CN117123199B - Acetic acid modified metal-organic framework adsorption material and preparation method and application thereof - Google Patents
Acetic acid modified metal-organic framework adsorption material and preparation method and application thereof Download PDFInfo
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- CN117123199B CN117123199B CN202311388013.6A CN202311388013A CN117123199B CN 117123199 B CN117123199 B CN 117123199B CN 202311388013 A CN202311388013 A CN 202311388013A CN 117123199 B CN117123199 B CN 117123199B
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 title claims abstract description 213
- 238000001179 sorption measurement Methods 0.000 title claims abstract description 190
- 239000000463 material Substances 0.000 title claims abstract description 124
- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 58
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 52
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000013110 organic ligand Substances 0.000 claims abstract description 42
- 229910052751 metal Inorganic materials 0.000 claims abstract description 35
- 239000002184 metal Substances 0.000 claims abstract description 35
- 150000003839 salts Chemical class 0.000 claims abstract description 26
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims abstract description 25
- 239000000243 solution Substances 0.000 claims abstract description 25
- 239000007788 liquid Substances 0.000 claims abstract description 22
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 238000000926 separation method Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 14
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical group [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 239000003463 adsorbent Substances 0.000 claims description 52
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 50
- 239000007789 gas Substances 0.000 claims description 44
- 239000001257 hydrogen Substances 0.000 claims description 37
- 229910052739 hydrogen Inorganic materials 0.000 claims description 37
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 29
- 239000002245 particle Substances 0.000 claims description 24
- 238000009210 therapy by ultrasound Methods 0.000 claims description 22
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- 238000002791 soaking Methods 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 8
- 150000002430 hydrocarbons Chemical class 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 238000005119 centrifugation Methods 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000008187 granular material Substances 0.000 claims 1
- 239000010949 copper Substances 0.000 abstract description 14
- 230000000694 effects Effects 0.000 abstract description 14
- 239000011148 porous material Substances 0.000 abstract description 13
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 6
- 229910052802 copper Inorganic materials 0.000 abstract description 5
- 150000002500 ions Chemical class 0.000 abstract description 5
- 230000009471 action Effects 0.000 abstract description 4
- 125000002843 carboxylic acid group Chemical group 0.000 abstract description 4
- 239000012634 fragment Substances 0.000 abstract description 4
- 239000003446 ligand Substances 0.000 abstract description 4
- 230000036961 partial effect Effects 0.000 abstract description 3
- 230000008859 change Effects 0.000 abstract description 2
- 239000002253 acid Substances 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 17
- 230000002829 reductive effect Effects 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000001914 filtration Methods 0.000 description 8
- 150000002431 hydrogen Chemical class 0.000 description 8
- 238000000746 purification Methods 0.000 description 8
- 230000007423 decrease Effects 0.000 description 7
- 238000003795 desorption Methods 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 239000012452 mother liquor Substances 0.000 description 6
- 238000003860 storage Methods 0.000 description 6
- 238000012546 transfer Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 239000013148 Cu-BTC MOF Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 239000012295 chemical reaction liquid Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000012530 fluid Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical group Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000004587 chromatography analysis Methods 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 239000011232 storage material Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- PLAZXGNBGZYJSA-UHFFFAOYSA-N 9-ethylcarbazole Chemical compound C1=CC=C2N(CC)C3=CC=CC=C3C2=C1 PLAZXGNBGZYJSA-UHFFFAOYSA-N 0.000 description 1
- 238000004438 BET method Methods 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920000742 Cotton Polymers 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical group [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000002808 molecular sieve Substances 0.000 description 1
- 239000010413 mother solution Substances 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000007420 reactivation Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 230000001502 supplementing effect Effects 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
- C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Combustion & Propulsion (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention relates to the field of adsorption materials, in particular to an acetic acid modified metal-organic framework adsorption material, and a preparation method and application thereof. A preparation method of an acetic acid modified metal-organic framework adsorption material comprises the steps of mixing active metal salt and an organic ligand to form a mixed solution in the presence of a solvent; adding acetic acid solution into the mixed solution, performing hydrothermal reaction, and performing solid-liquid separation to obtain a metal organic framework adsorption material; the active metal salt is copper nitrate, and the organic ligand is 1,3, 5-benzene tricarboxylic acid. According to the invention, acetic acid is adopted to modify the metal-organic framework, carboxylic acid groups in acetic acid solution are utilized to replace ligand fragments in the original material structure, partial dimeric copper falls off under the action of acid ions, so that the specific surface area is increased, meanwhile, acetic acid can change the forming degree of crystals to a certain degree, so that the material generates more pores, the adsorption of gas is facilitated, and the adsorption effect on methane and ethane is further improved.
Description
Technical Field
The invention relates to the field of adsorption materials, in particular to an acetic acid modified metal-organic framework adsorption material, and a preparation method and application thereof.
Background
The hydrogen energy has the advantages of low carbon footprint, higher energy density, easily available and renewable production raw materials, and the like, is far more environment-friendly than fossil energy, and is more urgent and important to develop and utilize along with the shortage of traditional fossil energy in recent years, and is taken as a main means for storing and transporting energy in the future.
The liquid organic hydrogen carrier is an effective method for storing hydrogen, which uses unsaturated liquid organic matters as a hydrogen storage agent and corresponding saturates as hydrogen carriers to carry out reversible hydrogen storage and release, but the method can be accompanied with the generation of a small amount of organic hydrocarbon in dehydrogenation reaction. Taking N-ethylcarbazole as an example, the reaction tail gas is accompanied by impurities such as methane, ethane, carbon monoxide and the like in addition to hydrogen, and the impurities have influence on the use of the hydrogen. Therefore, in the hydrogen storage process, the purification of hydrogen is crucial, an adsorption method is mainly adopted for the purification of hydrogen, and the selection of an adsorbent with good adsorption performance is the most important link for the adsorption method, and the adsorbents which are widely used and studied at present are porous carbon materials, zeolite molecular sieves, clay-based adsorbents, metal organic framework Materials (MOFs), ordered mesoporous silicon and the like, wherein the most advantageous activated carbon has good effect on hydrogen purification, but due to the large limitations on the aspects of pore size distribution, specific surface area, pore volume and the like, the storage capacity of the gas is difficult to improve, and therefore, the metal organic framework Materials (MOFs) formed by matching metal ions and organic ligands can achieve advantages in the aspects of storage and separation of different gases.
The prior art discloses an HKUST-1 material, a preparation method and application, wherein a copper source and trimesic acid react in an organic solvent, and the metal organic framework material is obtained through repeated centrifugation, but the specific surface area and the pore volume of the HKUST-1 prepared by the material are not high, so that the prepared adsorption material has poor purification effect on hydrogen.
Disclosure of Invention
Therefore, the technical problem to be solved by the invention is to overcome the defects of small specific surface area, small pore volume and poor adsorption effect of the adsorption material in the prior art, thereby providing the acetic acid modified metal-organic framework adsorption material, the preparation method and the application thereof, and improving the adsorption effect on methane and ethane in hydrogen.
The invention provides a preparation method of an acetic acid modified metal-organic framework adsorption material, which comprises the following steps of mixing active metal salt and an organic ligand to form a mixed solution in the presence of a solvent; adding acetic acid into the mixed solution in the step S1, performing hydrothermal reaction, and performing solid-liquid separation to obtain a metal-organic framework adsorption material; the active metal salt is copper nitrate, and the organic ligand is 1,3, 5-benzene tricarboxylic acid.
The temperature of the hydrothermal reaction is 75-120 ℃, and the time of the hydrothermal reaction is 12-24h.
The molar ratio of the acetic acid to the organic ligand is 1-20:1. Preferably, the molar ratio of acetic acid to organic ligand is 3-10:1.
In the step S1, the step of mixing the active metal salt and the organic ligand is to mix the active metal salt and the organic ligand in a solvent by ultrasonic treatment.
Preferably, the step of mixing the active metal salt with the organic ligand is to mix the active metal salt solution with the organic ligand solution by ultrasonic treatment.
And step S2, after adding acetic acid into the mixed solution in step S1, and before carrying out hydrothermal reaction, the method also comprises the step of ultrasonic treatment.
The solid-liquid separation comprises the specific steps of centrifugation, washing and drying, wherein the washing adopts an ethanol soaking method, and the soaking time of ethanol is 2-24 hours.
The frequency of the ultrasonic treatment for preparing the active metal salt solution, the organic ligand solution and mixing the active metal salt solution and the organic ligand solution in the step S1 is 20-80kHz, and the treatment time is 15-30min.
The step S1 is to mix the active metal salt and the organic ligand in the solvent, wherein the ultrasonic treatment frequency is 20-80kHz, and the treatment time is 15-30min.
The ultrasonic treatment frequency in the step S2 is 20-80kHz, and the treatment time is 15-30min.
The solvent in the step S1 comprises at least one of deionized water, DMF and ethanol.
The preparation method of the active metal salt solution comprises the step of dissolving active metal salt in at least one solvent of deionized water and DMF through ultrasonic treatment.
The preparation method of the organic ligand solution comprises the steps of dissolving the organic ligand in at least one solvent of ethanol solution and DMF solution through ultrasonic treatment.
And S3, adding active metal salt and organic ligand into the liquid after solid-liquid separation, and repeating the step S2 to prepare the metal-organic framework adsorption material.
The mass ratio of the active metal salt to the organic ligand in the step S1 and/or the step S3 is 2-7:2.5. Preferably, the mass ratio of the active metal salt to the organic ligand in the step S1 and/or the step S3 is 2:2.5.
the preparation method further comprises S4, wherein the prepared metal-organic framework adsorption material is made into particles, and the particle size of the particles is less than or equal to 50 meshes.
The invention provides an adsorption material prepared by the preparation method.
The invention provides an application of the adsorption material in dehydrogenation tail gas purification and hydrogen combustion batteries or adsorption of light hydrocarbon compounds in hydrogen. The adsorption pressure of the light hydrocarbon compounds in the adsorbed hydrogen is 2-10bar. The adsorption temperature is 25-45 ℃. The flow rate of the gas is 2-10 mL/min. The light hydrocarbon compound is at least one of methane and ethane.
The technical scheme of the invention has the following advantages:
1. the invention provides a preparation method of an acetic acid modified metal-organic framework adsorption material, which comprises the steps of mixing active metal salt and an organic ligand to form a mixed solution in the presence of a solvent; and (3) after ultrasonic treatment of the mixed solution, adding an acetic acid solution into the mixed solution, carrying out hydrothermal reaction, and carrying out solid-liquid separation to obtain the metal organic framework adsorption material. According to the invention, acetic acid is adopted to modify the metal organic framework to prepare the adsorption material, and the carboxylic acid group in the acetic acid solution is used for replacing ligand fragments in the original material structure, so that partial dimeric copper falls off under the action of acidic ions, thereby increasing the specific surface area.
2. The preparation method of the acetic acid modified metal-organic framework adsorption material provided by the invention limits the molar ratio of the acetic acid to the organic ligand to be 1-20:1, and more preferably, the molar ratio of the acetic acid to the organic ligand to be 3-10:1. According to the invention, a certain amount of acetic acid is added, so that the porosity can be effectively improved, but the excessive amount of acetic acid prevents the generation of crystal pore diameters, and meanwhile, as the dissolution amount of copper nitrate and trimesic acid in acetic acid is smaller than that of DMF, the dispersity of the copper nitrate and the trimesic acid in liquid is influenced, so that the problems of reduced adsorption capacity and reduced crystallization saturation of an adsorption material are caused, and therefore, the molar ratio of acetic acid to an organic ligand is better in a range of 3-10:1.
3. The preparation method of the acetic acid modified metal-organic framework adsorption material provided by the invention limits the soaking time of ethanol in the solid-liquid separation step. The polarity of carbonyl in the ethanol enables the copper nitrate ion compound which is weakly combined with the organic ligand to be dissolved in the ethanol, so that copper nitrate which is not completely reacted in the liquid is dissolved and removed. However, the soaking time of the ethanol is too long, which leads to that the mesopores with the aperture of 3-5mm in the adsorption material are gradually smaller, and the micropore ratio is gradually increased, so that the soaking time of the ethanol is kept at 2-24 hours, and the preferable soaking time is 2-12 hours, not only can completely remove unreacted impurities of the sample, but also can be beneficial to the generation of micropores and mesopores in the adsorption material, so that the larger the average aperture is, the larger the specific surface area of the mesopores is, and the larger the specific surface area is.
4. According to the preparation method of the acetic acid modified metal-organic framework adsorption material, provided by the invention, the mother liquor in the preparation process of the adsorption material is utilized, the mother liquor can be recycled by only supplementing active metal salt and organic ligand without adding a solvent, the resources are saved, and the cost is reduced.
5. According to the preparation method of the metal-organic framework adsorption material, as the solubility of the active metal salt or the organic ligand in the solvent is related to the crystallinity of the finally prepared product, the higher the solubility is, the more the collision opportunity of the active metal and the liquid ion in the organic ligand is, the more easily the product with high crystallinity is formed.
6. The preparation method of the metal-organic framework adsorption material provided by the invention further comprises the step of preparing the prepared metal-organic framework adsorption material into particles, wherein the particle size of the particles is less than or equal to 50 meshes. The difference in particle size affects the external mass transfer process, the smaller the particle size of the adsorbent material, the larger the surface area and porosity, the faster the material in the fluid contacts and diffuses to the adsorbent material, and the higher the external mass transfer rate, while the larger the particle size of the adsorbent material, the larger the pores between the adsorbent molecules will be. Gas molecules are more likely to form channels in the adsorbent column layer and are difficult to capture by the adsorbent at the edges. So that the adsorption amount becomes smaller and the adsorption rate becomes slower. Therefore, the invention prepares the adsorption material into particles with the particle diameter less than or equal to 50 meshes, improves the surface area and the pore volume density of the adsorption material, increases the adsorption surface area and the adsorption rate, improves the adsorption efficiency, and is convenient for the storage and the transportation of the adsorption material.
7. The adsorption material prepared by the preparation method of the metal-organic framework adsorption material can adsorb methane and ethane in hydrogen under a low pressure condition, so that the hydrogen can be purified, and meanwhile, the adsorption material prepared by the preparation method can circularly adsorb and desorb, and the purity of the hydrogen after adsorption purification can reach 99.9977% in the dehydrogenation tail gas of an actual liquid hydrogen storage medium.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings that are needed in the description of the embodiments or the prior art will be briefly described, and it is obvious that the drawings in the description below are some embodiments of the present invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic diagram of an adsorption permeation device according to the present invention;
FIG. 2 is an XRD pattern of the adsorbent material prepared in examples 1-4 of the present invention;
FIG. 3 is a schematic diagram showing the adsorption amount of methane by the adsorption material prepared in examples 1 to 4 and comparative example 1 according to the present invention, wherein HKUST-c is the adsorption material prepared in example 1, HKUST-a is the adsorption material prepared in example 2, HKUST-b is the adsorption material prepared in example 3, HKUST-d is the adsorption material prepared in example 4, and HKUST-1 is the adsorption material prepared in comparative example 1;
FIG. 4 is a schematic diagram showing the adsorption amounts of ethane by the adsorbents prepared in examples 1 to 4 and comparative example 1 according to the present invention, wherein HKUST-c is the adsorbent prepared in example 1, HKUST-a is the adsorbent prepared in example 2, HKUST-b is the adsorbent prepared in example 3, HKUST-d is the adsorbent prepared in example 4, and HKUST-1 is the adsorbent prepared in comparative example 1;
FIG. 5 is an adsorption-desorption cycle curve of methane for the adsorbent material prepared in example 1 of the present invention;
FIG. 6 is an adsorption-desorption cycle curve of ethane by the adsorption material prepared in example 1 of the present invention;
reference numerals:
1-a mixed gas cylinder; 2-a gas pressure reducing valve; 3-a gas flow meter; 4-an adsorption tube; 5-six way valve; 6, an evacuating device; 7-gas chromatograph.
Detailed Description
The following examples are provided for a better understanding of the present invention and are not limited to the preferred embodiments described herein, but are not intended to limit the scope of the invention, any product which is the same or similar to the present invention, whether in light of the present teachings or in combination with other prior art features, falls within the scope of the present invention.
The specific experimental procedures or conditions are not noted in the examples and may be followed by the operations or conditions of conventional experimental procedures described in the literature in this field. The reagents or apparatus used were conventional reagent products commercially available without the manufacturer's knowledge.
The chemical reagents and gases mentioned in the examples, comparative examples and experimental examples of the present invention are shown in Table I, and the mentioned instruments are shown in Table II.
In the invention, when the adsorption performance of the prepared metal-organic framework adsorption material is detected, a self-built adsorption device is adopted as shown in figure 1, and the specific detection steps are as follows, a sample is weighed and then is added into an adsorption tube 4 with the inner diameter of 8 mm and the length of 20 cm, and the packing height can reach 15 cm at the highest. The upper and lower parts are all filled up with glass beads to a certain height, and the upper and lower outlets are blocked by absorbent cotton. The adsorption tube 4 is a sleeve, and circulating water can be introduced to control the adsorption temperature during adsorption experiments. The valve of the gas pressure reducing valve 2 is opened and the gas flow meter 3 is adjusted to the corresponding indication. After the gas passes through the adsorption device, the gas is introduced into the chromatograph by adopting a six-way valve 5 automatic sampler, and an adsorption curve is obtained after analysis and data processing. And (5) evacuating the rest of the gas. Wherein, the adsorption material needs to be dried for 3 hours in a vacuum environment at 150 ℃ before the gas adsorption test is carried out.
The method for calculating the adsorption quantity comprises the following steps: taking methane measurement as an example, firstly, an empty adsorption tube is put into a device, and the gas concentration in a gas cylinder is measured and is marked as C 0 The concentration shown in the ith time chromatograph after the addition of m g adsorbent material was recorded as C i . Measuring the flow rate of tail gas to be S mL/min, recording the sample feeding time of the upper sample and the sample feeding time of the lower sample to be T, and recording M to be 10 -6 . The adsorption amount L can be calculated by the formula (1).
(1)
X-ray diffraction analysis method (XRD): the synthesized material was subjected to X-ray diffraction analysis (XRD) for determining its crystal structure. Firstly, grinding the materials into powder, wherein the scanning range is 4-50 degrees, the scanning step is 1 degree/min, the voltage is 40 kV, and the current is 40 mA. And (5) characterizing the metal organic framework adsorption material. XRD instrument model was Rigaku Ultima IV.
Pore structure and specific surface area (BET) analysis: the material is pretreated for 2h at 200 ℃, then N2 adsorption-desorption isotherm measurement is carried out by adopting a microphone 2020 HD88 surface area and porosity analyzer, an adsorption curve result is fitted by a BET method, the specific surface area is calculated, and the distribution result is analyzed by BJH and HK models.
The gas composition analysis method comprises the following steps: on-line detection of gas is carried out by using Shimadzu chromatography, and the type of the chromatography is as follows: GC2030, using SC-ST column, with helium as carrier gas. The total flow was 27.2. 27.2 mL/min and the column flow was 8.07. 8.07 mL/min. The temperature and pressure were initially 35℃and 250 bar, and at 6 min were raised to 245℃and 350 bar, both for 2 min. The average interval between two samples was about 15min (the interval time included the instrument preparation time).
Example 1
The embodiment provides a preparation method of an acetic acid modified metal organic framework adsorption material, which comprises the following specific steps and parameters:
with 5g Cu (NO) 3 ) 2 ·3H 2 O and 2.5 g of 1,3, 5-benzene tricarboxylic acid are mixed in 100mL of DMF solution, ultrasonic treatment is carried out for 20min at the frequency of 40kHz to obtain mixed solution, the mixed solution is mixed with acetic acid according to the mol ratio of acetic acid to 1,3, 5-benzene tricarboxylic acid of 10:1, ultrasonic treatment is carried out for 20min at the frequency of 40kHz, and the mixed solution is placed in a hydrothermal reaction kettle for reaction at the temperature of 75 ℃ for 24h. After cooling, the reaction liquid is subjected to solid-liquid separation by adopting a rotating speed of 8000 rpm, the centrifuged solid is soaked in DMF for 24 hours, and then is soaked in ethanol for 2 hours, and a blue product is obtained by filtering. And then drying overnight at 200 ℃ in a vacuum drying oven to obtain the adsorption material.
Example 2
The embodiment provides a preparation method of an acetic acid modified metal organic framework adsorption material, which has the same specific steps and parameters as those of embodiment 1, and is different in that the molar ratio of acetic acid to 1,3, 5-benzene tricarboxylic acid is 3:1.
Example 3
The embodiment provides a preparation method of an acetic acid modified metal organic framework adsorption material, which has the same specific steps and parameters as those of embodiment 1, and is different in that the molar ratio of acetic acid to 1,3, 5-benzene tricarboxylic acid is 5:1.
Example 4
The embodiment provides a preparation method of an acetic acid modified metal organic framework adsorption material, which has the same specific steps and parameters as those of embodiment 1, and is different in that the molar ratio of acetic acid to 1,3, 5-benzene tricarboxylic acid is 20:1.
Example 5
The embodiment provides a preparation method of an acetic acid modified metal organic framework adsorption material, which has the specific steps and parameters same as those of embodiment 1, except that the ethanol soaking time is 4h.
Example 6
The embodiment provides a preparation method of an acetic acid modified metal organic framework adsorption material, which has the specific steps and parameters same as those of embodiment 1, except that the ethanol soaking time is 12h.
Example 7
The embodiment provides a preparation method of an acetic acid modified metal organic framework adsorption material, which has the specific steps and parameters same as those of embodiment 1, except that the ethanol soaking time is 24 hours.
Example 8
The embodiment provides a preparation method of an acetic acid modified metal organic framework adsorption material, which comprises the following specific steps and parameters:
with 5g Cu (NO) 3 ) 2 ·3H 2 O and 2.5 g of 1,3, 5-benzene tricarboxylic acid are mixed in 100mL of DMF solution, ultrasonic treatment is carried out for 20min at the frequency of 40kHz, the acetic acid and the mixed solution are mixed according to the mol ratio of the acetic acid to the 1,3, 5-benzene tricarboxylic acid of 10:1, ultrasonic treatment is carried out for 20min at the frequency of 40kHz, and then the mixture is placed in a hydrothermal reaction kettle for reaction for 20h at the temperature of 100 ℃. After cooling, the reaction liquid is subjected to solid-liquid separation by adopting a rotating speed of 8000 rpm, the centrifuged solid is soaked in DMF for 24 hours, and then is soaked in ethanol for 2 hours, and a blue product is obtained by filtering. And then drying overnight at 200 ℃ in a vacuum drying oven to obtain the adsorption material.
Adding 5g Cu (NO) into the mother solution after filtering the adsorption material 3 ) 2 ·3H 2 O, 2.5 g of 1,3, 5-benzene tricarboxylic acid and 7.14g of acetic acid are treated by ultrasonic at 40kHz for 20min and then placed in a stainless steel hot pot for reaction at 75 ℃ for 24h. Cooling, centrifuging, washing with DMF 24, h, washing with ethanol 24, h, and filtering to obtain blueThe color product.
And drying the blue product in a vacuum drying oven at 200 ℃ overnight to obtain the metal-organic framework adsorbing material.
Example 9
The embodiment provides a preparation method of an acetic acid modified metal organic framework adsorption material, which comprises the following specific steps and parameters:
with 5g Cu (NO) 3 ) 2 ·3H 2 O and 2.5 g of 1,3, 5-benzene tricarboxylic acid are mixed in 100mL of DMF solution, ultrasonic treatment is carried out for 15min at the frequency of 80kHz, the acetic acid and the mixed solution are mixed according to the mol ratio of the acetic acid to the 1,3, 5-benzene tricarboxylic acid of 10:1, ultrasonic treatment is carried out for 30min at the frequency of 20 kHz, and then the mixture is placed in a hydrothermal reaction kettle for reaction at the temperature of 75 ℃ for 24h. After cooling, the reaction liquid is subjected to solid-liquid separation by adopting a rotating speed of 8000 rpm, the centrifuged solid is soaked in DMF for 24 hours, and then is soaked in ethanol for 2 hours, and a blue product is obtained by filtering. And then drying overnight at 200 ℃ in a vacuum drying oven to obtain the adsorption material.
To the mother liquor after filtration of the blue product was added 5g Cu (NO 3 ) 2 ·3H 2 After ultrasonic treatment of O, 2.5 g of 1,3, 5-benzene tricarboxylic acid and 7.14g of acetic acid at a frequency of 40kHz for 25min, the mixture was placed in a stainless steel hot pot and reacted at 75℃for 24h. After cooling centrifugation, 24 was washed with DMF h, then 24h with ethanol and filtered to give a blue product.
To the mother liquor after filtration of the blue product was added 5g Cu (NO 3 ) 2 ·3H 2 O and 2.5 g of 1,3, 5-benzene tricarboxylic acid are evenly dissolved and then are placed in a stainless steel hot pot for reaction at 75 ℃ for 24h. After cooling centrifugation, 24 was washed with DMF h, then 24h with ethanol and filtered to give a blue product.
And drying the blue product in a vacuum drying oven at 200 ℃ overnight to obtain the metal-organic framework adsorbing material.
Example 10
This example provides a method for preparing an acetic acid-modified metal-organic framework adsorbent material, which has the same specific steps and parameters as those of example 9, except that Cu (NO 3 ) 2 ·3H 2 The injection amount of O is 2g。
Example 11
This example provides a method for preparing an acetic acid-modified metal-organic framework adsorbent material, which has the same specific steps and parameters as those of example 9, except that Cu (NO 3 ) 2 ·3H 2 The O injection amount was 7g.
Example 12
The embodiment provides a preparation method of an acetic acid modified metal organic framework adsorption material, which comprises the following specific steps and parameters:
5g of Cu (NO) 3 ) 2 ·3H 2 O is dissolved in 50 mL deionized water, treated for 30min at an ultrasonic frequency of 40kHz to obtain a copper nitrate solution, 2.5 g trimesic acid is dissolved in 50 mL% ethanol with 99% purity, and treated for 30min at an ultrasonic frequency of 40kHz to obtain a trimesic acid solution. The trimesic acid solution is poured into a copper nitrate solution and treated for 30min at an ultrasonic frequency of 40kHz to prepare a mixed solution. The molar ratio of acetic acid to 1,3, 5-benzene tricarboxylic acid is 10:1, the acetic acid and the mixed solution are treated for 30min under the ultrasonic frequency of 40kHz, and then the mixed solution is put into a hydrothermal reaction kettle for reaction at 120 ℃ for 12h. Centrifuging at 8000 rpm, soaking in DMF for 24h, soaking in ethanol for 2h, filtering, collecting solid, and drying in vacuum oven at 75deg.C for 24h to obtain metal organic skeleton adsorbing material.
Example 13
The embodiment provides a preparation method of an acetic acid modified metal organic framework adsorption material, which has the specific steps and parameters the same as those of embodiment 1, and the preparation method also comprises the following granulating steps: after the acetic acid-modified metal organic framework adsorbent material prepared in example 1 was sufficiently ground, tabletting was performed using a tabletting machine at a pressure of 50 bar. And then grinding into particles with 0-10 meshes, 10-20 meshes, 20-30 meshes and 40-50 meshes again, which are named as HKUST-10, HKUST-20 and HKUST-40 respectively.
Comparative example 1
The comparative example provides a preparation method of a metal-organic framework adsorption material, which has the specific steps and parameters the same as those of the example 1, and the only difference is that the step of adding acetic acid is not included, namely, after active metal salt and organic ligand are mixed, hydrothermal reaction is carried out, and solid-liquid separation is carried out, so that the adsorption material is prepared.
Comparative example 2
This comparative example provides a method for preparing a metal organic framework adsorbent material, the specific steps and parameters of which are the same as those of example 1, except that acetic acid is replaced with a hydrochloric acid solution of the same molar amount.
Comparative example 3
The present example provides a method for preparing an acetic acid-modified metal-organic framework adsorbent, which has the same specific steps and parameters as those of example 1, except that the active metal salt is Ni (NO 3 ) 2 ·6H 2 O。
Comparative example 4
The present example provides a method for preparing an acetic acid-modified metal-organic framework adsorbent, which has the same specific steps and parameters as those of example 1, except that the active metal salt is Zn (NO 3 ) 2 ·6H 2 O。
Comparative example 5
The embodiment provides a preparation method of an acetic acid modified metal-organic framework adsorption material, which has the specific steps and parameters the same as those of embodiment 1, and the only difference is that the active metal salt is copper acetate.
Comparative example 6
The embodiment provides a preparation method of an acetic acid modified metal-organic framework adsorption material, which has the same specific steps and parameters as those of embodiment 1, and the only difference is that the organic ligand is terephthalic acid.
Experimental example 1
X-ray diffraction detection is carried out on the adsorption materials prepared in the examples 1-4 respectively, and the XRD patterns shown in figure 2 show that the crystal structures of the examples 1-4 are similar and are pure products.
Example 2
The BET and pore size of the adsorbent materials prepared in examples 1 to 12 and comparative examples 1 to 6 were measured, respectively, and the results are shown in Table III.
According to the data in Table III, it can be seen that the metal-organic framework prepared by taking copper nitrate as an active metal component and taking 1,3, 5-benzene tricarboxylic acid as an organic ligand has the advantages that after modification by acetic acid, the micropore area and the mesopore area of the prepared adsorption material are both increased, and the structural property parameters of other active metal materials or other organic ligands are poor, which means that the addition of acetic acid can change the crystal forming degree formed by copper nitrate and trimesic acid to a certain extent, so that the adsorption material generates more pores, the adsorption of gas is facilitated, and especially when the molar ratio of acetic acid to the organic ligand is 10:1, the maximum specific surface area of the adsorption material modified by acetic acid is 1780.5 m 2 And/g, which is much greater than the specific surface area of the adsorbent material prepared in comparative example 1. The specific surface area data of the adsorbent materials prepared by examples 1 and 5-7 are 1613.1-1780.5 m 2 The range of/g indicates that the specific surface area of the adsorption material is maximum when the soaking time of ethanol is 2 hours; comparing the data of example 1 with the data of comparative example 2, it can be seen that other acidic substances cannot replace the modification effect of acetic acid on the metal-organic framework in the application, because carboxylic acid groups in the acetic acid solution can replace ligand fragments in the original material structure, and under the action of acidic ions, part of dimeric copper falls off, so that the specific surface area is increased; in the embodiments 8-11, the mother liquor is recycled to prepare the adsorption material, and because additional copper source is needed, the pH value of the mother liquor is changed in the recycling process, and the structural property parameters of the prepared adsorption material are influenced to a certain extent.
Experimental example 3
The adsorption materials prepared in examples 1 to 12 and comparative examples 1 to 6 were used for adsorbing methane and ethane in a hydrogen atmosphere, and the results are shown in fig. 3 and 4 and table four.
According to fig. 3, fig. 4 and table four, it can be seen that acetic acid doped synthetic adsorption material can improve the adsorption capacity of methane and ethane, because carboxylic acid groups in acetic acid solution replace ligand fragments in original material structure, and under the action of acidic ions, part of dimeric copper units fall off, so that the specific surface area is increased, and the adsorption effect on methane and ethane is increased. At acetic acid addition levels less than 10:1, as the amount of acetic acid increases, the variation increases. However, when the amount of acetic acid added reaches a certain value, the solubility of copper nitrate and trimesic acid in acetic acid is smaller than that of DMF, and therefore the dispersibility in a liquid is affected, and there is a case where the adsorption content is lowered, the crystal saturation is lowered, and the effect is poor.
Application example 1
The adsorption amount of the adsorption material prepared in example 3 under the conditions of different pressures can be obtained by adopting a self-built adsorption device, wherein the gas flow rate is 5.5 mL/min, the gas inlet concentration is 1000ppm of methane and ethane respectively, the rest is hydrogen, and 3g of the adsorption material prepared in example 1 are respectively under the conditions of the adsorption pressures of 2 bar, 4 bar, 6.5 bar, 8 bar and 10bar, and the results are shown in Table five.
From Table five, it is clear that the adsorption amount increases with increasing pressure in adsorbing methane, and the increase is most remarkable between 6.5 bar and 8 bar. The slope also increases with increasing pressure and the rate of increase decreases. This means that the pressure increase will increase the methane adsorption performance, and the adsorption performance gradually decreases with the pressure increase to more than 10bar, under which conditions the adsorption factor is more biased towards other factors such as gas concentration and temperature. In terms of adsorption of ethane, we can observe that the adsorption amount is changed most obviously between 4 and 6.5 bar, the adsorption amount is increased from 3.978 mg/g to 7.561 mg/g, and the slope is basically unchanged, so that the concentration cannot meet the adsorption requirement of the adsorption material, in other words, almost all ethane molecules are adsorbed in a longer period of time until the adsorbent is gradually deactivated.
Application example 2
The adsorption material 3g prepared in example 1 is prepared under the conditions of temperature of 25 ℃, 35 ℃ and 45 ℃ respectively, and the adsorption amount of the adsorption material prepared in example 1 on methane and ethane is obtained under the conditions of different temperatures, and the results are shown in Table six.
From the data in Table six, it is seen that the adsorption of methane by the material was reduced by about 25% and the adsorption of ethane by 22% during the 25 ℃ temperature increase to 35 ℃, and the adsorption time was also correspondingly reduced. In the process of heating to 45 ℃ at 35 ℃, the adsorption performance of methane is reduced, and the adsorption time is shortened by 37 minutes; and the adsorption amount of ethane is reduced by 15%, and the adsorption time is reduced by 12.4% for about 422 min. FIGS. 5-6 also show that C, with increasing temperature t /C 0 >0 to C t /C 0 The slope of the partial curve of =1 is also increased, i.e. the ramp up shortens the penetration time, wherein C t Ci, i.e. the gas concentration at time t, C t /C 0 At time t, the adsorption amount with respect to the saturated adsorption is shown. The reason for the decrease in the adsorption amount is that the equilibrium concentration of the substance at the adsorption site is lowered due to the decrease in the attraction effect and the increase in the thermal motion which are caused by the physical adsorption by thermodynamics. And the adsorption rate also becomes faster with increasing temperature, and the time from just penetrating the adsorbent to saturation of the gas decreases with increasing temperature. This is due to the increased temperature which results in increased thermal movement of the gas molecules, thereby increasing the diffusion and transfer rates of the species and increasing the adsorption rate.
Application example 3
The adsorption material prepared in example 1 was used to obtain the adsorption amounts of methane and ethane under different gas flow rates by using a self-built adsorption device, wherein the gas inlet concentrations are 1000ppm for methane and ethane, the rest is hydrogen, the adsorption pressure is 6.5 bar, 3g of the adsorption material prepared in example 1 is subjected to gas flow rates of 2mL/min, 5.5 mL/min, 8 mL/min and 10 mL/min, and the results are shown in Table seven.
From the seventh data, it is seen that as the gas flow rate increases, the mass transfer rate of the mixture between the adsorbent and the gas increases, so that the adsorption rate increases and the equilibrium concentration of the species on the adsorbent decreases. This generally results in shorter adsorption times and higher adsorption efficiencies. And the faster the flow rate, the shorter the residence time of the fluid on the adsorbent surface, and the molecules flow through the conduit without having to diffuse deep into the adsorbent, meaning that adsorption efficiency and rate decrease with increasing flow rate.
Application example 4
The adsorption device shown in FIG. 1 was used to detect the adsorption effect of methane and ethane by using 3g of the metal-organic framework adsorbent material with different particle diameters prepared in example 13 under the conditions that the gas inlet concentration is 1000ppm for methane and ethane, the rest is hydrogen, the adsorption pressure is 6.5 bar, and the gas flow rate is 2mL/min, and the results are shown in Table eight.
From the data in Table eight, the adsorption effect was reduced as the particle size of the adsorbent increased. The methane adsorption was reduced from 0.116 mg/g to 0.086 mg/g, while the ethane adsorption was reduced from 6.83 mg/g to 4.24 mg/g. On the other hand, as the particle size increases, the adsorbed gas rate also gradually slows down. Starting from the detection of ethane in the tail gas, only 2765 min is needed until the adsorbent is fully saturated, and the time after increasing the particle size of the material is increased to 3300 min, and the slowing is 16.21%. The particle size has a certain influence on the adsorption effect and the adsorption rate. The reason why the particle size has an influence on the adsorption performance is that, on one hand, the particle size is different, the external mass transfer process is influenced, and the smaller the particle size of the adsorbent is, the larger the surface area and the porosity are, the faster the substance in the fluid contacts and diffuses to the adsorbent, and the higher the external mass transfer rate is. On the other hand, as the particle size of the adsorbent increases, particles accumulate or aggregate, and pores among the adsorbent molecules are larger. Gas molecules are more likely to form channels in the adsorbent column layer and are difficult to capture by the adsorbent at the edges. So that the adsorption amount becomes smaller and the adsorption rate becomes slower. And the smaller the particle size is, the larger the surface area and the pore volume density are, so that the adsorption surface area and the adsorption rate are increased, and the adsorption efficiency is improved.
Application example 5
The adsorption material prepared in example 1 was subjected to cyclic adsorption-desorption in purified hydrogen by the operations of pressure increasing and pressure decreasing, and other conditions were the same as those in application example 4, and as a result, as shown in fig. 5 and 6, it was found that in terms of adsorption of methane, the adsorption capacity was reduced from 0.20 mg/g to 0.18 mg/g, and finally to 0.172 mg/g, and the desorption rate finally reached 85%, which was good in terms of desorption rate, but the adsorption amount was still at a very low level. In the case of cyclic adsorption and desorption of ethane, the adsorption capacity is reduced to 5.20 mg/g after one cycle from 10.36 mg/g at the beginning, but the adsorption performance is still at a higher level. The desorption rate of the catalyst in the first desorption is about 50%, and then the catalyst is basically in a stable state. It can be seen that the first desorption has a greater impact on it, which persists in subsequent adsorption and desorption operations. This effect cannot be recovered by depressurization alone, and the need for a high temperature reactivation step can restore the adsorbent to its original adsorption level. The adsorbent material produced by the present invention is still a good adsorbent for purifying hydrogen at low pressure.
Application example 6
In performing adsorption experiments, small doses of adsorbent may produce good adsorption results, but adsorption results in small or pilot plants may be affected by a number of factors and may not reach the previous theoretical purification level. Therefore, a fixed bed small test device using an organic hydrogen storage material 12H-NEC as a raw material is adopted, and an adsorption device is added behind an exhaust port to check whether the adsorbent meets the requirement. The adsorbent material of the device was prepared in example 1, the amount used was 3g, the amount fed was 0.03. 0.03 mL/min, and the temperature was kept at 25 ℃. To meet the theoretical experiments before, the adsorption pressure and the fixed bed reaction pressure were adjusted to 6.5 bar. The results are shown in Table nine.
From the data in Table nine, it was found that the reaction off-gas had a methane concentration of 21.32 ppm, an ethane concentration of 31.00 ppm, a carbon monoxide concentration of 7.08 ppm, a carbon dioxide concentration of 22.97 ppm and the balance of hydrogen. After the adsorption material is treated, the concentration of the tail gas is reduced as follows: the methane concentration was 1.25 ppm and the remaining gases were hydrogen. Almost all impurities are adsorbed by the adsorption material and have the concentration lower than the minimum detection limit of the instrument, which indicates that the adsorbent has a certain hydrogen purification effect for practical application. The adsorbent in the embodiment of the invention can purify hydrogen to be purer under the condition. On the other hand, the separation method of industrial hydrogen, nitrogen and oxygen is mature, and if the adsorption method is simply utilized, the corresponding purpose can be achieved by multi-step adsorption, so that the existence of the hydrogen, the nitrogen and the oxygen is neglected in statistics. The purity of the purified hydrogen was 99.9977% by calculation.
It is apparent that the above examples are given by way of illustration only and are not limiting of the embodiments. Other variations or modifications of the above teachings will be apparent to those of ordinary skill in the art. It is not necessary here nor is it exhaustive of all embodiments. While still being apparent from variations or modifications that may be made by those skilled in the art are within the scope of the invention.
Claims (6)
1. The application of the acetic acid modified metal-organic framework adsorption material in adsorbing light hydrocarbon compounds in hydrogen is characterized in that the preparation method of the adsorption material comprises the following steps,
s1, mixing an active metal salt and an organic ligand in the presence of a solvent to form a mixed solution, wherein the step of mixing the active metal salt and the organic ligand is to carry out ultrasonic treatment and mixing on an active metal salt solution and the organic ligand solution, or to carry out ultrasonic treatment and mixing on the active metal salt and the organic ligand in the solvent, and the mass ratio of the active metal salt to the organic ligand is 2:2.5;
s2, adding acetic acid into the mixed solution obtained in the step S1, carrying out ultrasonic treatment, carrying out hydrothermal reaction and carrying out solid-liquid separation to obtain a metal organic framework adsorption material, wherein the molar ratio of the acetic acid to the organic ligand is 10:1;
the specific steps of solid-liquid separation are centrifugation, washing and drying, wherein the washing adopts an ethanol soaking method, and the soaking time of ethanol is 2 hours;
the active metal salt is copper nitrate, and the organic ligand is 1,3, 5-benzene tricarboxylic acid.
2. The use according to claim 1, wherein the temperature of the hydrothermal reaction is 75-120 ℃ and the time of the hydrothermal reaction is 12-24 hours.
3. The use according to any one of claims 1-2, further comprising S3 adding an active metal salt and an organic ligand to the liquid after solid-liquid separation, repeating said step S2 to produce a metal-organic framework adsorbent material; and/or the number of the groups of groups,
the frequency of ultrasonic treatment in the step S1 and/or the step S2 is 20-80kHz, and the treatment time is 15-30min.
4. The use according to claim 3, wherein the solvent in step S1 comprises at least one of deionized water, DMF, ethanol; and/or the number of the groups of groups,
the preparation method of the active metal salt solution comprises the steps of dissolving active metal salt in at least one solvent of deionized water and DMF through ultrasonic treatment; and/or the number of the groups of groups,
the preparation method of the organic ligand solution comprises the steps of dissolving the organic ligand in at least one solvent of ethanol solution and DMF solution through ultrasonic treatment.
5. The use according to claim 4, wherein the production method further comprises the step of S4 of granulating the produced metal-organic framework adsorbent material, the particle size of the granules being 50 mesh or less.
6. The use according to claim 1, wherein the adsorption pressure for the adsorption of light hydrocarbon compounds in hydrogen is 2-10bar; and/or the number of the groups of groups,
the adsorption temperature is 25-45 ℃; and/or the number of the groups of groups,
the flow rate of the gas is 2-10 mL/min; and/or the number of the groups of groups,
the light hydrocarbon compound is at least one of methane and ethane.
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| CN117123199A (en) | 2023-11-28 |
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