CN114433027B - Solid amine modified porous material and preparation method thereof - Google Patents
Solid amine modified porous material and preparation method thereof Download PDFInfo
- Publication number
- CN114433027B CN114433027B CN202011204612.4A CN202011204612A CN114433027B CN 114433027 B CN114433027 B CN 114433027B CN 202011204612 A CN202011204612 A CN 202011204612A CN 114433027 B CN114433027 B CN 114433027B
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- polycyclic aromatic
- aromatic hydrocarbon
- asphalt
- porous material
- amino
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- 239000011148 porous material Substances 0.000 title claims abstract description 60
- 239000007787 solid Substances 0.000 title claims abstract description 41
- 150000001412 amines Chemical class 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 239000010426 asphalt Substances 0.000 claims abstract description 89
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 55
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims abstract description 45
- 238000000034 method Methods 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- 238000005470 impregnation Methods 0.000 claims abstract description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 25
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 21
- -1 polycyclic amine compounds Chemical class 0.000 claims abstract description 20
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 230000002378 acidificating effect Effects 0.000 claims abstract description 7
- 238000001179 sorption measurement Methods 0.000 claims description 23
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 14
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 12
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 12
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 12
- 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 11
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- 229960000583 acetic acid Drugs 0.000 claims description 7
- 239000012362 glacial acetic acid Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 6
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 6
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthene Chemical compound C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 6
- 239000003208 petroleum Substances 0.000 claims description 6
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 5
- 239000001569 carbon dioxide Substances 0.000 claims description 5
- 239000003575 carbonaceous material Substances 0.000 claims description 5
- 239000011294 coal tar pitch Substances 0.000 claims description 5
- 239000002808 molecular sieve Substances 0.000 claims description 5
- DXBHBZVCASKNBY-UHFFFAOYSA-N 1,2-Benz(a)anthracene Chemical compound C1=CC=C2C3=CC4=CC=CC=C4C=C3C=CC2=C1 DXBHBZVCASKNBY-UHFFFAOYSA-N 0.000 claims description 4
- QPUYECUOLPXSFR-UHFFFAOYSA-N 1-methylnaphthalene Chemical compound C1=CC=C2C(C)=CC=CC2=C1 QPUYECUOLPXSFR-UHFFFAOYSA-N 0.000 claims description 4
- QIMMUPPBPVKWKM-UHFFFAOYSA-N 2-methylnaphthalene Chemical compound C1=CC=CC2=CC(C)=CC=C21 QIMMUPPBPVKWKM-UHFFFAOYSA-N 0.000 claims description 4
- FMMWHPNWAFZXNH-UHFFFAOYSA-N Benz[a]pyrene Chemical compound C1=C2C3=CC=CC=C3C=C(C=C3)C2=C2C3=CC=CC2=C1 FMMWHPNWAFZXNH-UHFFFAOYSA-N 0.000 claims description 4
- GYFAGKUZYNFMBN-UHFFFAOYSA-N Benzo[ghi]perylene Chemical group C1=CC(C2=C34)=CC=C3C=CC=C4C3=CC=CC4=CC=C1C2=C43 GYFAGKUZYNFMBN-UHFFFAOYSA-N 0.000 claims description 4
- AEMRFAOFKBGASW-UHFFFAOYSA-N Glycolic acid Chemical compound OCC(O)=O AEMRFAOFKBGASW-UHFFFAOYSA-N 0.000 claims description 4
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 4
- MWPLVEDNUUSJAV-UHFFFAOYSA-N anthracene Chemical compound C1=CC=CC2=CC3=CC=CC=C3C=C21 MWPLVEDNUUSJAV-UHFFFAOYSA-N 0.000 claims description 4
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 claims description 4
- PAFZNILMFXTMIY-UHFFFAOYSA-N cyclohexylamine Chemical compound NC1CCCCC1 PAFZNILMFXTMIY-UHFFFAOYSA-N 0.000 claims description 4
- NIHNNTQXNPWCJQ-UHFFFAOYSA-N fluorene Chemical compound C1=CC=C2CC3=CC=CC=C3C2=C1 NIHNNTQXNPWCJQ-UHFFFAOYSA-N 0.000 claims description 4
- 239000007789 gas Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- YNPNZTXNASCQKK-UHFFFAOYSA-N phenanthrene Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 4
- 239000011295 pitch Substances 0.000 claims description 4
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 229910002027 silica gel Inorganic materials 0.000 claims description 4
- 239000000741 silica gel Substances 0.000 claims description 4
- IMNIMPAHZVJRPE-UHFFFAOYSA-N triethylenediamine Chemical compound C1CN2CCN1CC2 IMNIMPAHZVJRPE-UHFFFAOYSA-N 0.000 claims description 4
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 3
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- KHNYNFUTFKJLDD-UHFFFAOYSA-N BCR-49 Natural products C1=CC(C=2C3=CC=CC=C3C=CC=22)=C3C2=CC=CC3=C1 KHNYNFUTFKJLDD-UHFFFAOYSA-N 0.000 claims description 2
- TXVHTIQJNYSSKO-UHFFFAOYSA-N BeP Natural products C1=CC=C2C3=CC=CC=C3C3=CC=CC4=CC=C1C2=C34 TXVHTIQJNYSSKO-UHFFFAOYSA-N 0.000 claims description 2
- HAXBIWFMXWRORI-UHFFFAOYSA-N Benzo[k]fluoranthene Chemical compound C1=CC(C2=CC3=CC=CC=C3C=C22)=C3C2=CC=CC3=C1 HAXBIWFMXWRORI-UHFFFAOYSA-N 0.000 claims description 2
- RPNUMPOLZDHAAY-UHFFFAOYSA-N Diethylenetriamine Chemical compound NCCNCCN RPNUMPOLZDHAAY-UHFFFAOYSA-N 0.000 claims description 2
- SXQBHARYMNFBPS-UHFFFAOYSA-N Indeno[1,2,3-cd]pyrene Chemical compound C=1C(C2=CC=CC=C22)=C3C2=CC=C(C=C2)C3=C3C2=CC=CC3=1 SXQBHARYMNFBPS-UHFFFAOYSA-N 0.000 claims description 2
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 2
- 125000004054 acenaphthylenyl group Chemical group C1(=CC2=CC=CC3=CC=CC1=C23)* 0.000 claims description 2
- HXGDTGSAIMULJN-UHFFFAOYSA-N acetnaphthylene Natural products C1=CC(C=C2)=C3C2=CC=CC3=C1 HXGDTGSAIMULJN-UHFFFAOYSA-N 0.000 claims description 2
- FTOVXSOBNPWTSH-UHFFFAOYSA-N benzo[b]fluoranthene Chemical compound C12=CC=CC=C1C1=CC3=CC=CC=C3C3=C1C2=CC=C3 FTOVXSOBNPWTSH-UHFFFAOYSA-N 0.000 claims description 2
- 239000002041 carbon nanotube Substances 0.000 claims description 2
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 2
- 150000001735 carboxylic acids Chemical class 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 239000011280 coal tar Substances 0.000 claims description 2
- LHRCREOYAASXPZ-UHFFFAOYSA-N dibenz[a,h]anthracene Chemical compound C1=CC=C2C(C=C3C=CC=4C(C3=C3)=CC=CC=4)=C3C=CC2=C1 LHRCREOYAASXPZ-UHFFFAOYSA-N 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000002798 polar solvent Substances 0.000 claims description 2
- 229920000728 polyester Polymers 0.000 claims description 2
- 230000000274 adsorptive effect Effects 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 11
- 238000001816 cooling Methods 0.000 description 11
- 238000007598 dipping method Methods 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 238000000921 elemental analysis Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 125000003277 amino group Chemical group 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- 239000000843 powder Substances 0.000 description 5
- 238000005086 pumping Methods 0.000 description 5
- 238000002791 soaking Methods 0.000 description 5
- 238000002336 sorption--desorption measurement Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000000746 purification Methods 0.000 description 4
- 150000001721 carbon Chemical group 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000003763 carbonization Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000006364 Duff aldehyde synthesis reaction Methods 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- 238000005004 MAS NMR spectroscopy Methods 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 239000004568 cement Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000005388 cross polarization Methods 0.000 description 1
- 238000005384 cross polarization magic-angle spinning Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical compound C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000000269 nucleophilic effect Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000012536 packaging technology Methods 0.000 description 1
- 239000011301 petroleum pitch Substances 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Classifications
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- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/103—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate comprising silica
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/10—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising silica or silicate
- B01J20/16—Alumino-silicates
- B01J20/18—Synthetic zeolitic molecular sieves
-
- 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
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
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- 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
- B01J20/262—Synthetic macromolecular compounds obtained otherwise than by reactions only involving carbon to carbon unsaturated bonds, e.g. obtained by polycondensation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/102—Carbon
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/106—Silica or silicates
- B01D2253/108—Zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/10—Inorganic adsorbents
- B01D2253/116—Molecular sieves other than zeolites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2253/00—Adsorbents used in seperation treatment of gases and vapours
- B01D2253/20—Organic adsorbents
- B01D2253/202—Polymeric adsorbents
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- 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
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- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/46—Materials comprising a mixture of inorganic and organic materials
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- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4806—Sorbents characterised by the starting material used for their preparation the starting material being of inorganic character
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- 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
- B01J2220/00—Aspects relating to sorbent materials
- B01J2220/40—Aspects relating to the composition of sorbent or filter aid materials
- B01J2220/48—Sorbents characterised by the starting material used for their preparation
- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The invention discloses a solid amine modified porous material and a preparation method thereof. The method comprises the steps of firstly preparing amino enriched asphalt through the reaction of polycyclic aromatic hydrocarbon and organic polycyclic amine compounds in an acidic organic solvent system, and then preparing a solid amine modified porous material through an impregnation method. The method has the advantages of simple preparation process, abundant raw material sources, controllable conditions, high nitrogen doping amount and easy large-scale preparation. The method not only can improve the economical efficiency of asphalt and reasonably and effectively utilize resources, but also can be used as a solid amine modified porous material raw material for CO 2 And (5) high-efficiency trapping.
Description
Technical Field
The invention relates to the technical field of porous material preparation, in particular to a solid amine modified porous material and a preparation method thereof.
Background
Environmental and climatic pressures have forced the world-wide world to begin implementing various CO' s 2 Emission reduction measures, china petrochemical industry is one of main enterprises for exploiting and transporting natural gas, and is also one of the industries except the thermal power generation industry and the cement industry in ChinaAnother CO 2 The emission reduction cost of the emission reduction of the large households becomes one of the main problems restricting the development of enterprises, and how to collect and store CO2 becomes the key of saving the emission reduction cost and improving the benefits of the enterprises. Development of an efficient CO 2 The trapping technology not only can solve the problems faced by the operation of enterprises, but also can promote the progress of environmental optimization in China. Thus, CO is captured separately 2 Has very important significance in the fields of environment, chemical industry, energy sources and the like. At present, the carbon dioxide capturing and packaging technology (CCS) in China mainly adopts an absorption method, a large amount of solvent is needed, the cost is high in the use and recovery processes, equipment corrosion is extremely easy to cause, and the national popularization is severely restricted. For this reason, many scientific research institutions in China have recently started to develop new carbon dioxide trapping technologies, and solid adsorbents with superior performance are one of the research hotspots in this respect.
The porous material with high specific surface area exhibits excellent CO under normal temperature and pressure conditions 2 Capture and selective adsorption capacity. However, in the long-term use process, the materials are exposed to the problems of poor selectivity, low adsorption capacity and the like. The solid amine adsorption method is to use the selective reversible adsorption of the porous material modified by the amine to trap and separate CO 2 . All amino group-containing materials in solid amines have basic and nucleophilic properties. The aminated porous material has the characteristics of large specific surface area, high adsorption capacity and the like, has the characteristics of amino, improves the application value, and is widely applied to various fields. Therefore, development of a porous material having an amino function has been attracting attention.
Petroleum asphalt is the residue after crude oil distillation. The medium petrochemical industry is one of the largest domestic oil refining enterprises, and has rich asphalt resources. The asphalt has the characteristics of rich reserve, low price, high carbonization yield and the like. At present, the combination of petroleum asphalt and porous materials for carbon dioxide adsorption has not been reported yet.
Disclosure of Invention
The invention aims at providing a solid amine modified porous material which can effectively reduce the hazard of asphalt and widen the application field of asphalt.
The second purpose of the invention is to provide a preparation method of the solid amine modified porous material, which has the advantages of simple preparation process, abundant raw material sources, controllable conditions, high nitrogen doping amount and easiness in large-scale preparation. Not only can improve the economy of asphalt and reasonably and effectively utilize resources, but also the obtained solid amine modified porous material can be used for CO 2 And (5) high-efficiency trapping.
The invention also provides the application of the solid amine modified porous material or the solid amine modified porous material prepared by the method in the field of gas adsorption separation.
In order to achieve one of the above purposes, the present invention firstly proposes the following technical scheme:
a solid amine-modified porous material comprising the reaction product of a porous material and an amino-enriched asphalt.
Examples of the term "amino" as used in the present invention include amino groups or amine groups, such as primary, secondary or tertiary amines.
The nitrogen content of asphalt exceeds 10% in the art, which can be called enrichment, and the amino enriched asphalt refers to asphalt containing amino with nitrogen content of more than 10%.
According to some embodiments of the invention, the porous material is selected from one or more of a porous carbon material, a silica gel, a polyester-based porous material, and a molecular sieve.
According to some embodiments of the invention, the porous material is selected from one or more of carbon nanotubes, activated carbon, silica gel, MCM molecular sieve series, ZSM molecular sieve series, SBA molecular sieve series, and KIT molecular sieve series.
According to some embodiments of the invention, the amino enriched bitumen has a nitrogen content of 10% -25%, for example 10.5%, 11%, 12%, 13%, 14%, 15%, 16%, 17%, 18%, 19%, 19.5%, 20%, 21%, 22%, 23% and any value therebetween.
In order to achieve the second object, the present invention further provides a method for preparing a solid amine-modified porous material, comprising the steps of:
s1: providing amino enriched bitumen;
s2: mixing the amino-enriched asphalt in the step S1 with a porous material to form a mixture, and carrying out an impregnation reaction on the mixture.
According to some embodiments of the invention, the amino-enriched asphalt is prepared by reacting a polycyclic aromatic hydrocarbon and/or a polycyclic aromatic hydrocarbon-containing asphalt with an organic polycyclic amine compound in an acidic organic solvent system.
According to some embodiments of the invention, the polyaromatic hydrocarbon-containing bitumen is selected from one or more of petroleum bitumen, coal tar bitumen, and natural bitumen.
According to some embodiments of the invention, the polycyclic aromatic hydrocarbon is selected from one or more of the C9-C30 polycyclic aromatic hydrocarbons.
According to some embodiments of the invention, the polycyclic aromatic hydrocarbon is selected from one or more of naphthalene, acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene, chrysene, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo (a) pyrene, indeno (1, 2, 3-cd) pyrene, dibenzo (a, h) anthracene, benzo (g, h, i) perylene, 1-methylnaphthalene, and 2-methylnaphthalene.
According to some embodiments of the invention, the organic polycyclic amine compound is selected from one or more of the group consisting of C4-C10 organic polycyclic amine compounds.
According to some embodiments of the invention, the organic polycyclic amine compound is selected from one or more of hexamethylenetetramine, triethylenediamine, diethylenetriamine and cyclohexylamine.
In some preferred embodiments of the invention, the organic polycyclic amine compound is hexamethylenetetramine. The inventors creatively found that the amino-enriched bitumen was more severe in reaction conditions, higher in reaction temperature and excess in HMTA than the classical Duff reaction. Therefore, multiple substitution reactions occur during the synthesis process, and the variety of substitution products and polycondensation products thereof is great, resulting in such a complex mass spectrum structure, which has not been reported in previous studies.
According to some embodiments of the invention, the acidic organic solvent system comprises an organic solvent and an organic carboxylic acid.
According to some embodiments of the invention, the organic solvent is selected from one or more of polar solvents.
According to some embodiments of the invention, the organic solvent is selected from one or more of N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide.
According to some embodiments of the invention, the organic carboxylic acid is selected from one or more of the C1-C6 organic carboxylic acids.
According to some embodiments of the invention, the organic carboxylic acid is selected from one or more of glacial acetic acid, glycolic acid, citric acid, and formic acid.
According to some embodiments of the invention, the molar ratio of the polycyclic aromatic hydrocarbon and/or the polycyclic aromatic hydrocarbon-containing bitumen to the organic polycyclic amine compound is 1 (0.5-5), preferably 1 (1.5-3).
According to some embodiments of the invention, the mass ratio of the polycyclic aromatic hydrocarbon and/or the polycyclic aromatic hydrocarbon-containing bitumen to the organic polycyclic amine compound is 1 (0.01-5), such as 1:1, 1:1.5, 1:2.0, 1:2.5, 1:3.5, 1:4.0, 1:4.5, and any value therebetween.
According to some embodiments of the invention, the mass ratio of the polycyclic aromatic hydrocarbon and/or the polycyclic aromatic hydrocarbon-containing bitumen to the organic polycyclic amine compound is 1 (0.5-3).
According to some embodiments of the invention, the molar ratio of the polycyclic aromatic hydrocarbon and/or the polycyclic aromatic hydrocarbon-containing bitumen to the organic carboxylic acid is from 1 (0.01 to 0.5), preferably from 1 (0.05 to 0.2).
According to some embodiments of the invention, the mass ratio of the polycyclic aromatic hydrocarbon and/or the polycyclic aromatic hydrocarbon-containing bitumen to the organic carboxylic acid is 1 (0.001-0.5), such as 1:0.05, 1:0.10, 1:0.12, 1:0.15, 1:0.25, 1:0.30, 1:0.35, 1:0.40, 1:0.45, and any value therebetween.
According to some embodiments of the invention, the mass ratio of the polycyclic aromatic hydrocarbon and/or the polycyclic aromatic hydrocarbon-containing bitumen to the organic carboxylic acid is 1 (0.01-0.2).
In some preferred embodiments of the present invention, the polycyclic aromatic hydrocarbon and/or the polycyclic aromatic hydrocarbon-containing pitch is in an amount of 0.1 to 50 parts by mass based on 10 parts by mass of the polycyclic aromatic hydrocarbon-containing pitch; 10-600 parts by mass of an organic solvent; preferably 100 to 300 parts by mass; the organic carboxylic acid is 0.01-5 parts by mass.
According to some embodiments of the invention, the temperature of the reaction is 100-200 ℃, preferably 150-200 ℃, preferably the reaction is carried out under an inert atmosphere.
According to some embodiments of the present invention, the product amino enriched bitumen may be further separated, extracted, purified, etc. after the reaction.
According to some specific embodiments of the invention, the purification can be performed by using a rotary vacuum evaporator to perform preliminary separation and purification on the amino-enriched asphalt product at 100-200 ℃, and then baking and purifying the preliminary separation and purification product in a vacuum oven at 100-200 ℃ for 5-15h, thus obtaining the amino-enriched asphalt product after purification, and the like.
The inventor finds that polycyclic aromatic hydrocarbon has an electron-rich structure, is easily oxidized into ketone, phenol, ester, carboxylic acid and the like under high-temperature acidic conditions, and can obtain amino-enriched asphalt after further reaction with organic polycyclic amine which is easy to protonate. The amino enriched asphalt is obtained through elemental analysis, and the N content in the amino enriched asphalt is 10-25%.
According to some embodiments of the invention, the impregnation reaction in step S2 is carried out in a plurality of stages, preferably in two stages. The multi-stage impregnation is adopted, so that the impregnation capability of the impregnation liquid on the porous material can be effectively improved, and the impregnation efficiency is improved.
According to some embodiments of the invention, the temperature of the first impregnation reaction stage in step S2 is 15-30 ℃, the pressure is less than 0.01MPa, and the reaction time is 0.2-1h.
According to some embodiments of the invention, the second impregnation stage in step S2 is at a temperature of 300 ℃ to 600 ℃, a pressure of 3 to 5MPa, and a reaction time of 3 to 5 hours.
According to some embodiments of the invention, in the second impregnation stage, the temperature is increased from the temperature of the first impregnation stage to the temperature of the second impregnation stage at a constant speed, preferably at a rate of 1 ℃/min to 5 ℃/min.
According to some embodiments of the invention, in the second impregnation stage, the inert gas is pressurized, preferably one of nitrogen, helium and argon.
According to some embodiments of the invention, the mass ratio of the porous material to the amino enriched bitumen is 1 (1-10), such as 1:1.5, 1:2.0, 1:2.5, 1:3.0, 1:3.5, 1:4.0, 1:4.5, 1:5.5, 1:6, 1:7, 1:8, 1:9 and any value therebetween.
According to some embodiments of the invention, the mass ratio of the porous material to the amino enriched bitumen is 1 (1-5).
According to some embodiments of the present invention, if the amino pitch is used in an excessive amount, the pores inside the porous structure are blocked, and the specific surface area is reduced. If the amount is too low, the specific surface of the porous structure cannot be completely covered, affecting the impregnation rate.
According to some embodiments of the invention, the impregnation reaction comprises the following specific steps: placing the mixture into an impregnating furnace, sealing, and vacuumizing until the pressure is lower than 0.01MPa, and keeping for 20-60 minutes, preferably 30 minutes. Heating the dipping furnace to a certain temperature, stopping vacuumizing, pressurizing with inert gas, and setting the dipping time to be 3-5 hours. And cooling to room temperature, and taking out to obtain the solid amine modified porous material.
In a third aspect of the present invention, there is provided an application of the solid amine-modified porous material of the first aspect or the solid amine-modified porous material prepared by the method of the second aspect in the fields of adsorption separation and the like, in particular in carbon dioxide adsorption separation.
The invention has the following beneficial effects:
(1) The preparation method has the advantages of simple process, high balling rate and controllable conditions, and is easy for large-scale preparation.
(2) The amino enriched asphalt prepared by the invention introduces high-content amino. The nitrogen atom contained in the amino group is close to the carbon atom structure, so that the material structure can not be obviously distorted in the process of substituting the carbon atom in the carbon skeleton by the nitrogen atom as a heteroatom, and the structure of the carbon material can be further modulated, and the surface property of the material can be changed, for example, a plurality of dislocation, bending, dislocation and the like with unpaired electron defect sites are generated in a graphite microcrystalline plane layer in the carbon layer. Therefore, the invention not only effectively reduces the harm of asphalt through amino modification, but also can further expand the application field of materials.
(3) The amino enriched asphalt is prepared by directly reacting polycyclic aromatic hydrocarbon with organic polycyclic amine compounds, and modified high-nitrogen carbon products can be obtained after carbonization. Compared with the traditional mode of carbonizing first and then modifying to obtain a modified carbon product, the method greatly reduces the complexity of reaction (the modification process of the carbonized product is generally complicated and difficult), improves the content of other components in the modified product and the strength and stability of the modified product combined with carbon, reduces the production cost and improves the product quality.
(4) The solid amine modified porous material of the invention still maintains higher specific surface area and has high specific surface area to CO 2 The saturated adsorption capacity of the catalyst is higher, and the catalyst still maintains higher saturated adsorption capacity after multiple adsorption-desorption cycles, so that the catalyst has a better application prospect.
Drawings
Fig. 1 shows the isothermal adsorption/desorption curves at 25 ℃ for the solid amine modified porous materials prepared in example 1 and example 2.
Fig. 2 shows the high pressure isothermal adsorption/desorption curves at 25 ℃ for the solid amine modified porous materials prepared in example 1 and example 2.
FIG. 3 is an infrared spectrum of amino enriched asphalt prepared in example 1 of the present invention.
FIG. 4 is a C nuclear magnetic spectrum of amino enriched asphalt prepared in example 1 of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific embodiments and examples. It should be understood that the embodiments and examples described herein are for the purpose of illustration and explanation only and are not intended to limit the present invention.
The solid amine modified porous material was tested for a 25 ℃ low pressure isothermal adsorption/desorption profile (as in fig. 1) and a 25 ℃ high pressure isothermal adsorption/desorption profile (as in fig. 2) using a high pressure gas adsorption test instrument.
Testing CO of solid amine modified porous material by using two-component gas physical adsorption analyzer 2 /N 2 Is used for the selectivity coefficient of (a).
The content of C, H, N element in the sample was measured by using a CE440 fully automatic elemental analyzer manufactured by EAI corporation in the united states.
Example 1
10g of coal tar pitch, 0.2mol of HMTA (28.04 g) were dissolved in 300ml of methylpyrrolidone. Slowly dropping 0.01mol (0.60 g) of glacial acetic acid at 200 ℃ and N 2 The reaction was stirred for 5 hours under atmosphere protection. After cooling to room temperature, the product was isolated and purified using a 180 ℃ rotary vacuum evaporator. The resulting bitumen was further purified in a 160 ℃ vacuum oven for 10 hours to give amino enriched bitumen.
The nitrogen content of the amino enriched asphalt obtained by the elemental analysis test was 19.91%.
To further explore the basic structure of the sample, it was subjected to infrared spectroscopy, as shown in fig. 3, which is an infrared spectrum of amino enriched bitumen. At 3423cm -1 The characteristic adsorption peak of N-H group is shown at 1607, 799-663cm -1 The aromatic ring characteristic peak appears at 2931-2853cm -1 Where represents CH 2 Characteristic adsorption peak of the group at 2207cm -1 The weak adsorption peak of the c=n group is shown. .
The nuclear magnetic spectrum of the amino enriched asphalt was observed using cross polarization/magic angle spinning solid state nuclear magnetic spectroscopy (CP/MAS 13C NMR) as shown in fig. 4. The chemical shift c=n groups of carbons was about 148 and 152ppm, the aromatic carbons were about 140, 134, 128 and 125ppm, and the methylene carbon alpha carbon linking the benzene ring and the amino group was about 49ppm.
Weighing 10g of amino enriched asphalt, grinding into powder, mixing with 40g of ultra-high specific surface area active carbon material (specific surface area-3000 m 2 And/g) uniformly mixing, and then placing the mixture into an impregnation furnace for sealing. Vacuum pumping is started until the pressure is lower than 0.01MPa, and the vacuum is maintained for 30 minutes. Then heating the dipping furnace to 350 ℃ at the speed of 2 ℃/min, stopping vacuumizing, and using N 2 Pressurizing to 4MPa, and soaking for 3 hours. And then cooling to room temperature and taking out to obtain the solid amine modified porous material.
CO of solid amine modified porous materials 2 The adsorption capacity of (3) was 24.1ml/g (1 bar), 363ml/g (50 bar), CO 2 /N 2 The selectivity coefficient of (2) was 6.63.
Example 2
10g of coal tar pitch, 0.2mol of HMTA (28.04 g) were dissolved in 300ml of methylpyrrolidone. Slowly dropping 0.01mol (0.60 g) of glacial acetic acid at 200 ℃ and N 2 The reaction was stirred for 5 hours under atmosphere protection. After cooling to room temperature, the product was isolated and purified using a 180 ℃ rotary vacuum evaporator. The resulting bitumen was further purified in a 160 ℃ vacuum oven for 10 hours to give amino enriched bitumen.
The nitrogen content of the amino enriched asphalt obtained by the elemental analysis test was 19.91%.
Weighing 30g of amino enriched asphalt, grinding into powder, mixing with 40g of ultra-high specific surface area active carbon material (specific surface area-3000 m 2 And/g) uniformly mixing, and then placing the mixture into an impregnation furnace for sealing. Vacuum pumping is started until the pressure is lower than 0.01MPa, and the vacuum is maintained for 30 minutes. Then heating the dipping furnace to 350 ℃ at the speed of 2 ℃/min, stopping vacuumizing, and using N 2 Pressurizing to 4MPa, and soaking for 3 hours. And then cooling to room temperature and taking out to obtain the solid amine modified porous material.
CO of solid amine modified porous materials 2 The adsorption capacity of (2) was 21.9ml/g (1 bar), 191ml/g (50 bar) CO 2 /N 2 The selectivity coefficient of (2) is 10.54. Increasing the content of amino enriched asphalt and CO 2 The adsorption amount of CO is reduced 2 /N 2 The selectivity coefficient of (c) is improved.
Example 3
10g of petroleum asphalt, 0.2mol of HMTA (28.04 g) were dissolvedIn 300ml of methylpyrrolidone. Slowly dropping 0.01mol (0.60 g) of glacial acetic acid at 200 ℃ and N 2 The reaction was stirred for 5 hours under atmosphere protection. After cooling to room temperature, the product was isolated and purified using a 180 ℃ rotary vacuum evaporator. The resulting bitumen was further purified in a 160 ℃ vacuum oven for 10 hours to give amino enriched bitumen.
The nitrogen content of the amino enriched asphalt obtained by the elemental analysis test is 17.81%.
Weighing 10g of amino enriched asphalt, grinding into powder, uniformly mixing with 40g of mesoporous molecular sieve MCM-48, and sealing in an impregnation furnace. Vacuum pumping is started until the pressure is lower than 0.01MPa, and the vacuum is maintained for 30 minutes. Then heating the dipping furnace to 350 ℃ at the speed of 2 ℃/min, stopping vacuumizing, and using N 2 Pressurizing to 4MPa, and soaking for 3 hours. And then cooling to room temperature and taking out to obtain the solid amine modified porous material.
CO of solid amine modified porous materials 2 The adsorption capacity of (2) was 18.6ml/g (1 bar), 251ml/g (50 bar), CO 2 /N 2 The selectivity coefficient of (2) is 7.08.
Example 4
10g of coal tar pitch, 0.2mol of HMTA were dissolved in 300ml of N, N-dimethylformamide. Slowly dripping 0.01mol glacial acetic acid at 153 deg.C and N 2 The reaction was stirred for 5 hours under atmosphere protection. After cooling to room temperature, the product was isolated and purified using a 180 ℃ rotary vacuum evaporator. The resulting bitumen was further purified in a 160 ℃ vacuum oven for 10 hours to give amino enriched bitumen.
The amino enriched asphalt obtained by the elemental analysis test has a nitrogen content of 15.31%.
Weighing 10g of amino enriched asphalt, grinding into powder, uniformly mixing with 40g of mesoporous molecular sieve MCM-41, and sealing in an impregnation furnace. Vacuum pumping is started until the pressure is lower than 0.01MPa, and the vacuum is maintained for 30 minutes. Then heating the dipping furnace to 400 ℃ at the speed of 2 ℃/min, stopping vacuumizing, and using N 2 Pressurizing to 4MPa, and soaking for 3 hours. And then cooling to room temperature and taking out to obtain the solid amine modified porous material.
CO of solid amine modified porous materials 2 The adsorption capacity of (2) was 16.40ml/g (1 bar), 241ml/g (50 bar), CO 2 /N 2 The selectivity coefficient of (2) was 4.19.
Example 5
5g of coal tar pitch, 5g of petroleum pitch, 0.2mol of HMTA were dissolved in 300ml of N, N-dimethylformamide. Slowly dripping 0.01mol glacial acetic acid at 153 deg.C and N 2 The reaction was stirred for 5 hours under atmosphere protection. After cooling to room temperature, the product was isolated and purified using a 180 ℃ rotary vacuum evaporator. The resulting bitumen was further purified in a 160 ℃ vacuum oven for 10 hours to give amino enriched bitumen.
The nitrogen content of the amino enriched asphalt obtained by the elemental analysis test is 12.68%.
Weighing 10g of amino enriched asphalt, grinding into powder, uniformly mixing with 40g of mesoporous molecular sieve SBA-15, and sealing in an impregnation furnace. Vacuum pumping is started until the pressure is lower than 0.01MPa, and the vacuum is maintained for 30 minutes. Then heating the dipping furnace to 350 ℃ at the speed of 2 ℃/min, stopping vacuumizing, and using N 2 Pressurizing to 4MPa, and soaking for 3 hours. And then cooling to room temperature and taking out to obtain the solid amine modified porous material.
CO of solid amine modified porous materials 2 The adsorption capacity of (2) was 12.89ml/g (1 bar), 183ml/g (50 bar), CO 2 /N 2 Has a selectivity coefficient of 3.76.
It should be noted that the above-described embodiments are only for explaining the present invention and do not limit the present invention in any way. The invention has been described with reference to exemplary embodiments, but it is understood that the words which have been used are words of description and illustration, rather than words of limitation. Modifications may be made to the invention as defined in the appended claims, and the invention may be modified without departing from the scope and spirit of the invention. Although the invention is described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, as the invention extends to all other means and applications which perform the same function.
Claims (17)
1. A solid amine-modified porous material comprising the reaction product of a porous material and an amino-enriched asphalt;
the porous material is selected from one or more of porous carbon materials, silica gel, polyester porous materials and molecular sieves, and the nitrogen content of the amino enriched asphalt is 10% -25%;
the preparation method of the solid amine modified porous material comprises the following steps:
s1: providing amino enriched bitumen;
s2: mixing the amino-enriched asphalt in the step S1 with a porous material to form a mixture, and carrying out an impregnation reaction on the mixture;
the preparation method of the amino enriched asphalt comprises the steps of reacting polycyclic aromatic hydrocarbon and asphalt containing polycyclic aromatic hydrocarbon with an organic polycyclic amine compound in an acidic organic solvent system;
the asphalt containing the polycyclic aromatic hydrocarbon is selected from one or more of petroleum asphalt, coal tar asphalt and natural asphalt;
the polycyclic aromatic hydrocarbon is selected from one or more of C9-C30 polycyclic aromatic hydrocarbons.
2. The solid amine-modified porous material of claim 1, wherein the porous material is selected from one or more of carbon nanotubes, activated carbon, silica gel, MCM molecular sieve series, ZSM molecular sieve series, SBA molecular sieve series, and KIT molecular sieve series.
3. A method of preparing the solid amine-modified porous material of claim 1 or 2, comprising the steps of:
s1: providing amino enriched bitumen;
s2: mixing the amino-enriched asphalt in the step S1 with a porous material to form a mixture, and carrying out an impregnation reaction on the mixture.
4. The method of claim 3, wherein the amino enriched bitumen is prepared by reacting a polycyclic aromatic hydrocarbon and a bitumen containing a polycyclic aromatic hydrocarbon with an organic polycyclic amine compound in an acidic organic solvent system.
5. The method of claim 4, wherein the polyaromatic hydrocarbon-containing bitumen is selected from one or more of petroleum bitumen, coal tar pitch, and natural bitumen;
the polycyclic aromatic hydrocarbon is selected from one or more of C9-C30 polycyclic aromatic hydrocarbons;
and/or the organic polycyclic amine compound is selected from one or more of C4-C10 organic polycyclic amine compounds.
6. The method of claim 5, wherein the polycyclic aromatic hydrocarbon is selected from one or more of naphthalene, acenaphthylene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene, chrysene, benzo (b) fluoranthene, benzo (k) fluoranthene, benzo (a) pyrene, indeno (1, 2, 3-cd) pyrene, dibenzo (a, h) anthracene, benzo (g, h, i) perylene, 1-methylnaphthalene, and 2-methylnaphthalene;
and/or the organic polycyclic amine compound is selected from one or more of hexamethylenetetramine, triethylenediamine, diethylenetriamine and cyclohexylamine.
7. The method of claim 4, wherein the acidic organic solvent system comprises an organic solvent and an organic carboxylic acid; the organic solvent is selected from one or more of polar solvents;
and/or the organic carboxylic acid is selected from one or more of C1-C6 organic carboxylic acids.
8. The method according to claim 7, wherein the organic solvent is selected from one or more of N-methylpyrrolidone, N-dimethylformamide and N, N-dimethylacetamide;
and/or the organic carboxylic acid is selected from one or more of glacial acetic acid, glycolic acid, citric acid and formic acid.
9. The method according to claim 7, wherein the mass ratio of the polycyclic aromatic hydrocarbon and the polycyclic aromatic hydrocarbon-containing asphalt to the organic polycyclic amine compound is 1 (0.01-5);
and/or the mass ratio of the polycyclic aromatic hydrocarbon and the asphalt containing the polycyclic aromatic hydrocarbon to the organic carboxylic acid is 1 (0.001-0.5);
and/or the temperature of the reaction is 100-250 ℃, and the reaction is carried out under inert atmosphere.
10. The method of claim 7, wherein the mass ratio of the polycyclic aromatic hydrocarbon and the polycyclic aromatic hydrocarbon-containing pitch to the organic carboxylic acid is 1 (0.01-0.2).
11. The method according to claim 7, wherein the mass ratio of the polycyclic aromatic hydrocarbon and the polycyclic aromatic hydrocarbon-containing asphalt to the organic polycyclic amine compound is 1 (0.5-3);
and/or the mass ratio of the polycyclic aromatic hydrocarbon and/or the asphalt containing the polycyclic aromatic hydrocarbon to the organic carboxylic acid is 1 (0.01-0.2);
and/or the temperature of the reaction is 150-200 ℃.
12. The method according to any one of claims 3 to 11, characterized in that the impregnation reaction in step S2 is performed in multiple stages.
13. The method according to any one of claims 3 to 11, wherein the impregnation reaction in step S2 is performed in two stages, the temperature of the first impregnation reaction stage being 15 to 30 ℃, the pressure being less than 0.01MPa, the reaction time being 0.2 to 1h; the temperature of the second impregnation reaction stage is 300-600 ℃, the pressure is 3-5MPa, and the reaction time is 3-5h.
14. The method according to any one of claims 3 to 11, wherein the mass ratio of the porous material to the amino enriched bitumen is 1 (1-10).
15. The method according to any one of claims 3 to 11, wherein the mass ratio of the porous material to the amino enriched bitumen is 1 (1-5).
16. Use of a solid amine-modified porous material according to claim 1 or 2 or prepared according to the method of any one of claims 3-15 in gas adsorption separation.
17. Use of a solid amine-modified porous material according to claim 1 or 2 or prepared according to the method of any one of claims 3-15 in carbon dioxide adsorptive separation.
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| JP2019209293A (en) * | 2018-06-07 | 2019-12-12 | 大阪瓦斯株式会社 | Carbon dioxide adsorbent and method for producing the same |
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