CN117339571A - Polyurethane CO modified by quaternary ammonium groups 2 Adsorbent and preparation method thereof - Google Patents
Polyurethane CO modified by quaternary ammonium groups 2 Adsorbent and preparation method thereof Download PDFInfo
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- CN117339571A CN117339571A CN202311314235.3A CN202311314235A CN117339571A CN 117339571 A CN117339571 A CN 117339571A CN 202311314235 A CN202311314235 A CN 202311314235A CN 117339571 A CN117339571 A CN 117339571A
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- 229920002635 polyurethane Polymers 0.000 title claims abstract description 91
- 239000004814 polyurethane Substances 0.000 title claims abstract description 91
- 239000003463 adsorbent Substances 0.000 title claims abstract description 77
- 125000001453 quaternary ammonium group Chemical group 0.000 title claims abstract description 53
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 238000001179 sorption measurement Methods 0.000 claims abstract description 41
- 239000000463 material Substances 0.000 claims abstract description 39
- 238000005342 ion exchange Methods 0.000 claims abstract description 12
- 238000005956 quaternization reaction Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 5
- 150000002500 ions Chemical class 0.000 claims abstract description 3
- 230000004048 modification Effects 0.000 claims abstract description 3
- 238000012986 modification Methods 0.000 claims abstract description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 56
- 239000007795 chemical reaction product Substances 0.000 claims description 47
- 238000005406 washing Methods 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 239000007864 aqueous solution Substances 0.000 claims description 28
- 239000001569 carbon dioxide Substances 0.000 claims description 28
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 28
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 22
- 238000002791 soaking Methods 0.000 claims description 22
- 238000001914 filtration Methods 0.000 claims description 17
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 claims description 17
- 239000000047 product Substances 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 230000008569 process Effects 0.000 claims description 12
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 10
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 6
- 239000003054 catalyst Substances 0.000 claims description 6
- 230000001590 oxidative effect Effects 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 5
- 235000019441 ethanol Nutrition 0.000 claims description 5
- 239000012948 isocyanate Substances 0.000 claims description 5
- 150000002513 isocyanates Chemical class 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 229920000570 polyether Polymers 0.000 claims description 5
- 230000009257 reactivity Effects 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims 1
- 239000008187 granular material Substances 0.000 abstract description 4
- 238000003795 desorption Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- 238000001514 detection method Methods 0.000 description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 239000002994 raw material Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 4
- 239000003014 ion exchange membrane Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 3
- 230000003993 interaction Effects 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 2
- 235000017491 Bambusa tulda Nutrition 0.000 description 2
- 241001330002 Bambuseae Species 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229920001661 Chitosan Polymers 0.000 description 2
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 2
- 239000004964 aerogel Substances 0.000 description 2
- 150000001412 amines Chemical group 0.000 description 2
- 239000003957 anion exchange resin Substances 0.000 description 2
- 239000011425 bamboo Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- -1 hydrogen ions Chemical class 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007783 nanoporous material Substances 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 1
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
- B01J20/265—Synthetic macromolecular compounds modified or post-treated polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/02—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—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 form
- B01J20/28016—Particle form
-
- 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)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a quaternary ammonium group modified polyurethane CO 2 An adsorbent and its preparation method are provided. The quaternary ammonium group modified polyurethane CO 2 The adsorbent comprises: a polyurethane porous carrier, and functional ions loaded therein. The preparation method comprises the following steps: hydrophilic modification treatment is carried out on polyurethane, then the hydrophilic polyurethane is contacted with functional quaternization mixed solution, soaked and heated, then filtered and washed, ion exchange is carried out on the obtained material, and the quaternary ammonium group modified polyurethane CO is prepared 2 An adsorbent. Polyurethane CO prepared by the invention 2 The adsorbent is in the form of granule and is matched with the existing powdery CO 2 Compared with the adsorbent, the adsorbent is more convenient for practical engineering application. At the same timeThe adsorbent has higher CO content 2 The adsorption performance can reach 1.80mmol/g, and the adsorption capacity is high after 10 adsorption and desorption cycles, so that the adsorption material has good application prospect.
Description
Technical Field
The invention relates to the technical field of carbon dioxide adsorption, in particular to a quaternary ammoniumRadical modified polyurethane CO 2 An adsorbent and its preparation method are provided.
Background
Currently, carbon dioxide is the primary driving force for global warming, and the primary sources of emissions include mobile and decentralized sources of emissions, such as exhaust emissions from automobiles and aircraft, in addition to centralized sources of emissions, such as power plants, steel plants. Carbon capture, utilization and sequestration technologies (CCUS) and direct air capture technologies are important means to address this problem, the latter not only being able to capture CO from mobile dispersed emissions sources 2 Can also capture CO leaked in the carbon sealing process 2 Can be used as an important supplement of the CCUS technology of a concentrated emission source to jointly realize the aim of carbon emission reduction.
Carbon dioxide adsorbents are the heart of direct air capture technology. The nano-porous material loaded with carbonate ions can be used as an adsorbent for the direct air trapping technology for adsorbing and desorbing carbon dioxide. The basic principle is that, during drying, the material adsorbs CO 2 When the ambient humidity increases, the material desorbs CO 2 The adsorption/desorption cycle can be realized by adjusting the humidity.
As shown in chemical reaction formulas (1) and (2), as the number of water molecules is reduced, the free energy of hydrolysis of carbonate ions becomes negative, and there is a tendency of spontaneous reaction in thermodynamics, namely, cheng Tansuan hydrogen ions and hydroxyl ions can be self-hydrolyzed to produce OH - For acidic CO 2 Has strong adsorption force. When the environmental humidity increases, the number of water molecules increases, and CO 2 And is released.
The current wet-changing adsorbent mainly comprises ion exchange resin powder, chitosan aerogel powder, quaternized bamboo cellulose powder and the like, but the powder material is unfavorable for large-scale engineering application, and only remains in the experiment at presentStage of room study. Some students combine ion exchange resin powder with polyvinyl chloride and other materials to prepare an ion exchange membrane to adsorb carbon dioxide, but the substrate material is inert material and cannot adsorb carbon dioxide, so the CO of the ion exchange membrane 2 The adsorption capacity is not strong. Meanwhile, in order to adapt to engineering application scenes, the planar ion exchange membrane needs to be processed into a three-position porous shape for the second time, so that the adsorption tower is filled with the adsorbent as much as possible, and meanwhile, the contact area between the ion exchange membrane and air is increased as much as possible, and more manpower and material resources are consumed in the step.
Disclosure of Invention
In order to overcome the problems of the prior art, the invention aims to provide a quaternary ammonium group modified polyurethane CO 2 The preparation method of the adsorbent has the advantages of low energy consumption cost, simple process, economy and environmental protection; polyurethane CO prepared 2 The adsorbent is in the form of granule and is matched with the existing powdery CO 2 Compared with the adsorbent, the adsorbent is more convenient for practical engineering application. At the same time, the adsorbent has no inert substrate material and higher CO 2 The adsorption performance and the engineering application prospect are good.
The invention provides a quaternary ammonium group modified polyurethane CO 2 The preparation method of the adsorbent comprises the following steps:
a) Mixing polyurethane black material (isocyanate) and polyurethane white material (combined polyether) at normal temperature, and then rapidly stirring to obtain a first reaction product;
b) Washing the first reaction product obtained in the step a) with water, airing, sequentially washing with acetone, absolute ethyl alcohol and deionized water in an ultrasonic cleaner for 10-20 min respectively, soaking in an oxidation solution, washing with water, airing for standby, soaking chemically oxidized polyurethane in glutaraldehyde solution for 24h, soaking in an acrylic acid solution at a certain temperature, carrying out grafting reaction, and washing with ethanol after completion to obtain a second reaction product;
c) Soaking the second reaction product obtained in the step b) in an aqueous solution of NaOH at room temperature for 2-6 hours to enhance the reactivity, washing with water and drying at 60-70 ℃, adding isopropanol and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, adding an aqueous solution of NaOH, carrying out quaternization reaction, and washing the obtained product with the aqueous solution of HCl and water in sequence until the pH value of a washing solution reaches neutrality to obtain a third reaction product;
d) Filtering the third reaction product obtained in the step c), adding Na 2 CO 3 Carrying out ion exchange reaction on the solution for a plurality of times, and finally washing, filtering and drying to obtain granular quaternary ammonium group modified polyurethane CO 2 An adsorbent.
The chemical reaction of the preparation process is as follows:
preferably, the mass ratio of the polyurethane black material to the polyurethane white material in the step a) is 1: (1-2).
Preferably, the oxidizing solution in step b) is 0.7 mass% nitric acid and 17 mass% sulfuric acid in a ratio of 1:1 to 3 (mass ratio) of a mixed solution; the soaking time is 6-8 h.
Preferably, the molar concentration of acrylic acid in step b) is 1.0 to 3.5mol/L; the time of the grafting reaction is 1.0-2.5 h; the temperature of the grafting reaction is 15-45 ℃.
Preferably, the mass fraction of the NaOH aqueous solution in the step c) is 20-40%.
Preferably, the amount of isopropanol used in step c) is from 20 to 40mL of isopropanol per 1g of second reaction product; the mass fraction of the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride is 60%, and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride is immersed in the second reaction product with the dosage of 3-5 mL for every 1 g; the volume ratio of the NaOH aqueous solution to the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride solution is (3-5): 5.
preferably, the quaternization reaction temperature in step c) is 25 to 40 ℃ and the reaction time is 3 to 5 hours.
Preferably, the molar concentration of the aqueous HCl in step c) is 0.1mol/L.
Preferably, the process of the ionic bonding reaction in the step d) is specifically:
adding Na of 0.4-0.6 mol/L into the third reaction product obtained in the step c) 2 CO 3 Stirring the solution for 2-6 h, filtering, washing with water, and filtering again to complete one-time ion exchange; the ion exchange is repeated 3 to 5 times.
The invention also provides a quaternary ammonium group modified polyurethane CO 2 The adsorbent is prepared by adopting the preparation method of the technical scheme, is granular and comprises a polyurethane porous carrier and functional ions loaded in the polyurethane porous carrier.
The invention also provides a method for directly capturing carbon dioxide by air, which adopts the quaternary ammonium group modified polyurethane CO 2 The adsorbent is used for adsorbing and desorbing carbon dioxide, and quaternary ammonium group modified polyurethane CO 2 Adsorbent pair CO 2 The adsorption amount of the catalyst is 1.40-1.80 mmol/g.
Compared with the prior art, the preparation method provided by the invention takes polyurethane as a raw material, and realizes better interaction under specific process steps and condition parameters, thereby preparing and obtaining the quaternary ammonium group modified polyurethane CO 2 An adsorbent; the quaternary ammonium group modified polyurethane CO 2 The adsorbent expands the application range of polyurethane, provides more possibility for selecting the carbon dioxide wet regeneration trapping material, and has higher carbon dioxide adsorption performance. Experimental results show that the quaternary ammonium group modified polyurethane CO provided by the invention 2 Adsorbent pair CO 2 The adsorption amount of the catalyst is 1.40-1.80 mmol/g.
Meanwhile, the raw materials selected by the invention and the preparation method provided by the invention have the advantages of low energy consumption cost, simple process, economy, environmental protection and the like, so that the method is used for preparing CO 2 Has good application prospect in the technical field of direct air trapping.
Drawings
FIG. 1 is a flow chart of the preparation method of the invention.
FIG. 2 is a block diagram of a quaternary ammonium group modified polyurethane CO according to the present invention 2 Infrared test patterns of the adsorbent;
FIG. 3 shows the present inventionPolyurethane CO modified by quaternary ammonium groups 2 Scanning electron microscope images of the adsorbent;
FIG. 4 is a block diagram of a quaternary ammonium group modified polyurethane CO according to the present invention 2 Adsorption plots for the examples of adsorbents versus the comparative examples;
FIG. 5 is a block diagram of a quaternary ammonium group modified polyurethane CO according to the present invention 2 A physical map of the adsorbent;
FIG. 6 is a block diagram of a quaternary ammonium group modified polyurethane CO according to the present invention 2 Physical diagram of the adsorbent placed in the small-sized adsorption tower.
Detailed Description
In order to make the technical content, the achieved objects, effects and advantages of the present invention more apparent, the following description is given with reference to the accompanying drawings.
As shown in FIG. 1, the invention provides a quaternary ammonium group modified polyurethane CO 2 The preparation method of the adsorbent comprises the following steps:
a) Mixing polyurethane black material (isocyanate) and polyurethane white material (combined polyether) at normal temperature, and then rapidly stirring to obtain a first reaction product;
b) Washing the first reaction product obtained in the step a) with water, airing, sequentially washing with acetone, absolute ethyl alcohol and deionized water in an ultrasonic cleaner for 10-20 min respectively, soaking in an oxidation solution, washing with water, airing for standby, soaking chemically oxidized polyurethane in glutaraldehyde solution for 24h, soaking in an acrylic acid solution at a certain temperature, carrying out grafting reaction, and washing with ethanol after completion to obtain a second reaction product;
c) Soaking the second reaction product obtained in the step b) in NaOH aqueous solution at room temperature for 2-6 h to enhance reactivity, filtering, washing with water, drying at 60-70 ℃, adding isopropanol and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, adding NaOH aqueous solution, maintaining the temperature at 40 ℃ for quaternization, and washing the obtained product with HCl aqueous solution and water in sequence until the pH value of the washing solution is neutral to obtain a third reaction product;
d) Filtering the third reaction product obtained in the step c), adding Na 2 CO 3 Carrying out ion exchange reaction on the solution for a plurality of times, and finally washing, filtering and drying to obtain the quaternary ammonium group modified polyurethane CO 2 An adsorbent.
Firstly, mixing polyurethane black material (isocyanate) and polyurethane white material (combined polyether) at normal temperature, and then rapidly stirring to obtain a first reaction product. In the invention, the mass ratio of the polyurethane black material to the polyurethane white material is preferably 1: (1-2), more preferably 1:1. the source of the polyurethane black and white material is not particularly limited, and commercially available products or self-made products well known to those skilled in the art can be adopted.
After the first reaction product is obtained, washing the obtained first reaction product with water, airing, sequentially washing the first reaction product with acetone, absolute ethyl alcohol and deionized water in an ultrasonic washer for 10-20 min respectively, soaking the first reaction product in an oxidizing solution, washing the first reaction product with water, airing for later use, soaking the chemically oxidized polyurethane in a glutaraldehyde solution for 24h, soaking the first reaction product in an acrylic acid solution at a certain temperature, carrying out grafting reaction, and washing the second reaction product with ethanol after the completion of the grafting reaction.
The sources of the acetone, the absolute ethyl alcohol, the nitric acid aqueous solution, the concentrated sulfuric acid aqueous solution, the glutaraldehyde and the acrylic acid solution are not particularly limited in the present invention, and commercially available products known to those skilled in the art may be used.
In the invention, the oxidizing solution is prepared from 0.7 percent (mass fraction) of nitric acid and 17 percent (mass fraction) of sulfuric acid according to the following weight percent of 1: (1-3) (mass ratio), preferably 1:1. in the invention, the soaking time is 6-8 h, preferably soaking reaction is 8h at 25 ℃. In the present invention, the molar concentration of the acrylic acid is preferably 1.0 to 3.5mol/L, more preferably 3.5mol/L. In the present invention, the time of the grafting reaction is preferably 1.0 to 2.5 hours, more preferably 1.5 hours. In the present invention, the temperature of the grafting reaction is preferably 15 to 45 ℃, more preferably 40 ℃.
And washing the product by absolute ethyl alcohol to obtain a second reaction product.
After the second reaction product is obtained, the obtained second reaction product is put into an aqueous solution of NaOH at room temperature to be soaked for 2-6 hours to enhance the reactivity, after being washed by water and dried at 60-70 ℃, isopropanol and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride are firstly added, then an aqueous solution of NaOH is added, the quaternization reaction is carried out, and the obtained product is sequentially washed by the aqueous solution of HCl and water until the pH value of a washing solution reaches neutrality, so that a third reaction product is obtained;
the sources of the aqueous NaOH solution, the isopropanol, the 3-chloro-2-hydroxypropyl trimethylammonium chloride and the aqueous HCl solution 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 aqueous NaOH solution is preferably 20 to 40% by mass, more preferably 30%. In the present invention, the amount of isopropanol is preferably 20 to 40mL of isopropanol per 1g of the second reaction product, more preferably 30mL. In the present invention, the mass fraction of 3-chloro-2-hydroxypropyl-trimethylammonium chloride is preferably 60%, and the amount is preferably 3 to 5mL of 3-chloro-2-hydroxypropyl-trimethylammonium chloride per 1g of the second reaction product, more preferably 5mL. In the present invention, the volume ratio of the NaOH aqueous solution to the 3-chloro-2-hydroxypropyl-trimethylammonium chloride solution is preferably (3 to 5): 5, more preferably 4:5.
the invention reacts for 3 to 5 hours at 25 to 40 ℃, preferably for 4 hours at 40 ℃.
In the present invention, the washing process is preferably specifically: and washing the filtered product with water for the first time, washing with 0.1mol/L hydrochloric acid aqueous solution, and washing with water for the second time to neutrality to obtain a third reaction product.
After the third reaction product is obtained, the invention filters the obtained third reaction product and adds Na 2 CO 3 Carrying out ion exchange reaction on the solution for a plurality of times, and finally washing, filtering and drying to obtain the quaternary ammonium group modified polyurethane CO 2 An adsorbent. The invention aims at the Na 2 CO 3 The source of the solution is not particularly limited, and commercially available commercial products or self-made 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:
will be washedThe third reaction product after washing and filtering is added with Na of 0.5mol/L 2 CO 3 Stirring the solution for 4 hours, filtering, washing with water, and filtering again to finish one-time ion exchange; the ion exchange was repeated 4 times.
The process of the present invention is not particularly limited, and the filtration may be carried out by washing with a large amount of deionized water, which is well known to those skilled in the art.
The quaternary ammonium group modified polyurethane CO prepared by the preparation method provided by the invention 2 The adsorbent is prepared by hydrophilic modification of polyurethane, grafting hydroxyl, and quaternizing, and can be seen from the infrared test chart of FIG. 2, at 1450-1600cm -1 In the interval, two obvious characteristic peaks of 1465cm respectively appear -1 And 1565cm -1 I.e., C-H bending vibrations and C-N stretching vibrations, which indicate that quaternary ammonium groups are already supported on the polyurethane. Compared with the traditional quaternary ammonium type anion exchange resin CO 2 The adsorbent improves the carbon dioxide adsorption performance, reduces the cost, is beneficial to realizing carbon emission reduction and accords with the sustainable development concept. Meanwhile, as shown in FIG. 5, the polyurethane CO prepared by the present invention 2 The adsorbent is in the form of granule and is matched with the existing powdery CO 2 Compared with the adsorbent, the adsorbent is more convenient for practical engineering application.
The invention also provides a quaternary ammonium group modified polyurethane CO 2 The adsorbent is prepared by adopting the preparation method of the technical scheme. The preparation method provided by the invention takes polyurethane as a raw material, and realizes better interaction under specific process steps and condition-level parameters, thereby preparing and obtaining the quaternary ammonium group modified polyurethane CO 2 An adsorbent; the carbon dioxide adsorption capacity of the common resin or anion exchange resin film is 0.4-0.8 mmol/g, and the carbon dioxide adsorption capacity of the quaternary amine chitosan aerogel and the quaternary amine bamboo cellulose is about 0.18mmol/g, the quaternary ammonium group modified polyurethane CO provided by the invention 2 The carbon dioxide of the adsorbent is placed in a small-sized adsorption tower shown in FIG. 6, the adsorption capacity can reach 1.40-1.80 mmol/g, and the adsorption curve chart of FIG. 4 shows that the CO of the embodiment 2 The adsorption capacity of the adsorbent is within this range.Therefore, it can be stated that under the same quality, the quaternary ammonium group modified polyurethane CO provided by the invention 2 The carbon dioxide adsorption performance of the adsorbent is better; meanwhile, as can be seen from a scanning electron microscope image of FIG. 3, the quaternary ammonium group modified polyurethane CO provided by the invention 2 The adsorbent still maintains the characteristics of high porosity and high specific surface area of polyurethane, and the adsorption rate of the adsorbent is the same as that of the existing CO 2 The adsorbent is not relatively superior or inferior. Thus the invention provides quaternary ammonium group modified polyurethane CO 2 The adsorbent improves the carbon dioxide adsorption performance on the premise of not affecting the adsorption rate.
The invention also provides a method for directly capturing carbon dioxide by air, which adopts the quaternary ammonium group modified polyurethane CO 2 The adsorbent is used for adsorption and desorption of carbon dioxide.
Compared with the prior art, the preparation method provided by the invention takes polyurethane as a raw material, and realizes better interaction under specific process steps, conditions and parameters, thereby preparing and obtaining the quaternary ammonium group modified polyurethane CO 2 An adsorbent. Polyurethane CO prepared by the invention 2 The adsorbent is in the form of granule and is matched with the existing powdery CO 2 Compared with the adsorbent, the adsorbent is more convenient for practical engineering application. At the same time, the adsorbent has higher CO 2 Adsorption performance, experimental results show that the quaternary ammonium group modified polyurethane CO provided by the invention 2 Adsorbent pair CO 2 The adsorption amount of the catalyst is 1.40-1.80 mmol/g.
Meanwhile, the raw materials selected by the invention and the preparation method provided by the invention have the advantages of low energy consumption cost, simple process, economy, environmental protection and the like, so that the method is used for preparing CO 2 Has good application prospect in the technical field of direct air trapping.
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) The polyurethane black material (isocyanate) and the polyurethane white material (combined polyether) are respectively taken to be 0.5g, and are mixed at normal temperature and rapidly stirred to obtain a first reaction product.
(2) Washing the first reaction product obtained in the step (1) with water, airing, sequentially washing with 6mL of acetone, absolute ethyl alcohol and deionized water in an ultrasonic cleaner for 15min respectively, soaking in an oxidizing solution (a mixed solution prepared by 0.7% of nitric acid and 17% of sulfuric acid according to a mass ratio of 1:1) for 8h, filtering, washing with a large amount of water, airing for later use; then soaking the polyurethane subjected to chemical oxidation in glutaraldehyde solution for 24 hours, then soaking in 3.5mol/L acrylic acid solution at 40 ℃ for 1.5 hours, performing grafting reaction, and washing with ethanol after the grafting reaction is finished to obtain a second reaction product.
(3) The second reaction product obtained in the step (2) is soaked in an aqueous solution of NaOH with the mass fraction of 30% for 4 hours at room temperature to enhance the reactivity, washed with a large amount of water and dried to constant weight at 60 ℃, then put into a mixed solution of 30mL of isopropanol and 5mL of 3-chloro-2-hydroxypropyl trimethylammonium chloride, and then added with 4mL of aqueous solution of NaOH to react for 4 hours, and the temperature is kept at 40 ℃. The obtained product is washed by HCl aqueous solution and water in turn until the pH value of the washing liquid reaches neutrality, thus obtaining a third reaction product.
(4) Filtering the third reaction product obtained in the step (3), adding 0.5mol/L Na 2 CO 3 50mL of solution is stirred for 4 hours for ion exchange, then is filtered, is washed by a large amount of deionized water, is filtered again, is repeatedly subjected to the ion exchange process for 4 times, is washed by a large amount of water, is filtered and is dried, and thus the quaternary ammonium group modified polyurethane CO is obtained 2 An adsorbent.
CO 2 The detection mode of adsorption is as follows: 0.1g of material and a carbon dioxide detector are placed into an organic glass box body (the volume in a detection system is 26.5L), the initial concentration of carbon dioxide is 876ppm, after 120min, the concentration of carbon dioxide in a test system is no longer changed, the concentration of carbon dioxide at the moment is 716ppm, and the concentration of the carbon dioxide is converted, so that the quaternary ammonium group modified polyurethane CO obtained by the preparation method provided by the embodiment 1 of the invention 2 Adsorbent pair CO 2 The adsorption amount of (C) was 1.73mmol/g. The other examples and comparative examples were examined in the same manner.
Example 2
The preparation method provided in example 1 was used, with the difference that: the grafting reaction of propylene in step (2)The concentration of the olefine acid is selected to be 2.5mol/L, and the quaternary ammonium group modified polyurethane CO is obtained 2 An adsorbent.
Through detection, the quaternary ammonium group modified polyurethane CO obtained by the preparation method provided by the embodiment 2 of the invention 2 Adsorbent pair CO 2 The adsorption amount of (C) was 1.53mmol/g.
Example 3
The preparation method provided in example 1 was used, with the difference that: the acrylic acid concentration of the grafting reaction in the step (2) is selected to be 1.0mol/L, and the quaternary ammonium group modified polyurethane CO is obtained 2 An adsorbent.
Through detection, the quaternary ammonium group modified polyurethane CO obtained by the preparation method provided by the embodiment 3 of the invention 2 Adsorbent pair CO 2 The adsorption amount of (C) was 1.41mmol/g.
Comparative example 1
The preparation method provided in example 1 was used, with the difference that: the grafting reaction temperature in the step (2) is 25 ℃, and the step (3) is omitted, so that the hydroxyl modified polyurethane CO is finally prepared 2 An adsorbent.
Through detection, the hydroxyl modified polyurethane CO obtained by the preparation method provided by the comparative example 1 2 Adsorbent pair CO 2 The adsorption quantity of (2) is 0, and the catalyst is used for CO 2 Has no adsorption capacity.
Comparative example 2
The preparation method provided in example 1 was used, with the difference that: the grafting reaction temperature in the step (2) is selected to be 55 ℃ to obtain the quaternary ammonium group modified polyurethane CO 2 An adsorbent.
Through detection, the quaternary ammonium group modified polyurethane CO obtained by the preparation method provided by the comparative example 2 2 Adsorbent pair CO 2 The adsorption amount of (C) was 0.87mmol/g.
Comparative example 3
The preparation method provided in example 1 was used, with the difference that: the grafting reaction time in the step (2) is selected to be 0.5h, and the quaternary ammonium group modified polyurethane CO is obtained 2 An adsorbent.
Through detection, the quaternary ammonium group modified polyurethane CO obtained by the preparation method provided by the comparative example 3 of the invention 2 Adsorbent pair CO 2 Adsorption of (3)The amount was 1.07mmol/g.
Comparative example 4
The preparation method provided in example 1 was used, with the difference that: in the step (3), the volume ratio of the NaOH aqueous solution to the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride solution is selected as 2:1, obtaining quaternary ammonium group modified polyurethane CO 2 An adsorbent.
Through detection, the quaternary ammonium group modified polyurethane CO obtained by the preparation method provided by the comparative example 4 of the invention 2 Adsorbent pair CO 2 The adsorption amount of (C) was 1.12mmol/g.
Comparative example 5
The preparation method provided in example 1 was used, with the difference that: in the step (3), the volume ratio of the NaOH aqueous solution to the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride solution is selected as 1:1, and omitting the step (4) to obtain the quaternary ammonium group modified polyurethane CO 2 An adsorbent.
Through detection, the quaternary ammonium group modified polyurethane CO obtained by the preparation method provided by the comparative example 5 of the invention 2 Adsorbent pair CO 2 The adsorption quantity of (2) is 0, and the catalyst is used for CO 2 Has no adsorption capacity.
Application examples
In practical application, the material has no special requirement on the adsorption environment, and the material is only required to be placed in a ventilated and dried environment for airing, so that in the process, the material can automatically adsorb carbon dioxide in the environment, and the drier the material is, the more the carbon dioxide is adsorbed.
If 1g of material is placed on a culture dish and placed in a baking oven at 40 ℃ for half an hour, the material is taken out, the material is adsorbed and saturated at the moment, then the material is placed in an organic glass cavity, atomization and humidification are carried out on the material at normal temperature, carbon dioxide is automatically released after the material is humidified, and the generated carbon dioxide can be pumped out by an air pump and used in other application scenes.
The above-mentioned embodiments are merely illustrative of the technical concept and features of the present invention, and it is to be understood that all embodiments which are obvious to those skilled in the art to which the present invention pertains without inventive faculty, are included in the present invention.
Claims (10)
1. Polyurethane CO modified by quaternary ammonium groups 2 The preparation method of the adsorbent is characterized by comprising the following steps: the method comprises the following steps:
a) Mixing polyurethane black material, namely isocyanate, and polyurethane white material, namely combined polyether) at normal temperature, and rapidly stirring to obtain a first reaction product;
b) Washing the first reaction product obtained in the step a) with water, airing, sequentially washing with acetone, absolute ethyl alcohol and deionized water in an ultrasonic cleaner for 10-20 min respectively, soaking in an oxidation solution, airing after washing, soaking in a glutaraldehyde solution for 24h, soaking in an acrylic acid solution at a certain temperature, carrying out grafting reaction, and washing with ethanol after completion to obtain a second reaction product;
c) Soaking the second reaction product obtained in the step b) in an aqueous solution of NaOH at room temperature for 2-6 hours to enhance the reactivity, filtering, washing with water, drying at 60-70 ℃, adding an aqueous solution of isopropanol and 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, adding an aqueous solution of NaOH, and carrying out quaternization reaction, wherein the obtained product is sequentially washed with the aqueous solution of HCl and water until the pH value of a washing solution reaches neutrality to obtain a third reaction product;
d) Filtering the third reaction product obtained in the step c), adding Na 2 CO 3 Carrying out ion exchange reaction on the solution for a plurality of times, and finally washing, filtering and drying to obtain granular quaternary ammonium group modified polyurethane CO 2 An adsorbent;
the chemical reaction of the preparation process is as follows:
2. the preparation method according to claim 1, wherein the mass ratio of the polyurethane black material to the polyurethane white material in the step a) is 1: (1-2).
3. The method according to claim 1, wherein the oxidizing solution in step b) is nitric acid with a mass concentration of 0.7% and sulfuric acid with a mass concentration of 17% according to 1:1 to 3 mass ratio of the mixed solution; the soaking time in the oxidizing solution is 6-8 h.
4. The process according to claim 1, wherein the molar concentration of acrylic acid in step b) is 1.0 to 3.5mol/L; the time of the grafting reaction is 1.0-2.5 h; the temperature of the grafting reaction is 15-45 ℃.
5. The preparation method according to claim 1, wherein the mass fraction of the aqueous NaOH solution in step c) is 20-40%.
6. The process according to claim 1, wherein the isopropanol is used in step c) in an amount of 20 to 40mL of isopropanol per 1g of the second reaction product; the mass fraction of the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride aqueous solution is 60%, and 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride aqueous solution with the dosage of 3-5 mL is used for immersing every 1g of the second reaction product; the volume ratio of the NaOH aqueous solution to the 3-chloro-2-hydroxypropyl-trimethyl ammonium chloride aqueous solution is (3-5): 5.
7. the process according to claim 1, wherein the quaternization reaction temperature in step c) is 25 to 40 ℃ and the reaction time is 3 to 5 hours.
8. The process according to claim 1, wherein the molar concentration of aqueous HCl in step c) is 0.1mol/L.
9. Polyurethane CO modified by quaternary ammonium groups 2 An adsorbent prepared by the method of any one of claims 1 to 8, in the form of particles comprising a porous polyurethane carrier and a function supported thereinAnd (3) a sex ion.
10. Modification of polyurethane CO with quaternary ammonium groups according to claim 9 2 The adsorbent is used for adsorbing and desorbing carbon dioxide, and quaternary ammonium group modified polyurethane CO 2 Adsorbent pair CO 2 The adsorption amount of the catalyst is 1.40-1.80 mmol/g.
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