CN116272912B - Efficient and stable MOFs composite material, preparation method and carbon neutralization application - Google Patents
Efficient and stable MOFs composite material, preparation method and carbon neutralization application Download PDFInfo
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- 239000012621 metal-organic framework Substances 0.000 title claims abstract description 37
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 6
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 6
- 238000006386 neutralization reaction Methods 0.000 title abstract description 4
- PTMHPRAIXMAOOB-UHFFFAOYSA-N phosphoramidic acid Chemical compound NP(O)(O)=O PTMHPRAIXMAOOB-UHFFFAOYSA-N 0.000 claims abstract description 16
- 239000013148 Cu-BTC MOF Substances 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 11
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 33
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 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 description 22
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 17
- 238000005406 washing Methods 0.000 claims description 17
- 239000004809 Teflon Substances 0.000 claims description 11
- 229920006362 Teflon® Polymers 0.000 claims description 11
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 11
- 230000003213 activating effect Effects 0.000 claims description 9
- 238000001291 vacuum drying Methods 0.000 claims description 8
- YHLWPOLSPCBOPC-UHFFFAOYSA-O butyl(2-phosphopropan-2-yl)azanium Chemical compound CCCCNC(C)(C)[P+](O)=O YHLWPOLSPCBOPC-UHFFFAOYSA-O 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- GSZQTIFGANBTNF-UHFFFAOYSA-N (3-aminopropyl)phosphonic acid Chemical compound NCCCP(O)(O)=O GSZQTIFGANBTNF-UHFFFAOYSA-N 0.000 claims description 3
- HMTLHFRZUBBPBS-UHFFFAOYSA-N 2-[2-(2-hydroxyethyl)hydrazinyl]ethanol Chemical compound OCCNNCCO HMTLHFRZUBBPBS-UHFFFAOYSA-N 0.000 claims description 3
- 238000010438 heat treatment Methods 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- QQVDJLLNRSOCEL-UHFFFAOYSA-N (2-aminoethyl)phosphonic acid Chemical compound [NH3+]CCP(O)([O-])=O QQVDJLLNRSOCEL-UHFFFAOYSA-N 0.000 claims 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 17
- 239000003546 flue gas Substances 0.000 abstract description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 abstract description 10
- 229910052751 metal Inorganic materials 0.000 abstract description 9
- 239000002802 bituminous coal Substances 0.000 abstract description 6
- 239000000463 material Substances 0.000 abstract description 6
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 abstract description 5
- 239000000779 smoke Substances 0.000 abstract description 5
- 238000009776 industrial production Methods 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract 1
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 28
- 238000001179 sorption measurement Methods 0.000 description 27
- 229910002092 carbon dioxide Inorganic materials 0.000 description 14
- 239000001569 carbon dioxide Substances 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000047 product Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 8
- 239000002184 metal Substances 0.000 description 6
- 239000011148 porous material Substances 0.000 description 6
- 239000003446 ligand Substances 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- KOPFEFZSAMLEHK-UHFFFAOYSA-N 1h-pyrazole-5-carboxylic acid Chemical compound OC(=O)C=1C=CNN=1 KOPFEFZSAMLEHK-UHFFFAOYSA-N 0.000 description 2
- CTJLHQOKWJEKHY-UHFFFAOYSA-N 5-aminopentylphosphonic acid Chemical compound NCCCCCP(O)(O)=O CTJLHQOKWJEKHY-UHFFFAOYSA-N 0.000 description 2
- CDXRGXUDSDPCOI-UHFFFAOYSA-N N.OP(O)=O Chemical compound N.OP(O)=O CDXRGXUDSDPCOI-UHFFFAOYSA-N 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000003345 natural gas Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 239000013257 coordination network Substances 0.000 description 1
- 239000013256 coordination polymer Substances 0.000 description 1
- 229920001795 coordination polymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000002459 sustained effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000011800 void material Substances 0.000 description 1
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- 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
- 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
- B01D53/02—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 by adsorption, e.g. preparative gas chromatography
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- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/46—Removing components of defined structure
- B01D53/62—Carbon oxides
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- 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
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/81—Solid phase processes
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- 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
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- 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
- B01J20/28002—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 physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D2251/00—Reactants
- B01D2251/80—Organic bases or salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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Abstract
The application relates to a high-efficiency stable MOFs composite material, a preparation method and carbon neutralization application, and belongs to the technical field of metal organic framework materials, wherein the preparation method of the MOFs composite material comprises the following steps: preparing HKUST-1 by a solvent thermal synthesis method; and (3) taking HKUST-1 as a carrier, loading organic amino phosphonic acid, and preparing the organic amino phosphonic acid@HKUST-1 composite material. The MOFs composite material prepared by the method has high stability, the phosphonic acid groups can be strongly combined with the metal center, and SO in the flue gas of the bituminous coal power plant is avoidedx、NOxAnd a small amount of hydrochloric acid can be exposed in the smoke environment for 30 days, the performance is reduced by only 12 percent, and the device can trap CO in a flue for a long time 2 Is provided). The application has low equipment requirement, economy and environmental protection, and regeneratesThe preparation process is simple, and is suitable for large-scale industrial production.
Description
Technical Field
The application relates to the technical field of metal organic framework materials, in particular to a high-efficiency stable MOFs composite material, a preparation method and carbon neutralization application.
Background
Carbon dioxide is a major artificial greenhouse gas that is emitted primarily through various social activities, such as burning fossil fuels and many chemical processes. About 44% of carbon dioxide worldwide is emitted from coal, oil, compressed natural gas, fuel combustion, and the like. Due to the rapid development of industrialization, the consumption of energy is multiplied in order to meet the ever-increasing human demand. Currently, 85% of the total energy required is produced by burning fossil fuels, which ultimately results in carbon dioxide being emitted into the environment, thereby increasing its concentration. The post-combustion carbon dioxide capture method belongs to one of the most adaptive methods to complement the retrofit options of existing power plants.
Emerging MOFs-based materials are considered to be effective adsorbents for carbon dioxide with large surface area, diverse structure, composition, high porosity, large void volume, and can be used to store gases. MOFs have a three-dimensional microporous crystalline structure consisting of a network of metal ligands having a central metal atom to which the ligands are attached, the central metal atom and the ligands being linked by covalent bonds. MOFs are also known as coordination networks or coordination polymers due to covalent bonds. In synthetic MOFs, pores and channels can be up to nanometers in size, which can accommodate carbon dioxide. MOFs can store 10-12 times more carbon dioxide than empty containers alone at high pressure. Once the carbon dioxide is contained by the MOFs, it can be stored in pores and channels.
The stability of MOFs is an important factor, determining that it plays a critical role in the capture of carbon dioxide in harsh environments that can be sustained. Typical constituents of the flue gas include 73% -77% N 2 15 to 16 percent of CO2, 5 to 7 percent of water vapor and 3 to 4 percent of O 2 Trace amounts of SOx, NOx and hydrochloric acid, which creates a very harsh corrosive environment for various carbon capture materials. It is critical to expose MOFs to such harsh environments and maintain their stability.
The prior patent with the publication number of CN 111225730A describes a high adsorption capacity supported polyamine metal organic framework Mg 2 (dobpdc) (dobpdc 4- 4,4 '-dioxybiphenyl-3, 3' -dicarboxylic acid radical), has high adsorption capacity and selectivity, stable and rapid adsorption kinetics, and can adsorb CO in flue gas 2 And (5) quick absorption. The adsorption material can be suitable for coal-fired power plants or natural gas power plants. However, the organic ligand in the framework is expensive, and needs to be synthesized independently, so that the industrial production steps are increased, and the production cost is increased. Meanwhile, the stability is poor, and the structure is easily damaged by corrosive gas in the flue gas environment, so that the flue gas is inactivated.
The prior patent with publication number CN 104258814A describes a pyrazole-carboxylic acid bifunctional ligand group MOFs which have high specific surface area and stability and are resistant to CO 2 Has high adsorption selectivity and can well separate CO from industrial waste gas 2 . However, the ligand is difficult to obtain, and the byproducts are more in the synthesis process, so that the environment pollution is easy to cause, and the method is not suitable for comprehensive popularization and application.
Disclosure of Invention
Aiming at the defects in the prior art, the application aims to provide a ring with simpler reaction, lower costEnvironmentally friendly high-efficiency stable MOFs composite material, CO 2 The adsorption performance is better, the performance is only reduced by 12 percent after the adsorption performance is exposed in a flue gas environment for 30 days, and the adsorption performance is improved in a CO of a bituminous coal power plant 2 The trapping field has better application. In order to achieve the above purpose, the present application is realized by the following technical scheme:
a preparation method of an efficient and stable MOFs composite material comprises the following steps:
step 1: preparing HKUST-1 by a solvent thermal synthesis method;
step 2: and (3) taking the HKUST-1 prepared in the step (1) as a carrier, loading organic amino phosphonic acid, and preparing the organic amino phosphonic acid@HKUST-1 composite material.
Wherein, the step 1 specifically includes the following steps:
step 101: adding anhydrous copper nitrate into N, N-dimethylformamide, marking as a solution A, and stirring;
step 102: adding trimesic acid powder into absolute ethyl alcohol, marking as solution B, and stirring;
step 103: slowly adding the solution A into the solution B, marking the solution A as the solution C, and stirring;
step 104: transferring the solution C into a Teflon reaction kettle for hydrothermal reaction;
step 105: after the hydrothermal reaction is finished, washing the product obtained in the step 104 by using absolute methanol, centrifuging, and vacuum drying and activating for later use.
Wherein the mass ratio of the trimesic acid to the anhydrous copper nitrate in the step 1 is 1:2.5-4.
In the step 101, the volume of the N, N-dimethylformamide is 30-50mL, and the stirring time is 10-30min;
the volume of the absolute ethyl alcohol in the step 102 is 30-50mL, and the stirring time is 10-30min;
in step 103, stirring for 10-30min;
in the step 104, the volume ratio of the Teflon reaction kettle to the solution C is 2:1, heating at 80-120 ℃ for 12-24 hours;
the centrifugal speed in the step 105 is 8000-10000rpm, the centrifugal time is 10-30min, the drying temperature is 120-150 ℃ and the drying time is 12-24h.
Preferably: the step 2 specifically comprises the following steps:
step 201: dissolving organic aminophosphonic acid in absolute ethyl alcohol to prepare solution F;
step 202: adding the dried and activated HKUST-1 into the solution F in the step 201, uniformly stirring, and transferring the solution F into a closed container for reaction;
step 203: and (3) after the reaction is finished, washing the product obtained in the step 202 by using absolute methanol, centrifuging, and drying in vacuum overnight to obtain the efficient and stable organic amino phosphonic acid@HKUST-1 composite material.
Wherein the organic amino phosphonic acid in the step 2 is selected from one of 3-aminopropyl phosphonic acid, 4-aminobutyl phosphonic acid, 5-aminopentyl phosphonic acid and 1- (butylamino) -1-methylethyl ] -phosphonic acid.
The molar mass of the organic amino phosphonic acid in the step 201 is 5-5.5mmol, and the volume of the absolute ethyl alcohol is 30-50mL.
The reaction temperature in the step 202 is room temperature, and the reaction time is 24-36h.
In the step 203, the centrifugal speed is 8000-10000rpm, the centrifugal time is 10-30min, the drying temperature is 120-150 ℃ and the drying time is 12-24h.
The application has the following beneficial effects:
the preparation method of the high-efficiency stable MOFs composite material is simple, mild in reaction condition, environment-friendly, has potential of industrial mass production, and is suitable for comprehensive popularization and application.
The efficient stable MOFs composite material can generate M-O-P bond because phosphonic acid in organic phosphonic acid ammonia is combined with MOFs unsaturated metal center, and is different from intermolecular acting force generated by combining general amino composite material and MOFs, the bonding capability of the bond is stronger, wherein M is metal with stronger charge capability such as Ti, zr, zn, al, SO that SO in flue gas of a bituminous coal power plant can be avoidedx、NOxAnd a small amount of hydrochloric acid corrodes the flue gas, the performance is only reduced by 12% after the flue gas is exposed in a flue gas environment for 30 days, and the flue gas is long-term in a flue gas of a bituminous coal power plantCO capture 2 Is provided).
The high-efficiency stable MOFs composite material improves the stability and simultaneously, the amino group carried on the modified material can be combined with CO 2 Reaction, R-NH 2 +CO 2 =r-NH-CO-OHR, so that its CO 2 The adsorption performance is greatly improved compared with that of the pure MOFs.
Drawings
FIG. 1 is a CO of the present application 2 Adsorption capacity map.
FIG. 2 is a graph of CO in the smoke environment of a bituminous coal power plant in accordance with the present application 2 Adsorption capacity change chart.
Detailed Description
The technical scheme of the present application is described in further detail below in conjunction with specific embodiments. It should be understood that these examples are intended to illustrate the application and are not intended to limit the scope of the application in any way.
Example 1
4g of anhydrous copper nitrate is dissolved in N, N-dimethylformamide and stirred for 10min at 25 ℃, and the solution is marked as solution A;1.5g of trimesic acid is dissolved in 30mL of absolute ethanol and stirred for 10min at 25 ℃ and is marked as solution B; solution A was slowly added to solution B, maintained at temperature, continuously stirred, noted as solution V, and then solution C was transferred to a Teflon reactor with a volume of solution C of one half of the total volume of the reactor and heated at 80℃for 12h. After the reaction is finished, washing the product with absolute ethyl alcohol for 3 times, centrifuging for 10min at 8000rpm, and drying and activating for 12h at 120 ℃ in vacuum for standby.
5mmol of 1- (butylamino) -1-methylethyl]Phosphonic acid in 30mL of absolute ethanol, noted solution D; adding activated 1g of HKUST-1 into the solution D, and stirring in a water bath at 25 ℃ for 24 hours; washing with anhydrous methanol for 3 times, centrifuging at 8000rpm for 10min, and vacuum drying at 120deg.C for 12 hr to obtain high-efficiency stable 1- (butylamino) -1-methylethyl]Phosphonic acid @ HKUST-1 composite material, CO thereof 2 The adsorption effect is shown in Table 1.
Example 2
4g of anhydrous copper nitrate is dissolved in N, N-dimethylformamide and stirred for 10min at 25 ℃, and the solution is marked as solution A;1.5g of trimesic acid is dissolved in 30mL of absolute ethanol and stirred for 10min at 25 ℃ and is marked as solution B; solution A was slowly added to solution B, maintained at temperature, continuously stirred, noted as solution V, and then solution C was transferred to a Teflon reactor with a volume of solution C of one half of the total volume of the reactor and heated at 80℃for 12h. After the reaction is finished, washing the product with absolute ethyl alcohol for 3 times, centrifuging for 10min at 8000rpm, and drying and activating for 12h at 120 ℃ in vacuum for standby.
5mmol of 3-aminopropyl phosphonic acid was dissolved in 30mL of absolute ethanol and noted as solution D; adding activated 1g of HKUST-1 into the solution D, and stirring in a water bath at 25 ℃ for 24 hours; washing with anhydrous methanol for 3 times, centrifuging at 8000rpm for 10min, and vacuum drying at 120deg.C for 12 hr to obtain high-efficiency stable 3-aminopropyl phosphonic acid @ HKUST-1 composite material with CO 2 The adsorption effect is shown in Table 1.
Example 3
4g of anhydrous copper nitrate is dissolved in N, N-dimethylformamide and stirred for 10min at 25 ℃, and the solution is marked as solution A;1.5g of trimesic acid is dissolved in 30mL of absolute ethanol and stirred for 10min at 25 ℃ and is marked as solution B; solution A was slowly added to solution B, maintained at temperature, continuously stirred, noted as solution V, and then solution C was transferred to a Teflon reactor with a volume of solution C of one half of the total volume of the reactor and heated at 80℃for 12h. After the reaction is finished, washing the product with absolute ethyl alcohol for 3 times, centrifuging for 10min at 8000rpm, and drying and activating for 12h at 120 ℃ in vacuum for standby.
5mmol of 4-aminobutylphosphonic acid was dissolved in 30mL of absolute ethanol and noted as solution D; adding activated 1g of HKUST-1 into the solution D, and stirring in a water bath at 25 ℃ for 24 hours; washing with anhydrous methanol for 3 times, centrifuging at 8000rpm for 10min, and vacuum drying at 120deg.C for 12 hr to obtain high-efficiency stable 4-aminobutylphosphonic acid @ HKUST-1 composite material with CO 2 The adsorption effect is shown in Table 1.
Example 4
4g of anhydrous copper nitrate is dissolved in N, N-dimethylformamide and stirred for 10min at 25 ℃, and the solution is marked as solution A;1.5g of trimesic acid is dissolved in 30mL of absolute ethanol and stirred for 10min at 25 ℃ and is marked as solution B; solution A was slowly added to solution B, maintained at temperature, continuously stirred, noted as solution V, and then solution C was transferred to a Teflon reactor with a volume of solution C of one half of the total volume of the reactor and heated at 80℃for 12h. After the reaction is finished, washing the product with absolute ethyl alcohol for 3 times, centrifuging for 10min at 8000rpm, and drying and activating for 12h at 120 ℃ in vacuum for standby.
5mmol of 5-aminopentylphosphonic acid was dissolved in 30mL of absolute ethanol and noted as solution D; adding activated 1g of HKUST-1 into the solution D, and stirring in a water bath at 25 ℃ for 24 hours; washing with anhydrous methanol for 3 times, centrifuging at 8000rpm for 10min, and vacuum drying at 120deg.C for 12 hr to obtain high-efficiency stable 5-aminopentylphosphonic acid @ HKUST-1 composite material, CO thereof 2 The adsorption effect is shown in Table 1.
Comparative example 1
4g of anhydrous copper nitrate is dissolved in N, N-dimethylformamide and stirred for 10min at 25 ℃, and the solution is marked as solution A;1.5g of trimesic acid is dissolved in 30mL of absolute ethanol and stirred for 10min at 25 ℃ and is marked as solution B; solution A was slowly added to solution B, maintained at temperature, continuously stirred, noted as solution V, and then solution C was transferred to a Teflon reactor with a volume of solution C of one half of the total volume of the reactor and heated at 80℃for 12h. After the reaction is finished, washing the product with absolute ethyl alcohol for 3 times, centrifuging for 10min at 8000rpm, and drying and activating for 12h at 120 ℃ in vacuum for standby.
Comparative example 2
4g of anhydrous copper nitrate is dissolved in N, N-dimethylformamide and stirred for 10min at 25 ℃, and the solution is marked as solution A;1.5g of trimesic acid is dissolved in 30mL of absolute ethanol and stirred for 10min at 25 ℃ and is marked as solution B; solution A was slowly added to solution B, maintained at temperature, continuously stirred, noted as solution V, and then solution C was transferred to a Teflon reactor with a volume of solution C of one half of the total volume of the reactor and heated at 80℃for 12h. After the reaction is finished, washing the product with absolute ethyl alcohol for 3 times, centrifuging for 10min at 8000rpm, and drying and activating for 12h at 120 ℃ in vacuum for standby.
2.5 mmol of 1- (butylamino) -1-methylethyl]Phosphonic acid in 30mL of absolute ethanol, noted solution D; adding activated 1g of HKUST-1 into the solution D, and stirring in a water bath at 25 ℃ for 24 hours; washing with anhydrous methanol for 3 times, centrifuging at 8000rpm for 10min, and vacuum drying at 120deg.C for 12 hr to obtain high-efficiency stable 1- (butylamino) -1-methylethyl]Phosphonic acid @ HKUST-1 complexComposite material-2, its CO 2 The adsorption effect is shown in Table 1.
Comparative example 3
4g of anhydrous copper nitrate is dissolved in N, N-dimethylformamide and stirred for 10min at 25 ℃, and the solution is marked as solution A;1.5g of trimesic acid is dissolved in 30mL of absolute ethanol and stirred for 10min at 25 ℃ and is marked as solution B; solution A was slowly added to solution B, maintained at temperature, continuously stirred, noted as solution V, and then solution C was transferred to a Teflon reactor with a volume of solution C of one half of the total volume of the reactor and heated at 80℃for 12h. After the reaction is finished, washing the product with absolute ethyl alcohol for 3 times, centrifuging for 10min at 8000rpm, and drying and activating for 12h at 120 ℃ in vacuum for standby.
10 mmol of 1- (butylamino) -1-methylethyl]Phosphonic acid in 30mL of absolute ethanol, noted solution D; adding activated 1g of HKUST-1 into the solution D, and stirring in a water bath at 25 ℃ for 24 hours; washing with anhydrous methanol for 3 times, centrifuging at 8000rpm for 10min, and vacuum drying at 120deg.C for 12 hr to obtain high-efficiency stable 1- (butylamino) -1-methylethyl]Phosphonic acid @ HKUST-1 composite-3, CO thereof 2 The adsorption effect is shown in Table 1.
TABLE 1 product CO 2 Adsorption capacity and CO thereof by flue gas environment 2 Influence of adsorption Capacity
| Case (L) | CO 2 Adsorption capacity/mmol/g | CO after 30 days in flue gas environment 2 Adsorption amount/mmol/g |
| Example 1 | 3.64 | 3.21 |
| Example 2 | 3.13 | 2.35 |
| Example 3 | 3.2 | 2.56 |
| Example 4 | 3.41 | 2.90 |
| Comparative example 1 | 3.04 | 0.15 |
| Comparative example 2 | 3.12 | 2.18 |
| Comparative example 3 | 2.85 | 3.14 |
As shown in fig. 2: the composite material of the examples and the comparative examples contains 73 to 77 percent of N in the smoke environment 2 ， 15%-16% CO 2 5% -7% of water vapor and 3% -4% of O 2 Trace amounts of SOx, NOx and CO of hydrochloric acid 2 Adsorption capacity change chart.
Examples 2, 3 and 4 have insufficient effects compared with example 1, mainly because the longer the alkyl long chain at the other side of the phosphonic acid is, the stronger the phosphonic acid in the organic phosphonic acid ammonia is combined with the MOFs unsaturated metal center to generate M-O-P bond, the less easy the M-O-P bond is fallen off, wherein M is a metal with stronger charge capacity such as Ti, zr, zn, al; comparative example 1 without any addition of organic aminophosphonic acid, a sharp decrease in carbon dioxide adsorption in the flue gas environment can be seen from table 1; the organic amino phosphonic acid added in the comparative example 2 is insufficient, the carbon dioxide adsorption amount is increased compared with that of the comparative example 1, but the carbon dioxide adsorption amount is still obviously reduced compared with that of the example 1 after the organic amino phosphonic acid is exposed for 30 days in a flue gas environment; the excessive amount of the organic amino phosphonic acid added in the comparative example 3 causes blocking of MOFs pore canal, the carbon dioxide adsorption amount of the MOFs pore canal is reduced compared with that of the comparative example 1, but after the MOFs pore canal is exposed in a smoke environment for a plurality of days, the excessive organic amino phosphonic acid volatilizes, and the adsorption amount of the MOFs pore canal is increased.
In conclusion, the organic amino phosphonic acid@HKUST-1 composite material prepared by the method has high stability, phosphonic acid groups can be strongly combined with metal centers, and SO in flue gas of bituminous coal power plants is avoidedx、NOxAnd a small amount of hydrochloric acid can be exposed in the smoke environment for 30 days, the performance is reduced by only 12 percent, and the device can trap CO in a flue for a long time 2 Is provided). The application has low equipment requirement, is economical and environment-friendly, is convenient to regenerate, has simple preparation process and is suitable for large-scale industrial production.
The foregoing describes specific embodiments of the present application. It is to be understood that the application is not limited to the particular embodiments described above, and that various changes or modifications may be made by those skilled in the art within the scope of the appended claims without affecting the spirit of the application. The embodiments of the application and the features of the embodiments may be combined with each other arbitrarily without conflict.
Claims (6)
1. The preparation method of the high-efficiency stable MOFs composite material is characterized by comprising the following steps of:
step 101: adding anhydrous copper nitrate into N, N-dimethylformamide, marking as a solution A, and stirring;
step 102: adding trimesic acid powder into absolute ethyl alcohol, marking as solution B, and stirring;
step 103: slowly adding the solution A into the solution B, marking the solution A as the solution C, and stirring;
step 104: transferring the solution C into a Teflon reaction kettle for hydrothermal reaction to prepare HKUST-1;
step 105: after the hydrothermal reaction is finished, washing the HKUST-1 obtained in the step 104 by absolute methanol, centrifuging, and vacuum drying and activating for later use;
step 201: dissolving any one of 3-aminopropyl phosphonic acid, 4-aminobutyl phosphonic acid, 2-aminoethyl phosphonic acid and 1- (butylamino) -1-methylethyl ] -phosphonic acid in absolute ethanol to prepare a solution F;
step 202: adding the HKUST-1 dried and activated in the step 105 into the solution F in the step 201, uniformly stirring, and then transferring the solution F into a closed container for reaction, wherein the reaction temperature is room temperature, and the reaction time is 24-36h;
step 203: and (3) after the reaction in the step 202 is finished, washing the product obtained in the step 202 by using absolute methanol, centrifuging, and drying in vacuum overnight to obtain the efficient and stable organic amino phosphonic acid@HKUST-1 composite material.
2. The method for preparing high-efficiency stable MOFs composite materials according to claim 1, wherein the mass ratio of trimesic acid in step 102 to anhydrous copper nitrate in step 101 is 1:2.5-4.
3. The method for preparing the efficient and stable MOFs composite material according to claim 1, wherein the method is characterized in that,
in the step 101, the volume of the N, N-dimethylformamide is 30-50mL, and the stirring time is 10-30min;
the volume of the absolute ethyl alcohol in the step 102 is 30-50mL, and the stirring time is 10-30min;
in the step 103, the stirring time is 10-30min;
in the step 104, the volume ratio of the Teflon reaction kettle to the solution C is 2:1, heating at 80-120 ℃ for 12-24 hours;
the centrifugal speed in the step 105 is 8000-10000rpm, the centrifugal time is 10-30min, the drying temperature is 120-150 ℃ and the drying time is 12-24h.
4. The method for preparing high-efficiency stable MOFs composite according to claim 1, wherein the molar mass of the organic amino phosphonic acid in the step 201 is 5-5.5mmol, and the volume of absolute ethyl alcohol is 30-50mL;
in the step 203, the centrifugal speed is 8000-10000rpm, the centrifugal time is 10-30min, the drying temperature is 120-150 ℃ and the drying time is 12-24h.
5. A highly stable MOFs composite material, characterized in that it is obtainable by the process according to any one of claims 1 to 4.
6. Use of the high efficiency stable MOFs composite of claim 5 as carbon neutralizer.
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114146688A (en) * | 2021-10-28 | 2022-03-08 | 中国科学院山西煤炭化学研究所 | Preparation method and application of water-resistant MOFs (metal-organic frameworks) based material |
| CN114570178A (en) * | 2022-03-29 | 2022-06-03 | 上海交通大学 | Carbon dioxide absorbent and preparation method and application thereof |
| CN114849668A (en) * | 2022-05-12 | 2022-08-05 | 上海交通大学 | Preparation method and carbon neutralization application of high-hydrophobicity acid-corrosion-resistant MOFs-based composite material |
| CN114849653A (en) * | 2022-05-12 | 2022-08-05 | 上海交通大学 | Amine modified porous molecular sieve for efficiently trapping carbon dioxide, and preparation method and application thereof |
| CN114887594A (en) * | 2022-06-06 | 2022-08-12 | 上海交通大学 | Hydrophobic HKUST-1 composite material, preparation method and carbon neutralization application |
-
2023
- 2023-05-18 CN CN202310561786.3A patent/CN116272912B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114146688A (en) * | 2021-10-28 | 2022-03-08 | 中国科学院山西煤炭化学研究所 | Preparation method and application of water-resistant MOFs (metal-organic frameworks) based material |
| CN114570178A (en) * | 2022-03-29 | 2022-06-03 | 上海交通大学 | Carbon dioxide absorbent and preparation method and application thereof |
| CN114849668A (en) * | 2022-05-12 | 2022-08-05 | 上海交通大学 | Preparation method and carbon neutralization application of high-hydrophobicity acid-corrosion-resistant MOFs-based composite material |
| CN114849653A (en) * | 2022-05-12 | 2022-08-05 | 上海交通大学 | Amine modified porous molecular sieve for efficiently trapping carbon dioxide, and preparation method and application thereof |
| CN114887594A (en) * | 2022-06-06 | 2022-08-12 | 上海交通大学 | Hydrophobic HKUST-1 composite material, preparation method and carbon neutralization application |
Non-Patent Citations (4)
| Title |
|---|
| 周玲玲 ; 汤立红 ; 宁平 ; 李凯 ; 包双友 ; 朱婷婷 ; 金旭 ; 张秀英 ; .金属有机骨架材料在气体吸附与分离中的应用研究进展.材料导报.2017,(19),全文. * |
| 牛照栋 ; 关清卿 ; 陈秋玲 ; 宁平 ; 谷俊杰 ; .膦酸类金属-有机骨架材料对CO_2的吸附性能研究进展.化工进展.2017,(05),第1782-1790页. * |
| 牛照栋 ; 张德华 ; 孟凡凡 ; 庙荣荣 ; 陈秋玲 ; 宁平 ; 谷俊杰 ; 关清卿 ; .锆基金属有机骨架材料的合成及其对CO_2/N_2的吸附与分离性能研究.化工新型材料.2018,(10),全文. * |
| 邵悦 ; 马勇 ; .氨基表面功能化的有序介孔杂合材料的一步法合成及其对重金属离子和CO_2的吸附特性.化学学报.2012,(18),全文. * |
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