WO2022174551A1 - Magnetic core-shell nanosphere for adsorption of phenolic pollutant, preparation method, and application - Google Patents
Magnetic core-shell nanosphere for adsorption of phenolic pollutant, preparation method, and application Download PDFInfo
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- WO2022174551A1 WO2022174551A1 PCT/CN2021/107019 CN2021107019W WO2022174551A1 WO 2022174551 A1 WO2022174551 A1 WO 2022174551A1 CN 2021107019 W CN2021107019 W CN 2021107019W WO 2022174551 A1 WO2022174551 A1 WO 2022174551A1
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- adsorption carrier
- magnetic core
- microspheres
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- 238000001179 sorption measurement Methods 0.000 title claims abstract description 140
- 239000011258 core-shell material Substances 0.000 title claims abstract description 72
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 50
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 50
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 239000002077 nanosphere Substances 0.000 title claims abstract description 10
- 229920000642 polymer Polymers 0.000 claims abstract description 30
- 230000004048 modification Effects 0.000 claims abstract description 29
- 238000012986 modification Methods 0.000 claims abstract description 29
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 69
- 239000004005 microsphere Substances 0.000 claims description 67
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical group [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 53
- 239000002131 composite material Substances 0.000 claims description 47
- 239000000243 solution Substances 0.000 claims description 43
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 36
- 238000006243 chemical reaction Methods 0.000 claims description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 33
- 239000001509 sodium citrate Substances 0.000 claims description 29
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 29
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 28
- 229910002651 NO3 Inorganic materials 0.000 claims description 26
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 26
- 229940094952 green tea extract Drugs 0.000 claims description 24
- 235000020688 green tea extract Nutrition 0.000 claims description 24
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 22
- 229910052742 iron Inorganic materials 0.000 claims description 20
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 18
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 claims description 18
- 239000002202 Polyethylene glycol Substances 0.000 claims description 18
- 235000014655 lactic acid Nutrition 0.000 claims description 18
- 239000004310 lactic acid Substances 0.000 claims description 18
- 229920001223 polyethylene glycol Polymers 0.000 claims description 18
- IXPNQXFRVYWDDI-UHFFFAOYSA-N 1-methyl-2,4-dioxo-1,3-diazinane-5-carboximidamide Chemical compound CN1CC(C(N)=N)C(=O)NC1=O IXPNQXFRVYWDDI-UHFFFAOYSA-N 0.000 claims description 17
- 229920001661 Chitosan Polymers 0.000 claims description 17
- 239000003607 modifier Substances 0.000 claims description 17
- 235000010413 sodium alginate Nutrition 0.000 claims description 17
- 239000000661 sodium alginate Substances 0.000 claims description 17
- 229940005550 sodium alginate Drugs 0.000 claims description 17
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 16
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 239000000654 additive Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 14
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 14
- 239000012266 salt solution Substances 0.000 claims description 14
- -1 salt ferric nitrate Chemical class 0.000 claims description 13
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 12
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 12
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 12
- 239000005642 Oleic acid Substances 0.000 claims description 12
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000004283 Sodium sorbate Substances 0.000 claims description 12
- 229910052799 carbon Inorganic materials 0.000 claims description 12
- 229910021389 graphene Inorganic materials 0.000 claims description 12
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 12
- 229910052750 molybdenum Inorganic materials 0.000 claims description 12
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 12
- 229910052698 phosphorus Inorganic materials 0.000 claims description 12
- 229910052710 silicon Inorganic materials 0.000 claims description 12
- LROWVYNUWKVTCU-STWYSWDKSA-M sodium sorbate Chemical compound [Na+].C\C=C\C=C\C([O-])=O LROWVYNUWKVTCU-STWYSWDKSA-M 0.000 claims description 12
- 235000019250 sodium sorbate Nutrition 0.000 claims description 12
- 229910052717 sulfur Inorganic materials 0.000 claims description 12
- 239000004094 surface-active agent Substances 0.000 claims description 12
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 11
- 244000269722 Thea sinensis Species 0.000 claims description 11
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 11
- 235000010323 ascorbic acid Nutrition 0.000 claims description 11
- 229960005070 ascorbic acid Drugs 0.000 claims description 11
- 239000011668 ascorbic acid Substances 0.000 claims description 11
- 239000007795 chemical reaction product Substances 0.000 claims description 11
- 238000010438 heat treatment Methods 0.000 claims description 11
- 238000002156 mixing Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 10
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 10
- 235000011152 sodium sulphate Nutrition 0.000 claims description 10
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims description 9
- 150000002505 iron Chemical class 0.000 claims description 9
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- 229910001447 ferric ion Inorganic materials 0.000 claims description 8
- 235000009569 green tea Nutrition 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 7
- 239000002270 dispersing agent Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(III) nitrate Inorganic materials [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000012752 auxiliary agent Substances 0.000 claims description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 4
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 239000003431 cross linking reagent Substances 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- 238000001556 precipitation Methods 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims 1
- 239000003463 adsorbent Substances 0.000 abstract description 16
- 239000002122 magnetic nanoparticle Substances 0.000 abstract description 15
- 239000000203 mixture Substances 0.000 description 15
- 239000012299 nitrogen atmosphere Substances 0.000 description 13
- 238000000926 separation method Methods 0.000 description 8
- 239000002244 precipitate Substances 0.000 description 7
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 229940051841 polyoxyethylene ether Drugs 0.000 description 6
- 229920000056 polyoxyethylene ether Polymers 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 3
- 239000008394 flocculating agent Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 235000013616 tea Nutrition 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 229910001448 ferrous ion Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- 229920000178 Acrylic resin Polymers 0.000 description 1
- 241000251468 Actinopterygii Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000034994 death Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 150000004676 glycans Chemical class 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 210000005260 human cell Anatomy 0.000 description 1
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000017074 necrotic cell death Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920001282 polysaccharide Polymers 0.000 description 1
- 239000005017 polysaccharide Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000011257 shell material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 230000009885 systemic effect Effects 0.000 description 1
Images
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
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28009—Magnetic properties
-
- 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
-
- 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
- B01J20/06—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising oxides or hydroxides of metals not provided for in group B01J20/04
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28002—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their physical properties
- B01J20/28004—Sorbent size or size distribution, e.g. particle size
- B01J20/28007—Sorbent size or size distribution, e.g. particle size with size in the range 1-100 nanometers, e.g. nanosized particles, nanofibers, nanotubes, nanowires or the like
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28014—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their form
- B01J20/28016—Particle form
- B01J20/28021—Hollow particles, e.g. hollow spheres, microspheres or cenospheres
-
- 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
-
- 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
- C02F1/281—Treatment of water, waste water, or sewage by sorption using inorganic 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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Definitions
- the invention belongs to the technical field of adsorption of phenolic pollutants, and in particular relates to magnetic core-shell nano-microspheres for adsorbing phenolic pollutants, a preparation method and an application.
- Phenol and its derivatives are important chemical raw materials, widely used in oil refining, papermaking, rubber, pesticides or pharmaceutical synthesis and other industries. They are relatively common organic compounds with high toxicity and refractory degradation. Phenolic pollutants are highly toxic and have certain toxic effects on living cells. When the concentration of phenolic pollutants in the water body is greater than 5mg/L, it can pose a threat to fish life or even death. When phenolic substances come into contact with the skin and mucous membranes, absorb them and invade the body through oral administration, they will cause damage, necrosis, and even systemic poisoning to human cells. The whole world attaches great importance to the treatment of phenol-containing wastewater, and phenolic pollutants are also listed as one of the priority pollutants in my country.
- resin polymers are widely used in the separation, purification and detection of bioengineering, drug synthesis, and food processing.
- various gel and macroporous styrene resins and acrylic resins have played an important role in the treatment and recycling of wastewater.
- most resin polymers have larger particle size, and the adsorption rate is affected by mass transfer.
- magnetic porous adsorbents In order to better realize the adsorption of phenolic pollutants, magnetic porous adsorbents have appeared, that is, the polymer porous adsorbent is combined with magnetic nanomaterials, and the pollutants are bound by the pores of the polymer layer, and the internal polymer is used to bind the pollutants.
- the magnetic material achieves rapid separation.
- the preparation process of the magnetic porous adsorbent is as follows: firstly, magnetic nanoparticles are prepared, then the magnetic nanoparticles are modified, the modified magnetic nanoparticles are polymerized, and a layer of polymer is wrapped on the magnetic nanoparticles to obtain the magnetic porous adsorbent .
- the reason for the modification of magnetic nanoparticles is that due to the high surface chemical activity of magnetic nanoparticles, agglomeration easily occurs, which affects the performance of magnetic nanoparticles. If the magnetic nanoparticles are not modified, it will affect the magnetic nanoparticles.
- the compatibility of nanoparticles with polymers thus affecting the adsorption operation of magnetic adsorbents.
- the present invention provides magnetic core-shell nano-microspheres for adsorbing phenolic pollutants, a preparation method and application thereof, and solves the problem that the preparation process of the existing magnetic porous adsorbent only modifies the magnetic nanoparticles once.
- the adsorption operation of the magnetic adsorbent in a high temperature environment will destroy the compatibility between the magnetic nanoparticles and the polymer, thereby affecting the adsorption operation of the magnetic adsorbent.
- the preparation method of the magnetic core-shell nano-microspheres for adsorbing phenolic pollutants of the present invention comprises the following steps:
- the second modified adsorption carrier is polymerized to obtain magnetic core-shell nano-microspheres.
- nano-scale adsorption carrier is nano-iron powder
- the preparation method of the nano iron powder specifically includes:
- reaction additives to the green tea extract, then mixing and stirring with the aqueous solution of ferrous nitrate to obtain a reaction product;
- the reaction product is filtered, washed and dried successively to obtain nano iron powder
- the reactive additive includes C, Si, Mo, S and P in powder state;
- the weight of the reaction additive accounts for 0.5-1% of the weight of the green tea extract
- the weight of the aqueous solution of ferrous nitrate accounts for 5-10% of the weight of the green tea extract
- the weight of ferrous nitrate accounts for 10-15% of the weight of water.
- nano-scale adsorption carrier is nano-iron tetroxide
- the preparation method of the nanometer iron tetroxide specifically includes:
- the mixed iron salt solution is added to the composite auxiliary, and the hydrothermal reaction is carried out at 155-160 ° C for 5-6 hours to obtain a reaction solution;
- reaction solution is filtered and dried to obtain nano ferric oxide
- the composite auxiliary includes a composite precipitant and a composite surfactant
- the composite auxiliary agent also includes a composite dispersant
- the first modification of the nano-scale adsorption carrier to obtain the first modified adsorption carrier specifically includes:
- nano-scale adsorption carrier into methanol solution, then adding a first modifier, stirring and reacting at 40-60° C. for 6-10 hours under an inert atmosphere, and separating and obtaining the first modified adsorption carrier;
- the first modifier is composed of a silane coupling agent, a polyoxyethylene chain and ammonia;
- the second modification of the first modified adsorption carrier to obtain the second modified adsorption carrier specifically includes:
- the second modifier is composed of polyethylene glycol, lactic acid and chitosan;
- polyethylene glycol:lactic acid:chitosan 5:1-3:2.
- the polymerization of the second modified adsorption carrier to obtain magnetic core-shell nano-microspheres specifically includes:
- N-vinylpyrrolidone as monomer
- divinylbenzene and methyl acrylate as crosslinking agent
- initiator azobisisobutyronitrile polymerization reaction occurs on the surface of the second modified adsorption carrier at 60-90°C , so that the surface of the second modified adsorption carrier is coated with a layer of polymer, thereby obtaining magnetic core-shell nano-microspheres.
- the surface of the second modified adsorption carrier is coated with a layer of polymer, it is soaked in a soaking solution at 30-40° C. for 0.5-1 h, and then magnetic core-shell nano-microspheres are obtained.
- the soaking solution is composed of sodium citrate, sodium alginate and water;
- the present invention also provides a magnetic core-shell nano-microsphere for adsorbing phenolic pollutants, which is prepared by the preparation method described in any one of the above;
- the size of the magnetic core-shell nanospheres is 50-500 nm.
- the present invention also provides the application of the magnetic core-shell nano-microspheres for adsorbing phenolic pollutants, and the magnetic core-shell nano-microspheres are used for the treatment of water bodies containing phenolic pollutants.
- the present invention provides a method for preparing magnetic core-shell nano-microspheres for adsorbing phenolic pollutants.
- the compatibility of the nano-scale adsorption carrier and the polymer is greatly improved, especially the adsorption operation of the magnetic adsorbent in a high temperature environment,
- the compatibility of the nanoscale adsorption carrier with the polymer is also not affected, thereby improving the adsorption efficiency and recovery efficiency of the magnetic core-shell nanospheres for phenolic pollutants.
- the present invention optimizes the modifier used in the first modification and the second modification, the first modifier is composed of silane coupling agent, polyoxyethylene chain and ammonia water, and the second modifier is composed of polyethylene glycol,
- the invention optimizes the preparation method of the nano iron powder, specifically, adding reaction additives including C, Si, Mo, S and P in powder state into the green tea extract, and then mixing and stirring with the aqueous solution of ferrous nitrate to obtain a reaction product , filter, wash and dry in turn to obtain nano iron powder, the obtained nano iron powder is not easy to agglomerate, and the weight of C, Si, Mo, S and P satisfies the following relational formula: 0.5 ⁇ (C+0.3Si)( When Mo+10S+2P+0.8) ⁇ 0.85, the stability of nano-iron powder is better.
- the invention optimizes the preparation method of nanometer ferric tetroxide, and specifically optimizes the composite auxiliary agent added in the hydrothermal reaction of the mixed iron salt solution.
- the composite auxiliary agent includes a composite precipitation agent and a composite surfactant. Sodium and graphene are formed, and the composite surfactant is formed of oleic acid, sodium sorbate and sodium citrate, so that the obtained nano-iron tetroxide is not easy to agglomerate, and the weight ratio of control ascorbic acid, sodium hydroxide and graphene is 1-3:2:5, when the weight ratio of oleic acid, sodium sorbate and sodium citrate is 0.0-1:3-5:2, the stability of nano ferric tetroxide is better.
- the invention improves the polymerization reaction of the nano-scale adsorption carrier, specifically using N-vinyl pyrrolidone as a monomer, divinyl benzene and methyl acrylate as cross-linking agents, under the action of an initiator, at 60-90 DEG C in a second modification Polymerization reaction occurs on the surface of the adsorption carrier, so that the surface of the second modified adsorption carrier is coated with a layer of polymer, so as to obtain magnetic core-shell nano-microspheres, so that the magnetic core-shell nano-microspheres have better performance than existing nano-adsorption materials. Therefore, it is more suitable for the treatment of water bodies containing phenolic pollutants.
- the magnetic core is obtained after being soaked in a soaking liquid composed of sodium citrate, sodium alginate and water for 0.5-1 h at 30-40° C.
- Shell nano-microspheres expand the adsorption pore size of polymers, thereby further improving the adsorption efficiency of magnetic core-shell nano-microspheres to phenolic pollutants.
- Fig. 1 is the scanning electron microscope picture of the magnetic core-shell nano-microspheres of the adsorption phenolic pollutants of Example 1 of the present invention
- Fig. 2 is the scanning electron microscope picture of the magnetic core-shell nano-microspheres of the adsorption phenolic pollutants of Example 4 of the present invention
- Fig. 3 is the scanning electron microscope picture of the magnetic core-shell nano-microspheres of the adsorption phenolic pollutants of Example 5 of the present invention.
- Example 4 is an adsorption isotherm curve diagram of the magnetic core-shell nano-microspheres for adsorbing phenolic pollutants according to Example 3 of the present invention.
- FIG. 5 is a partial enlarged view of the scanning electron microscope image of the magnetic core-shell nano-microspheres of FIG. 1 under the high temperature (600° C.) adsorption state;
- FIG. 6 is a partial enlarged view of a scanning electron microscope image of the magnetic core-shell nano-microspheres of Comparative Example 1 under a high temperature (600° C.) adsorption state.
- S1-1 gets green tea leaves to dry and pulverize and then adds deionized water to carry out heating reaction, obtains green tea extract after filtration, concretely, tea leaves are pulverized to 200 meshes in the present embodiment, and the weight ratio of green tea leaves and deionized water is 2: 30, the heating temperature is 60°C, the heating reaction time is 0.5h, and then the reaction solution is filtered to obtain a green tea extract;
- reaction additives to the green tea extract, namely adding C, Si, Mo, S and P in powder state, then mixing with the aqueous solution of ferrous nitrate, stirring and reacting at 20 ° C to obtain the reaction product;
- the weight of the reaction additive accounts for 0.5% of the weight of the green tea extract
- the weight of the aqueous solution of ferrous nitrate accounts for 5% of the weight of the green tea extract
- the weight of ferrous nitrate accounts for 10% of the weight of water.
- S2 modifies the nano iron powder for the first time to obtain the first modified adsorption carrier
- Disperse the prepared nano iron powder into methanol specifically, disperse each 10g nano iron powder into 400mL methanol, then add 200mL silane coupling agent, 80mL nonylphenol polyoxyethylene ether, 40mL ammonia water, in a nitrogen atmosphere. Under the protection, the mixture was stirred at 40 °C for 6 h, and then the black precipitate was separated and washed with methanol for 6 times to obtain the first modified adsorption carrier.
- the first modified adsorption carrier into 300ml of ethanol solution, then add 10g of the second modifier composed of polyethylene glycol, lactic acid and chitosan, and the weight ratio of polyethylene glycol, lactic acid and chitosan is 5 :1:2, and then in a nitrogen atmosphere, the reaction was stirred at 30 °C for 1 h, and the second modified adsorption carrier was obtained by separation.
- the second modifier composed of polyethylene glycol, lactic acid and chitosan, and the weight ratio of polyethylene glycol, lactic acid and chitosan is 5 :1:2
- S1-1 gets green tea leaves to dry and pulverize and then adds deionized water to carry out heating reaction, obtains green tea extract after filtration, concretely, tea leaves are pulverized to 300 meshes in the present embodiment, and the weight ratio of green tea leaves and deionized water is 1: 10.
- the heating temperature is 70°C
- the heating reaction time is 1h
- the reaction solution is filtered to obtain a green tea extract
- reaction additives to the green tea extract, namely adding C, Si, Mo, S and P in powder state, then mixing with the aqueous solution of ferrous nitrate, stirring and reacting at 20 ° C to obtain the reaction product;
- the weight of the reaction additive accounts for 1% of the weight of the green tea extract
- the weight of the aqueous solution of ferrous nitrate accounts for 10% of the weight of the green tea extract
- the weight of ferrous nitrate accounts for 15% of the weight of water.
- S2 modifies the nano iron powder for the first time to obtain the first modified adsorption carrier
- Disperse the prepared nano iron powder into methanol specifically, disperse each 20g nano iron powder into 400mL methanol, then add 120mL silane coupling agent, 80mL nonylphenol polyoxyethylene ether, 20mL ammonia water, in a nitrogen atmosphere. Under the protection, the mixture was stirred at 60 °C for 10 h, and then the black precipitate was separated and washed with methanol for 5 times to obtain the first modified adsorption carrier.
- the first modified adsorption carrier into 500ml of ethanol solution, then add 15g of the second modifier composed of polyethylene glycol, lactic acid and chitosan, and the weight ratio of polyethylene glycol, lactic acid and chitosan is 5 : 3: 2, and then in a nitrogen atmosphere, the reaction was stirred at 50 °C for 3 h, and the second modified adsorption carrier was obtained by separation.
- the second modifier composed of polyethylene glycol, lactic acid and chitosan, and the weight ratio of polyethylene glycol, lactic acid and chitosan is 5 : 3: 2
- S1-1 gets green tea leaves to dry and pulverize and then adds deionized water to carry out heating reaction, obtains green tea extract after filtration, concretely, tea leaves are pulverized to 500 meshes in the present embodiment, and the weight ratio of green tea leaves and deionized water is 3: 20, the heating temperature is 65°C, the heating reaction time is 1.5h, and then the reaction solution is filtered to obtain a green tea extract;
- reaction additives to the green tea extract, namely adding C, Si, Mo, S and P in powder state, then mixing with the aqueous solution of ferrous nitrate, stirring and reacting at 20 ° C to obtain the reaction product;
- the weight of the reaction additive accounts for 0.8% of the weight of the green tea extract
- the weight of the aqueous solution of ferrous nitrate accounts for 7% of the weight of the green tea extract
- the weight of ferrous nitrate accounts for 16% of the weight of water.
- S2 modifies the nano iron powder for the first time to obtain the first modified adsorption carrier
- each 30g nano-iron powder is dispersed in 500mL methanol, then add 150mL silane coupling agent, 90mL nonylphenol polyoxyethylene ether, 30mL ammonia water, in a nitrogen atmosphere. Under the protection, the mixture was stirred at 50 °C for 8 h, and then the black precipitate was separated and washed with methanol for 4 times to obtain the first modified adsorption carrier.
- the first modified adsorption carrier into 400ml of ethanol solution, then add the second modifier 20g of polyethylene glycol, lactic acid and chitosan, and the weight ratio of polyethylene glycol, lactic acid and chitosan is 5 : 2: 2, and then in a nitrogen atmosphere, the reaction was stirred at 40 °C for 2 h, and the second modified adsorption carrier was obtained by separation.
- the equilibrium concentration at adsorption equilibrium and the ordinate represents the equilibrium adsorption capacity at adsorption equilibrium. It can be seen from the figure that with the increase of substrate concentration, the adsorption capacity of magnetic core-shell nanospheres to p-nitrophenol gradually increases.
- ferric salt ferric nitrate solution and the ferrous salt ferrous nitrate solution are mixed according to the molar ratio of ferric ion and ferrous ion as 1:3 to obtain a mixed ferric salt solution;
- the mixed iron salt solution was added to the composite auxiliary, and the reaction solution was obtained by hydrothermal reaction at 155°C for 5h;
- reaction solution is filtered and dried at room temperature to obtain nano-iron tetroxide
- the weight ratio of the composite auxiliaries to the mixed iron salt solution is 2%;
- Composite additives include composite precipitants, composite surfactants and composite dispersants
- the composite precipitant is composed of ascorbic acid, sodium hydroxide and graphene, and the weight ratio of ascorbic acid, sodium hydroxide and graphene is 1:2:5;
- the composite surfactant is composed of oleic acid, sodium sorbate and sodium citrate, and the weight ratio of oleic acid, sodium sorbate and sodium citrate is 1:3:2;
- the compound is composed of sodium sulfate and sodium oleate, and the weight ratio of sodium sulfate and sodium oleate is 1:1.
- S2 carries out the first modification of nano-iron tetroxide to obtain the first modified adsorption carrier
- Disperse the prepared nano-iron tetroxide into methanol specifically, disperse each 10g of nano-iron tetroxide into 400 mL of methanol, then add 200 mL of silane coupling agent, 80 mL of nonylphenol polyoxyethylene ether, and 40 mL of ammonia water, Under the protection of a nitrogen atmosphere, the mixture was stirred at 40 °C for 6 h, and then the black precipitate was separated and washed with methanol for 6 times to obtain the first modified adsorption carrier.
- the first modified adsorption carrier into 300ml of ethanol solution, then add 10g of the second modifier composed of polyethylene glycol, lactic acid and chitosan, and the weight ratio of polyethylene glycol, lactic acid and chitosan is 5 :1:2, and then in a nitrogen atmosphere, the reaction was stirred at 30 °C for 1 h, and the second modified adsorption carrier was obtained by separation.
- the second modifier composed of polyethylene glycol, lactic acid and chitosan, and the weight ratio of polyethylene glycol, lactic acid and chitosan is 5 :1:2
- the mixed iron salt solution was added to the composite auxiliary, and the reaction solution was obtained by hydrothermal reaction at 160 °C for 6 h;
- reaction solution is filtered and dried at room temperature to obtain nano-iron tetroxide
- the weight ratio of the composite auxiliaries to the mixed iron salt solution is 3%;
- Composite additives include composite precipitants, composite surfactants and composite dispersants
- the composite precipitant is composed of ascorbic acid, sodium hydroxide and graphene, and the weight ratio of ascorbic acid, sodium hydroxide and graphene is 3:2:5;
- the composite surfactant is composed of oleic acid, sodium sorbate and sodium citrate, and the weight ratio of oleic acid, sodium sorbate and sodium citrate is 1:5:2;
- the compound is composed of sodium sulfate and sodium oleate, and the weight ratio of sodium sulfate and sodium oleate is 5:1.
- S2 carries out the first modification of nano-iron tetroxide to obtain the first modified adsorption carrier
- Disperse the prepared nano ferric oxide into methanol specifically, disperse each 20g of nano ferric oxide into 400 mL of methanol, then add 120 mL of silane coupling agent, 80 mL of nonylphenol polyoxyethylene ether, and 20 mL of ammonia water, Under the protection of a nitrogen atmosphere, the mixture was stirred at 60 °C for 10 h, and then the black precipitate was separated and washed with methanol for 5 times to obtain the first modified adsorption carrier.
- the first modified adsorption carrier into 500ml of ethanol solution, then add 15g of the second modifier composed of polyethylene glycol, lactic acid and chitosan, and the weight ratio of polyethylene glycol, lactic acid and chitosan is 5 : 3: 2, and then in a nitrogen atmosphere, the reaction was stirred at 50 °C for 3 h, and the second modified adsorption carrier was obtained by separation.
- the second modifier composed of polyethylene glycol, lactic acid and chitosan, and the weight ratio of polyethylene glycol, lactic acid and chitosan is 5 : 3: 2
- ferric salt ferric nitrate solution and the ferric salt ferrous nitrate solution are mixed according to the molar ratio of ferric ion and ferrous ion as 2:4 to obtain a mixed ferric salt solution;
- the mixed iron salt solution was added to the composite auxiliary, and the hydrothermal reaction was carried out at 158 ° C for 5.5 h to obtain a reaction solution;
- reaction solution is filtered and dried at room temperature to obtain nano-iron tetroxide
- the weight ratio of the composite auxiliaries to the mixed iron salt solution is 5%;
- Composite additives include composite precipitants, composite surfactants and composite dispersants
- the composite precipitant is composed of ascorbic acid, sodium hydroxide and graphene, and the weight ratio of ascorbic acid, sodium hydroxide and graphene is 2:2:5;
- the composite surfactant is composed of oleic acid, sodium sorbate and sodium citrate, and the weight ratio of oleic acid, sodium sorbate and sodium citrate is 1:4:2;
- the compound is composed of sodium sulfate and sodium oleate, and the weight ratio of sodium sulfate and sodium oleate is 3:1.
- S2 carries out the first modification of nano-iron tetroxide to obtain the first modified adsorption carrier
- Disperse the prepared nano-iron tetroxide into methanol specifically, disperse each 30g of nano-iron tetroxide into 500 mL of methanol, then add 150 mL of silane coupling agent, 90 mL of nonylphenol polyoxyethylene ether, and 30 mL of ammonia water, Under the protection of a nitrogen atmosphere, the mixture was stirred at 50 °C for 8 h, and then the black precipitate was separated and washed with methanol for 4 times to obtain the first modified adsorption carrier.
- the first modified adsorption carrier into 400ml of ethanol solution, then add the second modifier 20g of polyethylene glycol, lactic acid and chitosan, the weight ratio of polyethylene glycol, lactic acid and chitosan is 5 : 2: 2, and then in a nitrogen atmosphere, the reaction was stirred at 40 °C for 2 h, and the second modified adsorption carrier was obtained by separation.
- the magnetic core-shell nano-microspheres of the above-mentioned embodiments 1-6 can be used for the treatment of water bodies containing phenolic pollutants, and the specific treatment steps are as follows:
- the added flocculants include various existing organic, inorganic and organic-inorganic mixed flocculants;
- the magnetic core-shell nano-microspheres of the present embodiment 1-6 are placed in the pool to which the flocculant is added to adsorb phenolic pollutants;
- a magnetic field is applied to the pool, and the magnetic core-shell nano-microspheres are separated from the pool by the action of the external magnetic field;
- the phenolic pollutants are separated from the magnetic core-shell nano-microspheres to realize the recycling of the magnetic core-shell nano-microspheres.
- the preparation method of magnetic core-shell nano-microspheres for adsorbing phenolic pollutants provided in this example is different from Example 1 in that the nano-iron powder is modified once to obtain a modified adsorption carrier, and then the polymerization reaction is carried out,
- the first modification is to disperse the prepared nano iron powder into methanol, specifically, disperse each 10g nano iron powder into 400mL methanol, then add 200mL silane coupling agent and 50mL ammonia water, under the protection of nitrogen atmosphere, in After stirring at 40 °C for 6 h, the black precipitate was separated and washed with methanol for 6 times to obtain a modified adsorption carrier.
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Abstract
The present invention provides a magnetic core-shell nanosphere for the adsorption of a phenolic pollutant, a preparation method, and an application. The preparation method comprises the following steps: preparing a nanoscale adsorption carrier; performing a first round of modification on the nanoscale adsorption carrier, and obtaining a first modified adsorption carrier; performing a second round of modification on the first modified adsorption carrier, and obtaining a second modified adsorption carrier; and performing a polymerization reaction on the second modified adsorption carrier, and obtaining a magnetic core-shell nanosphere. The present invention solves the problem where only one round of modification on a magnetic nanoparticle is performed in current preparation processes for magnetic porous adsorbents, so if the magnetic adsorbent performs adsorption in a high temperature environment, the miscibility of the magnetic nanoparticle and a polymer will be destroyed, thereby affecting the adsorption function of the magnetic adsorbent.
Description
本公开要求于2021年02月20日在中国专利局提交的、申请号为202110194396.8、发明名称为“吸附酚类污染物的磁性核壳纳米微球、制备方法及应用”的优先权，其全部内容通过引用结合在本公开中。This disclosure claims the priority of the application number 202110194396.8 and the invention titled "Magnetic Core-Shell Nanoparticles for Adsorbing Phenol Pollutants, Preparation Method and Application" filed in the China Patent Office on February 20, 2021, all of which The contents are incorporated by reference in this disclosure.
本发明属于酚类污染物吸附技术领域，具体涉及吸附酚类污染物的磁性核壳纳米微球、制备方法及应用。The invention belongs to the technical field of adsorption of phenolic pollutants, and in particular relates to magnetic core-shell nano-microspheres for adsorbing phenolic pollutants, a preparation method and an application.
苯酚及其衍生物是一种重要的化工原料，广泛应用于炼油、造纸、橡胶、农药或医药合成等行业，是比较常见的高毒性、难降解有机物。酚类污染物毒性较大，对生物体细胞有一定的毒害作用。当水体中酚类污染物的浓度大于5mg/L时，可对鱼类生命构成威胁甚至死亡。当酚类物质与皮肤黏膜接触、吸收和经口服而侵入体内，对人体细胞会造成损伤、坏死，甚至全身中毒。全世界都非常重视含酚废水的处理，酚类污染物也被我国列为优先控制的污染物之一。Phenol and its derivatives are important chemical raw materials, widely used in oil refining, papermaking, rubber, pesticides or pharmaceutical synthesis and other industries. They are relatively common organic compounds with high toxicity and refractory degradation. Phenolic pollutants are highly toxic and have certain toxic effects on living cells. When the concentration of phenolic pollutants in the water body is greater than 5mg/L, it can pose a threat to fish life or even death. When phenolic substances come into contact with the skin and mucous membranes, absorb them and invade the body through oral administration, they will cause damage, necrosis, and even systemic poisoning to human cells. The whole world attaches great importance to the treatment of phenol-containing wastewater, and phenolic pollutants are also listed as one of the priority pollutants in my country.
为了有效回收废水中的酚类物质，结构稳定、性能好的吸附剂展现出较大的优势。目前，活性炭吸附剂在吸附酚类污染物中展现出较好的吸附能力，但是其解吸附困难，导致酚类物质回收效率偏低。In order to effectively recover phenolic substances in wastewater, adsorbents with stable structure and good performance show great advantages. At present, activated carbon adsorbents show good adsorption capacity in the adsorption of phenolic pollutants, but their desorption is difficult, resulting in low recovery efficiency of phenolic substances.
树脂聚合物作为一种新型的有机吸附材料，被广泛应用于生物工程、药物合成、食品加工的分离、提纯和检测中。近年来，各种凝胶、大孔的苯乙烯系树脂、丙烯酸系树脂在废水的治理和资源化中发挥了重要的作用。但多数树脂聚合物粒径较大，吸附速率受到传质影响。As a new type of organic adsorption material, resin polymers are widely used in the separation, purification and detection of bioengineering, drug synthesis, and food processing. In recent years, various gel and macroporous styrene resins and acrylic resins have played an important role in the treatment and recycling of wastewater. However, most resin polymers have larger particle size, and the adsorption rate is affected by mass transfer.
为了更好的实现对酚类污染物的吸附，现有出现了磁性多孔吸附剂，即将聚合物多孔吸附剂与磁性纳米材料相结合，借助聚合物层的孔穴绑定污染物，借助聚合物内部的磁性材料实现快速的分离。In order to better realize the adsorption of phenolic pollutants, magnetic porous adsorbents have appeared, that is, the polymer porous adsorbent is combined with magnetic nanomaterials, and the pollutants are bound by the pores of the polymer layer, and the internal polymer is used to bind the pollutants. The magnetic material achieves rapid separation.
磁性多孔吸附剂的制备工艺如下：首先制备磁性纳米粒子，然后对磁性纳米粒子改性，对改性的磁性纳米粒子进行聚合反应，在磁性纳米粒子表明包裹一层聚合物，得到磁性多孔吸附剂。The preparation process of the magnetic porous adsorbent is as follows: firstly, magnetic nanoparticles are prepared, then the magnetic nanoparticles are modified, the modified magnetic nanoparticles are polymerized, and a layer of polymer is wrapped on the magnetic nanoparticles to obtain the magnetic porous adsorbent .
对磁性纳米粒子进行改性的原因是由于磁性纳米粒子的表面化学活性很高，极易发生团聚现象，影响了磁性纳米粒子的性能，若不对磁性纳米粒子进行改性，则会影响磁性纳米粒子聚合反应中磁性纳米粒子与聚合物的相容性，但是现有磁性多孔吸附剂的制 备工艺仅对磁性纳米粒子进行一次改性，若磁性吸附剂在高温环境下进行吸附操作，则会破坏磁性纳米粒子与聚合物的相容性，从而影响磁性吸附剂的吸附操作。The reason for the modification of magnetic nanoparticles is that due to the high surface chemical activity of magnetic nanoparticles, agglomeration easily occurs, which affects the performance of magnetic nanoparticles. If the magnetic nanoparticles are not modified, it will affect the magnetic nanoparticles. The compatibility of magnetic nanoparticles and polymers in the polymerization reaction, but the preparation process of the existing magnetic porous adsorbent only modifies the magnetic nanoparticles once. If the magnetic adsorbent is adsorbed in a high temperature environment, the magnetic properties will be destroyed. The compatibility of nanoparticles with polymers, thus affecting the adsorption operation of magnetic adsorbents.
发明内容SUMMARY OF THE INVENTION
为了克服现有技术的缺陷，本发明提供吸附酚类污染物的磁性核壳纳米微球、制备方法及应用，解决现有磁性多孔吸附剂的制备工艺仅对磁性纳米粒子进行一次改性，若磁性吸附剂在高温环境下进行吸附操作，则会破坏磁性纳米粒子与聚合物的相容性，从而影响磁性吸附剂的吸附操作的问题。In order to overcome the defects of the prior art, the present invention provides magnetic core-shell nano-microspheres for adsorbing phenolic pollutants, a preparation method and application thereof, and solves the problem that the preparation process of the existing magnetic porous adsorbent only modifies the magnetic nanoparticles once. The adsorption operation of the magnetic adsorbent in a high temperature environment will destroy the compatibility between the magnetic nanoparticles and the polymer, thereby affecting the adsorption operation of the magnetic adsorbent.
本发明通过如下技术方案实现：The present invention is achieved through the following technical solutions:
本发明的吸附酚类污染物的磁性核壳纳米微球的制备方法包括如下步骤：The preparation method of the magnetic core-shell nano-microspheres for adsorbing phenolic pollutants of the present invention comprises the following steps:
制备纳米级吸附载体；Preparation of nano-scale adsorption carrier;
对所述纳米级吸附载体进行第一次改性，得到第一改性吸附载体；Carrying out the first modification on the nano-scale adsorption carrier to obtain a first modified adsorption carrier;
对所述第一改性吸附载体进行第二次改性，得到第二改性吸附载体；Carrying out the second modification on the first modified adsorption carrier to obtain a second modified adsorption carrier;
对所述第二改性吸附载体进行聚合反应，得到磁性核壳纳米微球。The second modified adsorption carrier is polymerized to obtain magnetic core-shell nano-microspheres.
进一步的，所述纳米级吸附载体为纳米铁粉；Further, the nano-scale adsorption carrier is nano-iron powder;
所述纳米铁粉的制备方法，具体包括：The preparation method of the nano iron powder specifically includes:
取绿茶叶烘干粉碎后加入去离子水进行加热反应，过滤后得到绿茶提取液；Take green tea leaves, dry and pulverize them, add deionized water for heating reaction, and filter to obtain green tea extract;
向绿茶提取液内加入反应添加剂，然后与硝酸亚铁的水溶液混合搅拌反应，得到反应产物；Adding reaction additives to the green tea extract, then mixing and stirring with the aqueous solution of ferrous nitrate to obtain a reaction product;
将反应产物依次进行过滤、洗涤以及干燥，得到纳米铁粉；The reaction product is filtered, washed and dried successively to obtain nano iron powder;
所述反应添加剂包括粉末状态的C、Si、Mo、S以及P；The reactive additive includes C, Si, Mo, S and P in powder state;
以重量份计算，C、Si、Mo、S以及P的重量满足如下关系式：Calculated in parts by weight, the weights of C, Si, Mo, S and P satisfy the following relation:
0.5≤(C+0.3Si)(Mo+10S+2P+0.8)≤0.85。0.5≤(C+0.3Si)(Mo+10S+2P+0.8)≤0.85.
进一步的，所述反应添加剂的重量占所述绿茶提取液重量的0.5-1％；Further, the weight of the reaction additive accounts for 0.5-1% of the weight of the green tea extract;
所述硝酸亚铁的水溶液的重量占所述绿茶提取液重量的5-10％；The weight of the aqueous solution of ferrous nitrate accounts for 5-10% of the weight of the green tea extract;
所述硝酸亚铁的水溶液中，硝酸亚铁的重量占水重量的10-15％。In the aqueous solution of ferrous nitrate, the weight of ferrous nitrate accounts for 10-15% of the weight of water.
进一步的，所述纳米级吸附载体为纳米四氧化三铁；Further, the nano-scale adsorption carrier is nano-iron tetroxide;
所述纳米四氧化三铁的制备方法，具体包括：The preparation method of the nanometer iron tetroxide, specifically includes:
将三价铁盐硝酸铁溶液与二价铁盐硝酸亚铁溶液按照三价铁离子与二价铁离子的摩尔比为1-2：3-5混合，得到混合铁盐溶液；Mixing the ferric salt ferric nitrate solution and the ferric salt ferrous nitrate solution according to the molar ratio of ferric ions and ferric ions as 1-2:3-5 to obtain a mixed ferric salt solution;
将所述混合铁盐溶液加入复合助剂，在155-160℃下水热反应5-6h，得到反应液；The mixed iron salt solution is added to the composite auxiliary, and the hydrothermal reaction is carried out at 155-160 ° C for 5-6 hours to obtain a reaction solution;
将所述反应液进行过滤、干燥处理，得到纳米四氧化三铁；The reaction solution is filtered and dried to obtain nano ferric oxide;
所述复合助剂包括复合沉淀剂、复合表面活性剂；The composite auxiliary includes a composite precipitant and a composite surfactant;
所述复合沉淀剂由抗坏血酸、氢氧化钠和石墨烯组成，按重量比计算，抗坏血酸：氢氧化钠：石墨烯＝1-3:2:5；The composite precipitation agent is composed of ascorbic acid, sodium hydroxide and graphene, and calculated by weight ratio, ascorbic acid: sodium hydroxide: graphene=1-3:2:5;
所述复合表面活性剂由油酸、山梨酸钠和柠檬酸钠组成，按重量比计算，油酸：山梨酸钠：柠檬酸钠＝1:3-5：2；The composite surfactant is composed of oleic acid, sodium sorbate and sodium citrate, and calculated by weight ratio, oleic acid: sodium sorbate: sodium citrate=1:3-5:2;
所述复合助剂还包括复合分散剂；The composite auxiliary agent also includes a composite dispersant;
所述复合分散剂由硫酸钠和油酸钠组成，按重量比，硫酸钠：油酸钠＝1-5:1。The composite dispersant is composed of sodium sulfate and sodium oleate, and by weight, sodium sulfate:sodium oleate=1-5:1.
进一步的，所述对所述纳米级吸附载体进行第一次改性，得到第一改性吸附载体，具体包括：Further, the first modification of the nano-scale adsorption carrier to obtain the first modified adsorption carrier specifically includes:
将所述纳米级吸附载体放入甲醇溶液中，然后加入第一改性剂，在惰性气氛下，于40-60℃下搅拌反应6-10h，分离得到第一改性吸附载体；Putting the nano-scale adsorption carrier into methanol solution, then adding a first modifier, stirring and reacting at 40-60° C. for 6-10 hours under an inert atmosphere, and separating and obtaining the first modified adsorption carrier;
所述第一改性剂由硅烷偶联剂、聚氧乙烯链和氨水组成；The first modifier is composed of a silane coupling agent, a polyoxyethylene chain and ammonia;
按体积比，硅烷偶联剂：聚氧乙烯链：氨水为＝5-6:2-4:1。By volume ratio, silane coupling agent: polyoxyethylene chain: ammonia water = 5-6:2-4:1.
进一步的，所述对所述第一改性吸附载体进行第二次改性，得到第二改性吸附载体，具体包括：Further, the second modification of the first modified adsorption carrier to obtain the second modified adsorption carrier specifically includes:
将所述第一改性吸附载体放入乙醇溶液中，然后加入第二改性剂，在惰性气氛下，于30-50℃下搅拌反应1-3h，分离得到第二改性吸附载体；Putting the first modified adsorption carrier into the ethanol solution, then adding the second modifier, under an inert atmosphere, stirring and reacting at 30-50° C. for 1-3 hours, and separating and obtaining the second modified adsorption carrier;
所述第二改性剂由聚乙二醇、乳酸和壳聚糖组成；The second modifier is composed of polyethylene glycol, lactic acid and chitosan;
按重量比，聚乙二醇：乳酸：壳聚糖＝5:1-3:2。By weight ratio, polyethylene glycol:lactic acid:chitosan=5:1-3:2.
进一步的，所述对第二改性吸附载体进行聚合反应，得到磁性核壳纳米微球，具体包括：Further, the polymerization of the second modified adsorption carrier to obtain magnetic core-shell nano-microspheres specifically includes:
以N-乙烯吡咯烷酮为单体，二乙烯苯和丙烯酸甲酯为交联剂，在引发剂偶氮二异丁腈作用下，于60-90℃下在第二改性吸附载体表面发生聚合反应，使得第二改性吸附载体表面包覆一层聚合物，从而得到磁性核壳纳米微球。Using N-vinylpyrrolidone as monomer, divinylbenzene and methyl acrylate as crosslinking agent, under the action of initiator azobisisobutyronitrile, polymerization reaction occurs on the surface of the second modified adsorption carrier at 60-90℃ , so that the surface of the second modified adsorption carrier is coated with a layer of polymer, thereby obtaining magnetic core-shell nano-microspheres.
进一步的，在第二改性吸附载体表面包覆一层聚合物后，置于浸泡液中在30-40℃下浸泡0.5-1h，然后得到磁性核壳纳米微球。Further, after the surface of the second modified adsorption carrier is coated with a layer of polymer, it is soaked in a soaking solution at 30-40° C. for 0.5-1 h, and then magnetic core-shell nano-microspheres are obtained.
所述浸泡液由柠檬酸钠、海藻酸钠和水组成；The soaking solution is composed of sodium citrate, sodium alginate and water;
按重量比，柠檬酸钠：海藻酸钠：水＝1:1:4-6。By weight, sodium citrate: sodium alginate: water=1:1:4-6.
对应的，本发明还提供了一种吸附酚类污染物的磁性核壳纳米微球，采用上述任一 项所述的制备方法制备得到；Correspondingly, the present invention also provides a magnetic core-shell nano-microsphere for adsorbing phenolic pollutants, which is prepared by the preparation method described in any one of the above;
磁性核壳纳米微球的尺寸为50-500nm。The size of the magnetic core-shell nanospheres is 50-500 nm.
本发明还提供了所述的吸附酚类污染物的磁性核壳纳米微球的应用，所述磁性核壳纳米微球用于含有酚类污染物的水体处理。The present invention also provides the application of the magnetic core-shell nano-microspheres for adsorbing phenolic pollutants, and the magnetic core-shell nano-microspheres are used for the treatment of water bodies containing phenolic pollutants.
和最接近的现有技术比，本发明的技术方案具备如下有益效果：Compared with the closest prior art, the technical scheme of the present invention has the following beneficial effects:
本发明提供吸附酚类污染物的磁性核壳纳米微球的制备方法，对纳米级吸附载体依次进行第一次改性和第二次改性，然后对第二次改性的吸附载体进行聚合反应，得到磁性核壳纳米微球，相较于现有仅采用一次改性操作，大大提高了纳米级吸附载体与聚合物的相容性，尤其是磁性吸附剂在高温环境下进行吸附操作，纳米级吸附载体与聚合物的相容性也不受影响，从而提高磁性核壳纳米微球对酚类污染物的吸附效率以及回收效率。The present invention provides a method for preparing magnetic core-shell nano-microspheres for adsorbing phenolic pollutants. Compared with the existing one-time modification operation, the compatibility of the nano-scale adsorption carrier and the polymer is greatly improved, especially the adsorption operation of the magnetic adsorbent in a high temperature environment, The compatibility of the nanoscale adsorption carrier with the polymer is also not affected, thereby improving the adsorption efficiency and recovery efficiency of the magnetic core-shell nanospheres for phenolic pollutants.
本发明优化第一次改性和第二次改性采用的改性剂，第一改性剂由硅烷偶联剂、聚氧乙烯链和氨水组成，第二改性剂由聚乙二醇、乳酸和壳聚糖组成，相较于现有比如单一采用硅烷偶联剂改性，在提高纳米级吸附载体与聚合物相容性的基础上，提高纳米级吸附载体与聚合物之间的结合力，从而提高磁性核壳纳米微球的力学性能，并且控制硅烷偶联剂、聚氧乙烯链和氨水的重量比为5-6:1-3:1，控制聚乙二醇、乳酸和壳聚糖的重量比为5:1-3:2，纳米级吸附载体与聚合物之间的结合性能更优异。The present invention optimizes the modifier used in the first modification and the second modification, the first modifier is composed of silane coupling agent, polyoxyethylene chain and ammonia water, and the second modifier is composed of polyethylene glycol, The composition of lactic acid and chitosan, compared with the existing ones such as single silane coupling agent modification, on the basis of improving the compatibility between the nano-scale adsorption carrier and the polymer, the combination between the nano-scale adsorption carrier and the polymer is improved. to improve the mechanical properties of magnetic core-shell nanospheres, control the weight ratio of silane coupling agent, polyoxyethylene chain and ammonia water to 5-6:1-3:1, control polyethylene glycol, lactic acid and shell The weight ratio of the polysaccharide is 5:1-3:2, and the binding performance between the nanoscale adsorption carrier and the polymer is more excellent.
本发明优化纳米铁粉的制备方法，具体是向提取绿茶提取液中加入包括粉末状态的C、Si、Mo、S以及P的反应添加剂，然后与硝酸亚铁的水溶液混合搅拌反应，得到反应产物，依次进行过滤、洗涤以及干燥，得到纳米铁粉，得到的纳米铁粉不易发生团聚现象，并且C、Si、Mo、S以及P的重量满足如下关系式：0.5≤(C+0.3Si)(Mo+10S+2P+0.8)≤0.85时，纳米铁粉的稳定性更佳。The invention optimizes the preparation method of the nano iron powder, specifically, adding reaction additives including C, Si, Mo, S and P in powder state into the green tea extract, and then mixing and stirring with the aqueous solution of ferrous nitrate to obtain a reaction product , filter, wash and dry in turn to obtain nano iron powder, the obtained nano iron powder is not easy to agglomerate, and the weight of C, Si, Mo, S and P satisfies the following relational formula: 0.5≤(C+0.3Si)( When Mo+10S+2P+0.8)≤0.85, the stability of nano-iron powder is better.
本发明优化纳米四氧化三铁的制备方法，具体是优化混合铁盐溶液水热反应中加入的复合助剂，复合助剂包括复合沉淀剂、复合表面活性剂，复合沉淀剂由抗坏血酸、氢氧化钠和石墨烯组成，复合表面活性剂由油酸、山梨酸钠和柠檬酸钠组成，使得得到的纳米四氧化三铁不易发生团聚现象，并且控制抗坏血酸、氢氧化钠和石墨烯的重量比为1-3:2:5，油酸、山梨酸钠和柠檬酸钠的重量比为0.0-1:3-5：2时，纳米四氧化三铁的稳定性更佳。The invention optimizes the preparation method of nanometer ferric tetroxide, and specifically optimizes the composite auxiliary agent added in the hydrothermal reaction of the mixed iron salt solution. The composite auxiliary agent includes a composite precipitation agent and a composite surfactant. Sodium and graphene are formed, and the composite surfactant is formed of oleic acid, sodium sorbate and sodium citrate, so that the obtained nano-iron tetroxide is not easy to agglomerate, and the weight ratio of control ascorbic acid, sodium hydroxide and graphene is 1-3:2:5, when the weight ratio of oleic acid, sodium sorbate and sodium citrate is 0.0-1:3-5:2, the stability of nano ferric tetroxide is better.
本发明改进纳米级吸附载体的聚合反应，具体是以N-乙烯吡咯烷酮为单体，二乙烯苯和丙烯酸甲酯为交联剂，在引发剂作用下，于60-90℃下在第二改性吸附载体表面发 生聚合反应，使得第二改性吸附载体表面包覆一层聚合物，从而得到磁性核壳纳米微球，使得磁性核壳纳米微球相较于现有纳米吸附材料具有更好的亲水性，从而更加适宜含酚类污染物水体的处理。The invention improves the polymerization reaction of the nano-scale adsorption carrier, specifically using N-vinyl pyrrolidone as a monomer, divinyl benzene and methyl acrylate as cross-linking agents, under the action of an initiator, at 60-90 DEG C in a second modification Polymerization reaction occurs on the surface of the adsorption carrier, so that the surface of the second modified adsorption carrier is coated with a layer of polymer, so as to obtain magnetic core-shell nano-microspheres, so that the magnetic core-shell nano-microspheres have better performance than existing nano-adsorption materials. Therefore, it is more suitable for the treatment of water bodies containing phenolic pollutants.
本发明在第二改性吸附载体表面包覆一层聚合物后，置于由柠檬酸钠、海藻酸钠和水组成的浸泡液中在30-40℃下浸泡0.5-1h后再获得磁性核壳纳米微球，扩展了聚合物的吸附孔径，从而进一步提高提高磁性核壳纳米微球对酚类污染物的吸附效率。In the present invention, after the surface of the second modified adsorption carrier is coated with a layer of polymer, the magnetic core is obtained after being soaked in a soaking liquid composed of sodium citrate, sodium alginate and water for 0.5-1 h at 30-40° C. Shell nano-microspheres expand the adsorption pore size of polymers, thereby further improving the adsorption efficiency of magnetic core-shell nano-microspheres to phenolic pollutants.
为了更清楚地说明本发明实施例或现有技术中的技术方案，下面将对实施例或现有技术描述中所需要使用的附图作简单地介绍，显而易见地，下面描述中的附图仅仅是本发明的一些实施例，对于本领域普通技术人员来讲，在不付出创造性劳动性的前提下，还可以根据这些附图获得其他的附图。In order to explain the embodiments of the present invention or the technical solutions in the prior art more clearly, the following briefly introduces the accompanying drawings that need to be used in the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only These are some embodiments of the present invention, and for those of ordinary skill in the art, other drawings can also be obtained from these drawings without any creative effort.
图1为本发明实施例1的吸附酚类污染物的磁性核壳纳米微球的扫描电子显微镜图；Fig. 1 is the scanning electron microscope picture of the magnetic core-shell nano-microspheres of the adsorption phenolic pollutants of Example 1 of the present invention;
图2为本发明实施例4的吸附酚类污染物的磁性核壳纳米微球的扫描电子显微镜图；Fig. 2 is the scanning electron microscope picture of the magnetic core-shell nano-microspheres of the adsorption phenolic pollutants of Example 4 of the present invention;
图3为本发明实施例5的吸附酚类污染物的磁性核壳纳米微球的扫描电子显微镜图；Fig. 3 is the scanning electron microscope picture of the magnetic core-shell nano-microspheres of the adsorption phenolic pollutants of Example 5 of the present invention;
图4为本发明实施例3的吸附酚类污染物的磁性核壳纳米微球的吸附等温曲线图。4 is an adsorption isotherm curve diagram of the magnetic core-shell nano-microspheres for adsorbing phenolic pollutants according to Example 3 of the present invention.
图5为高温(600℃)吸附状态下，图1的磁性核壳纳米微球的扫描电子显微镜图的局部放大图；FIG. 5 is a partial enlarged view of the scanning electron microscope image of the magnetic core-shell nano-microspheres of FIG. 1 under the high temperature (600° C.) adsorption state;
图6为高温(600℃)吸附状态下，对比实施例1的磁性核壳纳米微球的扫描电子显微镜图的局部放大图。FIG. 6 is a partial enlarged view of a scanning electron microscope image of the magnetic core-shell nano-microspheres of Comparative Example 1 under a high temperature (600° C.) adsorption state.
下面将结合本发明的实施例，对本发明的技术方案进行清楚、完整地描述，显然，所描述的实施例仅仅是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
实施例1Example 1
本实施例提供的吸附酚类污染物的磁性核壳纳米微球的制备方法，具体包括如下步骤：The preparation method of magnetic core-shell nano-microspheres for adsorbing phenolic pollutants provided in this embodiment specifically includes the following steps:
S1制备纳米铁粉S1 preparation of nano iron powder
S1-1取绿茶叶烘干粉碎后加入去离子水进行加热反应，过滤后得到绿茶提取液，具体的，本实施例中茶叶粉碎至200目，绿茶叶与去离子水的重量比为2:30，加热温度60℃，加热反应时间0.5h，然后过滤反应液得到绿茶提取液；S1-1 gets green tea leaves to dry and pulverize and then adds deionized water to carry out heating reaction, obtains green tea extract after filtration, concretely, tea leaves are pulverized to 200 meshes in the present embodiment, and the weight ratio of green tea leaves and deionized water is 2: 30, the heating temperature is 60°C, the heating reaction time is 0.5h, and then the reaction solution is filtered to obtain a green tea extract;
S1-2向绿茶提取液内加入反应添加剂，即加入粉末状态的C、Si、Mo、S以及P，然后与硝酸亚铁的水溶液混合，在20℃下搅拌反应，得到反应产物；S1-2 adds reaction additives to the green tea extract, namely adding C, Si, Mo, S and P in powder state, then mixing with the aqueous solution of ferrous nitrate, stirring and reacting at 20 ° C to obtain the reaction product;
其中，以重量份计算，C、Si、Mo、S以及P的重量满足如下关系式：Wherein, calculated in parts by weight, the weights of C, Si, Mo, S and P satisfy the following relational formula:
(C+0.3Si)(Mo+10S+2P+0.8)＝0.5；(C+0.3Si)(Mo+10S+2P+0.8)=0.5;
反应添加剂的重量占绿茶提取液重量的0.5％；The weight of the reaction additive accounts for 0.5% of the weight of the green tea extract;
硝酸亚铁的水溶液的重量占绿茶提取液重量的5％；The weight of the aqueous solution of ferrous nitrate accounts for 5% of the weight of the green tea extract;
硝酸亚铁的水溶液中，硝酸亚铁的重量占水重量的10％。In the aqueous solution of ferrous nitrate, the weight of ferrous nitrate accounts for 10% of the weight of water.
S1-3将反应产物过滤、洗涤后，在40℃下干燥1h，得到纳米铁粉。S1-3 After filtering and washing the reaction product, it was dried at 40° C. for 1 h to obtain nano iron powder.
S2对纳米铁粉进行第一次改性，得到第一改性吸附载体S2 modifies the nano iron powder for the first time to obtain the first modified adsorption carrier
将制备好的纳米铁粉分散到甲醇中，具体是每10g纳米铁粉分散到400mL甲醇中，然后加入200mL硅烷偶联剂、80mL壬基酚聚氧乙烯醚、40mL的氨水，在通氮气气氛保护下，在40℃下搅拌6h，然后分离出黑色沉淀，并使用甲醇反复清洗6次，得到第一改性吸附载体。Disperse the prepared nano iron powder into methanol, specifically, disperse each 10g nano iron powder into 400mL methanol, then add 200mL silane coupling agent, 80mL nonylphenol polyoxyethylene ether, 40mL ammonia water, in a nitrogen atmosphere. Under the protection, the mixture was stirred at 40 °C for 6 h, and then the black precipitate was separated and washed with methanol for 6 times to obtain the first modified adsorption carrier.
S3对第一改性吸附载体进行第二次改性，得到第二改性吸附载体S3 performs the second modification on the first modified adsorption carrier to obtain the second modified adsorption carrier
将第一改性吸附载体放入300ml乙醇溶液中，然后加入聚乙二醇、乳酸和壳聚糖组成的第二改性剂10g，聚乙二醇、乳酸和壳聚糖的重量比为5:1:2，然后在氮气气氛下，于30℃下搅拌反应1h，分离得到第二改性吸附载体。Put the first modified adsorption carrier into 300ml of ethanol solution, then add 10g of the second modifier composed of polyethylene glycol, lactic acid and chitosan, and the weight ratio of polyethylene glycol, lactic acid and chitosan is 5 :1:2, and then in a nitrogen atmosphere, the reaction was stirred at 30 °C for 1 h, and the second modified adsorption carrier was obtained by separation.
S4对第二改性吸附载体进行聚合反应，得到磁性核壳纳米微球S4 polymerizes the second modified adsorption carrier to obtain magnetic core-shell nano-microspheres
将第二改性吸附载体加入10gN-乙烯吡咯烷酮，10g二乙烯苯、10g丙烯酸甲酯以及0.1g偶氮二异丁腈混合均匀后，控制搅拌转速150rpm，并逐步加热升温到85℃，反应4h，使得第二改性吸附载体表面包覆一层聚合物，置于由柠檬酸钠、海藻酸钠和水组成的浸泡液中在30℃下浸泡0.5h，柠檬酸钠、海藻酸钠和水的重量比为1:1:4，从而得到磁性核壳纳米微球，所得微球粒径为50-500nm，扫描电子显微镜图片如图1所示。Add 10g of N-vinylpyrrolidone, 10g of divinylbenzene, 10g of methyl acrylate and 0.1g of azobisisobutyronitrile to the second modified adsorption carrier after mixing evenly, control the stirring speed to 150rpm, and gradually heat up to 85°C for 4h. , so that the surface of the second modified adsorption carrier is coated with a layer of polymer, placed in a soaking solution composed of sodium citrate, sodium alginate and water for 0.5h at 30 ° C, sodium citrate, sodium alginate and water The weight ratio of the magnetic core-shell nano-microspheres is 1:1:4, thereby obtaining the magnetic core-shell nano-microspheres.
实施例2Example 2
本实施例提供的吸附酚类污染物的磁性核壳纳米微球的制备方法，具体包括如下步骤：The preparation method of magnetic core-shell nano-microspheres for adsorbing phenolic pollutants provided in this embodiment specifically includes the following steps:
S1制备纳米铁粉S1 preparation of nano iron powder
S1-1取绿茶叶烘干粉碎后加入去离子水进行加热反应，过滤后得到绿茶提取液，具体的，本实施例中茶叶粉碎至300目，绿茶叶与去离子水的重量比为1:10，加热温度70℃，加热反应时间1h，然后过滤反应液得到绿茶提取液；S1-1 gets green tea leaves to dry and pulverize and then adds deionized water to carry out heating reaction, obtains green tea extract after filtration, concretely, tea leaves are pulverized to 300 meshes in the present embodiment, and the weight ratio of green tea leaves and deionized water is 1: 10. The heating temperature is 70°C, the heating reaction time is 1h, and then the reaction solution is filtered to obtain a green tea extract;
S1-2向绿茶提取液内加入反应添加剂，即加入粉末状态的C、Si、Mo、S以及P，然后与硝酸亚铁的水溶液混合，在20℃下搅拌反应，得到反应产物；S1-2 adds reaction additives to the green tea extract, namely adding C, Si, Mo, S and P in powder state, then mixing with the aqueous solution of ferrous nitrate, stirring and reacting at 20 ° C to obtain the reaction product;
其中，以重量份计算，C、Si、Mo、S以及P的重量满足如下关系式：Wherein, calculated in parts by weight, the weights of C, Si, Mo, S and P satisfy the following relational formula:
(C+0.3Si)(Mo+10S+2P+0.8)＝0.85；(C+0.3Si)(Mo+10S+2P+0.8)=0.85;
反应添加剂的重量占绿茶提取液重量的1％；The weight of the reaction additive accounts for 1% of the weight of the green tea extract;
硝酸亚铁的水溶液的重量占绿茶提取液重量的10％；The weight of the aqueous solution of ferrous nitrate accounts for 10% of the weight of the green tea extract;
硝酸亚铁的水溶液中，硝酸亚铁的重量占水重量的15％。In the aqueous solution of ferrous nitrate, the weight of ferrous nitrate accounts for 15% of the weight of water.
S1-3将反应产物过滤、洗涤后，在30℃下干燥1.5h，得到纳米铁粉。S1-3 After filtering and washing the reaction product, it was dried at 30° C. for 1.5 h to obtain nano iron powder.
S2对纳米铁粉进行第一次改性，得到第一改性吸附载体S2 modifies the nano iron powder for the first time to obtain the first modified adsorption carrier
将制备好的纳米铁粉分散到甲醇中，具体是每20g纳米铁粉分散到400mL甲醇中，然后加入120mL硅烷偶联剂、80mL壬基酚聚氧乙烯醚、20mL的氨水，在通氮气气氛保护下，在60℃下搅拌10h，然后分离出黑色沉淀，并使用甲醇反复清洗5次，得到第一改性吸附载体。Disperse the prepared nano iron powder into methanol, specifically, disperse each 20g nano iron powder into 400mL methanol, then add 120mL silane coupling agent, 80mL nonylphenol polyoxyethylene ether, 20mL ammonia water, in a nitrogen atmosphere. Under the protection, the mixture was stirred at 60 °C for 10 h, and then the black precipitate was separated and washed with methanol for 5 times to obtain the first modified adsorption carrier.
S3对第一改性吸附载体进行第二次改性，得到第二改性吸附载体S3 performs the second modification on the first modified adsorption carrier to obtain the second modified adsorption carrier
将第一改性吸附载体放入500ml乙醇溶液中，然后加入聚乙二醇、乳酸和壳聚糖组成的第二改性剂15g，聚乙二醇、乳酸和壳聚糖的重量比为5:3:2，然后在氮气气氛下，于50℃下搅拌反应3h，分离得到第二改性吸附载体。Put the first modified adsorption carrier into 500ml of ethanol solution, then add 15g of the second modifier composed of polyethylene glycol, lactic acid and chitosan, and the weight ratio of polyethylene glycol, lactic acid and chitosan is 5 : 3: 2, and then in a nitrogen atmosphere, the reaction was stirred at 50 °C for 3 h, and the second modified adsorption carrier was obtained by separation.
S4对第二改性吸附载体进行聚合反应，得到磁性核壳纳米微球S4 polymerizes the second modified adsorption carrier to obtain magnetic core-shell nano-microspheres
将第二改性吸附载体加入15gN-乙烯吡咯烷酮，15g二乙烯苯、15g丙烯酸甲酯以及0.1g偶氮二异丁腈混合均匀后，控制搅拌转速200rpm，并逐步加热升温到90℃，反应3h，使得第二改性吸附载体表面包覆一层聚合物，置于由柠檬酸钠、海藻酸钠和水组成的浸泡液中在40℃下浸泡1h，柠檬酸钠、海藻酸钠和水的重量比为1:1:6，从而得到磁性核壳纳米微球，所得微球粒径为50-500nm。Add 15g of N-vinylpyrrolidone, 15g of divinylbenzene, 15g of methyl acrylate and 0.1g of azobisisobutyronitrile to the second modified adsorption carrier and mix them evenly. , so that the surface of the second modified adsorption carrier is coated with a layer of polymer, placed in a soaking liquid composed of sodium citrate, sodium alginate and water at 40 ° C for 1 h, and the mixture of sodium citrate, sodium alginate and water The weight ratio is 1:1:6, thereby obtaining magnetic core-shell nano-microspheres, and the particle size of the obtained microspheres is 50-500 nm.
实施例3Example 3
本实施例提供的吸附酚类污染物的磁性核壳纳米微球的制备方法，具体包括如下步骤：The preparation method of magnetic core-shell nano-microspheres for adsorbing phenolic pollutants provided in this embodiment specifically includes the following steps:
S1制备纳米铁粉S1 preparation of nano iron powder
S1-1取绿茶叶烘干粉碎后加入去离子水进行加热反应，过滤后得到绿茶提取液，具体的，本实施例中茶叶粉碎至500目，绿茶叶与去离子水的重量比为3:20，加热温度65℃，加热反应时间1.5h，然后过滤反应液得到绿茶提取液；S1-1 gets green tea leaves to dry and pulverize and then adds deionized water to carry out heating reaction, obtains green tea extract after filtration, concretely, tea leaves are pulverized to 500 meshes in the present embodiment, and the weight ratio of green tea leaves and deionized water is 3: 20, the heating temperature is 65°C, the heating reaction time is 1.5h, and then the reaction solution is filtered to obtain a green tea extract;
S1-2向绿茶提取液内加入反应添加剂，即加入粉末状态的C、Si、Mo、S以及P，然后与硝酸亚铁的水溶液混合，在20℃下搅拌反应，得到反应产物；S1-2 adds reaction additives to the green tea extract, namely adding C, Si, Mo, S and P in powder state, then mixing with the aqueous solution of ferrous nitrate, stirring and reacting at 20 ° C to obtain the reaction product;
其中，以重量份计算，C、Si、Mo、S以及P的重量满足如下关系式：Wherein, calculated in parts by weight, the weights of C, Si, Mo, S and P satisfy the following relational formula:
(C+0.3Si)(Mo+10S+2P+0.8)＝0.7；(C+0.3Si)(Mo+10S+2P+0.8)=0.7;
反应添加剂的重量占绿茶提取液重量的0.8％；The weight of the reaction additive accounts for 0.8% of the weight of the green tea extract;
硝酸亚铁的水溶液的重量占绿茶提取液重量的7％；The weight of the aqueous solution of ferrous nitrate accounts for 7% of the weight of the green tea extract;
硝酸亚铁的水溶液中，硝酸亚铁的重量占水重量的16％。In the aqueous solution of ferrous nitrate, the weight of ferrous nitrate accounts for 16% of the weight of water.
S1-3将反应产物过滤、洗涤后，在35℃下干燥2h，得到纳米铁粉。S1-3 After filtering and washing the reaction product, it was dried at 35° C. for 2 h to obtain nano iron powder.
S2对纳米铁粉进行第一次改性，得到第一改性吸附载体S2 modifies the nano iron powder for the first time to obtain the first modified adsorption carrier
将制备好的纳米铁粉分散到甲醇中，具体是每30g纳米铁粉分散到500mL甲醇中，然后加入150mL硅烷偶联剂、90mL壬基酚聚氧乙烯醚、30mL的氨水，在通氮气气氛保护下，在50℃下搅拌8h，然后分离出黑色沉淀，并使用甲醇反复清洗4次，得到第一改性吸附载体。Disperse the prepared nano-iron powder into methanol, specifically, each 30g nano-iron powder is dispersed in 500mL methanol, then add 150mL silane coupling agent, 90mL nonylphenol polyoxyethylene ether, 30mL ammonia water, in a nitrogen atmosphere. Under the protection, the mixture was stirred at 50 °C for 8 h, and then the black precipitate was separated and washed with methanol for 4 times to obtain the first modified adsorption carrier.
S3对第一改性吸附载体进行第二次改性，得到第二改性吸附载体S3 performs the second modification on the first modified adsorption carrier to obtain the second modified adsorption carrier
将第一改性吸附载体放入400ml乙醇溶液中，然后加入聚乙二醇、乳酸和壳聚糖组成的第二改性剂20g，聚乙二醇、乳酸和壳聚糖的重量比为5:2:2，然后在氮气气氛下，于40℃下搅拌反应2h，分离得到第二改性吸附载体。Put the first modified adsorption carrier into 400ml of ethanol solution, then add the second modifier 20g of polyethylene glycol, lactic acid and chitosan, and the weight ratio of polyethylene glycol, lactic acid and chitosan is 5 : 2: 2, and then in a nitrogen atmosphere, the reaction was stirred at 40 °C for 2 h, and the second modified adsorption carrier was obtained by separation.
S4对第二改性吸附载体进行聚合反应，得到磁性核壳纳米微球S4 polymerizes the second modified adsorption carrier to obtain magnetic core-shell nano-microspheres
将第二改性吸附载体加入15gN-乙烯吡咯烷酮，15g二乙烯苯、15g丙烯酸甲酯以及0.1g偶氮二异丁腈混合均匀后，控制搅拌转速200rpm，并逐步加热升温到60℃，反应3h，使得第二改性吸附载体表面包覆一层聚合物，置于由柠檬酸钠、海藻酸钠和水组成的浸泡液中在35℃下浸泡1h，柠檬酸钠、海藻酸钠和水的重量比为1:1:5，从而得到磁性核壳纳米微球，所得微球粒径为50-500nm，磁性核壳纳米微球的吸附等温曲线图如图4所示，图中横坐标表示吸附平衡时平衡浓度，纵坐标表示吸附平衡时平衡吸附量，从图中可以看出随着底物浓度的增大，磁性核壳纳米微球对对硝基苯酚的吸附量逐渐增大。Add 15g of N-vinylpyrrolidone, 15g of divinylbenzene, 15g of methyl acrylate and 0.1g of azobisisobutyronitrile to the second modified adsorption carrier and mix them evenly, control the stirring speed to 200rpm, and gradually heat up to 60°C for 3h. , so that the surface of the second modified adsorption carrier is coated with a layer of polymer, placed in a soaking liquid composed of sodium citrate, sodium alginate and water for 1 h at 35 °C, and the mixture of sodium citrate, sodium alginate and water The weight ratio is 1:1:5, thereby obtaining magnetic core-shell nano-microspheres, and the particle size of the obtained micro-spheres is 50-500 nm. The equilibrium concentration at adsorption equilibrium, and the ordinate represents the equilibrium adsorption capacity at adsorption equilibrium. It can be seen from the figure that with the increase of substrate concentration, the adsorption capacity of magnetic core-shell nanospheres to p-nitrophenol gradually increases.
实施例4Example 4
本实施例提供的吸附酚类污染物的磁性核壳纳米微球的制备方法，具体包括如下步骤：The preparation method of magnetic core-shell nano-microspheres for adsorbing phenolic pollutants provided in this embodiment specifically includes the following steps:
S1制备纳米四氧化三铁S1 preparation of nano-iron tetroxide
将三价铁盐硝酸铁溶液与二价铁盐硝酸亚铁溶液按照三价铁离子与二价铁离子的摩尔比为1：3混合，得到混合铁盐溶液；The ferric salt ferric nitrate solution and the ferrous salt ferrous nitrate solution are mixed according to the molar ratio of ferric ion and ferrous ion as 1:3 to obtain a mixed ferric salt solution;
将混合铁盐溶液加入复合助剂，在155℃下水热反应5h，得到反应液；The mixed iron salt solution was added to the composite auxiliary, and the reaction solution was obtained by hydrothermal reaction at 155°C for 5h;
将反应液进行过滤、室温干燥处理，得到纳米四氧化三铁；The reaction solution is filtered and dried at room temperature to obtain nano-iron tetroxide;
复合助剂占混合铁盐溶液的重量比为2％；The weight ratio of the composite auxiliaries to the mixed iron salt solution is 2%;
复合助剂包括复合沉淀剂、复合表面活性剂以及复合分散剂；Composite additives include composite precipitants, composite surfactants and composite dispersants;
复合沉淀剂由抗坏血酸、氢氧化钠和石墨烯组成，抗坏血酸、氢氧化钠和石墨烯的重量比为1:2:5；The composite precipitant is composed of ascorbic acid, sodium hydroxide and graphene, and the weight ratio of ascorbic acid, sodium hydroxide and graphene is 1:2:5;
复合表面活性剂由油酸、山梨酸钠和柠檬酸钠组成，油酸、山梨酸钠、柠檬酸钠的重量比为1:3：2；The composite surfactant is composed of oleic acid, sodium sorbate and sodium citrate, and the weight ratio of oleic acid, sodium sorbate and sodium citrate is 1:3:2;
复合由硫酸钠和油酸钠组成，硫酸钠和油酸钠的重量比为1:1。The compound is composed of sodium sulfate and sodium oleate, and the weight ratio of sodium sulfate and sodium oleate is 1:1.
S2对纳米四氧化三铁进行第一次改性，得到第一改性吸附载体S2 carries out the first modification of nano-iron tetroxide to obtain the first modified adsorption carrier
将制备好的纳米四氧化三铁分散到甲醇中，具体是每10g纳米四氧化三铁分散到400mL甲醇中，然后加入200mL硅烷偶联剂、80mL壬基酚聚氧乙烯醚、40mL的氨水，在通氮气气氛保护下，在40℃下搅拌6h，然后分离出黑色沉淀，并使用甲醇反复清洗6次，得到第一改性吸附载体。Disperse the prepared nano-iron tetroxide into methanol, specifically, disperse each 10g of nano-iron tetroxide into 400 mL of methanol, then add 200 mL of silane coupling agent, 80 mL of nonylphenol polyoxyethylene ether, and 40 mL of ammonia water, Under the protection of a nitrogen atmosphere, the mixture was stirred at 40 °C for 6 h, and then the black precipitate was separated and washed with methanol for 6 times to obtain the first modified adsorption carrier.
S3对第一改性吸附载体进行第二次改性，得到第二改性吸附载体S3 performs the second modification on the first modified adsorption carrier to obtain the second modified adsorption carrier
将第一改性吸附载体放入300ml乙醇溶液中，然后加入聚乙二醇、乳酸和壳聚糖组成的第二改性剂10g，聚乙二醇、乳酸和壳聚糖的重量比为5:1:2，然后在氮气气氛下，于30℃下搅拌反应1h，分离得到第二改性吸附载体。Put the first modified adsorption carrier into 300ml of ethanol solution, then add 10g of the second modifier composed of polyethylene glycol, lactic acid and chitosan, and the weight ratio of polyethylene glycol, lactic acid and chitosan is 5 :1:2, and then in a nitrogen atmosphere, the reaction was stirred at 30 °C for 1 h, and the second modified adsorption carrier was obtained by separation.
S4对第二改性吸附载体进行聚合反应，得到磁性核壳纳米微球S4 polymerizes the second modified adsorption carrier to obtain magnetic core-shell nano-microspheres
将第二改性吸附载体加入10gN-乙烯吡咯烷酮，10g二乙烯苯、10g丙烯酸甲酯以及0.1g偶氮二异丁腈混合均匀后，控制搅拌转速150rpm，并逐步加热升温到85℃，反应4h，使得第二改性吸附载体表面包覆一层聚合物，置于由柠檬酸钠、海藻酸钠和水组成的浸泡液中在30℃下浸泡0.5h，柠檬酸钠、海藻酸钠和水的重量比为1:1:4，从而得到磁性核壳纳米微球，所得微球粒径为50-500nm，扫描电子显微镜图片如图2所示。Add 10g of N-vinylpyrrolidone, 10g of divinylbenzene, 10g of methyl acrylate and 0.1g of azobisisobutyronitrile to the second modified adsorption carrier after mixing evenly, control the stirring speed to 150rpm, and gradually heat up to 85°C for 4h. , so that the surface of the second modified adsorption carrier is coated with a layer of polymer, placed in a soaking solution composed of sodium citrate, sodium alginate and water for 0.5h at 30 ° C, sodium citrate, sodium alginate and water The weight ratio of the magnetic core-shell nano-microspheres is 1:1:4, thereby obtaining the magnetic core-shell nano-microspheres. The particle size of the obtained microspheres is 50-500 nm.
实施例5Example 5
本实施例提供的吸附酚类污染物的磁性核壳纳米微球的制备方法，具体包括如下步骤：The preparation method of magnetic core-shell nano-microspheres for adsorbing phenolic pollutants provided in this embodiment specifically includes the following steps:
S1制备纳米四氧化三铁S1 preparation of nano-iron tetroxide
将三价铁盐硝酸铁溶液与二价铁盐硝酸亚铁溶液按照三价铁离子与二价铁离子的摩尔比为2：5混合，得到混合铁盐溶液；Mixing the ferric salt ferric nitrate solution and the ferric salt ferrous nitrate solution according to the molar ratio of ferric ions and ferric ions to 2:5 to obtain a mixed ferric salt solution;
将混合铁盐溶液加入复合助剂，在160℃下水热反应6h，得到反应液；The mixed iron salt solution was added to the composite auxiliary, and the reaction solution was obtained by hydrothermal reaction at 160 °C for 6 h;
将反应液进行过滤、室温干燥处理，得到纳米四氧化三铁；The reaction solution is filtered and dried at room temperature to obtain nano-iron tetroxide;
复合助剂占混合铁盐溶液的重量比为3％；The weight ratio of the composite auxiliaries to the mixed iron salt solution is 3%;
复合助剂包括复合沉淀剂、复合表面活性剂以及复合分散剂；Composite additives include composite precipitants, composite surfactants and composite dispersants;
复合沉淀剂由抗坏血酸、氢氧化钠和石墨烯组成，抗坏血酸、氢氧化钠和石墨烯的重量比为3:2:5；The composite precipitant is composed of ascorbic acid, sodium hydroxide and graphene, and the weight ratio of ascorbic acid, sodium hydroxide and graphene is 3:2:5;
复合表面活性剂由油酸、山梨酸钠和柠檬酸钠组成，油酸、山梨酸钠、柠檬酸钠的重量比为1:5：2；The composite surfactant is composed of oleic acid, sodium sorbate and sodium citrate, and the weight ratio of oleic acid, sodium sorbate and sodium citrate is 1:5:2;
复合由硫酸钠和油酸钠组成，硫酸钠和油酸钠的重量比为5:1。The compound is composed of sodium sulfate and sodium oleate, and the weight ratio of sodium sulfate and sodium oleate is 5:1.
S2对纳米四氧化三铁进行第一次改性，得到第一改性吸附载体S2 carries out the first modification of nano-iron tetroxide to obtain the first modified adsorption carrier
将制备好的纳米四氧化三铁分散到甲醇中，具体是每20g纳米四氧化三铁分散到400mL甲醇中，然后加入120mL硅烷偶联剂、80mL壬基酚聚氧乙烯醚、20mL的氨水，在通氮气气氛保护下，在60℃下搅拌10h，然后分离出黑色沉淀，并使用甲醇反复清洗5次，得到第一改性吸附载体。Disperse the prepared nano ferric oxide into methanol, specifically, disperse each 20g of nano ferric oxide into 400 mL of methanol, then add 120 mL of silane coupling agent, 80 mL of nonylphenol polyoxyethylene ether, and 20 mL of ammonia water, Under the protection of a nitrogen atmosphere, the mixture was stirred at 60 °C for 10 h, and then the black precipitate was separated and washed with methanol for 5 times to obtain the first modified adsorption carrier.
S3对第一改性吸附载体进行第二次改性，得到第二改性吸附载体S3 performs the second modification on the first modified adsorption carrier to obtain the second modified adsorption carrier
将第一改性吸附载体放入500ml乙醇溶液中，然后加入聚乙二醇、乳酸和壳聚糖组成的第二改性剂15g，聚乙二醇、乳酸和壳聚糖的重量比为5:3:2，然后在氮气气氛下，于50℃下搅拌反应3h，分离得到第二改性吸附载体。Put the first modified adsorption carrier into 500ml of ethanol solution, then add 15g of the second modifier composed of polyethylene glycol, lactic acid and chitosan, and the weight ratio of polyethylene glycol, lactic acid and chitosan is 5 : 3: 2, and then in a nitrogen atmosphere, the reaction was stirred at 50 °C for 3 h, and the second modified adsorption carrier was obtained by separation.
S4对第二改性吸附载体进行聚合反应，得到磁性核壳纳米微球S4 polymerizes the second modified adsorption carrier to obtain magnetic core-shell nano-microspheres
将第二改性吸附载体加入15gN-乙烯吡咯烷酮，15g二乙烯苯、15g丙烯酸甲酯以及0.1g偶氮二异丁腈混合均匀后，控制搅拌转速200rpm，并逐步加热升温到90℃，反应3h，使得第二改性吸附载体表面包覆一层聚合物，置于由柠檬酸钠、海藻酸钠和水组成的浸泡液中在40℃下浸泡1h，柠檬酸钠、海藻酸钠和水的重量比为1:1:6，从而得到磁性核壳纳米微球，所得微球粒径为50-500nm，扫描电子显微镜图片如图3所示。Add 15g of N-vinylpyrrolidone, 15g of divinylbenzene, 15g of methyl acrylate and 0.1g of azobisisobutyronitrile to the second modified adsorption carrier and mix them evenly. , so that the surface of the second modified adsorption carrier is coated with a layer of polymer, placed in a soaking liquid composed of sodium citrate, sodium alginate and water at 40 ° C for 1 h, and the mixture of sodium citrate, sodium alginate and water The weight ratio is 1:1:6, thereby obtaining magnetic core-shell nano-microspheres, the particle size of the obtained microspheres is 50-500 nm, and the scanning electron microscope picture is shown in FIG. 3 .
实施例6Example 6
本实施例提供的吸附酚类污染物的磁性核壳纳米微球的制备方法，具体包括如下步骤：The preparation method of magnetic core-shell nano-microspheres for adsorbing phenolic pollutants provided in this embodiment specifically includes the following steps:
S1制备纳米四氧化三铁S1 preparation of nano-iron tetroxide
将三价铁盐硝酸铁溶液与二价铁盐硝酸亚铁溶液按照三价铁离子与二价铁离子的摩尔比为2：4混合，得到混合铁盐溶液；The ferric salt ferric nitrate solution and the ferric salt ferrous nitrate solution are mixed according to the molar ratio of ferric ion and ferrous ion as 2:4 to obtain a mixed ferric salt solution;
将混合铁盐溶液加入复合助剂，在158℃下水热反应5.5h，得到反应液；The mixed iron salt solution was added to the composite auxiliary, and the hydrothermal reaction was carried out at 158 ° C for 5.5 h to obtain a reaction solution;
将反应液进行过滤、室温干燥处理，得到纳米四氧化三铁；The reaction solution is filtered and dried at room temperature to obtain nano-iron tetroxide;
复合助剂占混合铁盐溶液的重量比为5％；The weight ratio of the composite auxiliaries to the mixed iron salt solution is 5%;
复合助剂包括复合沉淀剂、复合表面活性剂以及复合分散剂；Composite additives include composite precipitants, composite surfactants and composite dispersants;
复合沉淀剂由抗坏血酸、氢氧化钠和石墨烯组成，抗坏血酸、氢氧化钠和石墨烯的重量比为2:2:5；The composite precipitant is composed of ascorbic acid, sodium hydroxide and graphene, and the weight ratio of ascorbic acid, sodium hydroxide and graphene is 2:2:5;
复合表面活性剂由油酸、山梨酸钠和柠檬酸钠组成，油酸、山梨酸钠、柠檬酸钠的重量比为1:4：2；The composite surfactant is composed of oleic acid, sodium sorbate and sodium citrate, and the weight ratio of oleic acid, sodium sorbate and sodium citrate is 1:4:2;
复合由硫酸钠和油酸钠组成，硫酸钠和油酸钠的重量比为3:1。The compound is composed of sodium sulfate and sodium oleate, and the weight ratio of sodium sulfate and sodium oleate is 3:1.
S2对纳米四氧化三铁进行第一次改性，得到第一改性吸附载体S2 carries out the first modification of nano-iron tetroxide to obtain the first modified adsorption carrier
将制备好的纳米四氧化三铁分散到甲醇中，具体是每30g纳米四氧化三铁分散到500mL甲醇中，然后加入150mL硅烷偶联剂、90mL壬基酚聚氧乙烯醚、30mL的氨水，在通氮气气氛保护下，在50℃下搅拌8h，然后分离出黑色沉淀，并使用甲醇反复清洗4次，得到第一改性吸附载体。Disperse the prepared nano-iron tetroxide into methanol, specifically, disperse each 30g of nano-iron tetroxide into 500 mL of methanol, then add 150 mL of silane coupling agent, 90 mL of nonylphenol polyoxyethylene ether, and 30 mL of ammonia water, Under the protection of a nitrogen atmosphere, the mixture was stirred at 50 °C for 8 h, and then the black precipitate was separated and washed with methanol for 4 times to obtain the first modified adsorption carrier.
S3对第一改性吸附载体进行第二次改性，得到第二改性吸附载体S3 performs the second modification on the first modified adsorption carrier to obtain the second modified adsorption carrier
将第一改性吸附载体放入400ml乙醇溶液中，然后加入聚乙二醇、乳酸和壳聚糖组成的第二改性剂20g，聚乙二醇、乳酸和壳聚糖的重量比为5:2:2，然后在氮气气氛下，于40℃下搅拌反应2h，分离得到第二改性吸附载体。Put the first modified adsorption carrier into 400ml of ethanol solution, then add the second modifier 20g of polyethylene glycol, lactic acid and chitosan, the weight ratio of polyethylene glycol, lactic acid and chitosan is 5 : 2: 2, and then in a nitrogen atmosphere, the reaction was stirred at 40 °C for 2 h, and the second modified adsorption carrier was obtained by separation.
S4对第二改性吸附载体进行聚合反应，得到磁性核壳纳米微球S4 polymerizes the second modified adsorption carrier to obtain magnetic core-shell nano-microspheres
将第二改性吸附载体加入15gN-乙烯吡咯烷酮，15g二乙烯苯、15g丙烯酸甲酯以及0.1g偶氮二异丁腈混合均匀后，控制搅拌转速200rpm，并逐步加热升温到60℃，反应3h，使得第二改性吸附载体表面包覆一层聚合物，置于由柠檬酸钠、海藻酸钠和水组成的浸泡液中在35℃下浸泡1h，柠檬酸钠、海藻酸钠和水的重量比为1:1:5，从而得到磁性核壳纳米微球，所得微球粒径为50-500nm。Add 15g of N-vinylpyrrolidone, 15g of divinylbenzene, 15g of methyl acrylate and 0.1g of azobisisobutyronitrile to the second modified adsorption carrier and mix them evenly, control the stirring speed to 200rpm, and gradually heat up to 60°C for 3h. , so that the surface of the second modified adsorption carrier is coated with a layer of polymer, placed in a soaking liquid composed of sodium citrate, sodium alginate and water for 1 h at 35 °C, and the mixture of sodium citrate, sodium alginate and water The weight ratio is 1:1:5, thereby obtaining magnetic core-shell nano-microspheres, and the particle size of the obtained microspheres is 50-500 nm.
上述实施例1-6的磁性核壳纳米微球可用于含有酚类污染物的水体处理，具体处理步骤如下：The magnetic core-shell nano-microspheres of the above-mentioned embodiments 1-6 can be used for the treatment of water bodies containing phenolic pollutants, and the specific treatment steps are as follows:
向含有酚类污染物的水池内添加絮凝剂，添加的絮凝剂包括现有的各种有机、无机及有机-无机混合絮凝剂；Adding flocculants to the pool containing phenolic pollutants, the added flocculants include various existing organic, inorganic and organic-inorganic mixed flocculants;
向添加絮凝剂的水池内放置本实施例1-6的磁性核壳纳米微球，吸附酚类污染物；The magnetic core-shell nano-microspheres of the present embodiment 1-6 are placed in the pool to which the flocculant is added to adsorb phenolic pollutants;
对水池施加磁场，通过外加磁场作用，从水池内分离磁性核壳纳米微球；A magnetic field is applied to the pool, and the magnetic core-shell nano-microspheres are separated from the pool by the action of the external magnetic field;
从磁性核壳纳米微球内分离酚类污染物，实现磁性核壳纳米微球的再次循环使用。The phenolic pollutants are separated from the magnetic core-shell nano-microspheres to realize the recycling of the magnetic core-shell nano-microspheres.
对比实施例1Comparative Example 1
本实施例提供的吸附酚类污染物的磁性核壳纳米微球的制备方法，与实施例1的不同之处在于：纳米铁粉进行一次改性后得到改性吸附载体后即进行聚合反应，一次改性具体是将制备好的纳米铁粉分散到甲醇中，具体是每10g纳米铁粉分散到400mL甲醇中，然后加入200mL硅烷偶联剂、50mL的氨水，在通氮气气氛保护下，在40℃下搅拌6h，然后分离出黑色沉淀，并使用甲醇反复清洗6次，得到改性吸附载体。The preparation method of magnetic core-shell nano-microspheres for adsorbing phenolic pollutants provided in this example is different from Example 1 in that the nano-iron powder is modified once to obtain a modified adsorption carrier, and then the polymerization reaction is carried out, The first modification is to disperse the prepared nano iron powder into methanol, specifically, disperse each 10g nano iron powder into 400mL methanol, then add 200mL silane coupling agent and 50mL ammonia water, under the protection of nitrogen atmosphere, in After stirring at 40 °C for 6 h, the black precipitate was separated and washed with methanol for 6 times to obtain a modified adsorption carrier.
其他步骤以及工艺参数与实施例1相同。Other steps and process parameters are the same as in Example 1.
通过对比图5和图6可知，在高温吸附状态下，实施例1的吸附酚类污染物的磁性核壳纳米微球的纳米铁粉和聚合物之间分散均匀，相容性好，而对比实施例1的吸附酚类污染物的磁性核壳纳米微球的纳米铁粉之间发生团聚现象，纳米铁粉和聚合物之间分散性差，相容性差。By comparing Fig. 5 and Fig. 6, it can be seen that under the high-temperature adsorption state, the nano-iron powder and the polymer of the magnetic core-shell nano-microspheres adsorbing phenolic pollutants of Example 1 are uniformly dispersed and have good compatibility, while the comparison The agglomeration phenomenon occurs between the iron nanopowders of the magnetic core-shell nanospheres for adsorbing phenolic pollutants in Example 1, and the dispersibility and compatibility between the iron nanopowders and the polymer are poor.
以上实施例仅用以说明本发明的技术方案而非对其限制，尽管参照上述实施例对本发明进行了详细的说明，所属领域的普通技术人员依然可以对本发明的具体实施方式进行修改或者等同替换，这些未脱离本发明精神和范围的任何修改或者等同替换，均在申请待批的本发明的权利要求保护范围之内。The above embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the above embodiments, those of ordinary skill in the art can still modify or equivalently replace the specific embodiments of the present invention. , any modifications or equivalent replacements that do not depart from the spirit and scope of the present invention are all within the protection scope of the claims of the present invention for which the application is pending.
Claims (10)
- 吸附酚类污染物的磁性核壳纳米微球的制备方法，其特征在于，包括如下步骤：The preparation method of magnetic core-shell nano-microspheres for adsorbing phenolic pollutants is characterized in that, comprising the following steps:制备纳米级吸附载体；Preparation of nanoscale adsorption carrier;对所述纳米级吸附载体进行第一次改性，得到第一改性吸附载体；Carrying out the first modification on the nano-scale adsorption carrier to obtain a first modified adsorption carrier;对所述第一改性吸附载体进行第二次改性，得到第二改性吸附载体；Carrying out the second modification on the first modified adsorption carrier to obtain a second modified adsorption carrier;对所述第二改性吸附载体进行聚合反应，得到磁性核壳纳米微球。The second modified adsorption carrier is polymerized to obtain magnetic core-shell nano-microspheres.
- 根据权利要求1所述的吸附酚类污染物的磁性核壳纳米微球的制备方法，其特征在于，所述纳米级吸附载体为纳米铁粉；The method for preparing magnetic core-shell nano-microspheres for adsorbing phenolic pollutants according to claim 1, wherein the nano-scale adsorption carrier is nano-iron powder;所述纳米铁粉的制备方法，具体包括：The preparation method of the nano iron powder specifically includes:取绿茶叶烘干粉碎后加入去离子水进行加热反应，过滤后得到绿茶提取液；Take green tea leaves, dry and pulverize them, add deionized water for heating reaction, and filter to obtain green tea extract;向绿茶提取液内加入反应添加剂，然后与硝酸亚铁的水溶液混合搅拌反应，得到反应产物；Adding reaction additives to the green tea extract, then mixing and stirring with the aqueous solution of ferrous nitrate to obtain a reaction product;将反应产物依次进行过滤、洗涤以及干燥，得到纳米铁粉；The reaction product is filtered, washed and dried successively to obtain nano iron powder;所述反应添加剂包括粉末状态的C、Si、Mo、S以及P；The reactive additive includes C, Si, Mo, S and P in powder state;以重量份计算，C、Si、Mo、S以及P的重量满足如下关系式：Calculated in parts by weight, the weights of C, Si, Mo, S and P satisfy the following relation:0.5≤(C+0.3Si)(Mo+10S+2P+0.8)≤0.85。0.5≤(C+0.3Si)(Mo+10S+2P+0.8)≤0.85.
- 根据权利要求2所述的吸附酚类污染物的磁性核壳纳米微球的制备方法，其特征在于，所述反应添加剂的重量占所述绿茶提取液重量的0.5-1％；The method for preparing magnetic core-shell nano-microspheres for adsorbing phenolic pollutants according to claim 2, wherein the weight of the reaction additive accounts for 0.5-1% of the weight of the green tea extract;所述硝酸亚铁的水溶液的重量占所述绿茶提取液重量的5-10％；The weight of the aqueous solution of ferrous nitrate accounts for 5-10% of the weight of the green tea extract;所述硝酸亚铁的水溶液中，硝酸亚铁的重量占水重量的10-15％。In the aqueous solution of ferrous nitrate, the weight of ferrous nitrate accounts for 10-15% of the weight of water.
- 根据权利要求1所述的吸附酚类污染物的磁性核壳纳米微球的制备方法，其特征在于，所述纳米级吸附载体为纳米四氧化三铁；The method for preparing magnetic core-shell nano-microspheres for adsorbing phenolic pollutants according to claim 1, wherein the nano-scale adsorption carrier is nano-iron tetroxide;所述纳米四氧化三铁的制备方法，具体包括：The preparation method of the nanometer iron tetroxide, specifically includes:将三价铁盐硝酸铁溶液与二价铁盐硝酸亚铁溶液按照三价铁离子与二价铁离子的摩尔比为1-2：3-5混合，得到混合铁盐溶液；Mixing the ferric salt ferric nitrate solution and the ferric salt ferrous nitrate solution according to the molar ratio of ferric ions and ferric ions as 1-2:3-5 to obtain a mixed ferric salt solution;将所述混合铁盐溶液加入复合助剂，在155-160℃下水热反应5-6h，得到反应液；The mixed iron salt solution is added to the composite auxiliary, and the hydrothermal reaction is carried out at 155-160 ° C for 5-6 hours to obtain a reaction solution;将所述反应液进行过滤、干燥处理，得到纳米四氧化三铁；The reaction solution is filtered and dried to obtain nano ferric oxide;所述复合助剂包括复合沉淀剂、复合表面活性剂；The composite auxiliary includes a composite precipitant and a composite surfactant;所述复合沉淀剂由抗坏血酸、氢氧化钠和石墨烯组成，按重量比计算，抗坏血酸：氢氧化钠：石墨烯＝1-3:2:5；The composite precipitation agent is composed of ascorbic acid, sodium hydroxide and graphene, and calculated by weight ratio, ascorbic acid: sodium hydroxide: graphene=1-3:2:5;所述复合表面活性剂由油酸、山梨酸钠和柠檬酸钠组成，按重量比计算，油酸：山 梨酸钠：柠檬酸钠＝1:3-5：2；The composite surfactant is composed of oleic acid, sodium sorbate and sodium citrate, and calculated by weight ratio, oleic acid: sodium sorbate: sodium citrate=1:3-5:2;所述复合助剂还包括复合分散剂；The composite auxiliary agent also includes a composite dispersant;所述复合分散剂由硫酸钠和油酸钠组成，按重量比，硫酸钠：油酸钠＝1-5:1。The composite dispersant is composed of sodium sulfate and sodium oleate, and by weight, sodium sulfate:sodium oleate=1-5:1.
- 根据权利要求1所述的吸附酚类污染物的磁性核壳纳米微球的制备方法，其特征在于，所述对所述纳米级吸附载体进行第一次改性，得到第一改性吸附载体，具体包括：The method for preparing magnetic core-shell nano-microspheres for adsorbing phenolic pollutants according to claim 1, wherein the first modification of the nano-scale adsorption carrier is performed to obtain a first modified adsorption carrier , including:将所述纳米级吸附载体放入甲醇溶液中，然后加入第一改性剂，在惰性气氛下，于40-60℃下搅拌反应6-10h，分离得到第一改性吸附载体；Putting the nano-scale adsorption carrier into methanol solution, then adding a first modifier, stirring and reacting at 40-60° C. for 6-10 hours under an inert atmosphere, and separating and obtaining the first modified adsorption carrier;所述第一改性剂由硅烷偶联剂、聚氧乙烯链和氨水组成；The first modifier is composed of a silane coupling agent, a polyoxyethylene chain and ammonia;按体积比，硅烷偶联剂：聚氧乙烯链：氨水为＝5-6:2-4:1。By volume ratio, silane coupling agent: polyoxyethylene chain: ammonia water = 5-6:2-4:1.
- 根据权利要求1所述的吸附酚类污染物的磁性核壳纳米微球的制备方法，其特征在于，所述对所述第一改性吸附载体进行第二次改性，得到第二改性吸附载体，具体包括：The method for preparing magnetic core-shell nano-microspheres for adsorbing phenolic pollutants according to claim 1, wherein the second modification is performed on the first modified adsorption carrier to obtain the second modification Adsorption carriers, including:将所述第一改性吸附载体放入乙醇溶液中，然后加入第二改性剂，在惰性气氛下，于30-50℃下搅拌反应1-3h，分离得到第二改性吸附载体；Putting the first modified adsorption carrier into the ethanol solution, then adding the second modifier, under an inert atmosphere, stirring and reacting at 30-50° C. for 1-3 hours, and separating and obtaining the second modified adsorption carrier;所述第二改性剂由聚乙二醇、乳酸和壳聚糖组成；The second modifier is composed of polyethylene glycol, lactic acid and chitosan;按重量比，聚乙二醇：乳酸：壳聚糖＝5:1-3:2。By weight ratio, polyethylene glycol:lactic acid:chitosan=5:1-3:2.
- 根据权利要求1所述的吸附酚类污染物的磁性核壳纳米微球的制备方法，其特征在于，所述对第二改性吸附载体进行聚合反应，得到磁性核壳纳米微球，具体包括：The method for preparing magnetic core-shell nano-microspheres for adsorbing phenolic pollutants according to claim 1, characterized in that, performing a polymerization reaction on the second modified adsorption carrier to obtain magnetic core-shell nano-microspheres, which specifically comprises the following steps: :以N-乙烯吡咯烷酮为单体，二乙烯苯和丙烯酸甲酯为交联剂，在引发剂偶氮二异丁腈作用下，于60-90℃下在第二改性吸附载体表面发生聚合反应，使得第二改性吸附载体表面包覆一层聚合物，从而得到磁性核壳纳米微球。Using N-vinylpyrrolidone as monomer, divinylbenzene and methyl acrylate as crosslinking agent, under the action of initiator azobisisobutyronitrile, polymerization reaction occurs on the surface of the second modified adsorption carrier at 60-90℃ , so that the surface of the second modified adsorption carrier is coated with a layer of polymer, thereby obtaining magnetic core-shell nano-microspheres.
- 根据权利要求7所述的吸附酚类污染物的磁性核壳纳米微球的制备方法，其特征在于，在第二改性吸附载体表面包覆一层聚合物后，置于浸泡液中在30-40℃下浸泡0.5-1h，然后得到磁性核壳纳米微球；The method for preparing magnetic core-shell nano-microspheres for adsorbing phenolic pollutants according to claim 7, characterized in that, after the surface of the second modified adsorption carrier is coated with a layer of polymer, it is placed in a soaking solution for 30 minutes. Soak at -40℃ for 0.5-1h, and then obtain magnetic core-shell nanospheres;所述浸泡液由柠檬酸钠、海藻酸钠和水组成；The soaking solution is composed of sodium citrate, sodium alginate and water;按重量比，柠檬酸钠：海藻酸钠：水＝1:1:4-6。By weight, sodium citrate: sodium alginate: water=1:1:4-6.
- 一种吸附酚类污染物的磁性核壳纳米微球，其特征在于，采用如权利要求1-8任一项所述的制备方法制备得到；A magnetic core-shell nano-microsphere for adsorbing phenolic pollutants, characterized in that, it is prepared by the preparation method according to any one of claims 1-8;磁性核壳纳米微球的尺寸为50-500nm。The size of the magnetic core-shell nanospheres is 50-500 nm.
- 一种如权利要求9所述的吸附酚类污染物的磁性核壳纳米微球的应用，其特征在于，所述磁性核壳纳米微球用于含有酚类污染物的水体处理。An application of the magnetic core-shell nano-microspheres for adsorbing phenolic pollutants according to claim 9, wherein the magnetic core-shell nano-microspheres are used for the treatment of water bodies containing phenolic pollutants.
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| CN116603514A (en) * | 2023-07-18 | 2023-08-18 | 湖南亿康环保科技有限公司 | Sewage treatment agent for treating groundwater pollution and preparation method thereof |
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| CN112791714B (en) * | 2021-02-20 | 2023-03-17 | 山东省环境保护科学研究设计院有限公司 | Magnetic core-shell nano-microsphere for adsorbing phenolic pollutants, preparation method and application |
| CN114288996A (en) * | 2022-01-11 | 2022-04-08 | 三明医学科技职业学院 | Preparation method of printing and dyeing sewage treatment agent based on biomass |
| CN116272702B (en) * | 2022-11-22 | 2023-09-26 | 广州蔚捷生物医药科技有限公司 | Biological nanometer microsphere and preparation method and application thereof |
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