CN116510700A - 一种磁性海藻酸钠负载金属有机框架复合材料及其制备方法和应用 - Google Patents
一种磁性海藻酸钠负载金属有机框架复合材料及其制备方法和应用 Download PDFInfo
- Publication number
- CN116510700A CN116510700A CN202310108103.9A CN202310108103A CN116510700A CN 116510700 A CN116510700 A CN 116510700A CN 202310108103 A CN202310108103 A CN 202310108103A CN 116510700 A CN116510700 A CN 116510700A
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- China
- Prior art keywords
- sodium alginate
- magnetic
- composite material
- loaded metal
- metal organic
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 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 title claims abstract description 107
- 239000000661 sodium alginate Substances 0.000 title claims abstract description 107
- 235000010413 sodium alginate Nutrition 0.000 title claims abstract description 107
- 229940005550 sodium alginate Drugs 0.000 title claims abstract description 107
- 239000002131 composite material Substances 0.000 title claims abstract description 49
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 40
- 239000002184 metal Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000000126 substance Substances 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 25
- 239000007864 aqueous solution Substances 0.000 claims abstract description 23
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 22
- 150000001868 cobalt Chemical class 0.000 claims abstract description 21
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 20
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 19
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000012924 metal-organic framework composite Substances 0.000 claims abstract description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 235000012239 silicon dioxide Nutrition 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 9
- 238000004140 cleaning Methods 0.000 claims abstract description 7
- 239000011248 coating agent Substances 0.000 claims abstract description 3
- 238000000576 coating method Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 33
- 229910021641 deionized water Inorganic materials 0.000 claims description 33
- 239000002351 wastewater Substances 0.000 claims description 22
- 229940079593 drug Drugs 0.000 claims description 20
- 239000003814 drug Substances 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 20
- MYSWGUAQZAJSOK-UHFFFAOYSA-N ciprofloxacin Chemical compound C12=CC(N3CCNCC3)=C(F)C=C2C(=O)C(C(=O)O)=CN1C1CC1 MYSWGUAQZAJSOK-UHFFFAOYSA-N 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 14
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000004098 Tetracycline Substances 0.000 claims description 9
- 229960002180 tetracycline Drugs 0.000 claims description 9
- 229930101283 tetracycline Natural products 0.000 claims description 9
- 235000019364 tetracycline Nutrition 0.000 claims description 9
- 229910000859 α-Fe Inorganic materials 0.000 claims description 9
- 229960003405 ciprofloxacin Drugs 0.000 claims description 8
- 229940107698 malachite green Drugs 0.000 claims description 7
- GSDSWSVVBLHKDQ-JTQLQIEISA-N Levofloxacin Chemical compound C([C@@H](N1C2=C(C(C(C(O)=O)=C1)=O)C=C1F)C)OC2=C1N1CCN(C)CC1 GSDSWSVVBLHKDQ-JTQLQIEISA-N 0.000 claims description 6
- 229960001193 diclofenac sodium Drugs 0.000 claims description 6
- 229960003376 levofloxacin Drugs 0.000 claims description 6
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 claims description 6
- 229960000907 methylthioninium chloride Drugs 0.000 claims description 6
- JGMJQSFLQWGYMQ-UHFFFAOYSA-M sodium;2,6-dichloro-n-phenylaniline;acetate Chemical compound [Na+].CC([O-])=O.ClC1=CC=CC(Cl)=C1NC1=CC=CC=C1 JGMJQSFLQWGYMQ-UHFFFAOYSA-M 0.000 claims description 6
- 238000011065 in-situ storage Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 4
- 150000003522 tetracyclines Chemical class 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- 239000000356 contaminant Substances 0.000 claims 2
- 101001018064 Homo sapiens Lysosomal-trafficking regulator Proteins 0.000 claims 1
- 102100033472 Lysosomal-trafficking regulator Human genes 0.000 claims 1
- 235000010703 Modiola caroliniana Nutrition 0.000 claims 1
- 244000038561 Modiola caroliniana Species 0.000 claims 1
- 239000001045 blue dye Substances 0.000 claims 1
- 239000001046 green dye Substances 0.000 claims 1
- 238000000527 sonication Methods 0.000 claims 1
- 238000001179 sorption measurement Methods 0.000 abstract description 19
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 12
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 5
- 238000004065 wastewater treatment Methods 0.000 abstract description 5
- 230000015556 catabolic process Effects 0.000 abstract description 3
- 238000006731 degradation reaction Methods 0.000 abstract description 3
- 239000000975 dye Substances 0.000 description 10
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- 238000000926 separation method Methods 0.000 description 8
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- 238000007254 oxidation reaction Methods 0.000 description 7
- 230000008901 benefit Effects 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 239000007800 oxidant agent Substances 0.000 description 6
- 230000001590 oxidative effect Effects 0.000 description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 5
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 150000003254 radicals Chemical class 0.000 description 5
- OFVLGDICTFRJMM-WESIUVDSSA-N tetracycline Chemical compound C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O OFVLGDICTFRJMM-WESIUVDSSA-N 0.000 description 5
- 229960000623 carbamazepine Drugs 0.000 description 4
- FFGPTBGBLSHEPO-UHFFFAOYSA-N carbamazepine Chemical compound C1=CC2=CC=CC=C2N(C(=O)N)C2=CC=CC=C21 FFGPTBGBLSHEPO-UHFFFAOYSA-N 0.000 description 4
- 239000003344 environmental pollutant Substances 0.000 description 4
- 231100000719 pollutant Toxicity 0.000 description 4
- 238000009210 therapy by ultrasound Methods 0.000 description 4
- 230000003213 activating effect Effects 0.000 description 3
- 239000013543 active substance Substances 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 229910001429 cobalt ion Inorganic materials 0.000 description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 3
- 238000004132 cross linking Methods 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 239000000696 magnetic material Substances 0.000 description 3
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000012922 MOF pore Substances 0.000 description 2
- 239000003463 adsorbent Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000648 calcium alginate Substances 0.000 description 2
- 235000010410 calcium alginate Nutrition 0.000 description 2
- 229960002681 calcium alginate Drugs 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- OKHHGHGGPDJQHR-YMOPUZKJSA-L calcium;(2s,3s,4s,5s,6r)-6-[(2r,3s,4r,5s,6r)-2-carboxy-6-[(2r,3s,4r,5s,6r)-2-carboxylato-4,5,6-trihydroxyoxan-3-yl]oxy-4,5-dihydroxyoxan-3-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylate Chemical compound [Ca+2].O[C@@H]1[C@H](O)[C@H](O)O[C@@H](C([O-])=O)[C@H]1O[C@H]1[C@@H](O)[C@@H](O)[C@H](O[C@H]2[C@H]([C@@H](O)[C@H](O)[C@H](O2)C([O-])=O)O)[C@H](C(O)=O)O1 OKHHGHGGPDJQHR-YMOPUZKJSA-L 0.000 description 2
- HVYWMOMLDIMFJA-DPAQBDIFSA-N cholesterol Chemical compound C1C=C2C[C@@H](O)CC[C@]2(C)[C@@H]2[C@@H]1[C@@H]1CC[C@H]([C@H](C)CCCC(C)C)[C@@]1(C)CC2 HVYWMOMLDIMFJA-DPAQBDIFSA-N 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
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- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 241000512259 Ascophyllum nodosum Species 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 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
- 229930195725 Mannitol Natural products 0.000 description 1
- 206010043275 Teratogenicity Diseases 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- 229940035674 anesthetics Drugs 0.000 description 1
- 239000003242 anti bacterial agent Substances 0.000 description 1
- 230000003556 anti-epileptic effect Effects 0.000 description 1
- 229940088710 antibiotic agent Drugs 0.000 description 1
- 239000001961 anticonvulsive agent Substances 0.000 description 1
- 229960003965 antiepileptics Drugs 0.000 description 1
- 229940125715 antihistaminic agent Drugs 0.000 description 1
- 239000000739 antihistaminic agent Substances 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 235000012000 cholesterol Nutrition 0.000 description 1
- 229940107161 cholesterol Drugs 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005202 decontamination Methods 0.000 description 1
- 230000003588 decontaminative effect Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000010840 domestic wastewater Substances 0.000 description 1
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- 238000003912 environmental pollution Methods 0.000 description 1
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- 239000007789 gas Substances 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000003193 general anesthetic agent Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000007885 magnetic separation Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 238000007726 management method Methods 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 229940021182 non-steroidal anti-inflammatory drug Drugs 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000211 teratogenicity Toxicity 0.000 description 1
- 231100001234 toxic pollutant Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 239000013153 zeolitic imidazolate framework Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/24—Naturally occurring macromolecular compounds, e.g. humic acids or their derivatives
-
- 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
-
- 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
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/36—Organic compounds containing halogen
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
-
- 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
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Abstract
本发明属于废水处理技术领域,具体涉及一种磁性海藻酸钠负载金属有机框架复合材料及其制备方法和应用。该复合材料的制备包括:(1)用正硅酸乙酯对清洗后的磁性物质进行包覆,清洗干燥后得到二氧化硅包覆磁性物质;(2)将(1)所得的二氧化硅包覆磁性物质加入到海藻酸钠水溶液中,得到混合溶液A;(3)将(2)所得的混合溶液A滴入无水氯化钙水溶液中,得到磁性海藻酸钠;(4)将(3)所得的磁性海藻酸钠加入可溶性钴盐水溶液,将得到的紫黑色材料移至2‑甲基咪唑的无水乙醇溶液中,得到磁性海藻酸钠负载金属有机框架复合材料。该复合材料可对水中难降解有机污染物实现高效吸附和催化降解,应用于污染水体的净化与修复。
Description
技术领域
本发明属于废水处理技术领域,具体涉及一种磁性海藻酸钠负载金属有机框架复合材料及其制备方法和应用。
背景技术
随着人口数量的迅速增长和城市化进程的加快发展,大量含有难降解有机污染物的工业废水和城市生活污水被排入不同的接收介质中。染料是废水中的典型有机污染物,其一直是水环境污染研究领域的热点。染料废水的色泽较深,会减少水体的光透过性,致使水中光合细菌和水生植物的光合作用受阻,破坏水体生态环境。染料废水的有毒物质还对人类的生命健康带来不可逆转的危害,包括致畸、致癌和致突变。另外,抗生素、非甾体抗炎药、抗癫痫药、抗组胺剂、麻醉药和胆固醇等药物在不同水环境中被频繁检测出现,已成为环境水生基质中的潜在污染物。高产量、高消耗以及通过传统处理工艺/废水处理厂去除的有限,是世界范围内药物化合物在废水和水生环境中出现的主要原因。水生环境中存在的难降解药物会对水生生物的健康和生态系统的平衡产生严重威胁。因此,如何有效地处理染料废水和药物废水是环境治理研究的重点和难点,对于保障水安全和水资源的可持续发展具有重要的意义。
吸附法因具有操作灵活、成本低、无二次污染和吸附剂来源广泛等优点而被广泛研究和应用,是一种比较有吸引力的水体净化技术。但吸附法对于某些微量的(mg/L或ng/L)药物类污染物的吸附效果并不理想。为了克服这一缺点,能够产生活性物质的高级氧化技术(AOP)被开发出来,AOP也被认为是一种很有前景的废水处理技术。海藻酸钠是一种从海带或马尾藻中提取碘和甘露醇后的副产物,也是一种线性的生物聚合物,具有生物相容性高、生物可降解、可再生和胶凝作用等特性。其主链上分布着丰富的羟基和羧基官能团,这些官能团不仅能与废水中污染物相互作用,还能进行物理或化学修饰而引入别的功能化基团,是一种理想的生物基水处理材料,但也存在吸附能力有限、固液分离效率低等缺点。磁性材料具有磁性易分离的优点,在磁场的作用下能够从溶液中实现快速分离。将磁性材料和海藻酸钠结合制得的磁性海藻酸钠吸附剂具有易磁分离和易功能化的优点,在废水处理领域具有广阔的前景。
金属有机框架(MOFs)是一种独特的结晶多孔有机/无机杂化材料,由金属离子/簇和有机配体自组装而成。MOFs由于其在化学和结构上的可调性质,在气体捕获和分离、催化、传感和药物递送等领域显示出巨大的应用潜力。此外,MOFs具有丰富的配位不饱和位点、高比表面积和多孔特性,为水中痕量污染物的吸附提供了多种可能性。沸石-咪唑酸盐骨架(ZIF)是一种具有沸石拓扑结构的新型多孔MOFs,它的配体为咪唑或其衍生物。因此ZIF结合了MOFs和沸石的许多优点,包括制备简单、比表面积大、孔隙率组织良好、结构和孔径可调等。ZIF-67是由钴离子和2-甲基咪唑通过配位键构建的ZIF。然而在水处理领域,纳米级的ZIF-67存在分散性差、分离困难等缺点,这限制了它的适用性。为了克服这些缺陷,需要将其固定在适合的基质上。另外,已有研究表明,ZIF-67可作为AOP体系中的催化剂,活化自由基前驱体产生高活性的自由基,从而快速降解废水中有毒污染物。但查阅文献后发现,目前现有技术中没有关于磁性海藻酸钠负载ZIF-67复合材料催化自由基前驱体产生自由基氧化有机污染物的性能的报道。
发明内容
本发明提供一种磁性海藻酸钠负载金属有机框架复合材料的制备方法,该方法通过自组装法在磁性海藻酸钠上原位负载ZIF-67,得到磁性海藻酸钠负载金属有机框架复合材料,该方法具有工艺简单,操作方便,生产成本低等特点,所制备得到的复合材料具有吸附能力强、固液分离效率高、可循环利用以及催化效率高的优点,有效地提高了磁性海藻酸钠负载金属有机框架复合材料对有机污染物的去除性能;其可对水中难降解有机污染物实现高效吸附和催化降解,应用于污染水体的净化与修复。
本发明的目的还在于提供上述原材料价格低廉、可生物降解、环境友好的磁性海藻酸钠负载金属有机框架复合材料在处理难降解有机废水中的应用,该复合材料对有机污染物的吸附容量高、吸附时间短以及催化效率好。
实现本发明目的的技术方案是:
一种磁性海藻酸钠负载金属有机框架复合材料,其是在磁性海藻酸钠表面原位负载ZIF-67得到的复合材料,该复合材料是以海藻酸钠、二氧化硅包覆磁性物质、可溶性钴盐和2-甲基咪唑为原料,经混合搅拌、交联反应、自发组装、固液分离和洗涤干燥的简单工艺得到。
所述的磁性海藻酸钠负载金属有机框架复合材料的制备方法,包括如下具体步骤:
(1)用正硅酸乙酯对清洗后的磁性物质进行包覆,清洗、干燥后得到二氧化硅包覆磁性物质。具体为:
用盐酸对的磁性物质进行预处理后,将其移至装有氨水、去离子水和无水乙醇的体积之比为10mL:200mL:400mL的混合液中进行超声处理,再添加正硅酸乙酯,搅拌12~24h后用无水乙醇和去离子水洗涤数次,干燥后得到二氧化硅包覆磁性物质;
其中:所述的盐酸的浓度为0.1mol/L;所述的磁性物质为四氧化三铁、铁酸钴、铁酸锰或铁酸铜;磁性物质和正硅酸乙酯的比例为0.5~2g:2~12mL;所述的预处理是将磁性物质用盐酸进行浸泡,以清洗磁性物质表面的污渍;所述超声处理的目的是为了促进磁性物质在混合溶液中均匀分散。
(2)按照海藻酸钠的质量:去离子水的体积之比为0.5~2g:100mL的比例,将海藻酸钠溶解到去离子水中,充分搅拌后得到海藻酸钠水溶液;
(3)将(1)所得的二氧化硅包覆磁性物质加入(2)所得的海藻酸钠水溶液中,搅拌12~24h后得到混合溶液A;
其中,磁性物质和海藻酸钠的质量比为:0.5~2:0.5~2;搅拌的转速为800rpm/min;
(4)按照无水氯化钙的质量:去离子水的体积之比为0.5~3g:100mL的比例,将无水氯化钙溶解到去离子水中,充分搅拌后得到无水氯化钙水溶液。将(3)所得的混合溶液A滴入无水氯化钙水溶液中,继续搅拌12~24h后用去离子水洗涤多次,得到磁性海藻酸钠;
其中,海藻酸钠和无水氯化钙的质量比为0.5~2:0.5~3。无水氯化钙的在本步骤中起交联作用,水溶性的海藻酸钠与金属钙离子混合后,金属钙离子可以和溶液中的钠离子发生离子置换反应,生成海藻酸钙的凝胶小球。二氧化硅包覆磁性物质和海藻酸钙凝胶可能会通过氢键作用结合。
(5)按照可溶性钴盐的质量:去离子水的体积之比为1~3g:100mL的比例,将可溶性钴盐溶解到去离子水中,充分搅拌后得到可溶性钴盐水溶液;
其中:所述的可溶性钴盐为硝酸钴、氯化钴或乙酸钴;
(6)按照2-甲基咪唑的质量:无水乙醇的体积之比为1~3g:100mL的比例,将2-甲基咪唑溶解到无水乙醇中,充分搅拌后得到2-甲基咪唑的无水乙醇溶液;
(7)将(4)所得的磁性海藻酸钠加入(5)所得的可溶性钴盐水溶液搅拌12~24h,用去离子水清洗多次后,将得到的紫黑色材料移至(6)所得的2-甲基咪唑的无水乙醇溶液中,继续搅拌12~24h,然后用无水乙醇和去离子水依次洗涤,干燥后得到磁性海藻酸钠负载金属有机框架(ZIF-67)的复合材料;本步骤中,磁性海藻酸钠作为基质;磁性海藻酸钠吸附金属钴离子后,磁性海藻酸钠表面金属钴离子和溶液中的2-甲基咪唑通过自组装法在其表面原位合成ZIF-67,从而得到磁性海藻酸钠负载ZIF-67复合材料。
其中,海藻酸钠、可溶性钴盐、2-甲基咪唑的质量比为:0.5~2:1~3:1~3。
本发明还提供了一种上述磁性海藻酸钠负载金属有机框架复合材料在含难降解有机污染物废水处理中的应用。其中,所述难降解有机污染物为:四环素(TC)药物、马西平(CBZ)药物、亚甲基蓝(MB)染料、环丙沙星(CIP)药物、孔雀石绿(MG)染料、双氯酚酸钠(DS)药物、碱性品绿-4(BG-4)或左氧氟沙星(LFX)药物。
相比现有技术,本发明至少具有以下有益效果:
(1)本发明采用价格低廉、可生物降解和环境友好的海藻酸钠作为基质,在磁性海藻酸钠的表面原位合成ZIF-67,从结构上根本改善了磁性海藻酸钠与金属有机框架(ZIF-67)的结合方式,使得作为载体的磁性海藻酸钠与作为活性物质的ZIF-67结合成一个整体,有利于促进ZIF-67与磁性海藻酸钠的结合紧密性,从根本上解决了ZIF-67纳米颗粒在水溶液中的分散性难题,遏制了ZIF-67纳米颗粒之间的团聚现象,为ZIF-67活性物质的高效利用提供了有利条件。
(2)本发明制备的磁性海藻酸钠负载金属有机框架的活性位点丰富、比表面积大,对废水中有机污染物的吸附容量大,吸附速率快,吸附量和吸附速率都远高于磁性海藻酸钠,大幅提高了磁性海藻酸钠微粒的吸附性能。
(3)本发明制备的磁性海藻酸钠负载金属有机框架复合材料中的金属活性位点可以高效活化氧化剂,产生具有攻击有机污染物能力的活性自由基,将有机污染物氧化成低分子的物质,甚至最终氧化成无毒性的水和二氧化碳。
(4)本发明制备的磁性海藻酸钠负载金属有机框架复合材料在环境中易生物降解,易回收,可循环使用,经多次吸附解吸或催化降解后仍具有较好的脱污效果,实现了复合材料的再生利用。
(5)本发明方法所采用混合搅拌、交联反应、固液分离以及洗涤干燥制备磁性海藻酸钠负载金属有机框架复合材料,工艺简单,操作方便,生产效率高,环境负担小,有利于大规模化生产。
(6)本发明制备的磁性海藻酸钠负载金属有机框架复合材料,不仅减轻了工业提纯副产物海藻酸钠对环境的污染,同时提供了利用海藻酸钠的新途径,提高了海藻酸钠的利用价值,实现了工业提纯副产物高效的资源化利用,为生态环境保护做出了贡献。
附图说明
图1为实施例1制备出的磁性海藻酸钠负载金属有机框架复合材料的SEM电镜图一。
图2为实施例1制备出的磁性海藻酸钠负载金属有机框架复合材料的SEM电镜图二。
具体实施方式
下面结合具体实施方式,进一步说明本发明。
实施例1
本实施例提供了一种磁性海藻酸钠负载金属有机框架复合材料的制备方法,包括如下步骤:
(1)用0.1mol/L盐酸预处理1g的磁性物质,然后将其移至装有氨水、去离子水和无水乙醇的体积之比为10mL:200mL:400mL的混合液中进行超声处理,再添加8mL的正硅酸乙酯,搅拌12h后用无水乙醇和去离子水洗涤数次,干燥后得到二氧化硅包覆磁性物质;
其中:所述的磁性物质为四氧化三铁;所述预处理具体为:将磁性物质加入盐酸并超声15min,然后用去离子水清洗磁性物质,直到清洗液为中性液体。
(2)将1g海藻酸钠溶解到100mL去离子水中,充分搅拌后得到海藻酸钠水溶液;
(3)将(1)所得的二氧化硅包覆磁性物质加入(2)所得的海藻酸钠水溶液中,以800rpm/min的转速搅拌12h后得到混合溶液A;
(4)将2g无水氯化钙溶解到100mL去离子水中,充分搅拌后得到无水氯化钙水溶液。将(3)所得的混合溶液A滴入无水氯化钙水溶液中,继续搅拌12h后用去离子水洗涤多次,得到磁性海藻酸钠;
(5)将1.5g可溶性钴盐溶解到100mL去离子水中,充分搅拌后得到可溶性钴盐水溶液;
其中:所述的可溶性钴盐为硝酸钴;
(6)将1.5g的2-甲基咪唑溶解到100mL无水乙醇中,充分搅拌后得到2-甲基咪唑的无水乙醇溶液;
(7)将(4)所得的磁性海藻酸钠加入(5)所得的硝酸钴水溶液搅拌12h,用去离子水清洗多次后,将得到的紫黑色材料移至(6)所得的2-甲基咪唑的无水乙醇溶液,继续搅拌12h,然后用无水乙醇和去离子水依次洗涤,干燥后得到磁性海藻酸钠负载金属有机框架(ZIF-67)的复合材料。
使用本实施例所制备的磁性海藻酸钠负载金属有机框架复合材料处理四环素(TC)药物废水(浓度为100mg/L),最佳条件(温度为45℃,pH=6.5,磁性海藻酸钠负载金属有机框架复合材料的用量为0.5g/L)下其对TC的吸附容量为156.19mg/g。
使用本实施例所制备的磁性海藻酸钠负载金属有机框架复合材料活化过一硫酸盐降解卡马西平(CBZ)药物废水(浓度为10mg/L),最佳条件(温度为45℃,pH=7.0,磁性海藻酸钠负载金属有机框架复合材料的用量为0.1g/L,氧化剂(过硫酸氢钾)的浓度为0.5mM)下其对CBZ的氧化效率为91.44%。
实施例2
一种磁性海藻酸钠负载金属有机框架复合材料的制备方法,基本同实施例1,其中:
第(1)步中,磁性物质用量为1.5g,正硅酸乙酯的用量为6mL,搅拌时间为18h。其中:所述的磁性物质为铁酸钴;
第(2)步中,将1.5g海藻酸钠溶解到100mL去离子水中;
第(3)步中,搅拌18h后得到混合溶液A;
第(4)步中,将1.5g无水氯化钙溶解到100mL去离子水中;将混合溶液A滴入无水氯化钙水溶液中搅拌18h;
第(5)步中,将2g可溶性钴盐溶解到100mL去离子水中。其中:所述的可溶性钴盐为乙酸钴;
第(6)步中,将2g的2-甲基咪唑溶解到100mL无水乙醇中;
第(7)步中,搅拌时间都为18h。
使用本实施例所制备的磁性海藻酸钠负载金属有机框架复合材料处理亚甲基蓝(MB)染料废水(浓度为100mg/L),最佳条件(温度为45℃,pH=10,磁性海藻酸钠负载金属有机框架复合材料的用量为0.5g/L)下其对MB的吸附容量为225.4mg/g。
使用本实施例所制备的磁性海藻酸钠负载金属有机框架复合材料活化过一硫酸盐降解环丙沙星(CIP)药物废水(浓度为10mg/L),最佳条件(温度为45℃,pH=7.0,磁性海藻酸钠负载金属有机框架复合材料的用量为0.1g/L,氧化剂(过硫酸氢钾)的浓度为0.5mM)下其对CIP的氧化效率为93.15%。
实施例3
一种磁性海藻酸钠负载金属有机框架复合材料的制备方法,基本同实施例1,其中:
第(1)步中,磁性物质的用量为2g,正硅酸乙酯的用量为10mL,搅拌时间为24h。其中:所述的磁性物质为铁酸铜;
第(2)步中,将1g海藻酸钠溶解到100mL去离子水中;
第(3)步中,搅拌24h后得到混合溶液A;
第(4)步中,将1g无水氯化钙溶解到100mL去离子水中;将混合溶液A滴入无水氯化钙水溶液中搅拌24h;
第(5)步中,将1g可溶性钴盐溶解到100mL去离子水中。其中:所述的可溶性钴盐为氯化钴;
第(6)步中,将1g的2-甲基咪唑溶解到100mL无水乙醇中;
第(7)步中,搅拌时间都为24h。
使用本实施例所制备的磁性海藻酸钠负载金属有机框架复合材料处理孔雀石绿(MG)染料废水(浓度为100mg/L),最佳条件(温度为45℃,pH=6.0,磁性海藻酸钠负载金属有机框架复合材料的用量为0.5g/L)下其对MG的吸附容量为189.6mg/g。
使用本实施例所制备的磁性海藻酸钠负载金属有机框架复合材料活化过一硫酸盐降解双氯酚酸钠(DS)药物废水(浓度为10mg/L),最佳条件(温度为45℃,pH=7.0,磁性海藻酸钠负载金属有机框架复合材料的用量为0.1g/L,氧化剂(过硫酸氢钾)的浓度为0.5mM)下其对DS的氧化效率为94.25%。
实施例4
一种磁性海藻酸钠负载金属有机框架复合材料的制备方法,基本同实施例1,其中:
第(1)步中,磁性物质的用量为0.5g,正硅酸乙酯的用量为4mL,搅拌时间为18h。其中:所述的磁性物质为铁酸锰;
第(2)步中,将0.5g海藻酸钠溶解到100mL去离子水中;
第(3)步中,搅拌18h后得到混合溶液A;
第(4)步中,将0.5g无水氯化钙溶解到100mL去离子水中;将混合溶液A滴入无水氯化钙水溶液中搅拌24h;
第(5)步中,将2.5g可溶性钴盐溶解到100mL去离子水中。其中:所述的可溶性钴盐为硝酸钴;
第(6)步中,将2.5g的2-甲基咪唑溶解到100mL无水乙醇中;
第(7)步中,搅拌时间都为12h;
使用本实施例所制备的磁性海藻酸钠负载金属有机框架复合材料处理碱性品绿-4(BG-4)染料废水(浓度为100mg/L),最佳条件(温度为45℃,pH=6.0,磁性海藻酸钠负载金属有机框架复合材料的用量为0.5g/L)下其对BG-4的吸附容量为177.5mg/g。
使用本实施例所制备的磁性海藻酸钠负载金属有机框架复合材料活化过一硫酸盐降解左氧氟沙星(LFX)药物废水(浓度为10mg/L),最佳条件(温度为45℃,pH=7.0,磁性海藻酸钠负载金属有机框架复合材料的用量为0.1g/L,氧化剂(过硫酸氢钾)的浓度为0.5mM)下其对LFX的氧化效率为93.28%。
实施例5
一种磁性海藻酸钠负载金属有机框架复合材料的制备方法,基本同实施例1,其中:
第(1)步中,磁性物质的用量为1g,正硅酸乙酯的用量为8mL,搅拌时间为12h。其中:所述的磁性物质为四氧化三铁;
第(2)步中,将2g海藻酸钠溶解到100mL去离子水中;
第(3)步中,搅拌12h后得到混合溶液A;
第(4)步中,将2g无水氯化钙溶解到100mL去离子水中;将混合溶液A滴入无水氯化钙水溶液中搅拌12h;
第(5)步中,将3g可溶性钴盐溶解到100mL去离子水中。其中:所述的可溶性钴盐为硝酸钴;
第(6)步中,将3g的2-甲基咪唑溶解到100mL无水乙醇中;
第(7)步中,搅拌时间都为18h;
使用本实施例所制备的磁性海藻酸钠负载金属有机框架复合材料处理环丙沙星(CIP)染料废水(浓度为100mg/L),最佳条件(温度为45℃,pH=6.0,磁性海藻酸钠负载金属有机框架复合材料的用量为0.5g/L)下其对CIP的吸附容量为158.4mg/g。
使用本实施例所制备的磁性海藻酸钠负载金属有机框架复合材料活化过一硫酸盐降解四环素(TC)药物废水(浓度为10mg/L),最佳条件(温度为45℃,pH=7.0,磁性海藻酸钠负载金属有机框架复合材料的用量为0.1g/L,氧化剂(过硫酸氢钾)的浓度为0.5mM)下其对TC的氧化效率为92.15%。
以上所述是本发明的实施方式的举例,应当指出,对于所属技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和变型。凡是属于本发明的技术方案所引申出的显而易见的变化或变动仍处于本发明的保护范围之列。
Claims (10)
1.一种磁性海藻酸钠负载金属有机框架复合材料,其特征在于,所述复合材料是在磁性海藻酸钠表面原位负载ZIF-67后得到。
2.权利要求1所述的磁性海藻酸钠负载金属有机框架复合材料的制备方法,其特征在于,包括如下步骤:
(1)用正硅酸乙酯对清洗后的磁性物质进行包覆,清洗、干燥后得到二氧化硅包覆磁性物质;
(2)将(1)所得的二氧化硅包覆磁性物质加入到5~20g/L海藻酸钠水溶液中,搅拌后得到混合溶液A;
(3)将(2)所得的混合溶液A滴入5~30g/L无水氯化钙水溶液中,搅拌、洗涤,得到磁性海藻酸钠;
(4)将(3)所得的磁性海藻酸钠加入10~30g/L可溶性钴盐水溶液,搅拌、清洗,将得到的紫黑色材料移至10~30g/L的2-甲基咪唑的无水乙醇溶液中,搅拌、洗涤,干燥后得到磁性海藻酸钠负载金属有机框架复合材料。
3.根据权利要求2所述的制备方法,其特征在于,步骤(1)中所述的磁性物质为四氧化三铁、铁酸钴、铁酸锰或铁酸铜。
4.根据权利要求2所述的制备方法,其特征在于,步骤(1)中所述清洗后的磁性物质中的清洗为:用盐酸对磁性物质进行预处理后,将其移至氨水、去离子水和无水乙醇的体积之比为10mL:200mL:400mL的混合液中进行超声处理。
5.根据权利要求4所述的制备方法,其特征在于,所述的盐酸的浓度为0.1mol/L;磁性物质和正硅酸乙酯的比例为0.5~2g:2~12mL。
6.根据权利要求2所述的制备方法,其特征在于,磁性物质和海藻酸钠的质量比为:0.5~2:0.5~2。
7.根据权利要求2所述的制备方法,其特征在于,海藻酸钠和无水氯化钙的质量比为0.5~2:0.5~3。
8.根据权利要求2所述的制备方法,其特征在于,海藻酸钠、可溶性钴盐、2-甲基咪唑的质量比为:0.5~2:1~3:1~3。
9.权利要求1所述的复合材料在含有机污染物废水处理中的应用。
10.根据权利要求9所述的应用,其特征在于,所述有机污染物为:四环素药物、马西平药物、亚甲基蓝染料、环丙沙星药物、孔雀石绿染料、双氯酚酸钠药物、碱性品绿-4或左氧氟沙星药物。
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