CN116199612A - Porous adsorbent and preparation method and application thereof - Google Patents
Porous adsorbent and preparation method and application thereof Download PDFInfo
- Publication number
- CN116199612A CN116199612A CN202211449844.5A CN202211449844A CN116199612A CN 116199612 A CN116199612 A CN 116199612A CN 202211449844 A CN202211449844 A CN 202211449844A CN 116199612 A CN116199612 A CN 116199612A
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- China
- Prior art keywords
- porous adsorbent
- aryl
- adsorption
- unsubstituted
- substituted
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- 239000003463 adsorbent Substances 0.000 title claims abstract description 99
- 238000002360 preparation method Methods 0.000 title abstract description 15
- -1 bismaleimide compound Chemical class 0.000 claims abstract description 34
- 229920003192 poly(bis maleimide) Polymers 0.000 claims abstract description 24
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 238000003547 Friedel-Crafts alkylation reaction Methods 0.000 claims abstract description 11
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 7
- 230000035484 reaction time Effects 0.000 claims abstract description 5
- 238000001179 sorption measurement Methods 0.000 claims description 94
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 36
- 238000000034 method Methods 0.000 claims description 29
- 230000008929 regeneration Effects 0.000 claims description 26
- 238000011069 regeneration method Methods 0.000 claims description 26
- 239000011148 porous material Substances 0.000 claims description 20
- 239000004098 Tetracycline Substances 0.000 claims description 19
- 235000019364 tetracycline Nutrition 0.000 claims description 19
- 239000003242 anti bacterial agent Substances 0.000 claims description 17
- CYDMQBQPVICBEU-UHFFFAOYSA-N chlorotetracycline Natural products C1=CC(Cl)=C2C(O)(C)C3CC4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-UHFFFAOYSA-N 0.000 claims description 17
- 229960004475 chlortetracycline Drugs 0.000 claims description 17
- CYDMQBQPVICBEU-XRNKAMNCSA-N chlortetracycline Chemical compound C1=CC(Cl)=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-XRNKAMNCSA-N 0.000 claims description 17
- 235000019365 chlortetracycline Nutrition 0.000 claims description 17
- 229960002180 tetracycline Drugs 0.000 claims description 17
- 229930101283 tetracycline Natural products 0.000 claims description 17
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 15
- 150000003522 tetracyclines Chemical class 0.000 claims description 14
- 229940088710 antibiotic agent Drugs 0.000 claims description 12
- 239000003960 organic solvent Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 230000003115 biocidal effect Effects 0.000 claims description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical group Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 239000004100 Oxytetracycline Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 229960000625 oxytetracycline Drugs 0.000 claims description 7
- IWVCMVBTMGNXQD-PXOLEDIWSA-N oxytetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3[C@H](O)[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-PXOLEDIWSA-N 0.000 claims description 7
- 235000019366 oxytetracycline Nutrition 0.000 claims description 7
- IWVCMVBTMGNXQD-UHFFFAOYSA-N terramycin dehydrate Natural products C1=CC=C2C(O)(C)C3C(O)C4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O IWVCMVBTMGNXQD-UHFFFAOYSA-N 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 4
- 238000000944 Soxhlet extraction Methods 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 238000002390 rotary evaporation Methods 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 4
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- 125000000923 (C1-C30) alkyl group Chemical group 0.000 claims description 2
- 125000004178 (C1-C4) alkyl group Chemical group 0.000 claims description 2
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- KJYSFXXGQXIPIG-UHFFFAOYSA-N 1,3,5-trimethyl-2-(trichloromethyl)benzene Chemical group CC1=CC(C)=C(C(Cl)(Cl)Cl)C(C)=C1 KJYSFXXGQXIPIG-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000003118 aryl group Chemical group 0.000 claims description 2
- 125000005325 aryloxy aryl group Chemical group 0.000 claims description 2
- 125000004104 aryloxy group Chemical group 0.000 claims description 2
- 239000007795 chemical reaction product Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 238000000746 purification Methods 0.000 claims description 2
- 230000001172 regenerating effect Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- KYBJABUWKGOUSY-UHFFFAOYSA-N 5-butyl-2,5-dichlorocyclohexa-1,3-diene Chemical compound CCCCC1(Cl)CC=C(Cl)C=C1 KYBJABUWKGOUSY-UHFFFAOYSA-N 0.000 claims 1
- 238000004065 wastewater treatment Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 description 29
- 239000000203 mixture Substances 0.000 description 9
- 229940072172 tetracycline antibiotic Drugs 0.000 description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 6
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 6
- 239000012043 crude product Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- 229940063650 terramycin Drugs 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 241001465754 Metazoa Species 0.000 description 3
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- 238000001000 micrograph Methods 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- IPJGAEWUPXWFPL-UHFFFAOYSA-N 1-[3-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC(N2C(C=CC2=O)=O)=C1 IPJGAEWUPXWFPL-UHFFFAOYSA-N 0.000 description 2
- XQUPVDVFXZDTLT-UHFFFAOYSA-N 1-[4-[[4-(2,5-dioxopyrrol-1-yl)phenyl]methyl]phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C(C=C1)=CC=C1CC1=CC=C(N2C(C=CC2=O)=O)C=C1 XQUPVDVFXZDTLT-UHFFFAOYSA-N 0.000 description 2
- UPMLOUAZCHDJJD-UHFFFAOYSA-N 4,4'-Diphenylmethane Diisocyanate Chemical group C1=CC(N=C=O)=CC=C1CC1=CC=C(N=C=O)C=C1 UPMLOUAZCHDJJD-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 230000005526 G1 to G0 transition Effects 0.000 description 2
- 241000282414 Homo sapiens Species 0.000 description 2
- 150000001875 compounds Chemical group 0.000 description 2
- 125000004122 cyclic group Chemical group 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229940040944 tetracyclines Drugs 0.000 description 2
- 239000011800 void material Substances 0.000 description 2
- AQGZJQNZNONGKY-UHFFFAOYSA-N 1-[4-(2,5-dioxopyrrol-1-yl)phenyl]pyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=C(N2C(C=CC2=O)=O)C=C1 AQGZJQNZNONGKY-UHFFFAOYSA-N 0.000 description 1
- 244000144730 Amygdalus persica Species 0.000 description 1
- 208000035143 Bacterial infection Diseases 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000606161 Chlamydia Species 0.000 description 1
- 239000004971 Cross linker Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 239000004305 biphenyl Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000010041 electrostatic spinning Methods 0.000 description 1
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- 125000005842 heteroatom Chemical group 0.000 description 1
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- 244000144972 livestock Species 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- DOTMOQHOJINYBL-UHFFFAOYSA-N molecular nitrogen;molecular oxygen Chemical compound N#N.O=O DOTMOQHOJINYBL-UHFFFAOYSA-N 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 244000144977 poultry Species 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
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- 239000002689 soil Substances 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- FDDDEECHVMSUSB-UHFFFAOYSA-N sulfanilamide Chemical compound NC1=CC=C(S(N)(=O)=O)C=C1 FDDDEECHVMSUSB-UHFFFAOYSA-N 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
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Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D207/00—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom
- C07D207/02—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D207/44—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members
- C07D207/444—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5
- C07D207/448—Heterocyclic compounds containing five-membered rings not condensed with other rings, with one nitrogen atom as the only ring hetero atom with only hydrogen or carbon atoms directly attached to the ring nitrogen atom having three double bonds between ring members or between ring members and non-ring members having two doubly-bound oxygen atoms directly attached in positions 2 and 5 with only hydrogen atoms or radicals containing only hydrogen and carbon atoms directly attached to other ring carbon atoms, e.g. maleimide
-
- 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
- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/2808—Pore diameter being less than 2 nm, i.e. micropores or nanopores
-
- 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
- B01J20/28054—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 surface properties or porosity
- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
-
- 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
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
-
- 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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/3085—Chemical treatments not covered by groups B01J20/3007 - B01J20/3078
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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
- B01J20/30—Processes for preparing, regenerating, or reactivating
- B01J20/34—Regenerating or reactivating
- B01J20/3425—Regenerating or reactivating of sorbents or filter aids comprising organic materials
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention belongs to the technical field of wastewater treatment, and particularly relates to a porous adsorbent, a preparation method and application thereof, wherein the preparation method comprises the following steps: the bismaleimide compound, the cross-linking agent and the catalyst are subjected to Friedel-Crafts alkylation reaction in a solvent, wherein the temperature of the Friedel-Crafts alkylation reaction is 60-100 ℃, and the reaction time is 12-24 hours. The preparation method disclosed by the invention is simple, mild in reaction condition, environment-friendly and good in applicability.
Description
Technical Field
The invention belongs to the technical field of wastewater treatment, and particularly relates to a porous adsorbent, and a preparation method and application thereof.
Background
Tetracycline compounds are amphoteric substances, and C is contained in parent nucleus 10 And C 12 Phenolic hydroxyl group, enolic hydroxyl group, C having weak acidity 4 The position of the compound has alkalescent dimethylamino, and the tetracycline compound belongs to broad-spectrum antibiotics and has excellent bactericidal effect on gram (-) bacteria, gram (+) bacteria, chlamydia and the like. Tetracyclines have been widely used in the prevention and treatment of bacterial infections to improve human health, and at the same time, lower than therapeutic doses of tetracyclines are used as animal growth factors to improve feed, increase growth efficiency and promote weight gain in animals.
With the rapid development of the current world, especially the development of the medical care industry, the waste water containing tetracycline antibiotics generated in the process of medicine production is discharged into the environment in a large amount; meanwhile, 30% -90% of tetracycline antibiotics used in livestock and poultry cultivation cannot be absorbed, and the tetracycline antibiotics are discharged into the environment along with urine or feces in the form of original compounds.
The tetracycline compound is not easy to decompose, can exist in water and soil for a long time, changes the genetic characteristics of a microorganism system, causes serious toxicity to aquatic organisms, not only affects the development of agriculture and animal husbandry, but also causes great potential threat to human beings. Therefore, effective methods must be employed to remove the tetracycline antibiotics from water to ensure a healthy life of the individual.
Methods for treating tetracycline antibiotic pollutants are various and comprise more than ten methods such as a microwave method, an adsorption method, an electrochemical method and the like. The adsorption method is one of the most effective and reliable methods for removing the tetracycline antibiotics in the wastewater, but the adsorption efficiency of the common porous material on the tetracycline antibiotics is not ideal. The main reasons are the following two aspects: firstly, the surface chemistry of the traditional adsorbent is relatively difficult to regulate and control, and the specific surface area after modification is easy to be influencedSound, thus resulting in low adsorption capacity; for example: the patent document with application number 201710401886.4 discloses the application of a porous organic matter as an antibiotic adsorbent, which is obtained by carrying out Friedel-crafts alkylation reaction on a phenolic compound and alkoxymethane, wherein the maximum saturated adsorption capacity of the porous adsorbent for aureomycin is 189.5mg/g, the maximum saturated adsorption capacity for terramycin is 181.8mg/g, the maximum saturated adsorption capacity for aureomycin is 178.1mg/g, the time for reaching adsorption equilibrium is 300min, the adsorption capacity is smaller, and the time for reaching adsorption equilibrium is longer; secondly, most of the traditional adsorbents are mainly micropores, and the mass transfer process is limited by a microporous structure, so that the adsorption rate of the adsorbents on macromolecular antibiotics is slow, and the dynamic is not practical; s, S.
The TORRELLAS and the like prepare 2 kinds of active carbon by using peach pits and rice bran, the adsorption quantity reaches 845.9mg/g, but the whole adsorption needs 72 hours to reach adsorption balance, which limits the application of the active carbon material to a great extent. Patent document 202110025476.0 discloses a preparation method and application of an antibiotic quick adsorbent, which prepares an adsorbent for quickly adsorbing antibiotics, wherein the time for the adsorbent to reach adsorption equilibrium is 25min, but the intermediate is prepared through electrostatic spinning and then high-temperature calcination, the preparation process is complex, the cost is high, and whether the adsorbent has regeneration performance or not is uncertain, so that the large-scale application of the material is limited.
Disclosure of Invention
The adsorbent has high specific surface area and multistage pore structure, has higher adsorption capacity to various tetracycline antibiotics, has higher adsorption rate, can be used for adsorbing the tetracycline antibiotics in wastewater and can realize good regeneration and recycling; meanwhile, the adsorbent provided by the invention has the advantages of simple preparation method and low cost, and is suitable for popularization and application.
In order to achieve the above purpose, the invention adopts the following technical scheme:
in a first aspect, the present invention provides a method for preparing a porous adsorbent comprising the steps of:
the bismaleimide compound, the cross-linking agent and the catalyst are subjected to Friedel-Crafts alkylation reaction in a solvent, wherein the temperature of the Friedel-Crafts alkylation reaction is 60-100 ℃, and the reaction time is 12-24 hours.
According to an embodiment of the present invention, the bismaleimide compound has a structure represented by formula i:
the R is 1 Selected from the group consisting of substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 aryl, substituted or unsubstituted C2-C30 aryl-alkyl, substituted or unsubstituted C3-C30 aryl-alkyl-aryl, substituted or unsubstituted C3-C30 aryl-carbonyl-aryl, substituted or unsubstituted C2-C30 aryl-oxy-aryl, substituted or unsubstituted C2-C30 aryl-thio-aryl, substituted or unsubstituted C2-C30 aryl-sulfone-aryl;
wherein said substitution means substitution with one or more groups selected from the group consisting of: C1-C4 alkyl, C1-C4 haloalkyl, C1-C10 aryl-oxy.
Preferably, the bismaleimide compound is at least one selected from the group consisting of N, N '- (4, 4' -methylenediphenyl) bismaleimide, N '-1, 4-phenylenedimaleimide, and N, N' -1, 3-phenylenedimaleimide.
According to an embodiment of the present invention, the molar ratio of the bismaleimide compound to the crosslinker is 1: (1-4), preferably the molar ratio of the bismaleimide compound to the crosslinking agent is 1: (2-3), for example, 1:1, 1:2, 1:3, 1:4.
According to an embodiment of the invention, the cross-linking agent is selected from at least one of 1, 4-dichlorobenzyl, 1, 4-biphenyl chlorobenzyl, p-dichlorobenzyl-phenylbutane, trichloromethyl mesitylene, carbon tetrachloride, for example 1, 4-dichlorobenzyl and/or 1, 4-biphenyl chlorobenzyl.
According to an embodiment of the invention, the catalyst is ferric chloride and/or aluminium chloride.
According to an embodiment of the present invention, the molar ratio of the bismaleimide compound to the catalyst is 1: (5-9), preferably the molar ratio of the bismaleimide compound to the catalyst is 1: (6-8), for example, 1:5, 16, 1:7, 1:8, 1:9.
According to an embodiment of the present invention, the temperature of the reaction is 65 to 75 ℃, for example, 62 ℃, 70 ℃, 75 ℃, 80 ℃, 85 ℃, 90 ℃ or any value in the range of values consisting of any two points.
According to an embodiment of the invention, the reaction time is 15 to 20 hours, for example 18 hours, 20 hours, 22 hours.
According to an embodiment of the invention, the solvent is selected from organic solvents, preferably the organic solvent is selected from one or more of chloroform, dichloromethane, dichloroethane, for example 1, 2-dichloroethane.
According to an embodiment of the present invention, a preparation method for preparing the porous adsorbent includes the steps of: the bismaleimide compound, the cross-linking agent and the catalyst are dissolved in an organic solvent and then transferred into a reaction vessel to react for 12-24 hours at the temperature of 60-100 ℃.
According to an embodiment of the present invention, the concentration of the bismaleimide compound relative to the organic solvent is 0.01 to 0.015g/mL, preferably the concentration of the bismaleimide compound relative to the organic solvent is 0.05 to 0.010g/mL, for example, any value among 0.02g/mL, 0.04g/mL, 0.06g/mL, 0.08g/mL, 0.011g/mL, 0.013g/mL or any value in the range of any two points.
According to an embodiment of the present invention, the Friedel-Crafts alkylation reaction of the bismaleimide compound, the crosslinking agent and the catalyst in a solvent is followed by the following steps: the product of the Friedel-Crafts alkylation reaction is purified.
According to an embodiment of the invention, the purification comprises the steps of: and washing, soxhlet extraction and vacuum drying are sequentially carried out on the obtained reaction product, so that the porous adsorbent is obtained.
According to an embodiment of the present invention, the drying step is rotary evaporation at 60 to 90 ℃ for 15 to 24 hours. According to an embodiment of the invention, the soxhlet extraction comprises the steps of: the washed product is added into a Soxhlet extractor to extract until the extract is colorless.
According to an embodiment of the present invention, the extraction solvent of the soxhlet extraction is at least one of water, methanol, ethanol, acetone, diethyl ether, for example methanol.
According to an embodiment of the invention, the washing comprises washing several times with a washing solvent selected from at least one of water, methanol, ethanol, acetone, diethyl ether, for example methanol.
In a second aspect, the present invention provides a porous adsorbent prepared by the above method.
According to an embodiment of the invention, the porous adsorbent comprises a plurality of open ordered 3D cells formed by the stacking of nanoparticles.
According to an embodiment of the present invention, the pore channel includes a pore structure having a pore diameter of 0.5 to 5nm and a pore structure having a pore diameter of 5nm to 30 nm.
According to an embodiment of the present invention, the porous adsorbent has a nitrogen adsorption desorption profile substantially as shown in fig. 1.
According to an embodiment of the present invention, the porous adsorbent has a pore distribution map substantially as shown in fig. 2.
According to an embodiment of the present invention, the porous adsorbent has a scanning electron microscope image substantially as shown in fig. 4.
According to an embodiment of the invention, the porous adsorbent has an adsorption kinetics profile of a destetracycline antibiotic substantially as shown in fig. 5.
According to an embodiment of the present invention, the porous adsorbent has an adsorption isotherm of desaureomycin substantially as shown in fig. 6.
In a third aspect, the present invention provides the use of a porous adsorbent as described above for adsorbing an antibiotic, preferably a tetracycline compound, for example at least one of aureomycin, tetracycline or oxytetracycline.
In a fourth aspect, the present invention provides a method for adsorbing antibiotics by the above porous adsorbent, comprising the steps of: the porous adsorbent is dispersed in a solution containing antibiotics, mixed and adsorbed by standing.
According to an embodiment of the invention, the time of the stationary phase adsorption is less than 1h, preferably the time of the stationary phase adsorption is less than 45min, for example any value of 20min, 25min, 30min, 35min, 40min or any value in the range of values consisting of any two point values.
In a fourth aspect, the present invention provides a method for regenerating the porous adsorbent, comprising the steps of washing and adsorbing the porous adsorbent to be regenerated with a regeneration solvent several times, and drying.
Wherein the porous adsorbent to be regenerated is selected from porous adsorbents adsorbed with antibiotics.
According to an embodiment of the present invention, the regeneration solvent is at least one selected from deionized water, methanol, ethyl acetate, naOH aqueous solution, for example ethyl acetate.
According to an embodiment of the invention, the washing temperature of the organic solvent is 40-80 ℃, for example 60 ℃.
According to an embodiment of the present invention, the drying is performed at a temperature of 40 to 80 ℃, preferably 50 to 70 ℃, more preferably 60 to 75 ℃, for example 45 ℃, 50 ℃, 55 ℃, 60 ℃, 65 ℃, 70 ℃, 75 ℃, 80 ℃ or any value in the range of any two point values.
According to an embodiment of the invention, the drying time is 10 to 24 hours, preferably 15 to 20 hours, for example any value of 12 hours, 14 hours, 16 hours, 18 hours, 20 hours, 22 hours or any value in the range of values consisting of any two points.
Advantageous effects
1) The invention adopts a one-pot method, adopts bismaleimide compound as a main raw material, carries out Friedel-Crafts alkylation reaction to obtain the nitrogen-oxygen-containing high-efficiency porous adsorbent, and has the advantages of simple preparation method, mild reaction condition, environmental friendliness and good applicability.
2) The porous adsorbent has higher specific surface area, contains a multi-stage pore structure, has high content of heteroatom nitrogen and oxygen, can show excellent adsorption capacity and adsorption rate for various antibiotic organic matters, can realize good regeneration and recycling effects, and has important application and popularization values.
Drawings
FIG. 1 is a graph showing the adsorption and desorption of nitrogen from a porous adsorbent prepared in example 1 of the present invention;
FIG. 2 is a graph showing the void distribution of the porous adsorbent prepared in example 1 of the present invention;
FIG. 3 is a synthetic route for preparing porous adsorbents in accordance with example 1 of the present invention;
FIG. 4 is a scanning electron microscope image of the porous adsorbent prepared in example 1 of the present invention;
FIG. 5 is a graph showing adsorption kinetics of antibiotic removal by the porous adsorbent prepared in example 1 of the present invention;
FIG. 6 shows adsorption isotherms of the porous adsorbents prepared in example 1 according to the present invention for aureomycin removal at different temperatures.
Detailed Description
The adsorbent of the present invention, and the preparation method and application thereof will be described in further detail with reference to specific examples. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
The model sewage in the following application examples refers to an aqueous solution containing the corresponding antibiotics, and the concentration of the antibiotics in the aqueous solution is 500mg/L.
Example 1
A preparation method of the porous adsorbent comprises the following steps: n, N '- (4, 4' -methylenediphenyl) bismaleimide 5.02g,1, 4-diphenyl chlorobenzyl chloride 7.16g, anhydrous ferric trichloride 9.72g are added into 200mL of 1, 2-dichloroethane, ultrasonically dissolved, transferred into a 500mL single-neck flask, then placed into an oil bath at 80 ℃ for reaction for 24 hours to obtain a polymer crude product, the obtained polymer crude product is washed three times with 200mL of methanol to remove a large amount of anhydrous ferric trichloride, and then extracted by a methanol Soxhlet extractor until the extracting solution is colorless, and then rotary evaporated at 60 ℃ for 12 hours to obtain the efficient porous adsorbent.
FIG. 1 is a graph showing the adsorption and desorption curves of nitrogen gas of the porous adsorbent prepared in this example, and as can be seen from FIG. 1, the porous adsorbent prepared in this example has a relatively high specific surface area; fig. 2 shows the void distribution diagram of the porous adsorbent prepared in this example, and it can be seen from fig. 2 that the porous adsorbent prepared in this example has a good pore structure, the main pores of which are nano-pore structures of 0.5-5 nm, and a small amount of pore structures of 5-30 nm, and the nano-pore structures of various pore diameters enable the porous adsorbent to have a larger specific surface area and higher adsorption activity.
FIG. 3 is a synthetic route diagram of an efficient porous adsorbent in accordance with an embodiment of the present invention.
Fig. 4 is a scanning electron microscope image of the porous adsorbent prepared in example 1 of the present invention, and it can be seen from the image that the porous adsorbent prepared in this example is formed by stacking nano-sized particles to form open ordered 3D channels.
FIG. 5 shows adsorption kinetics curves of the porous adsorbent prepared in example 1 of the present invention for removing different antibiotics (aureomycin, oxytetracycline, and tetracycline), wherein the maximum adsorption amount of the porous adsorbent to aureomycin is 375mg/g, and the adsorption equilibrium is reached within about 30 min; the maximum adsorption capacity of the terramycin is 320mg/g, and the adsorption balance is achieved within about 30 min; the maximum adsorption capacity of the tetracycline is 270mg/g, and the adsorption balance is achieved within about 30 min.
Fig. 6 is an adsorption isothermal curve of the porous adsorbent prepared in example 1 according to the present invention for aureomycin removal at different temperatures, and it can be seen that the adsorption amount of the porous adsorbent increases with increasing temperature in the experimental temperature range, which indicates that the adsorption process of the porous adsorbent for aureomycin is an endothermic process.
Application example 1
(1) The mass ratio of porous adsorbent to sewage mixture prepared in example 1 was 0.001:1, the sewage is model sewage containing aureomycin, the initial aureomycin content in the sewage is 500mg/L, the adsorption temperature is 30 ℃, the adsorption time is 30min, and the maximum adsorption capacity is 375mg/g after adsorption operation.
(2) The mass ratio of porous adsorbent to sewage mixture prepared in example 1 was 0.001:1, the sewage is model sewage containing tetracycline, the initial tetracycline content is 500mg/L, the adsorption temperature is 30 ℃, the adsorption time is 30min, and the maximum adsorption capacity is 286mg/g after adsorption operation.
(3) The mass ratio of porous adsorbent to sewage mixture prepared in example 1 was 0.001:1, the sewage is model sewage containing terramycin, the initial terramycin content is 500mg/L, the adsorption temperature is 30 ℃, the adsorption time is 30min, and the maximum adsorption capacity is 318mg/g after adsorption operation.
Example 2
A preparation method of the porous adsorbent comprises the following steps: 5.36g of N, N' -1, 4-phenylene bismaleimide and 7.16g of 1, 4-diphenyl chlorobenzyl chloride are added into 200mL of 1, 2-dichloroethane, 9.72g of anhydrous ferric trichloride is ultrasonically dissolved, transferred into a 500mL single-neck flask, then placed into an oil bath pot at 80 ℃ to react for 24 hours, a polymer crude product is obtained, the obtained polymer crude product is washed three times with 200mL of methanol to remove a large amount of anhydrous ferric trichloride, and then extracted by a methanol Soxhlet extractor until the extracting solution is colorless, and then rotary evaporation is carried out for 12 hours at 60 ℃, thus obtaining the porous adsorbent.
Application example 2
(1) The mass ratio of the porous adsorbent prepared in example 2 to the sewage mixture is 0.001, the used sewage is model sewage containing aureomycin, the initial aureomycin content is 500mg/L, the adsorption temperature is 30 ℃, the adsorption time is 30min, and the maximum adsorption capacity is 306mg/g after the adsorption operation.
(2) The mass ratio of the porous adsorbent prepared in example 2 to the sewage mixture was 0.001, the used sewage was model sewage containing tetracycline, the initial tetracycline content was 500mg/L, the adsorption temperature was 30℃and the adsorption time was 30min, and the maximum adsorption amount was 241mg/g after the adsorption operation.
(3) The mass ratio of the porous adsorbent prepared in example 2 to the sewage mixture was 0.001, the used sewage was model sewage containing oxytetracycline, the initial oxytetracycline content was 500mg/L, the adsorption temperature was 30℃and the adsorption time was 30min, and the maximum adsorption capacity was 263mg/g after the adsorption operation.
Example 3
A preparation method of the efficient porous adsorbent for treating antibiotic-containing wastewater comprises the following steps: 5.36g of N, N' -1, 3-phenylene bismaleimide and 7.16g of 1, 4-diphenyl chlorobenzyl chloride are added into 200mL of 1, 2-dichloroethane, 9.72g of anhydrous ferric trichloride is ultrasonically dissolved, transferred into a 500mL single-neck flask, then placed into an oil bath pot at 80 ℃ to react for 24 hours, a polymer crude product is obtained, the obtained polymer crude product is washed three times with 200mL of methanol to remove a large amount of anhydrous ferric trichloride, and then extracted by a methanol Soxhlet extractor until the extracting solution is colorless, and then rotary evaporation is carried out for 12 hours at 60 ℃ to obtain the high-efficiency porous adsorbent.
Application example 3
(1) The mass ratio of the porous adsorbent prepared in example 3 to the sewage mixture is 0.001, the used sewage is model sewage containing aureomycin, the initial aureomycin content is 500mg/L, the adsorption temperature is 30 ℃, the adsorption time is 30min, and the maximum adsorption capacity is 298mg/g after the adsorption operation.
(2) The mass ratio of the porous adsorbent prepared in example 3 to the sewage mixture was 0.001, the used sewage was model sewage containing tetracycline, the initial tetracycline content was 500mg/L, the adsorption temperature was 30℃and the adsorption time was 30min, and the maximum adsorption amount was 233mg/g after the adsorption operation.
(3) The mass ratio of the porous adsorbent prepared in example 3 to the sewage mixture was 0.001, the used sewage was model sewage containing oxytetracycline, the initial oxytetracycline content was 500mg/L, the adsorption temperature was 30℃and the adsorption time was 30min, and the maximum adsorption capacity was 260mg/g after the adsorption operation.
Cyclic application testing
The high-efficiency porous adsorbent for adsorbing the organic matters containing the antibiotics obtained in the application example 1 is recovered and subjected to a cyclic regeneration application test, and the method specifically comprises the following steps: washing the adsorbent after adsorbing aureomycin, tetracycline and terramycin sulfanilamide by 0.01g respectively with 100mL ethyl acetate at 60 ℃; washing for 3 times, and drying at 60 ℃ for 12 hours to obtain a regenerated adsorbent; the adsorption performance of the regenerated adsorbent was tested and the substrate concentration in the residual liquid was measured as follows:
for an aureomycin aqueous solution system, the adsorption capacity of the adsorbent before regeneration is 375mg/g, the adsorption capacity of the adsorbent after the first regeneration is 370mg/g, the adsorption capacity of the adsorbent after the second regeneration is 365mg/g, the adsorption capacity of the adsorbent after the third regeneration is 363mg/g, the adsorption capacity after the fourth regeneration is 358mg/g, and the adsorption capacity after the fifth regeneration is 350mg/g.
For the tetracycline aqueous solution system, the adsorption capacity of the adsorbent before regeneration is 286mg/g, the adsorption capacity of the adsorbent after the first regeneration is 283mg/g, the adsorption capacity of the adsorbent after the second regeneration is 279mg/g, the adsorption capacity of the adsorbent after the third regeneration is 273mg/g, the adsorption capacity after the fourth regeneration is 265mg/g and the adsorption capacity after the fifth regeneration is 257mg/g.
For an terramycin aqueous solution system, the adsorption capacity of the adsorbent before regeneration is 318mg/g, the adsorption capacity of the adsorbent after the first regeneration is 315mg/g, the adsorption capacity of the adsorbent after the second regeneration is 311mg/g, the adsorption capacity of the adsorbent after the third regeneration is 295mg/g, the adsorption capacity after the fourth regeneration is 288mg/g, and the adsorption capacity after the fifth regeneration is 279mg/g.
The foregoing description of the specific embodiments of the present invention has been presented by way of example. However, the scope of the present invention is not limited to the above exemplary embodiments. Any modification, equivalent replacement, improvement, etc. made by those skilled in the art within the spirit and principle of the present invention should be included in the scope of protection of the claims of the present invention.
Claims (10)
1. A method for preparing a porous adsorbent, comprising the steps of:
the bismaleimide compound, the cross-linking agent and the catalyst are subjected to Friedel-Crafts alkylation reaction in a solvent, wherein the temperature of the Friedel-Crafts alkylation reaction is 60-100 ℃, and the reaction time is 12-24 hours.
2. The method of claim 1, wherein the bismaleimide compound has a structure represented by formula i:
wherein R is 1 Selected from the group consisting of substituted or unsubstituted C1-30 alkyl, substituted or unsubstituted C1-30 aryl, substituted or unsubstituted C2-C30 aryl-alkyl, substituted or unsubstituted C3-C30 aryl-alkyl-aryl, substituted or unsubstituted C3-C30 aryl-carbonyl-aryl, substituted or unsubstituted C2-C30 aryl-oxy-aryl, substituted or unsubstituted C2-C30 aryl-thio-aryl, substituted or unsubstituted C2-C30 aryl-sulfone-aryl; the substitution means substitution with one or more groups selected from the group consisting of: C1-C4 alkyl, C1-C4 haloalkyl, C1-C10 aryl-oxy.
3. The method according to claim 1, wherein the crosslinking agent is at least one selected from the group consisting of 1, 4-dichlorobenzyl, 1, 4-diphenyl chlorobenzyl, p-dichlorophenyl butane, trichloromethyl mesitylene, and carbon tetrachloride.
Preferably, the molar ratio of the bismaleimide compound to the crosslinking agent is 1: (1-4), preferably the molar ratio of the bismaleimide compound to the crosslinking agent is 1: (2-3).
Preferably, the catalyst is ferric chloride and/or aluminum chloride.
Preferably, the molar ratio of the bismaleimide compound to the catalyst is 1: (5-9), preferably the molar ratio of the bismaleimide compound to the catalyst is 1: (6-8).
4. The method according to claim 1, wherein the reaction temperature is 65 to 75 ℃ and the reaction time is 15 to 20 hours.
Preferably, the solvent is selected from organic solvents, preferably the organic solvent is selected from one or more of chloroform, dichloromethane, dichloroethane.
5. The method of preparing the porous adsorbent according to claim 1, comprising the steps of: the bismaleimide compound, the cross-linking agent and the catalyst are dissolved in an organic solvent and then transferred into a reaction vessel to react for 12-24 hours at the temperature of 60-100 ℃.
Preferably, the concentration of the bismaleimide compound relative to the organic solvent is 0.01-0.015 g/mL, and preferably the concentration of the bismaleimide compound relative to the organic solvent is 0.05-0.010 g/mL.
6. The method of manufacturing according to claim 1, further comprising the steps of: the product of the Friedel-Crafts alkylation reaction is purified.
Preferably, the purification comprises the steps of: and washing, soxhlet extraction and vacuum drying are sequentially carried out on the obtained reaction product, so that the porous adsorbent is obtained.
Preferably, the drying step is rotary evaporation at 60-90 ℃ for 15-24 h.
7. A porous adsorbent comprising a porous adsorbent prepared by the method of any one of claims 1-6.
Preferably, the porous adsorbent comprises a plurality of open ordered 3D cells formed by the stacking of nanoparticles.
Preferably, the pore channel comprises a pore structure with a pore diameter of 0.5-5 nm and a pore structure with a pore diameter of 5-30 nm.
8. Use of a porous adsorbent prepared according to any one of claims 1 to 6 for adsorbing an antibiotic, preferably a tetracycline compound, such as at least one of aureomycin, tetracycline or oxytetracycline.
9. A porous adsorbent prepared by the method of any one of claims 1 to 6 or a method of adsorbing an antibiotic by the porous adsorbent of claim 7, comprising the steps of: the porous adsorbent is dispersed in a solution containing antibiotics, mixed and adsorbed by standing.
Preferably, the time of the stationary adsorption is less than 1h.
10. A method of regenerating a porous adsorbent prepared by the method of any one of claims 1 to 6, comprising the steps of: the porous adsorbent to be regenerated is washed and adsorbed several times by using the regeneration solvent, and then dried.
Preferably, the porous adsorbent to be regenerated refers to a porous adsorbent to which antibiotics are adsorbed.
Preferably, the regeneration solvent is at least one selected from methanol, ethyl acetate and aqueous NaOH, for example ethyl acetate.
Preferably, the washing temperature of the organic solvent is 40-80 ℃, for example 60 ℃.
Preferably, the drying is performed at a temperature of 40 to 80 ℃ for a time of 10 to 24 hours.
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