CN115475663B - DABCO type high-performance carbon dioxide adsorbent and preparation method thereof - Google Patents
DABCO type high-performance carbon dioxide adsorbent and preparation method thereof Download PDFInfo
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 239000001569 carbon dioxide Substances 0.000 title claims abstract description 85
- 229910002092 carbon dioxide Inorganic materials 0.000 title claims abstract description 85
- 239000003463 adsorbent Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 43
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 239000012973 diazabicyclooctane Substances 0.000 title claims abstract 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 69
- 239000011347 resin Substances 0.000 claims abstract description 60
- 229920005989 resin Polymers 0.000 claims abstract description 60
- 238000005406 washing Methods 0.000 claims abstract description 57
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- 238000001914 filtration Methods 0.000 claims abstract description 41
- 239000007795 chemical reaction product Substances 0.000 claims abstract description 40
- 238000006243 chemical reaction Methods 0.000 claims abstract description 33
- 239000000243 solution Substances 0.000 claims abstract description 29
- 239000007864 aqueous solution Substances 0.000 claims abstract description 26
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000008961 swelling Effects 0.000 claims abstract description 22
- 238000005342 ion exchange Methods 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 19
- FTTATHOUSOIFOQ-UHFFFAOYSA-N 1,2,3,4,6,7,8,8a-octahydropyrrolo[1,2-a]pyrazine Chemical compound C1NCCN2CCCC21 FTTATHOUSOIFOQ-UHFFFAOYSA-N 0.000 claims abstract description 18
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001035 drying Methods 0.000 claims abstract description 15
- 239000011734 sodium Substances 0.000 claims abstract description 13
- INQOMBQAUSQDDS-UHFFFAOYSA-N iodomethane Chemical compound IC INQOMBQAUSQDDS-UHFFFAOYSA-N 0.000 claims abstract description 12
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims abstract description 12
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 238000000034 method Methods 0.000 claims description 22
- 239000000047 product Substances 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 239000000460 chlorine Substances 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000001514 detection method Methods 0.000 claims description 9
- 229920005990 polystyrene resin Polymers 0.000 claims description 5
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 4
- 229910052801 chlorine Inorganic materials 0.000 claims description 4
- 238000004132 cross linking Methods 0.000 claims description 4
- 238000005273 aeration Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 41
- 125000001453 quaternary ammonium group Chemical group 0.000 description 16
- 239000003957 anion exchange resin Substances 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 8
- -1 hydrogen ions Chemical class 0.000 description 8
- 239000000463 material Substances 0.000 description 8
- 230000007935 neutral effect Effects 0.000 description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 238000009423 ventilation Methods 0.000 description 5
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 2
- 150000001450 anions Chemical class 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000007783 nanoporous material Substances 0.000 description 2
- 239000010452 phosphate Substances 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 2
- AVQQQNCBBIEMEU-UHFFFAOYSA-N 1,1,3,3-tetramethylurea Chemical compound CN(C)C(=O)N(C)C AVQQQNCBBIEMEU-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O ammonium group Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004218 chloromethyl group Chemical group [H]C([H])(Cl)* 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000003795 desorption 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
- 230000000694 effects Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 239000002149 hierarchical pore Substances 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000010792 warming Methods 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
- B01J41/00—Anion exchange; Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/08—Use of material as anion exchangers; Treatment of material for improving the anion exchange properties
- B01J41/12—Macromolecular compounds
- B01J41/13—Macromolecular compounds obtained otherwise than by reactions only involving unsaturated carbon-to-carbon bonds
-
- 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
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/40—Capture or disposal of greenhouse gases of CO2
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention provides a DABCO type high-performance carbon dioxide adsorbent and a preparation method thereof; the preparation method comprises the following steps: a) Swelling resin, mixing with 1, 4-diazabicyclo [2, 2] octane, stirring at 25-60 ℃ for reaction for 10-14 h, filtering and washing to obtain a first reaction product; b) Draining the water of the first reaction product obtained in the step a), adding tetrahydrofuran, methyl iodide and sodium hydroxide aqueous solution, adding tetrabutylammonium bromide, stirring and reacting for 10-14 h at 50-60 ℃, and filtering and washing to obtain a second reaction product; c) Filtering the second reaction product obtained in the step b), adding Na 2CO3 solution for a plurality of ion exchange reactions, washing with water, filtering, and drying at 40-60 ℃ to obtain the DABCO type high-performance carbon dioxide adsorbent. The DABCO type high-performance carbon dioxide adsorbent prepared by the preparation method improves the adsorption performance of the carbon dioxide adsorbent resin on the premise of not affecting the adsorption rate.
Description
Technical Field
The invention relates to the technical field of carbon dioxide adsorption resins, in particular to a DABCO type high-performance carbon dioxide adsorbent and a preparation method thereof.
Background
The large use of fossil energy sources results in a large emission of carbon dioxide gas, the main component of which is greenhouse gas, and the continuous increase in the concentration of which in the atmosphere causes ecological problems such as global warming, seawater acidification, and the like. Carbon dioxide capture, utilization and sequestration technologies (CCUS) are considered as effective technological approaches to solving the carbon dioxide problem. The direct carbon dioxide air capture technology (DAC) is a technology which is commonly used at present and aims to solve the problems of small distributed source emission and large concentrated source emission, and a practical and effective method is provided for realizing negative emission of carbon dioxide.
Among these, carbon dioxide adsorbents are the core of this technological approach. The nano-porous material loaded with carbonate ions or phosphate ions can be used for carbon dioxide adsorption by the technology, can adsorb CO 2 in a dry environment and desorb CO 2 in a wet environment, and can realize adsorption/desorption cycle by only adjusting humidity. As shown in reaction (1), when the ambient humidity is low, as the interior of the material is a nano-level micropore, water molecules can be ionized to generate hydrogen ions and hydroxyl ions, and the hydrogen ions and the hydroxyl ions respectively react with carbonate ions loaded on the material and carbon dioxide molecules in the air to generate bicarbonate ions, so that the adsorption of carbon dioxide is completed, as shown in reactions (2) and (3); the humidity rises and the two bicarbonate ions react and the carbon dioxide is released as shown in reaction (4).
In the nanopore structure, the balance of carbonate ions and bicarbonate ions is affected by the number of water molecules. As the number of water molecules in the surrounding environment decreases (less than 7), the free energy of hydrolysis of carbonate ions is negative, which is energetically favorable for the formation of bicarbonate ions and hydroxyl ions; in a wet environment, the hydration reaction of bicarbonate ions is facilitated, namely, the reverse reaction is spontaneously carried out. Thus, the material may provide only humidity conditioning to effect the adsorption/desorption cycle.
The total reaction equation of this reaction is shown in reaction (5). In the nano pore structure, a considerable part of reversible reaction can be carried out, when the number of water molecules is small, the balance is shifted to the right, the number of hydroxyl ions is increased, and the absorption of carbon dioxide in the air is promoted; conversely, the hydroxide ions are reduced and the carbon dioxide release is increased.
The nano porous material can be subjected to ion exchange loading by using carbonate solution or phosphate solution and the like to realize the aim of adsorbing carbon dioxide, such as zeolite, graphite powder and the like. However, the load ions and the material are only physically loaded and have no available chemical bond connection, so the load ions and the material are quite unstable and easy to fall off. After multiple adsorption and desorption cycles, the adsorption performance of the material is greatly reduced because the available ions loaded by the material are very likely to be washed away by water.
At present, strong-base anion exchange resins are widely used in direct air trapping technology (DAC) because of their stable performance and their capability of exchanging anions in solution with hydroxyl ions. As shown in a formula (6) (the preparation process of the double quaternary ammonium type anion exchange resin), chloromethyl polystyrene resin reacts with 1, 3-tetramethylguanidine to generate double quaternary ammonium strong alkaline anion exchange resin, wherein a benzene ring is connected with double quaternary ammonium groups with two unit positive charges, and two chloride ions are loaded on the double quaternary ammonium groups as anion groups for balancing charges; and then carrying out ion exchange on the product by using carbonate solution or phosphate solution and the like, thus carrying out carbon dioxide adsorption.
The content of quaternary ammonium groups of the double-quaternary ammonium strong-alkali anion exchange resin prepared by the method is doubled, namely 1mol of resin can load 1mol of carbonate ions/phosphate ions, so that the carbon dioxide adsorption performance of the resin is improved; however, the adsorption performance is unstable, about 1.2-1.4 mmo1/g, and is greatly affected by environmental conditions, and the theoretical adsorption capacity is not achieved.
Disclosure of Invention
In view of the above, the present invention aims to provide a DABCO type high-performance carbon dioxide adsorbent and a preparation method thereof, wherein the DABCO type high-performance carbon dioxide adsorbent obtained by the preparation method provided by the present invention improves the adsorption performance of carbon dioxide adsorbent resin, namely, the resin with the same quality, on the premise of not affecting the adsorption rate, and the carbon dioxide adsorption amount of the DABCO type high-performance carbon dioxide adsorbent (double quaternary ammonium anion exchange resin) provided by the present invention is higher.
The invention provides a preparation method of a DABCO type high-performance carbon dioxide adsorbent, which comprises the following steps:
a) Swelling resin, mixing with 1, 4-diazabicyclo [2, 2] octane, stirring at 25-60 ℃ for reaction for 10-14 h, filtering and washing to obtain a first reaction product;
b) Draining the water of the first reaction product obtained in the step a), adding tetrahydrofuran, methyl iodide and sodium hydroxide aqueous solution, adding tetrabutylammonium bromide, stirring and reacting for 10-14 h at 50-60 ℃, and filtering and washing to obtain a second reaction product;
c) Filtering the second reaction product obtained in the step b), adding Na 2CO3 solution for a plurality of ion exchange reactions, washing with water, filtering, and drying at 40-60 ℃ to obtain the DABCO type high-performance carbon dioxide adsorbent.
Preferably, the resin in the step a) is chloromethylated polystyrene resin, the crosslinking degree is 5-10%, and the chlorine content is 3-6 mmol/g.
Preferably, the swelling agent used in the swelling process in step a) is selected from one or more of N, N-dimethylformamide, tetrahydrofuran, benzene and toluene; the dosage of the swelling agent is 4 ml-6 ml of swelling agent for every 1g of resin; the swelling time is 12-25 h.
Preferably, the molar ratio of resin to 1, 4-diazabicyclo [ 2.2.2 ] octane in step a) is 1: (2-4).
Preferably, the washing process in step a) is specifically:
And washing the filtered product with a hydrochloric acid aqueous solution of 0.5-1.5 mol/L, washing with a water solution of 0.5-1.5 mol/L for the first time, washing with a NaOH aqueous solution of the second time to neutrality, eluting until effluent liquid detection is free of Cl -, and washing with water for the third time to neutrality to obtain a first reaction product.
Preferably, the tetrahydrofuran is used in step b) in an amount of 0.5ml to 1.5ml of tetrahydrofuran per 1g of the resin of step a); the molar ratio of methyl iodide to the resin of step a) is (2-4): 1, a step of; the volume ratio of the tetrahydrofuran to the sodium hydroxide aqueous solution is 1: (2-5), wherein the molar concentration of the sodium hydroxide aqueous solution is 0.8-1.2 mol/L; the mass ratio of tetrabutylammonium bromide to the resin in the step a) is 1: (80-120).
Preferably, the process of the plurality of ion exchange reactions in step c) is specifically:
Adding 80ml to 120ml of Na 2CO3 solution with the concentration of 0.4mol/L to 0.6mol/L into the filtered second reaction product, stirring for 4 hours to 8 hours, filtering, washing with water, and filtering again to finish primary ion exchange; the ion exchange described above was repeated several times.
Preferably, the number of times is 4 to 6.
Preferably, the drying mode in the step c) is drying under ventilation condition, so as to obtain the DABCO type high-performance carbon dioxide adsorbent.
The invention also provides a DABCO type high-performance carbon dioxide adsorbent, which is prepared by adopting the preparation method of the technical scheme.
The invention provides a DABCO type high-performance carbon dioxide adsorbent and a preparation method thereof; the preparation method comprises the following steps: a) Swelling resin, mixing with 1, 4-diazabicyclo [2, 2] octane, stirring at 25-60 ℃ for reaction for 10-14 h, filtering and washing to obtain a first reaction product; b) Draining the water of the first reaction product obtained in the step a), adding tetrahydrofuran, methyl iodide and sodium hydroxide aqueous solution, adding tetrabutylammonium bromide, stirring and reacting for 10-14 h at 50-60 ℃, and filtering and washing to obtain a second reaction product; c) Filtering the second reaction product obtained in the step b), adding Na 2CO3 solution for a plurality of ion exchange reactions, washing with water, filtering, and drying at 40-60 ℃ to obtain the DABCO type high-performance carbon dioxide adsorbent. Compared with the prior art, the preparation method provided by the invention selects 1, 4-diazabicyclo [2, 2] octane as a reaction raw material, and realizes better overall interaction under specific process steps, conditions and parameters, so as to prepare the DABCO type high-performance carbon dioxide adsorbent; the DABCO type high-performance carbon dioxide adsorbent improves the adsorption performance of carbon dioxide adsorbent resin, namely the resin with the same quality on the premise of not affecting the adsorption rate, and the DABCO type high-performance carbon dioxide adsorbent (double quaternary ammonium anion exchange resin) provided by the invention has higher carbon dioxide adsorption capacity.
Meanwhile, the preparation method provided by the invention has the advantages of simple process, low energy consumption, economy, environmental protection and the like, and is low in cost, so that the preparation method has good application prospect and potential in the technical field of DAC.
Drawings
FIG. 1 is a FTIR characterization chart of a DABCO type high performance carbon dioxide adsorbent prepared by the preparation method provided in example 1 of the present invention;
FIG. 2 is a schematic diagram of an adsorption capacity test of CO 2 by a resin.
Detailed Description
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
The invention provides a preparation method of a DABCO type high-performance carbon dioxide adsorbent, which comprises the following steps:
a) Swelling resin, mixing with 1, 4-diazabicyclo [2, 2] octane, stirring at 25-60 ℃ for reaction for 10-14 h, filtering and washing to obtain a first reaction product;
b) Draining the water of the first reaction product obtained in the step a), adding tetrahydrofuran, methyl iodide and sodium hydroxide aqueous solution, adding tetrabutylammonium bromide, stirring and reacting for 10-14 h at 50-60 ℃, and filtering and washing to obtain a second reaction product;
c) Filtering the second reaction product obtained in the step b), adding Na 2CO3 solution for a plurality of ion exchange reactions, washing with water, filtering, and drying at 40-60 ℃ to obtain the DABCO type high-performance carbon dioxide adsorbent.
The invention firstly swells resin, then mixes with 1, 4-diazabicyclo [2, 2] octane, and then carries out stirring reaction for 10 h-14 h at 25 ℃ to 60 ℃, and then filters and washes to obtain a first reaction product. In the present invention, the resin is preferably a chloromethylated polystyrene resin, the crosslinking degree is preferably 5 to 10%, more preferably 6%, and the chlorine content is preferably 3 to 6mmol/g, more preferably 3.9 to 4mmol/g. The source of the resin is not particularly limited and commercially available products known to those skilled in the art may be used.
In the present invention, the swelling agent used in the swelling process is preferably one or more selected from the group consisting of N, N-dimethylformamide, tetrahydrofuran, benzene and toluene, more preferably N, N-Dimethylformamide (DMF); the source of the swelling agent is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the amount of the swelling agent is preferably 4ml to 6ml per 1g of the resin, more preferably 5ml per 1g of the resin.
In the present invention, the swelling time is preferably 12 to 25 hours, more preferably 24 hours.
In the present invention, the structural formula of the 1, 4-diazabicyclo [2, 2] octane (DABCO) is as follows:
The source of the 1, 4-diazabicyclo [2, 2] octane is not particularly limited in the present invention, and commercially available or self-made products known to those skilled in the art may be used.
In the present invention, the molar ratio of the resin to 1, 4-diazabicyclo [2, 2] octane is preferably 1: (2 to 4), more preferably 1:3.
The invention is stirred and reacted for 10 to 14 hours at the temperature of between 25 and 60 ℃, and preferably is reacted for 12 hours in the environment of between 50 and 60 ℃.
The process of the filtration is not particularly limited in the present invention, with the aim of obtaining a resin product.
In the present invention, the washing process is preferably specifically:
washing the filtered product with a hydrochloric acid aqueous solution of 0.5-1.5 mol/L, washing the filtered product with a second water solution to be neutral, eluting the filtered product with a NaOH aqueous solution of 0.5-1.5 mol/L until effluent liquid detection is free of Cl -, and washing the filtered product with a third water solution to be neutral to obtain a first reaction product;
More preferably:
And washing the filtered product with water for the first time, washing with 1mol/L hydrochloric acid aqueous solution, washing with water for the second time to be neutral, eluting with 1mol/L NaOH aqueous solution until effluent liquid detection is free of Cl -, and washing with water for the third time until effluent liquid is neutral (the effluent water phenolphthalein is not discolored) to obtain a first reaction product.
After the first reaction product is obtained, the first reaction product is drained, tetrahydrofuran, methyl iodide and sodium hydroxide aqueous solution are added, tetrabutylammonium bromide is added, stirring reaction is carried out for 10-14 h at 50-60 ℃, and then filtering and washing are carried out, so as to obtain a second reaction product.
The sources of the tetrahydrofuran, methyl iodide, aqueous sodium hydroxide solution and tetrabutylammonium bromide are not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the tetrahydrofuran is preferably used in an amount of 0.5ml to 1.5ml of tetrahydrofuran per 1g of the resin of step a), more preferably 1ml of tetrahydrofuran per 1g of the resin of step a); the molar ratio of methyl iodide to the resin of step a) is preferably (2 to 4): 1, more preferably 2:1, a step of; the volume ratio of the tetrahydrofuran to the sodium hydroxide aqueous solution is preferably 1: (2 to 5), more preferably 1:2.5; the molar concentration of the aqueous sodium hydroxide solution is preferably 0.8mol/L to 1.2mol/L, more preferably 1mol/L; the mass ratio of tetrabutylammonium bromide to the resin of step a) is preferably 1: (80 to 120), more preferably 1:100.
The invention is stirred and reacted for 10 to 14 hours at 50 to 60 ℃, preferably for 12 hours at 60 ℃.
The process of the filtration is not particularly limited in the present invention, with the aim of obtaining a resin product.
In the present invention, the washing process is preferably specifically:
Washing the filtered product with a hydrochloric acid aqueous solution of 0.5-1.5 mol/L, washing the filtered product with a second water solution to be neutral, eluting the filtered product with a NaOH aqueous solution of 0.5-1.5 mol/L until effluent liquid detection is free of Cl -, and washing the filtered product with a third water solution to be neutral to obtain a second reaction product;
More preferably:
And washing the filtered product with water for the first time, washing with 1mol/L hydrochloric acid aqueous solution, washing with water for the second time to be neutral, eluting with 1mol/L NaOH aqueous solution until effluent liquid detection is free of Cl -, and washing with water for the third time until effluent liquid is neutral (the effluent water phenolphthalein is not discolored) to obtain a second reaction product.
After the second reaction product is obtained, the obtained second reaction product is filtered, added with Na 2CO3 solution for a plurality of times of ion exchange reaction, washed and filtered, and dried at 40-60 ℃ to obtain the DABCO type high-performance carbon dioxide adsorbent.
The process of the filtration is not particularly limited in the present invention, with the aim of obtaining a resin product.
The source of the Na 2CO3 solution is not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the present invention, the process of the several ion exchange reactions is preferably specifically:
Adding 80ml to 120ml of Na 2CO3 solution with the concentration of 0.4mol/L to 0.6mol/L into the filtered second reaction product, stirring for 4 hours to 8 hours, filtering, washing with water, and filtering again to finish primary ion exchange; repeating the ion exchange for several times;
More preferably:
adding 100ml of Na 2CO3 solution with the concentration of 0.5mol/L into the filtered second reaction product, stirring for 6 hours, filtering, washing with water, and filtering again to finish one-time ion exchange; the ion exchange described above was repeated several times.
In the present invention, the number of times is preferably 4 to 6 times, more preferably 5 times.
In the present invention, drying is carried out at 40℃to 60℃and preferably at 40 ℃.
In the invention, the drying mode is preferably drying under ventilation condition, so as to obtain the DABCO type high-performance carbon dioxide adsorbent.
The reaction formula of the preparation method provided by the invention is as follows:
The preparation method provided by the invention selects 1, 4-diazabicyclo [2, 2] octane as a reaction raw material, and realizes better overall interaction under specific process steps, conditions and parameters, so as to prepare the DABCO type high-performance carbon dioxide adsorbent; the preparation method provided by the invention has the advantages of simple process, low energy consumption, economy, environmental protection and the like, and is low in cost, so that the preparation method has good application prospect and potential in the technical field of DAC.
The invention also provides a DABCO type high-performance carbon dioxide adsorbent, which is prepared by adopting the preparation method of the technical scheme.
The specific structural formula of the DABCO type high-performance carbon dioxide adsorbent provided by the invention is as follows:
The DABCO type high-performance carbon dioxide adsorbent improves the adsorption performance of carbon dioxide adsorbent resin, namely the resin with the same quality on the premise of not affecting the adsorption rate, and the DABCO type high-performance carbon dioxide adsorbent (double quaternary ammonium anion exchange resin) provided by the invention has higher carbon dioxide adsorption capacity.
The invention provides a DABCO type high-performance carbon dioxide adsorbent and a preparation method thereof; the preparation method comprises the following steps: a) Swelling resin, mixing with 1, 4-diazabicyclo [2, 2] octane, stirring at 25-60 ℃ for reaction for 10-14 h, filtering and washing to obtain a first reaction product; b) Draining the water of the first reaction product obtained in the step a), adding tetrahydrofuran, methyl iodide and sodium hydroxide aqueous solution, adding tetrabutylammonium bromide, stirring and reacting for 10-14 h at 50-60 ℃, and filtering and washing to obtain a second reaction product; c) Filtering the second reaction product obtained in the step b), adding Na 2CO3 solution for a plurality of ion exchange reactions, washing with water, filtering, and drying at 40-60 ℃ to obtain the DABCO type high-performance carbon dioxide adsorbent. Compared with the prior art, the preparation method provided by the invention selects 1, 4-diazabicyclo [2, 2] octane as a reaction raw material, and realizes better overall interaction under specific process steps, conditions and parameters, so as to prepare the DABCO type high-performance carbon dioxide adsorbent; the DABCO type high-performance carbon dioxide adsorbent improves the adsorption performance of carbon dioxide adsorbent resin, namely the resin with the same quality on the premise of not affecting the adsorption rate, and the DABCO type high-performance carbon dioxide adsorbent (double quaternary ammonium anion exchange resin) provided by the invention has higher carbon dioxide adsorption capacity.
Meanwhile, the preparation method provided by the invention has the advantages of simple process, low energy consumption, economy, environmental protection and the like, and is low in cost, so that the preparation method has good application prospect and potential in the technical field of DAC.
In order to further illustrate the present invention, the following examples are provided. The raw materials used in the following examples of the present invention are all commercially available.
Example 1
(1) 20G of resin (chloromethylated polystyrene resin, degree of crosslinking 6%, chlorine content 3.95 mmol/g) was swollen with 100ml of swelling agent N, N-Dimethylformamide (DMF) for 24h, filtered, washed with water and dried under vacuum to constant weight; then dropwise adding 3 times of 1, 4-diazabicyclo [2, 2] octane (DABCO) in molar quantity, reacting under magnetic stirring, and reacting for 12 hours at 60 ℃; filtering again, washing with 1mol/L hydrochloric acid aqueous solution to neutrality, eluting with 1mol/L NaOH aqueous solution until effluent liquid is detected to be free of Cl -, and washing with a large amount of water to neutrality.
(2) After draining, 20ml of Tetrahydrofuran (THF) and 2 times of the molar amount of methyl iodide and 50ml of aqueous sodium hydroxide solution (1 mol/L) are added, then 0.2g of tetrabutylammonium bromide is added for reaction under magnetic stirring, the reaction is stirred at 60 ℃ for 12 hours, the resin is filtered, a large amount of water is washed, 1mol/L of aqueous hydrochloric acid is used for washing, a large amount of water is used for washing to neutrality, 1mol/L of aqueous NaOH is used for washing until effluent liquid is detected to be free of Cl -, and a large amount of water is used for washing to neutrality.
(3) Filtering, adding 100ml of Na 2CO3 mol/L solution, stirring for 6h, filtering, washing with a large amount of DI water, filtering, repeating the ion exchange process for 5 times, washing with a large amount of DI water, filtering, and drying at 40deg.C under ventilation to obtain DABCO type high-performance carbon dioxide adsorbent (double quaternary ammonium carbon dioxide adsorbent resin).
The FTIR characterization of the DABCO type high-performance carbon dioxide adsorbent (DABCO type double quaternary ammonium anion exchange resin) prepared by the preparation method provided by the embodiment 1 of the invention is shown in the figure 1.
A schematic diagram of the adsorption capacity test of the resin on CO 2 is shown in fig. 2, and the specific test method is as follows:
Placing the material in a closed cavity, adjusting the initial concentration of CO 2 in the system, starting an air pump to increase the humidity in the system, releasing CO 2 by the sample until the concentration of CO 2 in the system is no longer increased, completely releasing CO 2 by the sample at the moment, and recording data. Finally, the CO 2 release amount of the sample is calculated through the concentration difference of the CO 2 at the initial and the end.
Through tests, the adsorption quantity of the DABCO type high-performance carbon dioxide adsorbent prepared by the preparation method provided by the embodiment 1 of the invention to CO 2 is 1.85mmol/g.
Example 2
The preparation method provided in example 1 was used, with the difference that: and (3) in the step (1), reacting for 12 hours at the temperature of 25 ℃ to obtain the DABCO type high-performance carbon dioxide adsorbent (double quaternary ammonium carbon dioxide adsorbent resin).
Through detection, the adsorption quantity of the DABCO type high-performance carbon dioxide adsorbent obtained by the preparation method provided by the embodiment 2 of the invention to CO 2 is 1.46mmol/g.
Example 3
The preparation method provided in example 1 was used, with the difference that: and (3) drying under the ventilation condition of 60 ℃ to obtain the DABCO type high-performance carbon dioxide adsorbent (double quaternary ammonium carbon dioxide adsorbent resin).
Through detection, the adsorption quantity of the DABCO type high-performance carbon dioxide adsorbent obtained by the preparation method provided by the embodiment 3 of the invention to CO 2 is 1.85mmol/g.
Comparative example 1
The preparation method provided in example 1 was used, with the difference that: 1, 3-tetramethyl guanidine is used as a reactant to replace 1, 4-diazabicyclo [2, 2] octane (DABCO) in the step (1) to obtain a carbon dioxide adsorbent (double quaternary ammonium CO 2 adsorbent resin).
The carbon dioxide adsorbent prepared in comparative example 1 has an adsorption capacity of 1.31mmol/g for CO 2.
Comparative example 2
The preparation method provided in example 1 was used, with the difference that: in the step (1), trimethylamine is used as a reactant to replace 1, 4-diazabicyclo [2, 2] octane (DABCO), and the step (2) is omitted to obtain a carbon dioxide adsorbent (monoquaternary ammonium CO 2 adsorbent resin).
The carbon dioxide adsorbent prepared in comparative example 2 has an adsorption capacity of 0.64mmol/g for CO 2.
Comparative example 3
The preparation method provided in example 1 was used, with the difference that: the step (1) uses tetramethyl urea as a reactant to replace 1, 4-diazabicyclo [2, 2] octane (DABCO) to obtain a carbon dioxide adsorbent (double quaternary ammonium CO 2 adsorbent resin).
The carbon dioxide adsorbent prepared in comparative example 3 has an adsorption capacity of 0.08mmol/g and <0.1mmol/g for CO 2, and has almost no adsorption capacity.
Comparative example 4
The preparation method provided in example 1 was used, with the difference that: and (3) drying under the ventilation condition of 80 ℃ to obtain the carbon dioxide adsorbent (double quaternary ammonium CO 2 adsorbent resin).
According to detection, the adsorption quantity of the carbon dioxide adsorbent obtained by the preparation method provided in the comparative example 4 to CO 2 is 0.93mmol/g; the analytical reason is that the terminal quaternary amine groups are unstable at higher temperatures.
In summary, the carbon dioxide adsorption capacity of the common resin or film is 0.55-0.9 mmol/g, the carbon dioxide adsorption capacity of the common double-quaternary ammonium resin is about 1.2-1.4 mmol/g (the carbon dioxide adsorption capacity of the existing common double-quaternary anion exchange resin is unstable and is greatly influenced by environmental conditions, the gap between the existing common double-quaternary anion exchange resin and the theoretical adsorption capacity is 2.1-2.2 mmol/g is large), and under the same mass, the carbon dioxide adsorption performance of the resin prepared by the preparation method is better and can reach 1.92mmol/g at most; meanwhile, the substrate of the resin prepared by the preparation method provided by the invention still has a hierarchical pore structure, and the adsorption rate of the substrate is almost consistent with that of the common resin; therefore, the technical scheme improves the carbon dioxide adsorption performance of the resin on the premise of not influencing the adsorption rate.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (8)
1. A preparation method of a DABCO type high-performance carbon dioxide adsorbent comprises the following steps:
a) Swelling resin, mixing with 1, 4-diazabicyclo [2, 2] octane, stirring at 25-60 ℃ for reaction for 10-14 h, and filtering and washing to obtain a first reaction product; the resin is chloromethylated polystyrene resin, the crosslinking degree is 5% -10%, and the chlorine content is 3-6 mmol/g;
The molar ratio of the resin to 1, 4-diazabicyclo [2, 2] octane is 1: (2-4);
b) Draining the water of the first reaction product obtained in the step a), adding tetrahydrofuran, methyl iodide and sodium hydroxide aqueous solution, adding tetrabutylammonium bromide, stirring at 50-60 ℃ for reaction for 10-14 h, and filtering and washing to obtain a second reaction product;
c) Filtering the second reaction product obtained in the step b), adding Na 2CO3 solution for a plurality of ion exchange reactions, washing with water, filtering, and drying at 40-60 ℃ to obtain the DABCO type high-performance carbon dioxide adsorbent.
2. The method according to claim 1, wherein the swelling agent used in the swelling process in step a) is selected from one or more of N, N-dimethylformamide, tetrahydrofuran, benzene and toluene; the dosage of the swelling agent is 4 ml-6 ml of swelling agent for every 1g of resin; the swelling time is 12-25 h.
3. The method according to claim 1, wherein the washing in step a) is specifically performed by:
And washing the filtered product with a hydrochloric acid aqueous solution of 0.5-1.5 mol/L, washing with a water solution of 0.5-1.5 mol/L for the first time, washing with a NaOH aqueous solution of the second time to neutrality, eluting until effluent liquid detection is free of Cl −, and washing with a water solution of the third time to neutrality to obtain a first reaction product.
4. The method according to claim 1, wherein the tetrahydrofuran is used in the amount of 0.5ml to 1.5ml of tetrahydrofuran per 1g of the resin of step a) in step b); the molar ratio of methyl iodide to the resin in the step a) is (2-4): 1, a step of; the volume ratio of the tetrahydrofuran to the sodium hydroxide aqueous solution is 1: (2-5), wherein the molar concentration of the sodium hydroxide aqueous solution is 0.8 mol/L-1.2 mol/L; the mass ratio of tetrabutylammonium bromide to the resin in the step a) is 1: (80-120).
5. The method according to claim 1, wherein the several ion exchange reactions in step c) are performed by:
Adding 80 ml-120 ml of Na 2CO3 solution with the concentration of 0.4 mol/L-0.6 mol/L into the filtered second reaction product, stirring for 4 h-8 h, filtering, washing with water, and filtering again to complete one-time ion exchange; the ion exchange described above was repeated several times.
6. The method of claim 5, wherein the number of times is 4 to 6.
7. The process according to claim 1, wherein the drying in step c) is carried out under aeration conditions to obtain a high-performance carbon dioxide adsorbent of the DABCO type.
8. A DABCO high performance carbon dioxide adsorbent, characterized in that it is prepared by the preparation method of any one of claims 1 to 7.
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