CN115957719A - Porous supported ionic liquid high-selectivity capture of extremely-low-concentration CO 2 Method (2) - Google Patents
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- 239000002608 ionic liquid Substances 0.000 title claims abstract description 98
- 238000000034 method Methods 0.000 title claims abstract description 19
- 238000001179 sorption measurement Methods 0.000 claims abstract description 54
- 239000003463 adsorbent Substances 0.000 claims abstract description 26
- 150000001413 amino acids Chemical class 0.000 claims abstract description 21
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 239000011343 solid material Substances 0.000 claims abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 7
- 230000008929 regeneration Effects 0.000 claims description 5
- 238000011069 regeneration method Methods 0.000 claims description 5
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002808 molecular sieve Substances 0.000 claims description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 9
- 238000003795 desorption Methods 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000000746 purification Methods 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 125000003277 amino group Chemical group 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 2
- 125000004122 cyclic group Chemical group 0.000 abstract description 2
- 239000007789 gas Substances 0.000 abstract description 2
- 229910052760 oxygen Inorganic materials 0.000 abstract description 2
- 239000001301 oxygen Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract 1
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 description 40
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 30
- 235000001014 amino acid Nutrition 0.000 description 18
- 238000002390 rotary evaporation Methods 0.000 description 13
- 238000003756 stirring Methods 0.000 description 13
- 239000007864 aqueous solution Substances 0.000 description 12
- 238000001291 vacuum drying Methods 0.000 description 10
- 235000019441 ethanol Nutrition 0.000 description 9
- 239000000243 solution Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000010521 absorption reaction Methods 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 238000001704 evaporation Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000004471 Glycine Substances 0.000 description 5
- 239000000706 filtrate Substances 0.000 description 5
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 5
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 5
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- FSYKKLYZXJSNPZ-UHFFFAOYSA-N sarcosine Chemical compound C[NH2+]CC([O-])=O FSYKKLYZXJSNPZ-UHFFFAOYSA-N 0.000 description 4
- -1 alcohol amine Chemical class 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- ONIBWKKTOPOVIA-BYPYZUCNSA-N L-Proline Chemical compound OC(=O)[C@@H]1CCCN1 ONIBWKKTOPOVIA-BYPYZUCNSA-N 0.000 description 2
- QNAYBMKLOCPYGJ-REOHCLBHSA-N L-alanine Chemical compound C[C@H](N)C(O)=O QNAYBMKLOCPYGJ-REOHCLBHSA-N 0.000 description 2
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 2
- 108010077895 Sarcosine Proteins 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 235000004279 alanine Nutrition 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 229940043230 sarcosine Drugs 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 1
- IQQRAVYLUAZUGX-UHFFFAOYSA-N 1-butyl-3-methylimidazolium Chemical compound CCCCN1C=C[N+](C)=C1 IQQRAVYLUAZUGX-UHFFFAOYSA-N 0.000 description 1
- NVNCRRUHFVDUGG-UHFFFAOYSA-N 1-methyl-3-(3-methylbutyl)-2H-imidazole Chemical compound CC(C)CCN1CN(C)C=C1 NVNCRRUHFVDUGG-UHFFFAOYSA-N 0.000 description 1
- MTPKWRZLHYIBDD-UHFFFAOYSA-M 2-[3-(2-aminoethyl)-2-methylimidazol-3-ium-1-yl]ethanamine bromide Chemical compound [Br-].NCC[N+]1=C(N(C=C1)CCN)C MTPKWRZLHYIBDD-UHFFFAOYSA-M 0.000 description 1
- JXIMCZHYOAYADC-UHFFFAOYSA-M [Cl-].C(CC(C)C)[N+]1=CN(C=C1)CCC[Si](OCC)(OCC)OCC Chemical compound [Cl-].C(CC(C)C)[N+]1=CN(C=C1)CCC[Si](OCC)(OCC)OCC JXIMCZHYOAYADC-UHFFFAOYSA-M 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000011067 equilibration Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 125000003698 tetramethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000001926 trapping method Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
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- 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
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Abstract
The invention relates to a porous supported ionic liquid high-selectivity adsorption separation method for extremely-low-concentration CO 2 Belonging to the technical field of gas separation and purification. The porous supported ionic liquid takes a solid material with a micro-mesoporous or mesoporous structure as a carrier, and the modified adsorbent is supported by the amino acid functional ionic liquid, so that the porous supported ionic liquid has the advantages of abundant and easily obtained raw materials, simple synthesis process and convenience for large-scale preparation, and amino groups, oxygen negative groups and CO in the ionic liquid 2 The multi-site effect between molecules and the micro-mesoporous or mesoporous effect can synergistically strengthen the extremely low concentration CO 2 Trapping or removing. At the same time, CO can be heated or decompressed 2 And (4) complete desorption is carried out, the regenerated load type ionic liquid can be recycled, and the adsorption performance is kept stable. The method has the advantages of simple synthesis of the adsorbent and low CO concentration 2 High capacity and selectivity, good stability, cyclic utilization, etc., in CO 2 Has great application potential in the aspects of capture and purification separation.
Description
Technical Field
The invention relates to the technical field of gas separation and purification, in particular to a porous load type ionic liquid high-selectivity capture of extremely-low-concentration CO 2 The porous supported ionic liquid is an adsorption material formed by loading amino acid functional ionic liquid on a micro-mesoporous or mesoporous solid material serving as a carrier, and the CO with extremely low concentration is synergistically enhanced by the multi-site effect of the ionic liquid and the pore structure effect of the porous carrier 2 High selectivity separation and removal.
Background
CO 2 Excessive emission is one of the main causes of greenhouse effect and global warming, and in order to relieve the problem of climate change on the environment, countries in the world set a series of carbon emission reduction measures. In recent years, CO has been extremely low in concentration in a closed space such as a space capsule or in the atmosphere 2 Trapping has become a key issue of international common attention, and the search for a high-efficiency carbon emission reduction method is urgent.
CO is currently industrially used 2 The trapping method is widely applied by a solvent absorption method, has the advantages of mature process, low cost, high absorption capacity and the like, but the physical absorption method generally has the defects of high requirement on equipment materials, high investment cost and the like; in the chemical absorption method, the alcohol amine solution is seriously degraded in the carbon capture process, the regeneration energy consumption is high, and the equipment is seriously corroded. Compared with traditional organic solvents, the ionic liquid has the advantages of lower vapor pressure, higher thermal stability, structural designability and the like, and CO is reported for the first time since Blancard et al (Nature, 1999,399, 28) 2 In ionic liquid 1-butyl-3-methylimidazole hexafluorophosphate ([ Bmim ]][PF 6 ]) Has high solubility at 25 deg.CAnd under 8MPa of CO 2 The solubility of the catalyst reaches 0.8mol of CO 2 After/mol IL, the ionic liquid serves as a CO trap 2 Has received much attention. To increase CO 2 Absorption properties, usually by introducing CO on the anion or cation 2 Designing a novel functional ionic liquid at a chemical action site. Zhang Suojiang et al (Ind. Eng. Chem. Res.,2013,52, 5835) designed to synthesize 1, 3-bis (2-aminoethyl) -2-methylimidazolium bromide (DAIL-Br) having two amino groups on the cation, and the results indicated that a 10wt% aqueous ionic liquid solution at 30 ℃ and atmospheric pressure was active against CO 2 Absorption capacity of 1.05mol CO 2 Per mol of IL. Dynasty et al (Angew. Chem. Int.Ed.,2016,55, 7166) reported a functional ionic liquid tributyl ethyl phosphoimino diacetate ([ P ] P 4442 ] 2 [IDA]) CO at 40 ℃ and atmospheric pressure 2 The absorption capacity is up to 1.69mol CO 2 (iii)/molIL. However, the ionic liquid, especially the amino acid functional ionic liquid, not only has high viscosity per se (25 ℃, 300-900 mPa & s), but also absorbs CO 2 The viscosity of the product increases exponentially (17000-100000 mPas at 25 ℃), and the mass transfer effect is seriously influenced. To overcome this problem, more researchers have attempted to combine ionic liquids and porous materials by physical or chemical means to form ionic liquid modified adsorbent materials. B.rb ara et al (mater. Res-Ibero-am.J.,2019,22, e0810) supported 20wt% of 1- (3-methylbutyl) -3-methylimidazol bistrifluoromethylsulfonyl imide salt to alumina, which showed that the ionic liquid modification material was towards CO compared to pure ionic liquid at 45 ℃ and 0.4MPa 2 The time for adsorption equilibration was reduced from 350min to 10min. CO compared with the carrier alumina 2 /N 2 The selectivity increased from 6.1 to 9.5 at 45 ℃ and 2.3 MPa. Rafael et al (J.Environ. Chem. Eng.,2020,8, 103740) loaded 1-isoamyl-3- (triethoxysilylpropyl) imidazolium chloride onto silica, CO 2 /N 2 The selectivity reaches 4.45 at 45 ℃ and 2MPa, which is improved by nearly two times compared with carrier silicon dioxide, but CO 2 The amount of adsorption is reduced by nearly a factor of two. CO still exists in most of ionic liquid adsorbing materials reported so far 2 /N 2 Selectivity to CO 2 The adsorption capacity is a bottleneck which is mutually restricted.
Adsorbing CO for the ionic liquid modified material 2 The invention provides a novel adsorption material which takes micro-mesoporous or mesoporous solid material as a carrier and is loaded and modified by amino acid functional ionic liquid, and the CO with extremely low concentration is realized by the synergistic enhancement of the multi-site effect of the ionic liquid and the pore structure effect of a porous carrier 2 High selectivity separation and removal.
Disclosure of Invention
The invention aims to provide a porous supported ionic liquid for high-selectivity capture of extremely low-concentration CO 2 The method of (1).
Porous supported ionic liquid high-selectivity capture of extremely-low-concentration CO 2 The method is characterized in that the related porous supported ionic liquid is a porous adsorbent formed by supporting amino acid functional ionic liquid on micro-mesoporous or mesoporous solid materials, wherein the anion structural general formula in the amino acid functional ionic liquid is as follows:
wherein R is C n H 2n+1 Or C n H 2n COOH (n is an integer, n is more than or equal to 0 and less than or equal to 4), cations are not limited, the mass fraction of the ionic liquid in the porous load type ionic liquid is 5-70%, and micro-mesoporous or mesoporous structure materials are molecular sieves (MCM-41, MCM-48, SBA-15, 13X, ZSM-5, ZSM-22 and CMK-3), silica gel and activated carbon.
The invention also provides a synthesis method of the amino acid ionic liquid and the porous supported ionic liquid, which comprises the following steps: amino acid and organic amine are used as raw materials, and the corresponding amino acid ionic liquid is obtained by one-step synthesis through room temperature reaction; and then stirring and ultrasonically treating the amino acid ionic liquid and the micro-mesoporous or mesoporous material in different proportions in an ethanol solvent at a certain temperature, then removing ethanol by rotary evaporation, and drying in vacuum to obtain the target porous supported ionic liquid.
The porous supported ionic liquid is used for CO 2 Temperature of adsorption: adsorption pressure at 10-100 ℃:0.04kPa to 0.1MPa; the porous supported ionic liquid can be used for adsorbent regeneration through heating or decompression, and the regeneration conditions are as follows: 50-200 ℃,0.01 kPa-0.1 MPa, and can be recycled after regeneration.
The method is suitable for the extremely low-concentration CO in atmospheric environment, closed spaces such as space cabins, submarines and underground mines, living or office environment and the like 2 And (4) adsorption separation and removal.
Compared with the ionic liquid modified porous material in the prior art, the porous supported ionic liquid takes a micro-mesoporous or mesoporous solid material as a carrier, and is loaded and modified by the amino acid functional ionic liquid, and mainly adopts the amino group and the oxygen negative group in the ionic liquid and CO 2 Intermolecular multi-site action and micro-mesoporous or mesoporous effect synergistically enhance extremely low concentration CO 2 Trapping or removing. At the same time, CO can be heated or decompressed 2 And (4) complete desorption is carried out, the regenerated porous load type ionic liquid can be recycled, and the adsorption performance is kept stable. The method has the advantages of simple synthesis of the adsorbent and low CO concentration 2 High capacity and selectivity, good stability, cyclic utilization and the like, breaks through the problem that the selectivity and the adsorption capacity are mutually restricted, and is extremely low-concentration CO 2 The purification and separation provides a new way.
Detailed Description
The technical solutions of the present invention will be described in more detail below with reference to specific examples, but the present invention is not limited to the following examples, and various modifications and implementations are included in the technical scope of the present invention without departing from the scope described before and after.
Example 1
1) Adding 0.1mol of tetraethylammonium hydroxide aqueous solution into a 500ml round-bottom flask, then slowly dropwise adding 0.12mol of L-glycine aqueous solution under stirring, reacting at 25 ℃ for 48 hours, carrying out reduced pressure rotary evaporation at 60 ℃ to remove residual deionized water, then adding 100ml of acetonitrile, standing at low temperature for 12 hours, and crystallizing to separate out unreacted glycine. Filtering, evaporating the filtrate under reduced pressure to remove acetonitrile, and vacuum evaporating at 60 deg.CAir-drying for 48h to obtain [ N 2222 ][Gly]. 1.5g of [ N ] 2222 ][Gly]Dissolving in absolute ethyl alcohol, slowly adding 8.5g of SBA-15 into the solution, stirring at room temperature for 24h, removing a large amount of ethanol solvent by rotary evaporation at 45 ℃, ultrasonically treating the sample at 45 ℃ for 2h, and finally drying in vacuum at 60 ℃ for 48h to obtain the porous load type amino acid ionic liquid [ N 2222 ][Gly]@ SBA-15 (ionic liquid content 15 wt%); other conditions are not changed, and [ N ] is taken 2222 ][Gly]And SBA-15 with the mass of 3g and 7g, 4.5g and 5.5g and 6g and 4g respectively to obtain the porous load type amino acid ionic liquid [ N ] 2222 ][Gly]@ SBA-15, having ionic liquid contents of 30wt%, 45wt% and 60wt%, respectively.
2) Adding 0.1mol of tetraethylammonium hydroxide aqueous solution into a 500ml round-bottom flask, then slowly dropwise adding 0.12mol of glycine aqueous solution under stirring, reacting at 25 ℃, carrying out decompression rotary evaporation at 60 ℃ to remove residual deionized water after 48 hours of reaction, adding 100ml of acetonitrile, standing at low temperature for 12 hours, and crystallizing and separating out unreacted glycine. Filtering, evaporating the filtrate under reduced pressure to remove acetonitrile, and vacuum drying at 60 deg.C for 48 hr to obtain [ N ] 2222 ][Gly]. 1.5g of [ N ] 2222 ][Gly]Dissolving in absolute ethyl alcohol, slowly adding 8.5g MCM-41 into the solution, stirring at room temperature for 24h, removing a large amount of ethanol solvent by rotary evaporation at 45 ℃, ultrasonically treating the sample at 45 ℃ for 2h, and finally vacuum drying at 60 ℃ for 48h to obtain the porous load type amino acid ionic liquid [ N 2222 ][Gly]@ MCM-41 (ionic liquid content 15 wt%); other conditions are not changed, and [ N ] is taken 2222 ][Gly]And MCM-41 with the mass of 3g and 7g, 4.5g and 5.5g and 6g and 4g respectively to obtain the porous load type amino acid ionic liquid [ N 2222 ][Gly]@ MCM-41 with ionic liquid contents of 30wt%, 45wt%, and 60wt%, respectively.
3) Adding 0.1mol of tetraethylammonium hydroxide aqueous solution into a 500ml round-bottom flask, then slowly dropwise adding 0.12mol of glycine aqueous solution under stirring, reacting at 25 ℃ for 48 hours, carrying out reduced pressure rotary evaporation at 60 ℃ to remove residual deionized water, adding 100ml of acetonitrile, standing at low temperature for 12 hours, and crystallizing to separate out unreacted glycine. Filtering, and depressurizing the filtrateEvaporating to remove acetonitrile, vacuum drying at 60 deg.C for 48h to obtain [ N 2222 ][Gly]. 3g of [ N ] 2222 ][Gly]Dissolving in anhydrous ethanol, slowly adding 7g of 13X into the solution, stirring at room temperature for 24h, removing a large amount of ethanol solvent by rotary evaporation at 45 ℃, performing ultrasonic treatment on a sample at 45 ℃ for 2h, and finally performing vacuum drying at 60 ℃ for 48h to obtain the porous supported amino acid ionic liquid [ N 2222 ][Gly]@13X (ionic liquid content 30 wt%).
4) Adding 0.1mol of tetraethylammonium hydroxide aqueous solution into a 500ml round-bottom flask, then slowly dropwise adding 0.12mol of sarcosine aqueous solution under stirring, reacting at 25 ℃ for 48h, carrying out reduced pressure rotary evaporation at 60 ℃ to remove residual deionized water, adding 100ml of acetonitrile, standing at low temperature for 12h, and crystallizing to separate out unreacted sarcosine. Filtering, evaporating the filtrate under reduced pressure to remove acetonitrile, and vacuum drying at 60 deg.C for 48h to obtain [ N ] 2222 ][Sar]. 3g of [ N ] 2222 ][Sar]Dissolving in absolute ethyl alcohol, slowly adding 7g of ZSM-5 into the solution, stirring at room temperature for 24 hours, removing a large amount of ethanol solvent by rotary evaporation at 45 ℃, then carrying out ultrasonic treatment on a sample at 45 ℃ for 2 hours, and finally carrying out vacuum drying at 60 ℃ for 48 hours to obtain the porous load type amino acid ionic liquid [ N 2222 ][Sar]@ ZSM-5 (30 wt% ionic liquid content).
5) Adding 0.1mol of tetraethylammonium hydroxide aqueous solution into a 500ml round-bottom flask, then slowly dropwise adding 0.12mol of proline aqueous solution under stirring, reacting at 25 ℃ for 48h, carrying out reduced pressure rotary evaporation at 60 ℃ to remove residual deionized water, adding 100ml of acetonitrile, standing at low temperature for 12h, and crystallizing to separate out unreacted proline. Filtering, evaporating the filtrate under reduced pressure to remove acetonitrile, and vacuum drying at 60 deg.C for 48 hr to obtain [ N ] 2222 ][Pro]. 3g of [ N ] 2222 ][Pro]Dissolving in absolute ethyl alcohol, slowly adding 7g of silica gel into the solution, stirring at room temperature for 24h, removing a large amount of ethanol solvent by rotary evaporation at 45 ℃, ultrasonically treating the sample at 45 ℃ for 2h, and finally vacuum-drying at 60 ℃ for 48h to obtain the porous supported amino acid ionic liquid [ N 2222 ][Pro]@ silica gel (ionic liquid content 30 wt%).
6) 0.1mol of tetramethyl oxyhydrogenAdding ammonium chloride aqueous solution into a 500ml round-bottom flask, slowly dropwise adding 0.12mol alanine aqueous solution under stirring, reacting at 25 ℃ for 48h, carrying out reduced pressure rotary evaporation at 60 ℃ to remove residual deionized water, adding 100ml acetonitrile, standing at low temperature for 12h, and crystallizing to separate out unreacted alanine. Filtering, evaporating the filtrate under reduced pressure to remove acetonitrile, and vacuum drying at 60 deg.C for 48 hr to obtain [ N ] 1111 ][Ala]. 3g of [ N ] 1111 ][Ala]Dissolving in absolute ethyl alcohol, slowly adding 7g of active carbon into the solution, stirring at room temperature for 24h, removing a large amount of ethanol solvent by rotary evaporation at 45 ℃, then carrying out ultrasonic treatment on a sample at 45 ℃ for 2h, and finally carrying out vacuum drying at 60 ℃ for 48h to obtain the porous supported amino acid ionic liquid [ N 1111 ][Ala]@ activated carbon (ionic liquid content 30 wt%).
Example 2
1) Using a physical adsorption apparatus, 0.13g of the porous supported ionic liquid [ N ] synthesized in 1) of example 1 was tested 2222 ][Gly]@ SBA-15 (ionic liquid content 15 wt%) CO 2 Adsorbing an isotherm at 40 ℃ and a pressure of 0.00005 to 0.10MPa to obtain CO of the adsorbent 2 The adsorption isotherm is shown in FIG. 1 of the drawing, in CO 2 CO of the adsorbent at a concentration of 0.00005MPa 2 The adsorption capacity was 0.09 gCO 2 /gadsorbent。
2) Using a physical adsorption apparatus, 0.13g of the porous supported ionic liquid [ N ] synthesized in 1) of example 1 was tested 2222 ][Gly]@ SBA-15 (30 wt% ionic liquid content) CO 2 Adsorbing an isotherm at 40 ℃ and a pressure of 0.00005 to 0.10MPa to obtain CO of the adsorbent 2 The adsorption isotherms are shown in FIG. 1 of the drawing, in CO 2 CO of the adsorbent at a concentration of 0.00005MPa 2 The adsorption capacity was 0.47 gCO 2 /gadsorbent。
3) Using a physical adsorption apparatus, 0.13g of the porous supported ionic liquid [ N ] synthesized in 1) of example 1 was tested 2222 ][Gly]@ SBA-15 (45 wt% ionic liquid content) CO 2 Adsorbing an isotherm at 40 ℃ and a pressure of 0.00005 to 0.10MPa to obtain CO of the adsorbent 2 The adsorption isotherm is shown in FIG. 1 of the drawingsCO 2 CO of the adsorbent at a concentration of 0.00005MPa 2 The adsorption capacity was 0.89 gCO 2 /gadsorbent。
4) Using a physical adsorption apparatus, 0.13g of the porous supported ionic liquid [ N ] synthesized in 1) of example 1 was tested 2222 ][Gly]@ SBA-15 (ionic liquid content 60 wt%) CO 2 Adsorption isotherm at 40 ℃ and a pressure of 0.0005 to 0.10MPa to obtain CO of the adsorbent 2 The adsorption isotherms are shown in FIG. 1 of the drawing, in CO 2 CO of the adsorbent at a concentration of 0.00005MPa 2 The adsorption capacity was 1.45 gCO 2 /gadsorbent。
Example 3
1) Using a physical adsorption apparatus, 0.13g of the porous supported ionic liquid [ N ] synthesized in 1) of example 1 was tested 2222 ][Gly]@ MCM-41 (15 wt% ionic liquid content) CO 2 Adsorbing an isotherm at 40 ℃ and a pressure of 0.00005 to 0.10MPa to obtain CO of the adsorbent 2 The adsorption isotherm is shown in FIG. 2 of the drawing, in CO 2 CO of the adsorbent at a concentration of 0.00005MPa 2 The adsorption quantity is 0.0052 gCO 2 /gadsorbent。
2) Using a physical adsorption apparatus, 0.13g of the porous supported ionic liquid [ N ] synthesized in 1) of example 1 was tested 2222 ][Gly]@ MCM-41 (30 wt% ionic liquid content) CO 2 Adsorbing an isotherm at 40 ℃ and a pressure of 0.00005 to 0.10MPa to obtain CO of the adsorbent 2 The adsorption isotherm is shown in FIG. 2 of the drawing, in CO 2 CO of the adsorbent at a concentration of 0.00005MPa 2 The adsorption capacity was 0.19 gCO 2 /gadsorbent。
3) Using a physical adsorption apparatus, 0.13g of the porous supported ionic liquid [ N ] synthesized in 1) of example 1 was tested 2222 ][Gly]@ MCM-41 (45 wt% ionic liquid content) CO 2 Adsorbing isotherm at 40 deg.C and 0.00005-0.10 MPa to obtain CO of the adsorbent 2 The adsorption isotherm is shown in FIG. 2 of the drawing, in CO 2 CO of the adsorbent at a concentration of 0.00005MPa 2 The adsorption capacity was 0.71 gCO 2 /gadsorbent。
4) Using a physical adsorption apparatus, 0.13g of the porous supported ionic liquid [ N ] synthesized in 1) of example 1 was tested 2222 ][Gly]@ MCM-41 (60 wt% ionic liquid content) CO 2 Adsorbing an isotherm at 40 ℃ and a pressure of 0.00005 to 0.10MPa to obtain CO of the adsorbent 2 The adsorption isotherm is shown in FIG. 2 of the drawing, in CO 2 CO of the adsorbent at a concentration of 0.00005MPa 2 The adsorption capacity was 1.26 gCO 2 /gadsorbent。
Example 4
1) Using a physical adsorption apparatus, 0.13g of the porous supported ionic liquid [ N ] synthesized in 1) of example 1 was tested 2222 ][Gly]N of @ SBA-15 (ionic liquid content 60 wt. -%) 2 And CO 2 Adsorption isotherm, temperature 15 ℃, pressure 0.0005-0.10 MPa, selectivity at different pressures as shown in Table 1, CO 2 Calculating CO of the adsorbent at a concentration of 0.0005MPa 2 /N 2 The ideal selectivity is 11545.
TABLE 1 [ N ] at 15 ℃ 2222 ][Gly]@ SBA-15 (ionic liquid content 60 wt.%) CO 2 /N 2 Selectivity is
Example 5
Using a physical adsorption apparatus, 0.13g of the porous supported ionic liquid [ N ] synthesized in 1) of example 1 was tested 2222 ][Gly]@ SBA-15 (ionic liquid content 60 wt%) CO 2 Adsorbing an isotherm at 40 ℃ and a pressure of 0.00005 to 0.10MPa to obtain CO of the adsorbent 2 Adsorption isotherms are shown. After the adsorption is finished, N is introduced 2 The flow rate is 140ml/min, the desorption temperature is 100 ℃, and the desorption time is about 240min 2 Substantially completely released. According to the above steps, adsorbing-desorbing for 5 times in a circulating manner for CO 2 The adsorption performance remained substantially stable, and the specific results are shown in table 2.
TABLE 2 [ N ] at 40 ℃ 2222 ][Gly]@ SBA-15 (ionic liquid content 60 wt.%) five cycles of CO 2 Adsorption results
Example 6
Using a physical adsorption apparatus, 0.13g of the porous supported ionic liquid [ N ] synthesized in 2) of example 1 was tested 2222 ][Gly]@ MCM-41 (ionic liquid content 60 wt%) CO 2 Adsorbing an isotherm at 40 ℃ and a pressure of 0.00005 to 0.10MPa to obtain CO of the adsorbent 2 Adsorption isotherms are shown. After the adsorption is finished, N is introduced 2 The flow rate is 140ml/min, the desorption temperature is 100 ℃, and the desorption time is about 240min 2 Is substantially completely released. According to the above steps, adsorbing-desorbing the solvent CO for 5 times 2 The adsorption performance of (2) was substantially stable, and the specific results are shown in table 3.
TABLE 3 [ N ] at 40 ℃ 2222 ][Gly]@ MCM-41 (60 wt% ionic liquid content) five cycles of CO 2 Adsorption results
Drawings
FIG. 1 is a graph of [ N ] for different ionic liquid contents at 40 ℃ 2222 ][Gly]CO of @ SBA-15 2 Adsorption isotherm.
FIG. 2 is the [ N ] of different ionic liquid contents at 40 ℃ 2222 ][Gly]CO of @ MCM-41 2 Adsorption isotherm.
Claims (4)
1. Porous supported ionic liquid high-selectivity capture of extremely-low-concentration CO 2 The method is characterized in that the related porous supported ionic liquid is a porous adsorbent formed by supporting amino acid functional ionic liquid on micro-mesoporous or mesoporous solid materials, wherein the anion structural general formula in the amino acid functional ionic liquid is as follows:
wherein R is C n H 2n+1 Or C n H 2n COOH (n is an integer, n is more than or equal to 0 and less than or equal to 4), cations are not limited, the mass fraction of the ionic liquid in the porous load type ionic liquid is 5-70%, and micro-mesoporous or mesoporous structure materials are molecular sieves (MCM-41, MCM-48, SBA-15, 13X, ZSM-5, ZSM-22 and CMK-3), silica gel and activated carbon.
2. The method according to claim 1, wherein the adsorption temperature of the porous supported ionic liquid is as follows: adsorption pressure at 10-100 ℃:0.04kPa to 0.1MPa.
3. The method according to claim 1, wherein the porous supported ionic liquid is recycled, and the regeneration conditions are as follows: 50-200 ℃ and 0.01 kPa-0.1 MPa.
4. The method of claim 1, wherein the method is suitable for the treatment of CO with extremely low concentration in different conditions such as atmospheric environment, closed space such as space capsule, submarine, underground mine, and residential or office environment 2 And (4) adsorption separation and removal.
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| CN1709553A (en) * | 2005-06-02 | 2005-12-21 | 中国科学院过程工程研究所 | Amino acid ion liquid for acidic gas absorption |
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| CN107376584A (en) * | 2016-09-07 | 2017-11-24 | 中国矿业大学 | The preparation method of efficient dry ion liquid absorbent |
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| CN1709553A (en) * | 2005-06-02 | 2005-12-21 | 中国科学院过程工程研究所 | Amino acid ion liquid for acidic gas absorption |
| CN101724619A (en) * | 2009-12-24 | 2010-06-09 | 南京工业大学 | Application of functionalized ionic liquid modified mesoporous molecular sieve in enzyme immobilization |
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