CN116870870A - Antioxidant solid amine adsorbent and preparation method and application thereof - Google Patents
Antioxidant solid amine adsorbent and preparation method and application thereof Download PDFInfo
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- CN116870870A CN116870870A CN202310796823.9A CN202310796823A CN116870870A CN 116870870 A CN116870870 A CN 116870870A CN 202310796823 A CN202310796823 A CN 202310796823A CN 116870870 A CN116870870 A CN 116870870A
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- amine
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- solid amine
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- 150000001412 amines Chemical class 0.000 title claims abstract description 153
- 239000007787 solid Substances 0.000 title claims abstract description 79
- 239000003463 adsorbent Substances 0.000 title claims abstract description 51
- 230000003078 antioxidant effect Effects 0.000 title claims abstract description 51
- 239000003963 antioxidant agent Substances 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title abstract description 19
- 235000006708 antioxidants Nutrition 0.000 claims abstract description 49
- ADRVNXBAWSRFAJ-UHFFFAOYSA-N catechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3ccc(O)c(O)c3 ADRVNXBAWSRFAJ-UHFFFAOYSA-N 0.000 claims abstract description 40
- 235000005487 catechin Nutrition 0.000 claims abstract description 40
- 229950001002 cianidanol Drugs 0.000 claims abstract description 39
- -1 catechin compound Chemical class 0.000 claims abstract description 28
- 230000003647 oxidation Effects 0.000 claims description 18
- 238000007254 oxidation reaction Methods 0.000 claims description 18
- PFTAWBLQPZVEMU-DZGCQCFKSA-N (+)-catechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-DZGCQCFKSA-N 0.000 claims description 16
- 239000003431 cross linking reagent Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- 239000003960 organic solvent Substances 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000002131 composite material Substances 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- XMOCLSLCDHWDHP-IUODEOHRSA-N epi-Gallocatechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@H]2O)=CC(O)=C(O)C(O)=C1 XMOCLSLCDHWDHP-IUODEOHRSA-N 0.000 claims description 6
- PFTAWBLQPZVEMU-ZFWWWQNUSA-N (+)-epicatechin Natural products C1([C@@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-ZFWWWQNUSA-N 0.000 claims description 5
- WMBWREPUVVBILR-WIYYLYMNSA-N (-)-Epigallocatechin-3-o-gallate Chemical compound O([C@@H]1CC2=C(O)C=C(C=C2O[C@@H]1C=1C=C(O)C(O)=C(O)C=1)O)C(=O)C1=CC(O)=C(O)C(O)=C1 WMBWREPUVVBILR-WIYYLYMNSA-N 0.000 claims description 5
- PFTAWBLQPZVEMU-UKRRQHHQSA-N (-)-epicatechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@H]2O)=CC=C(O)C(O)=C1 PFTAWBLQPZVEMU-UKRRQHHQSA-N 0.000 claims description 5
- WMBWREPUVVBILR-UHFFFAOYSA-N GCG Natural products C=1C(O)=C(O)C(O)=CC=1C1OC2=CC(O)=CC(O)=C2CC1OC(=O)C1=CC(O)=C(O)C(O)=C1 WMBWREPUVVBILR-UHFFFAOYSA-N 0.000 claims description 5
- 229920002873 Polyethylenimine Polymers 0.000 claims description 5
- 150000001765 catechin Chemical class 0.000 claims description 5
- LPTRNLNOHUVQMS-UHFFFAOYSA-N epicatechin Natural products Cc1cc(O)cc2OC(C(O)Cc12)c1ccc(O)c(O)c1 LPTRNLNOHUVQMS-UHFFFAOYSA-N 0.000 claims description 5
- 235000012734 epicatechin Nutrition 0.000 claims description 5
- 229940030275 epigallocatechin gallate Drugs 0.000 claims description 5
- LSHROXHEILXKHM-UHFFFAOYSA-N n'-[2-[2-[2-(2-aminoethylamino)ethylamino]ethylamino]ethyl]ethane-1,2-diamine Chemical compound NCCNCCNCCNCCNCCN LSHROXHEILXKHM-UHFFFAOYSA-N 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 229920002401 polyacrylamide Polymers 0.000 claims description 5
- FAGUFWYHJQFNRV-UHFFFAOYSA-N tetraethylenepentamine Chemical compound NCCNCCNCCNCCN FAGUFWYHJQFNRV-UHFFFAOYSA-N 0.000 claims description 5
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 238000001704 evaporation Methods 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- XMOCLSLCDHWDHP-UHFFFAOYSA-N L-Epigallocatechin Natural products OC1CC2=C(O)C=C(O)C=C2OC1C1=CC(O)=C(O)C(O)=C1 XMOCLSLCDHWDHP-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- DZYNKLUGCOSVKS-UHFFFAOYSA-N epigallocatechin Natural products OC1Cc2cc(O)cc(O)c2OC1c3cc(O)c(O)c(O)c3 DZYNKLUGCOSVKS-UHFFFAOYSA-N 0.000 claims description 3
- BRLQWZUYTZBJKN-UHFFFAOYSA-N Epichlorohydrin Chemical compound ClCC1CO1 BRLQWZUYTZBJKN-UHFFFAOYSA-N 0.000 claims description 2
- SXRSQZLOMIGNAQ-UHFFFAOYSA-N Glutaraldehyde Chemical compound O=CCCCC=O SXRSQZLOMIGNAQ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 5
- 238000001179 sorption measurement Methods 0.000 description 37
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 9
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- 238000011068 loading method Methods 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 230000032683 aging Effects 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- 235000013824 polyphenols Nutrition 0.000 description 5
- 125000003277 amino group Chemical group 0.000 description 4
- 238000003795 desorption Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000004372 Polyvinyl alcohol Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 3
- 230000003064 anti-oxidating effect Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000009849 deactivation Effects 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003607 modifier Substances 0.000 description 3
- 229920002451 polyvinyl alcohol Polymers 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N o-dihydroxy-benzene Natural products OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 150000003141 primary amines Chemical group 0.000 description 2
- 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 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 150000004753 Schiff bases Chemical group 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 241001122767 Theaceae Species 0.000 description 1
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 125000002947 alkylene group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 229960004279 formaldehyde Drugs 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 230000000144 pharmacologic effect Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 150000003512 tertiary amines Chemical group 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 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
-
- 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
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28011—Other properties, e.g. density, crush strength
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2256/00—Main component in the product gas stream after treatment
- B01D2256/12—Oxygen
-
- 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
Abstract
The application discloses an antioxidant solid amine adsorbent, a preparation method and application thereof, wherein the antioxidant solid amine adsorbent comprises a porous carrier and antioxidant amine loaded in the porous carrier; the antioxidant amine comprises organic amine, and catechin compound covalently bonded with organic amine, and has antioxidant and CO adsorbing effects 2 Has good performance.
Description
Technical Field
The application relates to the technical field of adsorption materials, in particular to an antioxidant solid amine adsorbent, and a preparation method and application thereof.
Background
Carbon capture is to discharge CO in the industries of electric power, nonferrous metal smelting, petroleum processing, nonmetallic mineral product industry, coal exploitation and the like 2 Separating and purifying to realize CO 2 Recycling and reusing. CO 2 Adsorption is a novel carbon capture technology, which hasThe method has the advantages of high adsorption capacity, strong adsorption selectivity, easy preparation of materials, mild operation conditions, potential low energy consumption and the like, and is praised as a carbon capture technology with the most industrial application prospect in the future. At present, solid amine adsorbents are widely used for CO in air, industrial flue gas and natural gas 2 Adsorption has wide application prospect. The solid amine adsorbent usually adopts a porous solid material as a carrier, and organic amine is loaded on the surface of the solid amine adsorbent.
In the practical application scene, the solid amine adsorption material is exposed in 3-10VOL% oxygen atmosphere for a long time, and the active components of the solid amine adsorption material are easily oxidized and degraded, so that the recycling efficiency of the solid amine is reduced, and the practical application of the solid amine adsorption material is limited.
In the prior art, the oxidation degradation of solid amine is inhibited by introducing a sulfur-containing antioxidant or modifying and treating the solid amine material by using additives such as polyethylene glycol, alkylene oxide and the like and introducing hydroxyl functional groups, but the technologies also have the problems of large antioxidant taste, non-renewable petrochemical products derived from the additives and the like, and are not environment-friendly.
Disclosure of Invention
In view of the above, the present application provides an antioxidant solid amine adsorbent, its preparation method and application, and antioxidant and CO adsorption method 2 Has good performance.
In order to achieve the technical purpose, the application adopts the following technical scheme:
in a first aspect, the present application provides an antioxidant solid amine adsorbent comprising a porous support, and an antioxidant amine supported within the porous support; the antioxidant amine comprises organic amine and catechin compound covalently bound with the organic amine.
In a second aspect, the present application provides a method for preparing an antioxidant solid amine adsorbent comprising the steps of:
s1, dispersing organic amine and a porous carrier in an organic solvent, stirring and uniformly mixing, and evaporating the solvent to obtain solid amine;
s2, mixing solid amine with the organic solution of the catechin compound under inert atmosphere, and then distilling under reduced pressure to obtain the solid amine composite material.
S3, dispersing the cross-linking agent in an organic solvent, mixing the solid amine composite material with the cross-linking agent solution, separating a solid sample, and drying in vacuum to obtain the antioxidant solid amine adsorbent.
Preferably, the organic amine comprises one or more of diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, polyethyleneimine and polyacrylamide.
Preferably, the catechin compound comprises one or more of catechin (C), epigallocatechin gallate (EGCG), epicatechin (EC) and Epigallocatechin (ECG).
Preferably, the crosslinking agent comprises one or more of common crosslinking agents such as epichlorohydrin, glutaraldehyde and the like.
Preferably, the mass ratio of the catechin compound to the organic amine is 0.5-10:100.
preferably, the mass ratio of porous carrier to organic amine is 2-9:1-3.
Preferably, the mass ratio of the cross-linking agent to the organic amine is 1.0-5.0 per mill to 1.
Preferably, in step S2, the temperature of the vacuum drying is 50-80 ℃, and the time of the vacuum drying is 6-24 hours.
Preferably, in the step S1, the stirring speed is 300-800r/min, and the stirring time is 3-48h.
Preferably, the organic solvent comprises one or more of methanol, ethanol, ethylene glycol and glycerol.
In a third aspect, the present application provides an antioxidant solid amine adsorbent for CO adsorption in an oxygen atmosphere of 3-10VOL% 2 Is used in the application of (a).
The beneficial effects of the application are as follows:
the catechin compound with abundant hydroxyl functional groups is used as the modifier, has good oxidation resistance, can provide abundant hydrogen bond network with the amino compound through bridging action, improves the dispersibility of the organic amine, and prevents O 2 Into amine sites, reduce O 2 The probability of contacting with the organic amine can be further improved, so that the oxidation resistance of the solid amine adsorption material can be further improved. On the other hand, catechin modificationThe molecular weight of the solid amine adsorbent can be further increased, the boiling point of the organic amine is improved, the organic amine is prevented from volatilizing at high temperature or being carried out by other carrier gases, and the physical deactivation of the solid amine adsorbent caused by the loss of amine functional groups is effectively inhibited. In addition, the crosslinking of the organic amine and catechin enables partial primary amine groups of the organic amine to be converted into secondary amine groups, the hydroxyl groups on the modified organic amine molecular chain also play a certain degree of shielding effect on the alkalinity of the amine groups, and the organic amine and catechin cooperate to reduce the energy consumption of absorption/desorption, particularly in the desorption regeneration stage, the chemical deactivation of the solid amine adsorbent caused by the formation of urea chains is effectively inhibited, and the stability of the adsorbent is improved.
The preparation process of the antioxidant solid amine provided by the application is simple, and the renewable biomass derivative is used as the modifier, so that the use of petrochemical products is avoided, and the environment is friendly.
Drawings
Fig. 1 is a preparation flow chart of the scheme.
Detailed Description
The present application will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present application more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the application.
The application provides an antioxidant solid amine adsorbent, which comprises a porous carrier and antioxidant amine loaded in the porous carrier; the antioxidant amine comprises organic amine and catechin compound covalently bound with the organic amine. The loading rate of the organic amine in the antioxidant solid amine adsorbent is 10-60wt%.
Catechin compounds with abundant hydroxyl functional groups are used as modifiers, have good oxidation resistance, can form a rich hydrogen bond network with amino compounds, improve the dispersibility of organic amine and prevent O 2 Into amine sites, reduce O 2 The probability of contacting with the organic amine can be further improved, so that the oxidation resistance of the solid amine adsorption material can be further improved. In addition, catechin modified organic amine can not only increase molecular weight of organic amine and boiling point thereof and inhibit high temperature volatilization thereof, but also screenThe alkalinity of amine groups is shielded, the desorption energy consumption is reduced, and the circulation stability of the solid amine adsorbent is improved.
Notably, the loading rate of the organic amine in the antioxidant solid amine adsorbent is 10-60wt%, excessive loading does not improve the efficiency of the adsorbent, and the preparation cost of the adsorbent is increased; below this loading range, the adsorption capacity is weak. The application realizes the loading capacity by controlling the concentration of the organic amine.
As shown in fig. 1, the application provides a preparation method of an antioxidant solid amine adsorbent, which comprises the following steps:
s1, dispersing organic amine and a porous carrier in an organic solvent, stirring and uniformly mixing, and evaporating the solvent to obtain solid amine;
s2, mixing solid amine with the organic solution of the catechin compound under inert atmosphere, and then distilling under reduced pressure to obtain the solid amine composite adsorbent.
S3, dispersing the cross-linking agent in an organic solvent, mixing the solid amine composite material with the cross-linking agent solution, separating a solid sample, and drying in vacuum to obtain the antioxidant solid amine adsorbent.
The preparation method of the antioxidant solid amine provided by the application takes silicon dioxide, aluminum oxide, ion exchange resin and the like as carriers, takes Diethylenetriamine (DEEA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEEA), polyethyleneimine (PEI), polyacrylamide (PAA) and other organic amines as active components, firstly places a porous carrier material into an organic amine solution and an organic solvent to physically mix the organic amine and the carrier material, and organic amine molecules diffuse into the pore structure of the carrier due to concentration gradient and chemical affinity and are uniformly dispersed in pore channels, and then removes the organic solvent by means of evaporation and the like after impregnation, thus preparing the solid amine. Catechin and its derivatives are phenolic compounds with ortho-hydroxyl, and widely exist in natural plants such as tea. Catechin and its derivatives have antioxidant pharmacological action, and their polyhydroxy groups impart significant chemical diversity. In one aspect, catechins and derivatives thereof may form hydrogen bond networks with organic amines, promoting dispersibility of the organic amines. On the other hand, catechinAnd its derivatives, and organic amine, can give the adsorption material excellent oxidation resistance. The synergistic effect of the two can promote catechin to act as an antioxidant film on the surface of organic amine to prevent O 2 Into amine sites, reduce O 2 Probability of contact with organic amine. In addition, the introduction of catechin can also effectively inhibit the physical and chemical deactivation of the solid amine adsorbent, thereby improving the stability of the solid amine adsorbent. Thus, the antioxidant solid amine prepared in the examples of the present application has CO 2 High adsorption capacity, good antioxidation effect and high stability. In addition, the preparation method of the antioxidant solid amine is simple, the operation condition is mild, and the used modified raw materials are easy to regenerate.
The organic amine comprises one or more of diethanolamine, triethanolamine, tetraethylenepentamine, pentaethylenehexamine, polyethylenimine and polyacrylamide. The organic amine of the present application is a hydrophilic organic amine containing primary/tertiary amine groups and has a medium strong basicity (10.5 > pka > 8.0). On the one hand, too strong basicity can lead to the preparation of solid amines with CO 2 The combination is tight, and the desorption is difficult; strong alkalinity promotes oxidation of catechin compounds to form aldehyde and ketone compounds, and further forms p-CO with organic amine 2 Schiff base functional groups with low adsorption capacity consume active adsorption sites of organic amines and reduce the oxidation resistance of the material and result in reduced adsorption efficiency. On the other hand, solid amine and CO prepared by loading weak alkaline organic amine 2 The combination is weaker and is easily influenced by other impurity gases, CO 2 The adsorption selectivity is low.
The catechin compound comprises one or more of catechin (C), epigallocatechin gallate (EGCG), epicatechin (EC) and Epigallocatechin (ECG). The gamma-pyran ring of catechol compound is connected with 2 or more phenolic hydroxyl groups, wherein the B-ring phenolic hydroxyl group with antioxidant activity is connected with the gamma-pyran ring through 2-site carbon atoms, and the A-ring phenolic hydroxyl group is directly connected with 5, 6-site carbon atoms on the gamma-pyran ring to form a double ring. The catechol compound is further characterized in that the B-ring phenolic hydroxyl group has stronger electron donating ability and oxidation resistance, and the A-ring phenolic hydroxyl group can accept electrons and combine with organic amine to form an amino compound with larger molecular weight under the action of a cross-linking agent. The catechin compound is a biomass derivative, has the characteristics of environmental protection, biodegradability and the like, and is a substitute of petrochemical products. Compared with polyethylene glycol modification, the solid amine obtained by catechin modification has higher oxidation resistance.
The mass ratio of the catechin compound to the organic amine is 0.5-10:100; below this range, the catechin compound is added in a small amount, and the effect of antioxidation is not obvious; above this range, catechin is too much to be added, and is more densely combined with organic amine, affecting mass transfer; the concentration of catechin compound is 0.15-3g/L.
The mass ratio of the porous carrier to the organic amine is 2-9:1-3, the using amount of the organic amine is 0.66-15 parts by mass, and the using amount of the carrier is 1-10 parts by mass.
The mass ratio of the cross-linking agent to the organic amine is 1-5%o: 1, a step of; below the range, the binding effect of the catechin compound and the organic amine is not obvious, for example, a cross-linking agent is not added, and the catechin and the organic amine are combined mainly through weak hydrogen bonding, so that the recycling of the solid amine adsorbent is not facilitated; above this range, the crosslinker may consume too much organic amine active sites, resulting in reduced adsorption performance.
In the step S2, the temperature of vacuum drying is 50-80 ℃, and the time of vacuum drying is 6-24h.
In the step S1, the stirring speed is 300-800r/min, the stirring time is 3-48h, and the stirring temperature is 25-65 ℃.
The organic solvent comprises one or more of methanol, ethanol, ethylene glycol and glycerol.
The application provides an antioxidant solid amine adsorbent for adsorbing CO in an oxygen atmosphere of 3-10VOL percent 2 Is used in the application of (a).
The present application will be further described by way of specific embodiments.
Examples 1 to 5
An antioxidant solid amine adsorbent comprising a porous carrier and an antioxidant amine supported within the porous carrier; the antioxidant amine comprises organic amine and catechin compound covalently bound with the organic amine.
The preparation method of the antioxidant solid amine adsorbent comprises the following steps:
s1, dissolving organic amine in 25 parts by volume of methanol, and stirring for 30min at room temperature to obtain a transparent solution; dispersing a porous carrier subjected to degassing treatment for 2 hours at 110 ℃ in 5 parts by volume of methanol solution, mixing the porous carrier with the transparent solution in the step S1 according to the volume ratio of 1:5, stirring at 50 ℃ at the rotating speed of 300rpm until the solvent is completely evaporated, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain solid amine;
s2, dissolving catechin compound in 10 volume parts of ethanol solution, and adding into N 2 Stirring in gas at 500rpm for 15 min to obtain homogeneous transparent solution; mixing the solid amine in the step S1 and the transparent solution in the step S2 according to the mass ratio of 1:10, and N 2 Stirring for 24 hours at 500rpm in the atmosphere, and distilling under reduced pressure to obtain the solid amine composite material.
S3, dispersing epoxy chloropropane in 5ml of ethanol, mixing the solid amine composite material obtained in the step S2 with the epoxy chloropropane solution according to the mass ratio of 1:4, stirring for 3 hours, separating a solid sample, and vacuum drying at 60 ℃ for 12 hours to obtain the antioxidant solid amine adsorbent.
Wherein the amounts of the raw materials in examples 1 to 5 and comparative examples 1 to 3 are referred to Table 1.
TABLE 1 amounts of raw materials for examples 1-5 and comparative examples 1-3
Comparative example 1
An adsorbent was the same as in example 1 except that the catechin compound was not included, and steps S2 and S3 were not included in the preparation process.
Comparative example 3
An adsorbent was the same as in example 1 except that the cross-linking agent was not included, and the preparation process did not include step S3.
Comparative example 3
An adsorbent was the same as in example 1 except that the catechin compound was not included, and polyethylene glycol was used in step S2 of the preparation process.
Comparative example 4
An adsorbent was the same as in example 1 except that it did not include catechin compounds, and polyvinyl alcohol was used in step S2 of the preparation process.
Evaluation test
Test examples 1 to 5 and comparative examples 1 to 3 for CO 2 Adsorption performance and oxidation resistance, wherein the oxidation resistance is formed by CO 2 The adsorption decay rate was used for the reaction, and the results are shown in Table 1.
Adsorption of CO 2 And (3) testing: 0.2g of adsorbent was placed in a tube furnace for 15VOL% CO at 70 DEG C 2 Adsorption of CO in gas streams 2 Setting the time to be 60min, and calculating the adsorption quantity;
oxidation resistance: 0.2g of adsorbent was treated with 3% O 2 And 97% N 2 Aging at 110deg.C for 24 hr at 70deg.C, and using 15VOL% CO 2 Adsorption of CO in gas streams 2 Adsorption is carried out for 60min, and the adsorption quantity and the attenuation rate are calculated.
Table 1 test results
As can be seen from examples 1-5, CO 2 The adsorption amount of (2) is directly related to the load of organic amine, and the antioxidation efficiency of (2) is closely related to the addition amount of catechin compound. In comparative example 1, only the hydrophilic organic amine was supported, and although the adsorption capacity was similar to that of example 1, the adsorption decay rate after aging reached 55.40%, indicating that the oxidation resistance was weak. In comparative example 2, the adsorption capacity was slightly reduced without adding a crosslinking agent, but the adsorption capacity of the material was reduced by 25.73% after aging. Catechin as material in comparative example 2The organic amine is combined through weak hydrogen bonds, a stable oxidation-resistant polymeric chain is not formed, and partial organic amine functional groups are oxidized and degraded during aging, so that the adsorption capacity is reduced. Comparative examples 3 and 4 modified solid amine adsorbents with polyethylene glycol and polyvinyl alcohol, respectively, with higher adsorption capacity, but the adsorption decay rate after aging was higher than that in example 1, indicating that catechin compound modified solid amine could significantly enhance its antioxidant capacity, and the performance was superior to polyethylene glycol and polyvinyl alcohol. In conclusion, the oxidation resistance solid amine prepared by modifying catechin has the advantages of high adsorption capacity, good oxidation resistance, green preparation process and the like.
The present application is not limited to the above-mentioned embodiments, and any changes or substitutions that can be easily understood by those skilled in the art within the technical scope of the present application are intended to be included in the scope of the present application.
Claims (10)
1. An antioxidant solid amine adsorbent, characterized in that it comprises a porous carrier, and antioxidant amine supported in the porous carrier; the antioxidant amine comprises an organic amine and a catechin compound covalently bound with the organic amine.
2. A method for preparing the antioxidant solid amine adsorbent of claim 1, comprising the steps of:
s1, dispersing organic amine and a porous carrier in an organic solvent, stirring and uniformly mixing, and evaporating the solvent to obtain solid amine;
s2, mixing the solid amine with an organic solution of catechin compounds in an inert atmosphere, and then distilling under reduced pressure to obtain a solid amine composite material;
s3, dispersing the cross-linking agent in an organic solvent, mixing the solid amine composite material with the cross-linking agent solution, separating a solid sample, and drying in vacuum to obtain the antioxidant solid amine adsorbent.
3. The method for preparing an antioxidant solid amine adsorbent according to claim 2, wherein the organic amine comprises one or more of diethylenetriamine, tetraethylenepentamine, pentaethylenehexamine, polyethyleneimine and polyacrylamide.
4. The method for preparing an antioxidant solid amine adsorbent according to claim 2, wherein the catechin compound comprises one or more of catechin, epigallocatechin gallate epicatechin, and epigallocatechin.
5. The method for preparing an antioxidant solid amine adsorbent according to claim 2, wherein the crosslinking agent is one of epichlorohydrin and glutaraldehyde.
6. The method for preparing an antioxidant solid amine adsorbent according to claim 2, wherein the mass ratio of the catechin compound to the organic amine is 0.5-10:100.
7. the method for preparing an antioxidant solid amine adsorbent of claim 2 wherein the mass ratio of the porous support to the organic amine is 2-9:1-3.
8. The method for preparing an antioxidant solid amine adsorbent according to claim 2, wherein the mass ratio of the crosslinking agent to the organic amine is 1.0-5.0%1.
9. The method for preparing an antioxidant solid amine adsorbent according to claim 2, wherein in step S2, the temperature of vacuum drying is 50-80 ℃ and the time of vacuum drying is 6-24 hours.
10. An oxidation-resistant solid amine adsorbent obtained by the production method as claimed in any one of claims 2 to 9 for adsorbing CO in an oxygen atmosphere of 3 to 10VOL% 2 Is used in the application of (a).
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07238078A (en) * | 1994-02-24 | 1995-09-12 | Taiyo Kagaku Co Ltd | Purification method of polyphenolic compound |
| CN107661748A (en) * | 2017-10-30 | 2018-02-06 | 淮北师范大学 | Organic amino-functionalization large aperture capacity silicon oxide CO2Adsorbent and preparation method thereof |
| CN110368904A (en) * | 2019-06-26 | 2019-10-25 | 浙江跃维新材料科技有限公司 | A kind of preparation method and applications of the gas adsorption material of solid porous |
| CN114192122A (en) * | 2020-09-02 | 2022-03-18 | 中国船舶重工集团公司第七一八研究所 | Renewable nano-porous adsorption material for removing carbon dioxide and preparation method thereof |
| CN114700049A (en) * | 2022-02-23 | 2022-07-05 | 浙江跃维新材料科技有限公司 | Solid porous desulfurization adsorbent and preparation method thereof |
| CN115779860A (en) * | 2022-11-29 | 2023-03-14 | 华中科技大学 | Chitosan and organic amine composite solid adsorbent for adsorbing carbon dioxide in coal-fired flue gas, and preparation method, application and regeneration method thereof |
-
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- 2023-06-30 CN CN202310796823.9A patent/CN116870870B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07238078A (en) * | 1994-02-24 | 1995-09-12 | Taiyo Kagaku Co Ltd | Purification method of polyphenolic compound |
| CN107661748A (en) * | 2017-10-30 | 2018-02-06 | 淮北师范大学 | Organic amino-functionalization large aperture capacity silicon oxide CO2Adsorbent and preparation method thereof |
| CN110368904A (en) * | 2019-06-26 | 2019-10-25 | 浙江跃维新材料科技有限公司 | A kind of preparation method and applications of the gas adsorption material of solid porous |
| CN114192122A (en) * | 2020-09-02 | 2022-03-18 | 中国船舶重工集团公司第七一八研究所 | Renewable nano-porous adsorption material for removing carbon dioxide and preparation method thereof |
| CN114700049A (en) * | 2022-02-23 | 2022-07-05 | 浙江跃维新材料科技有限公司 | Solid porous desulfurization adsorbent and preparation method thereof |
| CN115779860A (en) * | 2022-11-29 | 2023-03-14 | 华中科技大学 | Chitosan and organic amine composite solid adsorbent for adsorbing carbon dioxide in coal-fired flue gas, and preparation method, application and regeneration method thereof |
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