/L, to give a metal-organic framework material (38) having a moisture adsorption rate of 31.86 wt%.
Preparation example 35
The procedure was carried out as described in preparation example 18, except that the initial concentration of aluminum nitrate was increased from 0.28mol/L to 0.33mol/L to give a metal-organic framework material (39) having a moisture adsorption rate of 30.68 wt%.
Preparation example 36
The procedure was carried out as described in preparation example 18, except that the initial concentration of aluminum nitrate was increased from 0.28mol/L to 0.56mol/L to give a metal-organic framework material (40) having a moisture adsorption rate of 30.67 wt%.
Preparation example 37
The procedure was carried out in the same manner as described in preparation example 18, except that the initial concentration of aluminum nitrate was increased from 0.28mol/L to 0.66mol/L to obtain a metal-organic framework material (41) having a moisture adsorption rate of 30.24 wt%.
As can be seen from preparation examples 18, 34 to 37, when the solvent of the composition for preparing a metal organic framework material is water, the initial concentration of aluminum nitrate in the composition may be 0.22mol/L to 0.66 mol/L.
Preparation example 38
The procedure was carried out in the manner as described in preparation example 18, except that 3mL of ethanol was further added to the composition before the reaction, to obtain a metal-organic framework material (42) having a moisture adsorption rate of 32.71 wt%.
Preparation example 39
The procedure was carried out in the manner as described in preparation example 18, except that 6mL of ethanol was further added to the composition before the reaction, to obtain a metal-organic framework material (43) having a water vapor adsorption rate of 33.92 wt%.
Preparation example 40
The procedure was carried out in the manner as described in preparation example 18, except that 9mL of ethanol was further added to the composition before the reaction, to obtain a metal-organic framework material (44) having a moisture adsorption rate of 33.88 wt%.
Table 3 shows the moisture adsorption rates of the metal organic framework materials of preparation examples 18, and 38 to 40.
TABLE 3
| Ethanol addition amount (mL) | Water gas adsorption rate (wt%) | |
| Preparation example 18 | 0 | 33.65 |
| Preparation example38 | 3 | 32.71 |
| Preparation example 39 | 6 | 33.92 |
| Preparation example 40 | 9 | 33.88 |
As can be seen from Table 3, when the solvent of the composition for preparing the metal organic framework material is water, the moisture adsorption rate of the metal organic framework material is not significantly affected by the addition or non-addition of ethanol.
Thermogravimetric analysis of metal-organic framework materials
Example 1
The metal-organic framework material described in preparation example 1 was subjected to Thermogravimetric analysis (TGA), and the results of desorption amount and desorption temperature of moisture in preparation example 1 were observed.
The metal-organic framework material of preparation example 1 was placed in a thermogravimetric analyzer and the loss of weight was observed at a set temperature (heating rate of 10 ℃/min). As can be seen from FIG. 1, the weight of the metal organic framework material of preparation example 1 rapidly decreased at 50 ℃ to 100 ℃. Its weight loss at 100 ℃ was about 30 wt%. This shows that the metal organic framework material of the present invention can be used for adsorbing moisture, and the moisture desorption can be performed at low temperature (about 50 ℃). As can be seen from fig. 1, the weight loss was not observed until the heating temperature reached about 400 ℃. This indicates that the metal-organic framework material of the present invention has high thermal stability (thermal stability can reach more than about 400 ℃).
Isothermal adsorption curve testing of metal organic framework materials
Example 2
FIG. 2 is a graph showing isothermal adsorption of the metal-organic framework material of preparation example 1. Firstly, the material is desorbed in a vacuum environment at 80 ℃, then, the partial pressure of water vapor is gradually increased in the vacuum environment at 25 ℃, the partial pressure of water vapor is given once at 0.1 partial pressure, so that the material slowly adsorbs the water vapor (under different partial pressures of water vapor), and the water vapor adsorption rate of the sample is measured at a specific partial pressure of water vapor. As shown in fig. 2, when the water vapor partial pressure is increased to 0.2, the water vapor adsorption rate is rapidly increased to 35 wt%, and then the water vapor partial pressure is slowly increased, so that the water vapor adsorption rate can reach more than 40 wt%. It was shown that the metal organic framework material of preparation example 1 has high moisture absorption capacity under low humidity conditions.
Comparison of adsorption rates at Low humidity
Example 3
The metal-organic framework material and the adsorbent (available from preparation example 1) were provided separately
Article No. a520), activated alumina (available from exxonmi, ltd), and 4A zeolite powder (available from exxonmi, ltd) were subjected to adsorption tests in a low humidity environment. First, after drying and desorbing each sample at 80 ℃ for 30 minutes, the sample was placed in a hygrostat at 25 ℃ and 30% RH, and after 30 minutes of adsorption, the moisture adsorption rate of each sample was measured, and then the relative humidity was raised to 40%, and after 30 minutes of adsorption, the moisture adsorption rate of each sample was measured, and the relative humidity was sequentially increased to 90% to obtain an adsorption curve, and the results are shown in fig. 3. As can be seen from FIG. 3, the moisture absorption rate of the metal organic framework material of preparation example 1 at RH 30% for 30 minutes can reach 33 wt%, compared to the absorption material (obtained from absorption material)
The product code A520) has a moisture absorption rate of only 14 wt% at RH 30% after 30 minutes of moisture absorption. Thus, purchased from
The adsorbent material of (a) cannot achieve the effect of rapid moisture absorption at low humidity. From the figure3, it can be further observed that the conventional adsorbing material, namely activated alumina and 4A zeolite powder, is also dried and desorbed at 80 ℃ for 30 minutes, but because the pores of the material are small and water cannot be completely desorbed at low temperature (80 ℃), the pores still occupy water, and therefore, the moisture adsorption rate is lower than 6 wt% even under the high humidity environment of 90% RH. This indicates that these materials have poor moisture absorption at low humidity.
Example 4
The metal organic framework material and the adsorbing material (purchased from preparation example 1) were used
Article No. a520) was subjected to adsorption time comparison in a low humidity environment. The metal-organic framework material and the adsorbent (available from preparative example 1) were similarly prepared
Article No. A520) was dried at 80 ℃ for 30 minutes, and then placed in a hygrostat of 30% RH at 25 ℃ to observe changes in moisture absorption. As shown in FIG. 4 and Table 4, the metal organic framework material of preparation example 1 had a moisture adsorption rate of more than 30 wt% at 25 minutes, and was reversely observed as an adsorbent (obtained from a commercial product of
Article No. a520) had to absorb moisture for 60 minutes to achieve the same result as that of preparation example 1 (moisture adsorption rate of 30 wt%), demonstrating that the metal organic framework material of preparation example 1 can achieve rapid moisture absorption in a low-humidity environment.
TABLE 4
Example 5
Proceeding as described in example 4, the difference is that the relative humidity is increased from 30% RH to 80% RH. As can be seen from the results of fig. 5, the metal organic framework material of preparation example 1 can achieve the effect of having a moisture adsorption rate of more than 30 wt% after adsorbing for 10 minutes (the moisture adsorption rate can reach 34 wt% after adsorbing for 30 minutes), which proves that the metal organic framework material of preparation example 1 also has good adsorption capacity under high humidity environment.
Example 6
The results of measuring the moisture adsorption rate after 30 minutes from the metal organic framework materials of comparative examples 1, 3 and 4, which were first dry-desorbed at 80 ℃ for 30 minutes and then placed in an environment of 25 ℃ and 30% RH and an environment of 25 ℃ and 80% RH, respectively, are shown in table 5.
TABLE 5
| Preparation example 1 | Comparative example 1 | Comparative example 3 | Comparative example 4 | |
| |
34wt％ | 5.43 |
0 | 9.8 |
| 30% RH for 30 min | 33wt％ | 0.79 |
0 | 6.08wt％ |
As can be seen from table 5, the moisture absorption rate of the metal organic frame material of the present invention under high humidity (RH 80%) is 34 wt%, which is better than that of the other comparative examples. The metal organic framework material can achieve the moisture adsorption rate of 33 wt% even under the low humidity condition (RH 30%).
From the above examples, it can be seen that the metal organic framework material of the present invention has a high moisture absorption rate (greater than 30 wt%) in both low humidity environment and high humidity environment. In addition, compared with the traditional adsorbent (such as 4A zeolite and activated alumina) which can desorb the adsorbed moisture at a higher temperature (namely about 100 ℃), the metal organic framework material can easily desorb the adsorbed moisture at a lower temperature (80 ℃) to recover the moisture adsorption capacity, and the effects of quick moisture absorption and low-temperature desorption in a low-humidity environment are realized.
Although the present invention has been described with reference to several embodiments, it should be understood that various changes and modifications can be made therein by those skilled in the art without departing from the spirit and scope of the invention as defined by the appended claims.
Claims (13)
1. A preparation method of a metal organic framework material comprises the following steps:
providing a composition, wherein the composition comprises 3, 5-pyridinedicarboxylic acid, a metal compound, and a solvent; and
heating the composition to react the 3, 5-pyridinedicarboxylic acid with the metal compound to obtain the metal-organic framework material,
wherein the solvent is water and the composition further comprises an alkali metal hydroxide,
the molar ratio of the 3, 5-pyridinedicarboxylic acid to the metal compound is between 3:1 and 1:2, and
the metal compound is at least one of the group consisting of an aluminum salt, a chromium salt, and a zirconium salt.
2. The method of preparing a metal-organic framework material according to claim 1, wherein the metal compound is at least one of the group consisting of aluminum nitrate, aluminum sulfate, aluminum chloride, aluminum phosphate, chromium nitrate, chromium phosphate, zirconium nitrate, zirconium phosphate, and zirconium oxychloride.
3. The method of claim 1, wherein the initial concentration of the metal compound in the composition is between 0.15mol/L and 0.66 mol/L.
4. The method for preparing a metal organic framework material according to claim 1, wherein the alkali metal hydroxide is at least one of the group consisting of lithium hydroxide, sodium hydroxide, and potassium hydroxide.
5. The method of preparing a metal organic framework material according to claim 1, wherein the molar ratio of the alkali metal hydroxide to the 3, 5-pyridinedicarboxylic acid is 1.8 to 2.2.
6. The method of making a metal organic framework material as recited in claim 1, wherein said composition further comprises an aluminate.
7. The method of preparing a metal organic framework material according to claim 6, wherein the aluminate is at least one of the group consisting of lithium aluminate, sodium aluminate, potassium aluminate, magnesium aluminate, and calcium aluminate.
8. The method of claim 6, wherein the initial concentration of the aluminate in the composition is between 0.05mol/L and 0.20 mol/L.
9. The method of claim 1, wherein the heating temperature is between 100 ℃ and 150 ℃.
10. The method of claim 1, wherein the heating time is between 1 hour and 66 hours.
11. A metal-organic framework material prepared by the method for preparing a metal-organic framework material according to claim 1, comprising:
3, 5-pyridinedicarboxylic acids; and
a metal ion, wherein the metal ion is an aluminum ion, a chromium ion, or a zirconium ion, wherein the 3, 5-pyridinedicarboxylic acid is coordinated to the metal ion.
12. An adsorption device comprising:
a carrier; and
an adsorbent material disposed on the support, wherein the adsorbent material is the metal organic framework material of claim 11.
13. The sorption arrangement of claim 12, wherein the sorption arrangement has a moisture sorption rate of 18 wt% to 40 wt% after being placed in an environment of 30% RH at 25 ℃ for 30 minutes.
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