CN115430426B - Nickel-iron bimetallic oxide modified biochar catalyst and preparation method and application thereof - Google Patents
Nickel-iron bimetallic oxide modified biochar catalyst and preparation method and application thereof Download PDFInfo
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- CN115430426B CN115430426B CN202210899005.7A CN202210899005A CN115430426B CN 115430426 B CN115430426 B CN 115430426B CN 202210899005 A CN202210899005 A CN 202210899005A CN 115430426 B CN115430426 B CN 115430426B
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- catalyst
- nickel
- oxide modified
- modified biochar
- ferronickel
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- 239000003054 catalyst Substances 0.000 title claims abstract description 146
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 title claims description 28
- 229910000863 Ferronickel Inorganic materials 0.000 claims abstract description 96
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 53
- 230000003197 catalytic effect Effects 0.000 claims abstract description 50
- 238000011282 treatment Methods 0.000 claims abstract description 49
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 48
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 38
- 239000001301 oxygen Substances 0.000 claims abstract description 37
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 25
- 239000002028 Biomass Substances 0.000 claims abstract description 21
- 238000001354 calcination Methods 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 77
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 62
- 239000004098 Tetracycline Substances 0.000 claims description 47
- 235000019364 tetracycline Nutrition 0.000 claims description 47
- 229960002180 tetracycline Drugs 0.000 claims description 45
- 229930101283 tetracycline Natural products 0.000 claims description 45
- 238000006731 degradation reaction Methods 0.000 claims description 44
- 150000003522 tetracyclines Chemical class 0.000 claims description 41
- 238000000034 method Methods 0.000 claims description 38
- 239000003242 anti bacterial agent Substances 0.000 claims description 34
- 229940088710 antibiotic agent Drugs 0.000 claims description 34
- 230000015556 catabolic process Effects 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 25
- 230000003115 biocidal effect Effects 0.000 claims description 19
- 229910052742 iron Inorganic materials 0.000 claims description 16
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 15
- 235000013399 edible fruits Nutrition 0.000 claims description 15
- 230000008569 process Effects 0.000 claims description 15
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 239000002351 wastewater Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 11
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 9
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 9
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 238000004140 cleaning Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 239000000463 material Substances 0.000 claims description 7
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 7
- 238000007873 sieving Methods 0.000 claims description 7
- 150000002815 nickel Chemical class 0.000 claims description 6
- 229910000480 nickel oxide Inorganic materials 0.000 claims description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims description 5
- 230000000630 rising effect Effects 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 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 4
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 229910002555 FeNi Inorganic materials 0.000 claims description 3
- 239000002245 particle Substances 0.000 claims description 3
- KIPLYOUQVMMOHB-MXWBXKMOSA-L [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O Chemical compound [Ca++].CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O.CN(C)[C@H]1[C@@H]2[C@@H](O)[C@H]3C(=C([O-])[C@]2(O)C(=O)C(C(N)=O)=C1O)C(=O)c1c(O)cccc1[C@@]3(C)O KIPLYOUQVMMOHB-MXWBXKMOSA-L 0.000 claims description 2
- 229940106691 bisphenol a Drugs 0.000 claims description 2
- CYDMQBQPVICBEU-UHFFFAOYSA-N chlorotetracycline Natural products C1=CC(Cl)=C2C(O)(C)C3CC4C(N(C)C)C(O)=C(C(N)=O)C(=O)C4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-UHFFFAOYSA-N 0.000 claims description 2
- 229960004475 chlortetracycline Drugs 0.000 claims description 2
- CYDMQBQPVICBEU-XRNKAMNCSA-N chlortetracycline Chemical compound C1=CC(Cl)=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(O)=C(C(N)=O)C(=O)[C@@]4(O)C(O)=C3C(=O)C2=C1O CYDMQBQPVICBEU-XRNKAMNCSA-N 0.000 claims description 2
- 235000019365 chlortetracycline Nutrition 0.000 claims description 2
- 229960003405 ciprofloxacin Drugs 0.000 claims description 2
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 2
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000010802 sludge Substances 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 239000010902 straw Substances 0.000 claims description 2
- 229940063650 terramycin Drugs 0.000 claims description 2
- 244000269722 Thea sinensis Species 0.000 claims 1
- 240000001398 Typha domingensis Species 0.000 claims 1
- 239000003610 charcoal Substances 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 16
- 230000008901 benefit Effects 0.000 abstract description 12
- 150000004706 metal oxides Chemical class 0.000 abstract description 11
- 238000000197 pyrolysis Methods 0.000 abstract description 11
- 239000002957 persistent organic pollutant Substances 0.000 abstract description 10
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 6
- 230000003213 activating effect Effects 0.000 abstract description 5
- 230000008878 coupling Effects 0.000 abstract description 5
- 238000010168 coupling process Methods 0.000 abstract description 5
- 238000005859 coupling reaction Methods 0.000 abstract description 5
- 229910052759 nickel Inorganic materials 0.000 description 18
- 230000010355 oscillation Effects 0.000 description 13
- 230000000052 comparative effect Effects 0.000 description 11
- 241001122767 Theaceae Species 0.000 description 9
- 238000006243 chemical reaction Methods 0.000 description 9
- 238000003359 percent control normalization Methods 0.000 description 8
- 238000001179 sorption measurement Methods 0.000 description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 6
- 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 6
- 241000526900 Camellia oleifera Species 0.000 description 5
- 241000233948 Typha Species 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- -1 nickel metal oxide Chemical class 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 235000013980 iron oxide Nutrition 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 230000002085 persistent effect Effects 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 238000005265 energy consumption Methods 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 238000005485 electric heating Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- VBMVTYDPPZVILR-UHFFFAOYSA-N iron(2+);oxygen(2-) Chemical class [O-2].[Fe+2] VBMVTYDPPZVILR-UHFFFAOYSA-N 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000000051 modifying effect Effects 0.000 description 2
- 238000011369 optimal treatment Methods 0.000 description 2
- 125000000962 organic group Chemical group 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 229940040944 tetracyclines Drugs 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 2
- 208000035143 Bacterial infection Diseases 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 241000282412 Homo Species 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000035508 accumulation Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 208000022362 bacterial infectious disease Diseases 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 229940068911 chloride hexahydrate Drugs 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000010419 fine particle Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- VOAPTKOANCCNFV-UHFFFAOYSA-N hexahydrate;hydrochloride Chemical compound O.O.O.O.O.O.Cl VOAPTKOANCCNFV-UHFFFAOYSA-N 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 230000005415 magnetization Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000008239 natural water Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000013307 optical fiber Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 238000000844 transformation Methods 0.000 description 1
- 239000002699 waste material 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0213—Preparation of the impregnating solution
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/088—Decomposition of a metal salt
-
- 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
- C02F2101/38—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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a ferronickel bimetallic oxide modified biochar catalyst and a preparation method and application thereof, wherein the preparation method of the catalyst comprises the following steps: impregnating biomass to Ni-containing 2+ And Fe (Fe) 3+ The mixed solution of the catalyst is subjected to low-oxygen baking treatment and calcination to obtain the biochar precursor, and the ferronickel bimetallic oxide modified biochar catalyst is obtained. The invention adopts low-oxygen baking coupling pyrolysis to prepare the modified biochar catalyst for the first time, and the prepared ferronickel bimetallic oxide modified biochar catalyst has higher content of ferronickel metal oxide, better load stability, very high-efficiency electron transfer capability and very excellent catalytic performance, has the advantages of stable structure, strong catalytic activity, environment friendliness and the like, can be used for activating persulfate to degrade organic pollutants in water, has very excellent removal effect, has no secondary pollution, has higher use value in the aspect of treating polluted water, and has wide application prospect.
Description
Technical Field
The invention belongs to the technical field of catalyst materials, relates to a nickel-iron bimetal oxide modified biochar catalyst, a preparation method and application thereof, and in particular relates to a method for preparing the nickel-iron bimetal oxide modified biochar catalyst by low-oxygen baking coupling pyrolysis and application of the nickel-iron bimetal oxide modified biochar catalyst in treating antibiotic wastewater.
Background
Antibiotics have been widely used in the animal and human medical fields to prevent and treat bacterial infections. However, antibiotics exist in large amounts stably for a long period in the environment due to the complexity and nondegradability of the structure of the antibiotics themselves. In addition, antibiotics are also biotoxic and can pose a serious threat to humans and the ecosystem through environmental transformations and accumulation and transmission of food chains, and it is seen that the use of even abused antibiotics in large quantities has become an alarming emerging contaminant.
At present, the treatment methods for the antibiotics organic pollutants in the environment mainly comprise an adsorption method, an acousto-optic and electric heating technology and the like, and the methods have defects, such as the adsorption method, only can realize the transfer of antibiotics, but can not effectively decompose the antibiotics, and the treatment efficiency is low, and the adsorbent after adsorbing the antibiotics is used as a waste and has secondary pollution risk; the acousto-optic and electric heating technology has high energy consumption cost, strict technical condition requirements and complex operation. Thus, the prior art for the treatment of antibiotic-based organic pollutants in the environment generally suffers from the following drawbacks: (1) high production cost; (2) the technical route is complex, and the operation difficulty is high; (3) secondary pollution may be caused; (4) Some existing technologies have high requirements on reaction conditions and high energy consumption, and cannot be popularized and used on a large scale; (5) The reaction rate is slow, the time is long, the efficiency is low, and the result is unstable. In addition, advanced oxidation systems using biochar as a catalyst and persulfate as an oxidant are receiving increasing attention, however, the following drawbacks still exist in the used biochar-based catalysts when the advanced persulfate-based oxidation technology is used for treating organic pollutants in water: the degradation system of the persulfate activated by the biochar-based catalyst is still difficult to realize efficient and complete removal of organic pollutants and has poor adaptability when being used for treating pollutants in water. In addition, the metal oxide modified biochar catalyst prepared by the conventional method still has the following defects: the metal oxide is difficult to stably load on the biochar, the catalytic performance is poor due to the fact that the load of the metal oxide is small, the catalytic performance is poor due to the fact that the metal oxide is easy to fall off from the biochar, the secondary pollution problem is easy to occur, meanwhile, the conventional preparation method is easy to damage the structure of the biochar with the catalytic performance, the catalytic performance of the conventional metal oxide modified biochar catalyst is still poor, and therefore persulfate is difficult to effectively activate, and organic pollutants in a water body are difficult to efficiently and thoroughly remove.
Therefore, the biochar-based catalyst with stable structure and strong catalytic activity is obtained, and has important significance for effectively activating persulfate and realizing high-efficiency degradation of antibiotics and effectively relieving environmental pollution caused by the antibiotics.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a preparation method of a nickel-iron bimetal oxide modified biochar catalyst with excellent catalytic performance and high stability and application of the nickel-iron bimetal oxide modified biochar catalyst in treating antibiotic wastewater.
In order to solve the technical problems, the invention adopts the following technical scheme.
The preparation method of the ferronickel bimetallic oxide modified biochar catalyst comprises the following steps:
s1, will beImpregnation of biomass to Ni-containing 2+ And Fe (Fe) 3+ Standing and drying the mixture solution to obtain a biochar precursor;
s2, performing low-oxygen baking treatment on the biochar precursor obtained in the step S1 in a nitrogen atmosphere containing oxygen;
and S3, calcining the product obtained after the low-oxygen baking treatment in the step S2 to obtain the ferronickel bimetallic oxide modified biochar catalyst.
In the above preparation method, further improved, in step S1, the Ni-containing alloy 2+ And Fe (Fe) 3+ The ratio of the mixed solution of (C) and the biomass is 100mL to 10 g-30 g, and the Ni-containing solution 2+ And Fe (Fe) 3+ Ni in the mixed solution of (2) 2+ Is 0.2mol/L, fe 3+ The concentration of (C) was 0.1mol/L.
In the above preparation method, further improved, in step S1, the Ni-containing alloy 2+ And Fe (Fe) 3+ The mixed solution of the nickel salt and the ferric salt is prepared by dissolving the nickel salt and the ferric salt in water; the nickel salt is at least one of nickel chloride hexahydrate, nickel nitrate and nickel sulfate; the ferric salt is at least one of anhydrous ferric trichloride, ferric sulfate and ferric nitrate; the biomass is at least one of oil tea fruit cattail, straw and sludge; the particle size of the biomass is 250-450 mu m; the biomass also includes the following treatments prior to use: the biomass is cleaned, dried, crushed, ground and sieved by a sieve with 40 meshes to 60 meshes.
In the preparation method, further improved, in the step S1, the standing time is 24 hours; the drying is carried out at a temperature of 80-105 ℃.
In the preparation method, in step S2, the volume percentage of oxygen in the system is controlled to be 8% in the low-oxygen baking treatment process; the total flow rate of the gas in the low-oxygen baking treatment process is 200mL/min; the temperature rising rate in the low-oxygen baking treatment process is 3-8 ℃/min; the low-oxygen baking treatment is carried out at the temperature of 200-300 ℃; the time of the low-oxygen baking treatment is 30-60 min.
In a further improvement of the above preparation method, in step S3, the calcining is performed under nitrogen atmosphere; the total flow rate of the gas in the calcination process is 200mL/min; the temperature rising rate in the calcination process is 3-8 ℃/min; the calcination temperature is 500-700 ℃, and the calcination time is 1-2 h; the calcination further comprises the following treatment: and cleaning, drying, grinding and sieving the calcined product with a 100-300-mesh sieve.
As a general technical conception, the invention also provides the ferronickel bimetallic oxide modified biochar catalyst prepared by the preparation method.
The ferronickel bimetal oxide modified biochar catalyst is further improved, wherein the ferronickel bimetal oxide modified biochar catalyst comprises biochar, and ferronickel bimetal oxide is loaded on the surface and the inside of the biochar; the ferronickel bimetallic oxide comprises elemental iron, iron oxide, nickel oxide and nickel-iron compound; the iron oxide includes Fe 2 O 3 And Fe (Fe) 3 O 4 The method comprises the steps of carrying out a first treatment on the surface of the The nickel oxide comprises NiO and Ni 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The nickel-iron compound is FeNi 3 。
As a general technical concept, the invention also provides application of the ferronickel bimetallic oxide modified biochar catalyst in treating antibiotic wastewater.
The above application, further improved, comprising the steps of: mixing a ferronickel bimetallic oxide modified biochar catalyst with a water body containing antibiotics, adding persulfate, and carrying out catalytic degradation reaction to finish the degradation of the antibiotics in the water body; the addition amount of the ferronickel bimetal oxide modified biochar catalyst is 0.1 g-0.4 g of the ferronickel bimetal oxide modified biochar catalyst added into each liter of water body containing antibiotics; the adding amount of the persulfate is 0.2 g-0.65 g of persulfate added into each liter of water body containing antibiotics.
According to the application, the initial concentration of the antibiotics in the water body containing the antibiotics is less than or equal to 20mg/L, the initial pH value of the water body containing the antibiotics is 2-5, the antibiotics in the water body containing the antibiotics comprise at least one of tetracycline, aureomycin, terramycin, ciprofloxacin and bisphenol A, the persulfate is at least one of sodium persulfate and potassium persulfate, the mixing is performed under the oscillation condition of the rotation speed of 100 rpm-200 rpm, the temperature of the oscillation is 25-35 ℃, the time of the oscillation is 1h, and the time of the catalytic degradation reaction is 1 h-1.5 h.
Compared with the prior art, the invention has the advantages that:
(1) Aiming at the defects of unstable structure, weak catalytic activity and the like of the existing biochar-based catalyst, the invention provides a preparation method of a nickel-iron bimetallic oxide modified biochar catalyst, which comprises the following steps of adsorbing Ni 2+ And Fe (Fe) 3+ Is subjected to low-oxygen baking treatment in nitrogen atmosphere containing oxygen, and is subjected to more Ni 2+ And Fe (Fe) 3+ The nickel-iron bimetallic oxide modified biochar catalyst with excellent catalytic performance and high stability is prepared by oxidizing the nickel metal oxide and the iron metal oxide into nickel and iron metal oxides, stably loading the nickel metal oxide into the surface and inner pores of the biomass, and further pyrolyzing the biomass into biochar through calcination (pyrolysis) treatment, and stably loading more nickel-iron metal oxide into the surface and inner pores of the biochar on the premise of not damaging the structure of the biochar with catalytic performance. Compared with the conventional preparation method, the method has the advantages that the metal ions loaded on the biochar are fully contacted with oxygen through low-oxygen baking coupling pyrolysis, the metal ions are easier to form oxides and compounds and can be more stably attached to the surface of the biochar, so that the prepared ferronickel bimetallic oxide modified biochar catalyst is higher in content of ferronickel metal oxides, better in loading stability, and high in efficient electron transfer capability and excellent in catalytic performance, and therefore, when the catalyst is used for activating persulfate in a water body, the persulfate can be activated more efficiently, high-efficiency degradation of organic pollutants in the water body can be realized, and the metal oxides in the catalyst are not easy to fall off and are not easy to be separated out into water, so that the catalytic performance can be exerted more stably, and secondary pollution can be avoided. In addition, in the case of the optical fiber,in the ferronickel bimetal oxide modified biochar catalyst prepared by the invention, biochar is used as a main material, the biochar has a certain adsorption capacity to pollutants, and functional groups and persistent free radicals on the surface of the biochar can carry out electron transfer to activate persulfate to generate various free radicals, and most of the free radicals can oxidize organic pollutants which are difficult to degrade; furthermore, the ferronickel bimetallic oxide is used as a modification material, and the material has the advantages of good catalytic performance, strong magnetism, high stability, low cost, environmental friendliness and the like, and has stronger persulfate activation capability, so that the catalytic performance of the biochar can be remarkably improved by attaching the ferronickel bimetallic oxide/compound to the biochar and modifying the biochar by utilizing the synergistic effect of the ferronickel bimetallic oxide/compound, and the method comprises the following steps of: on the one hand, the ferronickel bimetallic oxide is utilized to modify the biochar, so that the content of persistent free radicals on the surface of the biochar can be increased, and the persistent free radicals can be subjected to electron transfer with persulfate to generate sulfate radical, hydroxyl radical, superoxide radical and the like; on the other hand, ferrous iron and divalent nickel in the ferronickel bimetallic oxide can react with persulfate, namely the persulfate is activated as an active site to generate more sulfate radicals, hydroxyl radicals, superoxide radicals and the like, and due to the oxidation-reduction potential difference between the iron element and the nickel element, an electron transfer process can be spontaneously carried out between the iron element and the nickel element in the reaction process, so that the persulfate is activated to generate various free radicals, and then high-valence iron and high-valence nickel are reduced to be divalent again in a catalytic degradation system, and the persulfate can be continuously activated as a new active site; more importantly, the ferronickel bimetallic oxide/compound is uniformly dispersed on the surface of the biochar, so that the problem that the monomer is easy to agglomerate and deactivate is effectively solved, and the biochar is easier to recycle from the wastewater after magnetization. In addition, in the ferronickel bimetallic oxide modified biochar catalyst prepared by the invention, iron and nickel are microelements required by human bodies, and trace leaching does not produce toxic action on ecology, animals and plants in the environment so as to cause harm, thereby being more in line with the modern scientific and technical standards of environmental protection, high quality and low price. Thus, the present inventionThe ferronickel bimetal oxide modified biochar catalyst prepared by the invention has the advantages of stable structure, strong catalytic activity, green environmental protection and the like, can be used for activating persulfate to degrade organic pollutants in water, has very excellent removal effect, has no secondary pollution, has higher use value in the aspect of treating polluted water, and has wide application prospect.
(2) In the preparation method, the adopted biomass widely exists in the nature, the iron and nickel elements widely exist in the nature, the preparation method has the advantages of wide raw material sources, low price and the like, and meanwhile, the preparation method also has the advantages of simple process, convenient operation, wide raw material sources, low cost, mild reaction conditions, environmental friendliness and the like, is suitable for large-scale preparation, is beneficial to industrial utilization, and accords with the concept of current sustainable development.
(3) The preparation method of the invention optimizes the Ni content 2+ And Fe (Fe) 3+ The ratio of the mixed solution of (C) and the biomass is 100mL to 10 g-30 g, and Ni is contained 2+ And Fe (Fe) 3+ Ni in the mixed solution of (2) 2+ 、Fe 3+ The concentration of the catalyst is 0.2mol/L and 0.1mol/L in sequence, the ferronickel bimetallic oxide modified biochar catalyst with more stable structure and more excellent catalytic performance can be obtained, and the preparation cost is reduced, because when Ni 2+ And Fe (Fe) 3+ When the dosage of the catalyst is relatively small, it is difficult to attach enough ferronickel metal oxide on the surface of the biochar, and at the moment, the quantity of phenotype sites on the surface of the biochar is too small easily because the load of the ferronickel metal oxide is low, so that the catalyst is unfavorable for improving the catalytic performance of the catalyst; while Ni 2+ And Fe (Fe) 3+ When the dosage of the catalyst is relatively large, the formed ferronickel bimetallic oxide is easy to agglomerate and cover the surface of the biochar, so that the structure of the biochar with catalytic performance is easy to be damaged, the number of active sites on the surface of the biochar is easy to be reduced, the catalytic performance of the catalyst is also poor, and the outstanding problem is that excessive ferronickel metal oxide is easy to eliminate persistent free radicals on the surface of the material and easy to increase the preparation cost, therefore, the invention has the advantage of optimizing the Ni-containing catalyst by optimizing the preparation cost 2+ And Fe (Fe) 3+ The ratio of the mixed solution of (2) and the biomass contains Ni 2+ And Fe (Fe) 3+ Ni in the mixed solution of (2) 2+ 、Fe 3+ The concentration of the catalyst is favorable for controlling the ratio of the biochar to the ferronickel bimetallic oxide in the catalyst, and the modified biochar catalyst of the ferronickel bimetallic oxide with better catalytic performance is more favorable for being obtained by regulating and controlling the ratio of the biochar to the ferronickel bimetallic oxide in the catalyst.
(4) The invention also provides application of the ferronickel bimetal oxide modified biochar catalyst in treating antibiotic wastewater, and the ferronickel bimetal oxide modified biochar catalyst is mixed with a water body containing the antibiotic, and persulfate is added for catalytic degradation reaction, so that the high-efficiency degradation of the antibiotic in the water body can be realized. The invention discloses a method for degrading antibiotics in water by utilizing nickel-iron bimetallic oxide modified biochar catalyst to activate persulfate, which is a high-grade oxidation technology based on persulfate, and the principle is as follows: on one hand, ferrous iron and ferrous nickel on the surface of the ferronickel bimetal oxide modified biochar catalyst react with persulfate to generate sulfate radicals, and meanwhile, ferrous iron and ferrous nickel are oxidized into high-valence iron and nickel, the high-valence iron and the high-valence nickel can be reduced into ferrous iron and ferrous nickel again through a series of reactions, so that effective regeneration of active sites is realized, and the sulfate radicals can also react with hydroxyl or water to generate hydroxyl radicals; on the other hand, the permanent free radicals on the surface of the ferronickel bimetallic oxide modified biochar catalyst can also carry out electron transfer to activate persulfate to generate sulfate radical and hydroxyl radical. Therefore, various free radicals generated in the catalytic degradation reaction process can effectively attack antibiotics in the water body, so that the efficient degradation of the antibiotics (such as tetracycline) in the water body is realized, and the principle is shown in formulas (1) - (5). In addition, the catalytic system of the invention also has a non-radical path, namely persulfate generates singlet oxygen through combination with hydroxyl, and simultaneously superoxide radicals generated in the catalytic system can also react with hydroxyl radicals to generate singlet oxygen, and the principle is shown in formulas (6) to (10). Compared with the traditional treatment technology, the method for degrading the antibiotics in the water body by using the nickel-iron bimetal oxide modified biochar catalyst to activate persulfate can be carried out at normal temperature and normal pressure, has low energy consumption, can thoroughly destroy the antibiotics and has high decomposition rate, and meanwhile, the used nickel-iron bimetal oxide modified biochar catalyst can also be effectively separated from the wastewater, so that the method has the advantages of simple process, convenient operation, low cost, high removal efficiency, good removal effect, wide application range, environmental friendliness, easy recovery of the catalyst and the like, is a method which can be widely adopted, can efficiently remove the antibiotics in the water body, and has high application value and commercial value.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
FIG. 1 is a schematic diagram of the preparation process of the ferronickel bimetallic oxide modified biochar catalyst in example 1 of the present invention.
FIG. 2 is an SEM image of a ferronickel bimetallic oxide modified biochar catalyst prepared in example 1 of the present invention.
FIG. 3 is a graph showing FTIR comparison before and after the catalytic degradation reaction of the ferronickel bimetallic oxide modified biochar catalyst in example 2 of the present invention.
FIG. 4 is a graph showing the effect of varying amounts of ferronickel bi-metal oxide modified biochar catalyst (TPBC) on tetracycline degradation when persulfate is activated in example 3 of the present invention.
FIG. 5 is a graph showing the effect of the ferronickel bimetallic oxide modified biochar catalyst (TPBC) of example 4 on tetracycline degradation when used to activate various amounts of persulfate.
FIG. 6 is a graph showing the effect of nickel-iron bimetallic oxide modified biochar catalyst (TPBC) on tetracycline degradation when persulfate is activated at different pH conditions in example 5 of the present invention.
Detailed Description
The invention is further described below in connection with the drawings and the specific preferred embodiments, but the scope of protection of the invention is not limited thereby. The materials and instruments used in the examples below are all commercially available.
Example 1:
the preparation method of the ferronickel bimetallic oxide modified biochar catalyst disclosed by the invention, as shown in figure 1, comprises the following steps of:
(1) Selecting camellia oleifera fruit cattail (pericarp of camellia oleifera fruit) as biomass, cleaning, drying, crushing, grinding and sieving the camellia oleifera fruit cattail, and taking camellia oleifera fruit Pu Fenmo with 40-60 meshes, namely the camellia oleifera fruit Pu Fenmo with the particle size of 250-450 μm.
(2) 30g of oil tea fruits Pu Fenmo are mixed with 100mL of mixed solution of nickel chloride hexahydrate and anhydrous ferric trichloride, stirred uniformly, and kept stand at normal temperature overnight, namely kept stand for 24 hours, nickel ions and iron ions are adsorbed and attached to the oil tea fruits Pu Fenmo through impregnation treatment, and then transferred into an oven for drying at 80 ℃ to obtain a biochar precursor. Ni in the mixed solution of the nickel chloride hexahydrate and the anhydrous ferric trichloride 2+ The concentration of (C) is 0.2mol/L, fe 3+ The concentration of (C) was 0.1mol/L.
(3) Taking dried organism precursors, moving the dried organism precursors into a tube furnace in a quartz boat for carrying out low-oxygen baking treatment, wherein the method comprises the following steps of: nitrogen is taken as carrier gas, nitrogen containing oxygen with the total flow rate of 200mL/min is input into a furnace tube, the volume percentage content (volume concentration) of oxygen in the system is controlled to be 8%, and the temperature is raised to 200 ℃ and maintained for 40min under the low oxygen atmosphere according to the temperature raising rate of 5 ℃/min.
(4) After the low-oxygen baking treatment is finished, pure nitrogen is introduced, the protective gas in the furnace tube is changed into pure nitrogen, the temperature is raised to 600 ℃ and kept for 2 hours under the nitrogen atmosphere according to the temperature rising rate of 5 ℃/min, the calcined product is taken out and is sequentially cleaned, dried, ground and screened by a 100-300-mesh screen, and the ferronickel bimetallic oxide modified biochar catalyst is recorded as TPBC.
FIG. 2 is an SEM image of a ferronickel bimetallic oxide modified biochar catalyst prepared in example 1 of the present invention. As can be seen from FIG. 2, the surface of the ferronickel bimetal oxide modified biochar catalyst prepared according to the present invention contains a large amount of fine particles, which may be related to Ni and Fe compounds, which are the surface and interior of biochar in the ferronickel bimetal oxide modified biochar catalyst loaded with ferronickel bimetal oxides, including elemental iron, iron oxides, nickel oxides and nickel iron compounds, wherein the iron oxides include Fe 2 O 3 And Fe (Fe) 3 O 4 Oxides of nickelComprising NiO and Ni 2 O 3 The nickel-iron compound is FeNi 3 。
According to the measurement, the nickel atom content in the nickel-iron bimetallic oxide modified biochar catalyst prepared in the embodiment 1 is 3.49% by mass, and the iron atom content in the modified biochar catalyst is 1.4% by mass.
Comparative example 1:
the preparation method of the ferronickel bimetal modified biochar catalyst is basically the same as that of the embodiment 1, and differs only in the pyrolysis mode, and comprises the following steps:
(1) Selecting oil tea fruit cattail as biomass, cleaning, drying, crushing, grinding, sieving, and collecting 40-60 mesh oil tea fruit Pu Fenmo.
(2) 30g of oil tea fruits Pu Fenmo are mixed with 100mL of mixed solution of nickel chloride hexahydrate and anhydrous ferric trichloride, stirred uniformly, and kept stand overnight at normal temperature for soaking treatment, namely kept stand for 24 hours, and then moved into an oven for drying at 80 ℃ to obtain a biochar precursor. Ni in the mixed solution of the nickel chloride hexahydrate and the anhydrous ferric trichloride 2+ The concentration of (C) is 0.2mol/L, fe 3+ The concentration of (C) was 0.1mol/L.
(3) Taking the dried organism precursor, transferring into a tube furnace in a quartz boat for pyrolysis treatment, namely, carrying out pyrolysis treatment on N 2 Heating to 600 ℃ at a heating rate of 5 ℃/min under the atmosphere, and preserving the temperature for 2 hours, wherein the total gas flow rate of the nitrogen atmosphere is 200mL/min, so as to obtain the biochar.
(4) And cooling to room temperature, taking out the biochar, cleaning, drying, grinding, and sieving with a 100-300 mesh sieve to obtain the ferronickel bimetal modified biochar catalyst, which is named as PBC.
Comparative example 2:
the preparation method of the metallic nickel modified biochar catalyst is basically the same as example 1, except that the metallic nickel modified biochar catalyst is impregnated in Ni 2+ The method comprises the following steps:
(1) Selecting oil tea fruit cattail as biomass, cleaning, drying, crushing, grinding, sieving, and collecting 40-60 mesh oil tea fruit Pu Fenmo.
(2) 30g of oil tea fruits Pu Fenmo and 100mLNickel chloride hexahydrate solution (Ni) 2+ The concentration of (2) is 0.2 mol/L), and the mixture is stirred uniformly, and is kept stand overnight at normal temperature for impregnation treatment, namely, is kept stand for 24 hours, and is then moved into an oven for drying at 80 ℃ to obtain the biochar precursor.
(3) And taking the dried organism precursor, moving the dried organism precursor into a tube furnace in a quartz boat, and carrying out low-oxygen baking coupling pyrolysis treatment. In the low-oxygen baking stage, the temperature is heated to 200 ℃ at a heating rate of 5 ℃/min under a low-oxygen atmosphere, wherein the mass percent of oxygen in the low-oxygen atmosphere is 8%, and the total flow rate of gas is 200mL/min. In the pyrolysis stage, i.e. after the end of the low-oxygen baking process, the tube furnace shielding gas is completely exchanged for N 2 Then, the temperature is continuously increased to 600 ℃ at a heating rate of 5 ℃/min under the nitrogen atmosphere, and the temperature is kept for 2 hours, wherein the total gas flow rate of the nitrogen atmosphere is 200mL/min, and the biochar is obtained.
(4) And cooling to room temperature, taking out the biochar, cleaning, drying, grinding, and sieving with a 100-300 mesh sieve to obtain the metal nickel modified biochar catalyst, which is named as NiBC.
Comparative example 3:
the preparation method of the metallic iron modified biochar catalyst is basically the same as that of comparative example 2, except that: in the step (2), anhydrous ferric trichloride solution is adopted to replace nickel chloride hexahydrate solution, and Fe in the anhydrous ferric trichloride solution 3+ The concentration of (C) was 0.1mol/L.
The metallic iron modified biochar catalyst prepared in this comparative example was designated FeBC.
Example 2:
the application of the ferronickel bimetal oxide modified biochar catalyst in treating antibiotic wastewater, in particular to the use of the ferronickel bimetal oxide modified biochar catalyst to activate persulfate to degrade tetracycline in water, comprising the following steps:
taking 0.02g of the ferronickel bimetallic oxide modified biochar catalyst (TPBC) prepared in the embodiment 1, adding 100mL of a tetracycline solution (initial pH value is 5) with the concentration of 20mg/L, carrying out oscillation treatment for 1h, wherein the temperature of the oscillation treatment is 30 ℃, the rotating speed is 150rpm, reaching adsorption balance, then adding 0.05g of sodium persulfate into the system, carrying out catalytic degradation reaction for 1h, and completing the degradation of the tetracycline in the water body.
Control group one (PS): only sodium persulfate was added without adding any catalyst, and the other conditions were the same as in example 2.
Control group Two (TPBC): the ferronickel bimetallic oxide modified biochar catalyst (TPBC) prepared in example 1 was added alone, and sodium persulfate was not added, except that the conditions were the same as in example 2.
Control group three (PBC): only the ferronickel bimetal modified biochar catalyst (PBC) prepared in comparative example 1 was added to degrade tetracycline in water, sodium persulfate was not added, and other conditions were the same as in example 2.
Control group four (pbc+ps): the ferronickel bimetal modified biochar catalyst (PBC) prepared in comparative example 1 was added instead of the ferronickel bimetal oxide modified biochar catalyst (TPBC), and the other conditions were the same as in example 2.
Control group five (NiBC): only the metallic nickel modified biochar catalyst (NiBC) prepared in comparative example 2 was added to degrade tetracycline in water, sodium persulfate was not added, and other conditions were the same as in example 2.
Control group six (nibc+ps): the metallic nickel modified biochar catalyst (NiBC) prepared in comparative example 2 was added instead of the ferronickel bi-metallic oxide modified biochar catalyst (TPBC), and the other conditions were the same as in example 2.
Control group seven (FeBC): only the metallic iron modified biochar catalyst (FeBC) prepared in comparative example 3 was added to degrade tetracycline in water, sodium persulfate was not added, and other conditions were the same as in example 2.
Control group eight (febc+ps): the metal iron modified biochar catalyst (FeBC) prepared in comparative example 3 was added instead of the nickel iron bi-metal oxide modified biochar catalyst (TPBC), and the other conditions were the same as in example 2.
After the catalytic degradation reaction, the supernatant was sucked by a syringe, filtered through a 0.45 μm filter membrane, the concentration of tetracycline was measured at a maximum wavelength of 355nm by an ultraviolet-visible spectrophotometer, and the removal rate of tetracycline was calculated, and the degradation effects of different biochars were used as a control, and the results are shown in Table 1.
TABLE 1 comparison of removal rates for tetracyclines with different catalytic systems
| Sequence number | Catalytic system | Removal rate of |
| Example 2 | TPBC+PS | 99.8％ |
| Control group one | PS | 30.1％ |
| Control group two | TPBC | 56.6％ |
| Control group III | PBC | 29.2％ |
| Control group four | PBC+PS | 51.2％ |
| Control group five | NiBC | 24.7％ |
| Control group six | NiBC+PS | 72.8％ |
| Control group seven | FeBC | 35.7％ |
| Control group eight | FeBC+PS | 68.5％ |
As shown in Table 1, the ferronickel bimetallic oxide modified biochar catalyst prepared by the invention can efficiently activate sodium persulfate, can remarkably improve the degradation effect on antibiotics, and can achieve the removal rate of tetracycline of 99.8%. Compared with direct pyrolysis, the method can improve the catalytic effect of the ferronickel bimetal oxide modified biochar from 51.2% to 99.8% by means of low-oxygen baking coupling pyrolysis. In addition, compared with a Ni or Fe single metal modified biochar catalyst, the nickel-iron bimetallic modification strategy adopted by the invention has better modifying effect on the biochar.
FIG. 3 is a graph showing FTIR comparison before and after the catalytic degradation reaction of the ferronickel bimetallic oxide modified biochar catalyst in example 2 of the present invention. As can be seen from FIG. 3, 3430cm -1 、2920cm -1 、2850cm -1 、1630cm -1 Corresponding to-OH, -CH respectively 2 Asymmetric stretching, -CH 2 Symmetric stretching and c=c. The spectrum of the ferronickel bi-metal oxide modified biochar catalyst after catalytic degradation reaction showed many characteristic peaks added compared to the FTIR results before catalytic degradation reaction, indicating the presence of functional groups on the ferronickel bi-metal oxide modified biochar catalyst that were not present before catalytic degradation reaction. In addition, in FTIR spectrum, the spectrum of the film is 2000-1000cm -1 There are several characteristic peaks in the range, which are related to the attachment of organic groups or degradation products of contaminants to the biochar that occur after the catalyst reaction; within this range mainly correspond toThe organic groups of (C) include C= C, N-H, C = O, C-O, etc., wherein 2350cm -1 And 875cm -1 Corresponding to the stretching vibrations of c=o and C-H, respectively.
After the catalytic degradation reaction is finished, the metal precipitation condition of the ferronickel bimetal oxide modified biochar catalyst (TPBC) is measured, and the Ni precipitation concentration in the reaction solution is 3.176ppm and the Fe precipitation concentration is only 0.17ppm, so that the ferronickel bimetal oxide in the ferronickel bimetal oxide modified biochar catalyst disclosed by the invention is not easy to fall off and separate out, and the ferronickel bimetal oxide modified biochar catalyst has very excellent stability and can stably exert excellent catalytic performance.
Example 3:
the application of the ferronickel bimetal oxide modified biochar catalyst in treating antibiotic wastewater, in particular to the use of the ferronickel bimetal oxide modified biochar catalyst to activate persulfate to degrade tetracycline in water, comprising the following steps:
taking 0.01g, 0.02g, 0.03g and 0.04g of the ferronickel bimetallic oxide modified biochar catalyst (TPBC) prepared in the embodiment 1, adding 100mL of a 20mg/L tetracycline solution (with an initial pH value of 5), carrying out oscillation treatment for 1h, wherein the temperature of the oscillation treatment is 30 ℃, the rotating speed is 150rpm, reaching adsorption balance, then adding 0.05g of sodium persulfate into the system, carrying out catalytic degradation reaction for 1.5h, and completing the degradation of the tetracycline in the water body.
FIG. 4 is a graph showing the effect of varying amounts of ferronickel bi-metal oxide modified biochar catalyst (TPBC) on tetracycline degradation when persulfate is activated in example 3 of the present invention. As can be seen from fig. 4, the degradation efficiency of Tetracycline (TC) increases from 10% to 99% or more with increasing catalyst usage, which indicates that the ferronickel bi-metal oxide modified biochar catalyst was able to successfully activate sodium persulfate (Na 2 S 2 O 8 ) And can realize high-efficiency degradation of Tetracycline (TC). Meanwhile, when the catalyst dosage is continuously increased from 0.2g/L, the improvement effect on TC degradation is not obvious, so that when the catalyst dosage is 0.15g/L-0.25g/L, the high-efficiency treatment on antibiotics can be realized under the condition of lower cost, and particularly, when the catalyst dosage is 0.2g/L, the optimal treatment can be obtainedThe effect, i.e. 0.2g/L, can be used as the optimum amount of catalyst.
Example 4:
the application of the ferronickel bimetal oxide modified biochar catalyst in treating antibiotic wastewater, in particular to the use of the ferronickel bimetal oxide modified biochar catalyst to activate persulfate to degrade tetracycline in water, comprising the following steps:
five parts of the ferronickel bimetallic oxide modified biochar catalyst (TPBC) prepared in the example 1 are taken, 0.02g of each catalyst is respectively added into 100mL of tetracycline solution (initial pH value is 5) with the concentration of 20mg/L for oscillation treatment for 1h, the temperature of oscillation treatment is 30 ℃ and the rotation speed is 150rpm, adsorption balance is achieved, and then 0g, 0.02g, 0.035g, 0.05g and 0.065g of sodium persulfate are respectively added into the system for catalytic degradation reaction for 1.5h, so that the degradation of the tetracycline in the water body is completed.
FIG. 5 is a graph showing the effect of the ferronickel bimetallic oxide modified biochar catalyst (TPBC) of example 4 on tetracycline degradation when used to activate various amounts of persulfate. As can be seen from fig. 5, sodium persulfate (Na 2 S 2 O 8 ) When the dosage of (C) is increased from 0 to 0.65g/L, the removal rate of TC is also increased from 37% to more than 99% in 60min. From the downward trend of the curve, na was added 20 minutes before the reaction 2 S 2 O 8 The TC concentration in each catalyst system is reduced sharply, and then the reduction rate is slowed down. Therefore, when the amount of the persulfate to be added is 0.4g/L to 0.65g/L, the persulfate can be efficiently activated with less catalyst and the antibiotic can be efficiently treated, and particularly, when the amount of the persulfate to be added is 0.45g/L to 0.60g/L, a better treatment effect can be obtained, and at the same time, when the amount of the persulfate to be added is 0.5g/L, an optimal treatment effect can be exhibited and the persulfate can be used as the optimal amount of the catalyst to be added.
Example 5:
the application of the ferronickel bimetal oxide modified biochar catalyst in treating antibiotic wastewater, in particular to the use of the ferronickel bimetal oxide modified biochar catalyst to activate persulfate to degrade tetracycline in water, comprising the following steps:
five parts of the ferronickel bimetallic oxide modified biochar catalyst (TPBC) prepared in the example 1 are taken, 0.02g of each catalyst is added into tetracycline solutions with initial pH values of 2.5, 5, 7, 9 and 11.5 (the volume of the solutions is 100mL and the concentration is 20 mg/L) respectively, the oscillation treatment is carried out for 1h, the temperature of the oscillation treatment is 30 ℃ and the rotating speed is 150rpm, the adsorption balance is reached, then 0.05g of sodium persulfate is added into the system, and the catalytic degradation reaction is carried out for 1.5h, so that the degradation of the tetracycline in the water body is completed.
FIG. 6 is a graph showing the effect of nickel-iron bimetallic oxide modified biochar catalyst (TPBC) on tetracycline degradation when persulfate is activated at different pH conditions in example 5 of the present invention. As can be seen from FIG. 6, when the initial pH of the tetracycline solution was 2.5 and 5, no Tetracycline (TC) was detected in the catalytic system, i.e., the removal rate of tetracycline was 100%. When the initial pH values of the tetracycline solution are 7, 9 and 11.5, the removal rates of the tetracycline within 90min are 83%, 73% and 71%, respectively.
Example 6:
the application of the ferronickel bimetal oxide modified biochar catalyst in treating antibiotic wastewater, in particular to the use of the ferronickel bimetal oxide modified biochar catalyst to activate persulfate to degrade tetracycline in water, comprising the following steps:
taking two parts of ferronickel bimetallic oxide modified biochar catalyst (TPBC) prepared in example 1, respectively adding 0.02g of each catalyst into ultrapure water and river water containing tetracycline (the parameters of the water body are 100mL, the concentration is 20mg/L, the initial pH value is 5), carrying out oscillation treatment for 1h, the temperature of the oscillation treatment is 30 ℃, the rotating speed is 150rpm, reaching adsorption balance, then adding 0.05g of sodium persulfate into the system, and carrying out catalytic degradation reaction to finish the degradation of the tetracycline in the water body.
After the catalytic degradation reaction was completed, the supernatant was aspirated by a syringe, passed through a 0.45 μm filter, and the tetracycline concentration was measured at a maximum wavelength of 355nm by an ultraviolet-visible spectrophotometer, and the tetracycline removal rate was calculated, and the results are shown in Table 2.
TABLE 2 comparison of removal rates of tetracyclines under different Water conditions
| Solution medium | Reaction time (min) | Removal rate (%) |
| Ultrapure water | 60 | 99％ |
| River water | 45 | 99％ |
As can be seen from Table 2, the ferronickel bimetallic oxide modified biochar catalyst prepared by the invention has rapid and efficient catalytic degradation effect on antibiotics under laboratory conditions and in natural water, and has excellent adaptability.
In conclusion, the preparation method of the ferronickel bimetal oxide modified biochar catalyst has the advantages of simple process, convenient operation, wide raw material sources, low cost, mild reaction conditions, environment friendliness and the like, and the prepared ferronickel bimetal oxide modified biochar catalyst has the advantages of stable structure, strong catalytic activity and the like, can be used for activating persulfate to catalyze and degrade organic pollutants such as antibiotics in water, has high removal efficiency and no secondary pollution, has higher use value in the aspect of treating polluted water, and has wide application prospect.
The above description is only of the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. While the invention has been described in terms of preferred embodiments, it is not intended to be limiting. Any person skilled in the art can make many possible variations and modifications to the technical solution of the present invention or equivalent embodiments using the method and technical solution disclosed above without departing from the spirit and technical solution of the present invention. Therefore, any simple modification, equivalent substitution, equivalent variation and modification of the above embodiments according to the technical substance of the present invention, which do not depart from the technical solution of the present invention, still fall within the scope of the technical solution of the present invention.
Claims (10)
1. The preparation method of the ferronickel bimetallic oxide modified biochar catalyst is characterized by comprising the following steps of:
s1, soaking biomass into Ni-containing material 2+ And Fe (Fe) 3+ Standing and drying the mixture solution to obtain a biochar precursor;
s2, performing low-oxygen baking treatment on the biochar precursor obtained in the step S1 in a nitrogen atmosphere containing oxygen; controlling the volume percentage of oxygen in the system to be 8% in the low-oxygen baking treatment process; the low-oxygen baking treatment is carried out at the temperature of 200-300 ℃;
and S3, calcining the product obtained after the low-oxygen baking treatment in the step S2 to obtain the ferronickel bimetallic oxide modified biochar catalyst.
2. The method for preparing a nickel-iron bimetallic oxide modified biochar catalyst according to claim 1, wherein in step S1, the Ni-containing catalyst comprises 2+ And Fe (Fe) 3+ The ratio of the mixed solution of (C) and the biomass is 100mL to 10 g-30 g, and the Ni-containing solution 2+ And Fe (Fe) 3+ Ni in the mixed solution of (2) 2+ Is 0.2mol/L, fe 3+ The concentration of (C) was 0.1mol/L.
3. The method for preparing a nickel-iron bimetallic oxide modified biochar catalyst according to claim 2, wherein in step S1, the Ni-containing catalyst comprises 2+ And Fe (Fe) 3+ Is a mixture of (3)The solution is prepared by dissolving nickel salt and ferric salt in water; the nickel salt is at least one of nickel chloride hexahydrate, nickel nitrate and nickel sulfate; the ferric salt is at least one of anhydrous ferric trichloride, ferric sulfate and ferric nitrate; the biomass is at least one of oil tea fruit cattail, straw and sludge; the particle size of the biomass is 250-450 mu m; the biomass also includes the following treatments prior to use: the biomass is cleaned, dried, crushed, ground and sieved by a sieve with 40 meshes to 60 meshes.
4. The method for preparing a ferronickel bimetal oxide modified biochar catalyst according to any one of claims 1 to 3, wherein in step S1, the standing time is 24 hours; the drying is carried out at a temperature of 80-105 ℃.
5. The method for preparing a ferronickel bimetal oxide modified biochar catalyst according to any one of claims 1 to 3, wherein in step S2, the total flow rate of gas during the low oxygen baking treatment is 200mL/min; the temperature rising rate in the low-oxygen baking treatment process is 3-8 ℃/min; the time of the low-oxygen baking treatment is 30-60 min;
in step S3, the calcination is performed under a nitrogen atmosphere; the total flow rate of the gas in the calcination process is 200mL/min; the temperature rising rate in the calcination process is 3-8 ℃/min; the calcination temperature is 500-700 ℃, and the calcination time is 1-2 h; the calcination further comprises the following treatment: and cleaning, drying, grinding and sieving the calcined product with a 100-300-mesh sieve.
6. A ferronickel bimetallic oxide modified biochar catalyst prepared by the preparation method of any one of claims 1 to 5.
7. The nickel iron bi-metal oxide modified biochar catalyst according to claim 6, wherein the nickel iron bi-metal oxide modified biochar catalyst comprises biochar, the greenThe surface and the inside of the charcoal are loaded with nickel-iron bimetallic oxide; the ferronickel bimetallic oxide comprises elemental iron, iron oxide, nickel oxide and nickel-iron compound; the iron oxide includes Fe 2 O 3 And Fe (Fe) 3 O 4 The method comprises the steps of carrying out a first treatment on the surface of the The nickel oxide comprises NiO and Ni 2 O 3 The method comprises the steps of carrying out a first treatment on the surface of the The nickel-iron compound is FeNi 3 。
8. Use of the ferronickel bimetallic oxide modified biochar catalyst according to claim 6 or 7 for treating antibiotic wastewater.
9. The use according to claim 8, characterized by the steps of: mixing a ferronickel bimetallic oxide modified biochar catalyst with a water body containing antibiotics, adding persulfate, and carrying out catalytic degradation reaction to finish the degradation of the antibiotics in the water body; the addition amount of the ferronickel bimetal oxide modified biochar catalyst is 0.1 g-0.4 g of the ferronickel bimetal oxide modified biochar catalyst added into each liter of water body containing antibiotics; the adding amount of the persulfate is 0.2 g-0.65 g of persulfate added into each liter of water body containing antibiotics.
10. The use according to claim 9, wherein the initial concentration of the antibiotic in the antibiotic-containing water body is less than or equal to 20mg/L, the initial pH value of the antibiotic-containing water body is 2-5, the antibiotic in the antibiotic-containing water body comprises at least one of tetracycline, aureomycin, terramycin, ciprofloxacin and bisphenol a, the persulfate is at least one of sodium persulfate and potassium persulfate, the mixing is performed under the condition of shaking at a rotational speed of 100 rpm-200 rpm, the shaking temperature is 25-35 ℃, the shaking time is 1h, and the catalytic degradation reaction time is 1 h-1.5 h.
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