CN106669677A - Preparation method of magnetic iron-based heterogeneous Fenton catalyst taking graphene as carrier and application - Google Patents
Preparation method of magnetic iron-based heterogeneous Fenton catalyst taking graphene as carrier and application Download PDFInfo
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- CN106669677A CN106669677A CN201710006700.5A CN201710006700A CN106669677A CN 106669677 A CN106669677 A CN 106669677A CN 201710006700 A CN201710006700 A CN 201710006700A CN 106669677 A CN106669677 A CN 106669677A
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- fenton catalyst
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 152
- 239000003054 catalyst Substances 0.000 title claims abstract description 116
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 93
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 68
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000000034 method Methods 0.000 claims abstract description 33
- 239000003344 environmental pollutant Substances 0.000 claims abstract description 4
- 231100000719 pollutant Toxicity 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 50
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 48
- 229910001868 water Inorganic materials 0.000 claims description 48
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 26
- 239000002351 wastewater Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 21
- 239000000047 product Substances 0.000 claims description 21
- 238000004140 cleaning Methods 0.000 claims description 14
- 239000006185 dispersion Substances 0.000 claims description 14
- 229910052603 melanterite Inorganic materials 0.000 claims description 14
- 238000003756 stirring Methods 0.000 claims description 13
- 239000000203 mixture Substances 0.000 claims description 11
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 8
- PQUXFUBNSYCQAL-UHFFFAOYSA-N 1-(2,3-difluorophenyl)ethanone Chemical compound CC(=O)C1=CC=CC(F)=C1F PQUXFUBNSYCQAL-UHFFFAOYSA-N 0.000 claims description 7
- 206010013786 Dry skin Diseases 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 7
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 7
- 239000006227 byproduct Substances 0.000 claims description 7
- 230000000593 degrading effect Effects 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000000227 grinding Methods 0.000 claims description 7
- 229940047670 sodium acrylate Drugs 0.000 claims description 7
- 239000012279 sodium borohydride Substances 0.000 claims description 7
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 6
- 239000001632 sodium acetate Substances 0.000 claims description 6
- 235000017281 sodium acetate Nutrition 0.000 claims description 6
- 150000002989 phenols Chemical class 0.000 claims description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims 1
- 238000002604 ultrasonography Methods 0.000 claims 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 abstract description 29
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 abstract description 17
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 abstract description 15
- 229910001447 ferric ion Inorganic materials 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 239000000126 substance Substances 0.000 abstract description 10
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 8
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 238000011065 in-situ storage Methods 0.000 abstract description 3
- 239000010802 sludge Substances 0.000 abstract description 2
- 238000012546 transfer Methods 0.000 abstract description 2
- 238000004220 aggregation Methods 0.000 abstract 1
- 230000002776 aggregation Effects 0.000 abstract 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 26
- 239000000243 solution Substances 0.000 description 22
- 238000006243 chemical reaction Methods 0.000 description 19
- 230000008569 process Effects 0.000 description 19
- -1 hydroxyl radical free radical Chemical class 0.000 description 16
- 235000013824 polyphenols Nutrition 0.000 description 14
- 238000006555 catalytic reaction Methods 0.000 description 11
- 238000005516 engineering process Methods 0.000 description 11
- 229960002163 hydrogen peroxide Drugs 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 239000004005 microsphere Substances 0.000 description 8
- 238000004065 wastewater treatment Methods 0.000 description 8
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000004090 dissolution Methods 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 150000002505 iron Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 235000017166 Bambusa arundinacea Nutrition 0.000 description 4
- 235000017491 Bambusa tulda Nutrition 0.000 description 4
- 241001330002 Bambuseae Species 0.000 description 4
- 235000015334 Phyllostachys viridis Nutrition 0.000 description 4
- 239000011425 bamboo Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 239000003610 charcoal Substances 0.000 description 4
- 239000002086 nanomaterial Substances 0.000 description 4
- 229910052624 sepiolite Inorganic materials 0.000 description 4
- 235000019355 sepiolite Nutrition 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000012028 Fenton's reagent Substances 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 229960000892 attapulgite Drugs 0.000 description 3
- 239000004568 cement Substances 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 229910052625 palygorskite Inorganic materials 0.000 description 3
- 239000002957 persistent organic pollutant Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical class OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 240000007594 Oryza sativa Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000008030 elimination Effects 0.000 description 2
- 238000003379 elimination reaction Methods 0.000 description 2
- 229940056319 ferrosoferric oxide Drugs 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- 239000002808 molecular sieve Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000013384 organic framework Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000011084 recovery Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 2
- 229910052596 spinel Inorganic materials 0.000 description 2
- 239000011029 spinel Substances 0.000 description 2
- 238000005303 weighing Methods 0.000 description 2
- HFZWRUODUSTPEG-UHFFFAOYSA-N 2,4-dichlorophenol Chemical class OC1=CC=C(Cl)C=C1Cl HFZWRUODUSTPEG-UHFFFAOYSA-N 0.000 description 1
- 229920000858 Cyclodextrin Polymers 0.000 description 1
- NIQCNGHVCWTJSM-UHFFFAOYSA-N Dimethyl phthalate Chemical class COC(=O)C1=CC=CC=C1C(=O)OC NIQCNGHVCWTJSM-UHFFFAOYSA-N 0.000 description 1
- 229910017061 Fe Co Inorganic materials 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- 229910000708 MFe2O4 Inorganic materials 0.000 description 1
- 239000013291 MIL-100 Substances 0.000 description 1
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 102000004160 Phosphoric Monoester Hydrolases Human genes 0.000 description 1
- 108090000608 Phosphoric Monoester Hydrolases Proteins 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 239000004141 Sodium laurylsulphate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000000783 alginic acid Substances 0.000 description 1
- 235000010443 alginic acid Nutrition 0.000 description 1
- 229960001126 alginic acid Drugs 0.000 description 1
- 229920000615 alginic acid Polymers 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 239000001045 blue dye Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000012018 catalyst precursor Substances 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000010586 diagram 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
- 230000005611 electricity Effects 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 231100000049 endocrine disruptor Toxicity 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 239000003205 fragrance Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 239000002122 magnetic nanoparticle Substances 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 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 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 150000008442 polyphenolic compounds Polymers 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- HFHDHCJBZVLPGP-UHFFFAOYSA-N schardinger α-dextrin Chemical compound O1C(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC(C(O)C2O)C(CO)OC2OC(C(C2O)O)C(CO)OC2OC2C(O)C(O)C1OC2CO HFHDHCJBZVLPGP-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 235000011091 sodium acetates Nutrition 0.000 description 1
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 1
- 239000002594 sorbent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 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
- B01J23/745—Iron
-
- B01J35/33—
-
- B01J35/393—
-
- 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
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention relates to a preparation method of a magnetic iron-based heterogeneous Fenton catalyst taking graphene as a carrier and an application. According to the method, the graphene serves as the carrier, magnetic nano-scale ferroferric oxide and nano-scale zero-valent iron (Fe0) are compounded to the surface of the graphene to serve as the heterogeneous Fenton catalyst in an in-situ growth mode, aggregation of catalytic active nano-particles can be effectively prevented by the graphene serving as the carrier, and more active sites are exposed. Besides, the graphene has high electron transfer capability, Fe0 easily transfers electrons to Fe3+ by taking the graphene as the carrier, Fe3+ is promoted to be transformed into Fe2+, so that catalytic activity of the catalyst is improved, the catalyst is easily recovered and reusable, pollutant removal efficiency is improved, phenol removal efficiency reaches 99% or more, and the used catalyst is recovered by an external magnetic field. The preparation method solves the problems that traditional Fenton catalysts are difficultly recycled and generate a lot of chemical sludge, and the preparation method has a certain economic value and practical value.
Description
Technical field
The present invention relates to a kind of preparation method of the heterogeneous class fenton catalyst of the magnetic iron-based with Graphene as carrier and
Using belonging to nano material and environmental science.
Background technology
In recent years, the organic dirt of poisonous and harmful of the high-concentration hardly-degradable such as phenols, antibiotic, pesticide, endocrine disruptors
Dye thing is constantly discharged in water body, and by accumulation, is enriched to human body, is seriously threatened the life and health of the mankind, therefore open
It is extremely urgent that sends out new and effective removes the technology and method of this pollutant.
Classical homogeneous Fenton reagent is Fe2+With H2O2Combination, the hydroxyl radical free radical produced under acid condition (HO),
Hydroxyl radical free radical has high oxidizing potential (2.8V), can be effectively by organic contamination oxidative degradation into CO2And H2O, Huo Zhe little
Molecular substance, is a kind of eco-friendly green catalysis technique.But traditional Fenton's reaction system is carried out in homogeneous,
The ferrous ion for being used can become ferric ion, itself be consumed and produce a large amount of iron cements, therefore this oxidized catalyst precursor
System can not recycle iron ion, and substantial amounts of iron cement is easily produced in processing procedure, and these shortcomings greatly limit sweet smell
Reaction degraded organic pollutants in application.
Heterogeneous Fenton technology is a kind of high-level oxidation technology grown up on the basis of traditional Fenton reagent.From broad sense
On say, in addition to classical Fenton reagent, other produce hydroxyl radical free radical isoreactivity free radical to aoxidize drop using hydrogen peroxide
The technology of solution organic pollution is referred to as class Fenton technology, such as electric Fenton technology, light Fenton technology, heterogeneous class Fenton technology
Deng.In recent years, heterogeneous class Fenton technology is because of pH value high with degradation efficiency, reducing secondary pollution, can widen solution reaction
The advantages of and by extensive concern.
For heterogeneous class fenton catalyst has had more report, Applied Catalysis B in prior art:
Environmental 2008,84(12):Modification with Fe zeolite is reported in 9-15 ferrum modified catalyst is obtained, in ultraviolet light
Under irradiation, with reference to hydrogen peroxide degradable acid blue dye.
Applied Catalysis B:Report in Environmental 188 (2016) 113-122 and repaiied with cyclodextrin
The ferroso-ferric oxide of decorations is the research of heterogeneous class fenton catalyst degraded 4- chlorophenols.
Applied Catalysis B:Report with four oxygen in Environmental 123-124 (2012) 117-126
Change the research that three-iron is heterogeneous class fenton catalyst degraded 2,4- Dichlorophenols.
Environ.Sci.Technol.2012,46,10145-10153 is reported with Fe3O4/CeO2It is fragrant for heterogeneous class
The research of catalyst degradation 4- chlorophenols.
Applied Catalysis B:Coated magnetic is reported in Environmental 172-173 (2015) 73-81
The phenol that the carbon ball of nano zero valence iron is used to degrade in aqueous solution as fenton catalyst.The preparation method of the catalyst：First
The carbon ball of enwrapping ferric oxide, Ran Hou are prepared by the way of a step hydro-thermal with tripolycyanamide, glucose and iron salt as raw material
High temperature reduction ferrum oxide under nitrogen atmosphere, prepares the carbon ball of coated magnetic nano zero valence iron.
J.Phys.Chem.C 2015,119,23068-23074 report sodium lauryl sulphate modification FeCo2O4As
Fenton catalyst is used for degradation of methylene blue dyestuff.
Journal of Hazardous Materials B129 (2006) 171-178 report Fe, Co, Mn, Ni doping
Fe3-xMxO4Material is used as fenton catalyst.
Chinese invention patent (publication number CN101549294A) discloses a kind of magnetic for organic pollution process and receives
Rice material, wherein described magnetic Nano material includes Fe2O3And Fe3O4Magnetic nanoparticle, the magnetic Nano material can be urged
Change H2O2Hydroxyl radical free radical is produced, recovery use can be carried out to catalyst material with the method for Magneto separate.
Chinese patent (application number CN201310293883.5) discloses the magnetic core-shell type Fenton-like catalysis of kind of tool
Agent and its preparation method and application, the kernel of the core-shell type type Fenton catalyst is nano level Fe3O4Particle packing is formed
Fe3O4Microsphere, shell are cationic polyelectrolyte and Nano-meter SiO_22Granuloplastic alternating sorbent sequence layer.
Chinese patent (application number CN201410418795.8) discloses a kind of multiphase Fenton catalyst Fe3O4@EDTA's
Prepare and apply.Fe is prepared initially with chemical coprecipitation3O4Presoma, by surface modification, obtains the magnetic of nanoscale
Fe3O4@EDTA catalyst.For persistent organic pollutants such as the dimethyl phthalates in catalytic elimination water.Chinese patent
(application number CN201510005587.X) open a kind of magnetic heterogeneous type Fenton catalyst of knowing clearly, with three-decker
Core-shell microsphere Fe3O4@rGO@TiO2, wherein, with the Fe of submicron order3O4Microsphere is kernel, and outermost layer is TiO2Nanometer is little
Granule, Fe3O4Microsphere and TiO2It is combined together by the rGO layers that thickness is 2~5nm between nanometer little particle.
Chinese patent (application number CN201410743333.3) discloses a kind of class of graphene coated ferroso-ferric oxide microsphere
Fenton catalyst and its preparation method and application.Aqueous solution with inorganic molysite and graphene oxide as presoma, using spray
Mist dry technology prepares the iron salt presoma microsphere of graphene oxide cladding, then further in protective atmosphere (N2、Ar、CO2、
H2) calcined in environment, make graphene oxide be reduced into graphene sheet layer, iron salt is changed into Fe3O4Granule, finally gives stone
Black alkene coats Fe3O4Microsphere.The catalyst can be catalyzed embryonic stem-like cells, and material can be separated and recovered by externally-applied magnetic field.
It is many that Chinese patent (application number CN201210264664.X) reports Fe-Co bimetallic as carrier with modified meerschaum
The preparation method of similar fenton catalyst.Chinese patent (application number CN201410166243.2) discloses a kind of load-type iron-based
The preparation method and applications of metallic organic framework heterophase Fenton catalyst, based on MIL-100 (Fe), by hydro-thermal method
Load ferrous irons component, obtains load-type iron-based metallic organic framework heterophase Fenton catalyst.
Chinese patent (application number CN201310411593.6) discloses a kind of based on the heterogeneous class that meerschaum is carrier
Fenton catalyst and preparation method thereof.Using acid treatment and heat-treating methods, meerschaum is activated, then supported active
Composition.Prepare heterogeneous type Fenton catalyst.
Chinese patent (application number CN201310000494.9) discloses a kind of heterogeneous class Fenton of ferrum attapulgite that carries and urges
The preparation method of agent, prepares the class fenton catalyst of load iron salt with attapulgite as carrier.
Chinese patent (application number CN201610130380.X) discloses a kind of alginic acid salt core outer cladding copper/magnetic
Heterogeneous class fenton catalyst of nanometer of Fe3O4 and preparation method thereof.
Chinese patent (application number CN201510781846.8) discloses a kind of AuPd/Fe3O4The preparation side of fenton catalyst
Method can be applicable to organic wastewater degraded.
Chinese patent (application number CN201410158761.X) discloses a kind of preparation method of multiphase-fenton fenton catalyst,
It is related to the preparation method of class fenton catalyst.The catalyst is by reduced iron powder, activated carbon powder, electrolytic copper powder, silicate and shallow lake
Powder is made.
Chinese patent (application number CN201410546489.2) discloses a kind of heterogeneous class fenton catalyst and application thereof,
Using Graphene it is modified-mesopore molecular sieve (MCM-41) complex carrier, area load bloodstone prepares heterogeneous class Fenton and is catalyzed
Agent and its purposes of catalytic elimination organic pollutants in water body.
Chinese patent (application number CN201210489713.X) discloses a kind of heterogeneous class fenton catalyst of load ferrum bamboo charcoal
Preparation method.Iron ion is carried on bamboo charcoal carrier using cooking process repeatedly, is given full play in wastewater treatment process
The strong oxidizing property of the absorption property and Fenton's reaction of bamboo charcoal.
Chinese patent (application number CN201410440630.0) discloses a kind of sulfur load spinel oxides Fenton
Catalyst and preparation method thereof, described sulfur load spinel oxides are MFe2O4, M=Zn, Co, Ni.Will be sulfur load point brilliant
Stone-type oxide M Fe2O4Catalyst is applied to Fenton reactions, replaces traditional iron salt catalyst, forms new heterogeneous class anti-
Answer system.
Chinese patent (application number CN201310439830.X) discloses a kind of poly- hydroquinone/Graphene/Fe3O4Class
The preparation method of Fenton catalyst.Poly- hydroquinone is prepared using chemical oxidative polymerization, is grafted in by sonochemical method
On Graphene, then by ultrasonic wave added coprecipitation by Fe3O4It is deposited on poly- hydroquinone/Graphene, obtains poly- to benzene two
Phenol/Graphene/Fe3O4Catalyst.
Chinese patent (publication number CN103537323A) discloses a kind of system of mesoporous magnetic iron ore base type Fenton catalyst
Preparation Method, prepares poly phenol/magnetic iron ore type Fenton catalyst for rhodamine B degradation.
The catalytic mechanism of the generally heterogeneous class fenton catalyst of iron-based is as follows：
Fe2++H2O2→Fe3++HO-+·OH k1=63M s-1 (1)
Fe3++H2O2→Fe2++H++HO2· k2=2 × 10-3M s-1 (2)
·OH+H2O2→H2O+HO2· k3=3.3 × 107M s-1 (3)
Fe3++HO2·→Fe2++H2O2 k4=1.3 × 106M s-1 (4)
In the Fe on the surface of the heterogeneous class fenton catalyst of iron-based2+Can be with catalyzing and decomposing H2O2Produce highly active hydroxyl certainly
By base (OH), due to the HO in Fenton's reaction2Concentration it is generally very low, by reacting (2), (3), (4), it is seen that
During whole Fenton catalysis produces hydroxyl radical free radical, Fe3+→Fe2+It is to limit the control step that hydroxyl radical free radical produces speed
Suddenly, this does not only result in reaction rate slowly, and causes H2O2Decomposition is oxygen, consumes H excessively2O2, its utilization rate is usually low
In 30%.A kind of can accelerate Fe based in this, designing3+→Fe2+Process improves catalysis activity, effectively can prevent again
The heterogeneous class fenton catalyst that active component is reunited is a urgent need to resolve technical barrier.
Graphene is a kind of Novel Carbon Nanomaterials, with unique monoatomic layer two dimensional crystal structure, with larger
Specific surface area, high chemical stability, preferable mechanical strength and stronger electron transfer capacity, are a kind of ideal carrier materials
Material.If catalytic active component is combined with Graphene, the electron transfer capacity that Graphene can be made full use of good (can
To accelerate electronics to Fe3+Transfer), big specific surface area is so as to putting forward the efficiency of Fenton's reaction；Active catalytic can be solved simultaneously to receive
The problem that rice corpuscles are easily reunited, therefore be ideal carrier prepared by class Fenton-type catalysts.
In sum, appeared in the newspapers with regard to heterogeneous class fenton catalyst both at home and abroad at present.Such as magnetic ferroferric oxide and
The class fenton catalyst for preparing the preparations such as two layers of nucleocapsid, three-layer nuclear shell structure is modified to which, this kind of catalyst generally has activity
Component is easily reunited, and reduces exposed active site, the not high shortcoming of catalytic efficiency.With with bamboo charcoal, mesopore molecular sieve,
The heterogeneous class fenton catalyst of the carrier loaded ferrum oxide such as meerschaum, attapulgite, although active component reunion can be solved
Problem, but some preparation methoies are relatively cumbersome, and Fe3+It is reduced Fe2+Process it is still very slow, constrain catalytic reaction
The raising of speed.In addition Fe can be improved in catalyst surface grafting organic semiconductor3+It is reduced Fe2+Speed, but this kind of urge
The preparation method of agent is typically more complicated loaded down with trivial details, and the stability of catalyst is generally poor.
It is contemplated that designing a kind of preparation method simply, active component reunion can be prevented effectively from, Fe is quickly realized3+
It is reduced to Fe2+, with greater catalytic efficiency, catalyst can be with the heterogeneous class fenton catalyst of high recycling rate.
The content of the invention
It is an object of the present invention to provide a kind of system of the heterogeneous class fenton catalyst of the magnetic iron-based with Graphene as carrier
Preparation Method and application, the method with Graphene as carrier, using the mode of growth in situ by magnetic nano ferroferric oxide
(Fe3O4) and nano zero valence iron (Fe0) graphenic surface is compound to as heterogeneous class fenton catalyst, Graphene is used as carrier
The reunion of catalytic active nano particle can be effectively prevented, more avtive spots are exposed.Additionally, Graphene have it is superpower
Electron transfer capacity, Fe0It is easy to electron transfer by Graphene as carrier to Fe3+, promote Fe3+It is converted into Fe2+, and then
The catalysis activity of catalyst is improved, contaminant removal efficiency is improved.The clearance of phenol reaches more than 99%.Used catalysis
Agent is reclaimed by externally-applied magnetic field, is solved traditional fenton catalyst and is difficult to recycle, and produces the difficulty of a large amount of chemical sludges
Topic.With certain economic worth and practical value.
A kind of preparation method of the heterogeneous class fenton catalyst of magnetic iron-based with Graphene as carrier of the present invention,
It follow these steps to carry out：
A, 1.0-2.0g graphene oxides are weighed, be added in the mixed liquor of ethylene glycol and diethylene glycol of 200ml, surpassed
Sound, adds FeCl3·6H2O, sodium acetate and sodium acrylate, stir under room temperature so as to fully dissolve, obtain mixed liquor, wherein
The volume ratio of ethylene glycol and diethylene glycol is 19:1；
B, the mixed liquor obtained in a is transferred in polytetrafluoro reactor, 200 DEG C of temperature, is incubated 10-15h, then cools down
Room temperature, is 1 by the product volume ratio for obtaining:1 second alcohol and water is cleaned repeatedly, and the product after cleaning is distributed to 600ml's
In the middle of deionized deoxygenated water, Fe is obtained3O4The aqueous dispersions of-Graphene；
C, weigh 1.5-2.0g FeSO4·7H2O is dissolved in the deionized deoxygenated water of 50ml；
D, the deionized deoxygenated water pH value of 50ml in step c is adjusted to into 9 with the NaOH solution of 1mol/L, is subsequently adding
1.36-2.0g NaBH4Dissolving；
E, by FeSO4·7H2O solution is slowly dropped to the Fe obtained by step b3O4In the aqueous dispersions of-Graphene, room temperature
Lower stirring 1h；
F, NaBH prepared by step d4Solution is slowly dropped in the mixed liquor obtained by step e, reacts 1h, using Magnet
Product is collected, is 1 by product volume ratio:1 ethanol:The mixture cleaning of water, is put into the 40 DEG C of dryings of vacuum drying oven temperature
24h, after grinding is sieved, that is, obtains Fe0-Fe3O4The heterogeneous class fenton catalyst of-Graphene.
The heterogeneous class fenton catalyst of the magnetic iron-based with Graphene as carrier that methods described is obtained is in degrading waste water
Pollutant phenols in purposes.
The preparation method of the heterogeneous class fenton catalyst of the magnetic iron-based with Graphene as carrier of the present invention, the party
The preparation of graphene oxide in method is prepared using the method for prior art, and concrete operations follow these steps to carry out：
Configuration concentrated sulphuric acid 360ml, phosphatase 24 0ml mixed liquors；3g graphite and 18g potassium permanganate are weighed, by graphite and permanganic acid
Potassium mixing is placed in there-necked flask, then flask is fixed in ice-water bath；The sour mixed liquor of configuration is dropwise instilled, and machinery is stirred
Mix, micro external heat can be produced, outside thermal control is made at 35-40 DEG C；After mixed liquor is completely added to there-necked flask, then will
There-necked flask is placed in the pot of constant temperature waters, is allowed to be maintained at temperature 50 C, mechanical agitation 12h；Room is cooled to after the completion of to be mixed
Temperature, pours in the ice-water bath of 400ml, adds dropwise 30% hydrogenperoxide steam generator, till mixed liquor is changed into glassy yellow；
Glassy yellow mixed liquor is first used pickling 1 time, it is neutrality that then deionized water is cleaned repeatedly up to supernatant, reddish brown by what is obtained
Color colloidal substance, is put into 40 degrees Celsius of vacuum drying oven and is dried 24h, that is, obtain graphene oxide.
The preparation method of the heterogeneous class fenton catalyst of the magnetic iron-based with Graphene as carrier of the present invention and should
With being with Graphene as carrier, using the mode of growth in situ by magnetic nano ferroferric oxide (Fe3O4) and nano zero valence iron
(Fe0) to graphenic surface as heterogeneous class fenton catalyst.Mainly solve and pollute in heterogeneous class Fenton catalytic degradation
Fe during thing3+It is reduced to Fe2+Relatively slow, iron ion is lost in a large number, produces the problem of a large amount of secondary pollution iron cements.This
Bright resolving ideas are that have superpower electron transfer capacity, Fe based on Graphene0It is carrier by electricity to be easy to by Graphene
Son is transferred to Fe3O4The Fe on surface3+, promote Fe3+It is converted into Fe2+Effect, and then accelerate the generation of hydroxyl radical free radical, it is difficult to promote
The decomposition and the removal of COD of degradation material.The heterogeneous class fenton catalyst of magnetic iron-based with Graphene as carrier of the present invention
High catalytic efficiency, easily reclaim, it is reusable, process the effect of phenolic waste water preferably, after reaction 30min, the clearance of phenol
After reaching more than 99%, 90min, COD clearances are up to 70%.The utilization of hydrogen peroxide is higher, and utilization rate is up to 70%
Left and right.Total iron ion of dissolution is less, and in reacting the waste water after 90min post processings, total iron content is only at least 5.2mg/L.This
Outward, under used catalyst can be reclaimed by externally-applied magnetic field, solve traditional fenton catalyst and be difficult to recycle, and
Produce a difficult problem for a large amount of chemical sludges.
The preparation method of the heterogeneous class fenton catalyst of the magnetic iron-based with Graphene as carrier of the present invention and should
With, the heterogeneous class fenton catalyst of the magnetic iron-based with Graphene as carrier and H2O2React with phenol wastewater in the presence of simultaneously, drop
Phenolic comp ' ds pollution in solution waste water；After the completion of wastewater treatment, using the heterogeneous class Fenton of magnetic iron-based with Graphene as carrier
Mixture is settled by the magnetic of catalyst, the heterogeneous class fenton catalyst of the magnetic iron-based with Graphene as carrier of bottom precipitation
It is reusable after recovered.
Beneficial effects of the present invention are embodied in：(1) catalyst has magnetic, easily reclaims, and repeats and utilizes；(2) prepare
Fe3O4Microsphere, with good superparamagnetism；(3) presence of Graphene can effectively prevent the reunion of active nanoparticles；(4)
Graphene has superpower electron transfer capacity, Fe0It is easy to electron transfer by Graphene as carrier to Fe3+, promote Fe3+
It is converted into Fe2+Effect, and then accelerate hydroxyl radical free radical generation, promote hard-degraded substance decomposition and COD removal；(5)
Compared with traditional Fenton-like system, and reduce the chemical sludge of Fenton-like system generation；(6) process the effect of phenolic waste water very
Good, after reaction 30min, after the clearance of phenol reaches more than 99%, 90min, COD clearances reach 70%；(7) hydrogen peroxide
Utilization it is higher, utilization rate up to 70% or so；(8) in the waste water after processing, total iron content is relatively low；(9) catalyst Reusability
Property preferably, it is still higher that Jing is used for multiple times activity.
Description of the drawings
Fig. 1 is the transmission electron microscope shape of 80000 times of the amplification of the heterogeneous class fenton catalyst that the present invention is prepared
Looks figure；
Fig. 2 is the Fe that the present invention is prepared0-Fe3O4The heterogeneous class fenton catalyst hysteresis curve figure of-Graphene；
Fig. 3 is the Fe that the present invention is prepared0-Fe3O4Phenol under the heterogeneous class fenton catalyst of-Graphene and other systems
Clearance kinetics figure；
Fig. 4 is the Fe that the present invention is prepared0-Fe3O4COD during the heterogeneous class fenton catalyst degradation of phenol of-Graphene
The kinetics figure of clearance；
Fig. 5 is the Fe that the present invention is prepared0-Fe3O4The heterogeneous class fenton catalyst of-Graphene is during degradation of phenol
The variation diagram of solution total iron content and concentration of hydrogen peroxide.
Specific embodiment
By the following examples the present invention is specifically described.
Embodiment 1
A, the graphene oxide for weighing 1.0g are added to 200mL volume ratios for 19:1 ethylene glycol and the mixing of diethylene glycol
In liquid, ultrasonic disperse 1h adds 10g sodium acrylate, 15g sodium acetates, 5.4g FeCl3·6H230min is stirred under O, room temperature,
Fully dissolve, obtain mixed liquor；
B, the mixed liquor obtained in a is transferred in polytetrafluoro reactor, 200 DEG C of temperature, is incubated 10h, then cooling chamber
Temperature, the product volume ratio for obtaining are 1:1 second alcohol and water is cleaned repeatedly, and the product after cleaning is distributed to the deoxidation of 600ml
In the middle of deionized water, Fe is obtained3O4The aqueous dispersions of-Graphene；
C, weigh 1.5g FeSO4·7H2O is dissolved in the deionized deoxygenated water of 50ml；
D, the deionized deoxygenated water pH value of 50ml in step c is adjusted to into 9 with the NaOH solution of 1mol/L, is subsequently adding
1.36g NaBH4Dissolving；
E, by FeSO4·7H2O solution is slowly dropped to the Fe obtained by step b3O4In the aqueous dispersions of-Graphene, room temperature
Lower stirring 1h；
F, NaBH prepared by step d4Solution is slowly dropped in the mixed liquor obtained by step e, reacts 1h, using Magnet
Product is collected, is 1 by product volume ratio:1 ethanol:The mixture cleaning of water, is put into the 40 DEG C of dryings of vacuum drying oven temperature
24h, after grinding is sieved, that is, obtains Fe0-Fe3O4The heterogeneous class fenton catalyst of-Graphene.
Characterize
To implementing 1 Fe for preparing0-Fe3O4The heterogeneous class fenton catalyst of-Graphene carries out transmission electron microscope (TEM) table
Seek peace the sign of hysteresis curve.Fe can be seen by Fig. 1 TEM photos3O4(size is about 8nm) is uniformly dispersed in Graphene table
Face, additionally, nanometer Fe0Also graphenic surface (size is about 80nm) is compounded in, this shows that Graphene can be prevented effectively from activity
The reunion of nanoparticle；Fig. 2 is shown in by the sign of magnetic loop line, is changed catalyst and be there is superparamagnetism, it is strong with higher magnetic
Degree (maximum saturation magnetic intensity is 42eu/g), can realize rapidly the recovery of catalyst by exterior magnetic field.
The heterogeneous class fenton catalyst of the magnetic iron-based with Graphene as carrier that embodiment 1 is obtained is used for degrading waste water
In phenolic comp ' ds pollution：
Using heterogeneous class Fenton process Phenol-Containing Wastewater Treatment, with conical flask as reactor, waste water initial concentration is 50mg/L,
The Fe for adding 1g/L embodiments 1 to prepare simultaneously0-Fe3O4The H of the heterogeneous class fenton catalyst of-Graphene and 5mmoL/L2O2, will be anti-
Device is answered to be placed in water bath chader, rotating speed is 150rpm, and temperature is 25 DEG C；As a result show：The catalyst that embodiment 1 is obtained is anti-
During answering, with Fe0-Fe3O4- Graphene fenton catalyst processes phenolic waste water as the heterogeneous class Fenton process of catalyst
Preferably, after reaction 30min, after the clearance of phenol reaches 99%, 90min, COD clearances reach 70% to effect, hydrogen peroxide
Using higher, utilization rate up to 70% or so, the total iron ion of ferrum of dissolution is less, reacts total iron content in the waste water after 90min
Only 5.2mg.
Embodiment 2
A, the graphene oxide for weighing 1.5g are added to 200mL volume ratios for 19:1 mixing for obtaining ethylene glycol and diethylene glycol
In liquid, ultrasonic disperse 1h adds 7.5g FeCl3·6H2O, 15g sodium acetate and 10g sodium acrylate, stir 30min under room temperature,
Which is fully dissolved, obtain mixed liquor；
B, the mixed liquor obtained in a is transferred in the polytetrafluoro reactor of 100ml, 200 DEG C of temperature, is incubated 10h, then
Cooling room temperature, the product volume ratio for obtaining are 1:1 second alcohol and water is cleaned repeatedly, and the product after cleaning is distributed to 600ml
Deionized deoxygenated water in the middle of, obtain Fe3O4The aqueous dispersions of-Graphene；
C, weigh 2.0g FeSO4·7H2O is dissolved in the deionized deoxygenated water of 50ml；
D, the deionized deoxygenated water pH value of 50ml in step c is adjusted to into 9 with the NaOH solution of 1mol/L, is subsequently adding
2.0g NaBH4Dissolving；
E, by FeSO4·7H2O solution is slowly dropped to the Fe obtained by step b3O4In the aqueous dispersions of-Graphene, room temperature
Lower stirring 1h；
F, NaBH prepared by step d4Solution is slowly dropped in the mixed liquor obtained by step e, reacts 1h, using Magnet
Product is collected, is 1 by product volume ratio:1 ethanol:The mixture cleaning of water, is put into the 40 DEG C of dryings of vacuum drying oven temperature
24h, after grinding is sieved, that is, obtains Fe0-Fe3O4The heterogeneous class fenton catalyst of-Graphene.
The heterogeneous class fenton catalyst of the magnetic iron-based with Graphene as carrier that embodiment 2 is obtained is used for degrading waste water
In phenolic comp ' ds pollution：
Using heterogeneous class Fenton process Phenol-Containing Wastewater Treatment, with conical flask as reactor, waste water initial concentration is 50mg/L,
The Fe for adding 1g/L embodiments 2 to prepare simultaneously0-Fe3O4The H of the heterogeneous class fenton catalyst of-Graphene and 5mmoL/L2O2, will be anti-
Device is answered to be placed in water bath chader, rotating speed is 150rpm, and temperature is 25 DEG C；As a result show：Made with the catalyst that embodiment 2 is obtained
Heterogeneous class Fenton process for catalyst is processed in phenolic waste water, and after reaction 30min, the clearance of phenol reaches 99%, 90min
COD clearances reach 68% afterwards, and the utilization of hydrogen peroxide is higher, utilization rate up to 65% or so, the total iron ion of ferrum of dissolution compared with
Few, in reacting the waste water after 90min, total iron content is 5.6mg.
Embodiment 3
A, 1.5g graphene oxides are weighed, 200ml volume ratios are added to for 19:1 ethylene glycol and the mixing of diethylene glycol
In liquid, ultrasonic disperse 1h adds 5.4g FeCl3·6H2O, 15g sodium acetate and 10g sodium acrylate, stir under room temperature so as to
Fully dissolve, obtain mixed liquor；
B, the mixed liquor obtained in a is transferred in the polytetrafluoro reactor of 100ml, 200 DEG C of temperature, is incubated 12h, then
Cooling room temperature, the product volume ratio for obtaining are 1:1 second alcohol and water is cleaned repeatedly, and the product after cleaning is distributed to 600ml
Deionized deoxygenated water in the middle of, obtain Fe3O4The aqueous dispersions of-Graphene；
C, weigh 1.8g FeSO4·7H2O is dissolved in the deionized deoxygenated water of 50ml；
D, the deionized deoxygenated water pH value of 50ml in step c is adjusted to into 9 with the NaOH solution of 1mol/L, is subsequently adding
2.0g NaBH4Dissolving；
E, by FeSO4·7H2O solution is slowly dropped to the Fe obtained by step b3O4In the aqueous dispersions of-Graphene, room temperature
Lower stirring 1h；
F, NaBH prepared by step d4Solution is slowly dropped in the mixed liquor obtained by step e, reacts 1h, using Magnet
Product is collected, is 1 by product volume ratio:1 ethanol:The mixture cleaning of water, is put into the 40 DEG C of dryings of vacuum drying oven temperature
24h, after grinding is sieved, that is, obtains Fe0-Fe3O4The heterogeneous class fenton catalyst of-Graphene.
The heterogeneous class class fenton catalyst of the magnetic iron-based with Graphene as carrier that embodiment 3 is obtained is useless for degrading
Phenolic comp ' ds pollution in water：
Using heterogeneous class Fenton process Phenol-Containing Wastewater Treatment, with conical flask as reactor, waste water initial concentration is 50mg/L,
The Fe for adding 1g/L embodiments 3 to prepare simultaneously0-Fe3O4The H of the heterogeneous class fenton catalyst of-Graphene and 5mmoL/L2O2, will be anti-
Device is answered to be placed in water bath chader, rotating speed is 150rpm, and temperature is 25 DEG C；As a result show：Made with the catalyst that embodiment 3 is obtained
Heterogeneous class Fenton process for catalyst is processed in phenolic waste water, and after reaction 30min, the clearance of phenol reaches 99%, 90min
COD clearances reach 66% afterwards.The utilization of hydrogen peroxide is higher, utilization rate up to 64% or so, reacts in the waste water after 90min
Total iron content is 5.5mg.
Embodiment 4
A, 2.0g graphene oxides are weighed, 200ml volume ratios are added to for 19:1 ethylene glycol and the mixing of diethylene glycol
In liquid, ultrasonic disperse 1h adds 5.4g FeCl3·6H2O, 15g sodium acetate and 10g sodium acrylate, stir under room temperature so as to
Fully dissolve, obtain mixed liquor；
B, the mixed liquor obtained in a is transferred in the polytetrafluoro reactor of 100ml, 200 DEG C of temperature, is incubated 15h, then
Cooling room temperature, the product volume ratio for obtaining are 1:1 second alcohol and water is cleaned repeatedly, and the product after cleaning is distributed to 600ml
Deionized deoxygenated water in the middle of, obtain Fe3O4The aqueous dispersions of-Graphene；
C, weigh 2.0g FeSO4·7H2O is dissolved in the deionized deoxygenated water of 50ml；
D, the deionized deoxygenated water pH value of 50ml in step c is adjusted to into 9 with the NaOH solution of 1mol/L, is subsequently adding
1.36g NaBH4Dissolving；
E, by FeSO4·7H2O solution is slowly dropped to the Fe obtained by step b3O4In the aqueous dispersions of-Graphene, room temperature
Lower stirring 1h；
F, NaBH prepared by step d4Solution is slowly dropped in the mixed liquor obtained by step e, reacts 1h, using Magnet
Product is collected, is 1 by product volume ratio:1 ethanol:The mixture cleaning of water, is put into the 40 DEG C of dryings of vacuum drying oven temperature
24h, after grinding is sieved, that is, obtains Fe0-Fe3O4The heterogeneous class fenton catalyst of-Graphene.
The heterogeneous class class fenton catalyst of the magnetic iron-based with Graphene as carrier that embodiment 4 is obtained is useless for degrading
Phenolic comp ' ds pollution in water：
Using heterogeneous class Fenton process Phenol-Containing Wastewater Treatment, with conical flask as reactor, waste water initial concentration is 50mg/L,
The Fe for adding 1g/L embodiments 4 to prepare simultaneously0-Fe3O4The H of the heterogeneous class fenton catalyst of-Graphene and 5mmoL/L2O2, will be anti-
Device is answered to be placed in water bath chader, rotating speed is 150rpm, and temperature is 25 DEG C；As a result show：Made with the catalyst that embodiment 4 is obtained
Heterogeneous class Fenton process for catalyst is processed in phenolic waste water, and after reaction 30min, the clearance of phenol reaches 99%, 90min
COD clearances reach 67% afterwards.The utilization of hydrogen peroxide is higher, utilization rate up to 63% or so, and total iron ion of dissolution is less,
In waste water after reaction 90min, total iron content is 5.2mg.
Embodiment 5
A, 1.8g graphene oxides are weighed, 200ml volume ratios are added to for 19:1 ethylene glycol and the mixing of diethylene glycol
In liquid, ultrasonic disperse 1h adds 5.4g FeCl3·6H2O, 15g sodium acetate and 10g sodium acrylate, stir under room temperature so as to
Fully dissolve, obtain mixed liquor；
B, the mixed liquor obtained in a is transferred in the polytetrafluoro reactor of 100ml, 200 DEG C of temperature, is incubated 12h, then
Cooling room temperature, the product volume ratio for obtaining are 1:1 second alcohol and water is cleaned repeatedly, and the product after cleaning is distributed to 600ml
Deionized deoxygenated water in the middle of, obtain Fe3O4The aqueous dispersions of-Graphene；
C, weigh 1.5g FeSO4·7H2O is dissolved in the deionized deoxygenated water of 50ml；
D, the deionized deoxygenated water pH value of 50ml in step c is adjusted to into 9 with the NaOH solution of 1mol/L, is subsequently adding
2.0g NaBH4Dissolving；
E, by FeSO4·7H2O solution is slowly dropped to the Fe obtained by step b3O4In the aqueous dispersions of-Graphene, room temperature
Lower stirring 1h；
F, NaBH prepared by step d4Solution is slowly dropped in the mixed liquor obtained by step e, reacts 1h, using Magnet
Product is collected, is 1 by product volume ratio:1 ethanol:The mixture cleaning of water, is put into the 40 DEG C of dryings of vacuum drying oven temperature
24h, after grinding is sieved, that is, obtains Fe0-Fe3O4The heterogeneous class fenton catalyst of-Graphene.
The heterogeneous class class fenton catalyst of the magnetic iron-based with Graphene as carrier that embodiment 5 is obtained is useless for degrading
Phenolic comp ' ds pollution in water：
Using heterogeneous class Fenton process Phenol-Containing Wastewater Treatment, with conical flask as reactor, waste water initial concentration is 50mg/L,
The Fe for adding 1g/L embodiments 5 to prepare simultaneously0-Fe3O4The H of the heterogeneous class fenton catalyst of-Graphene and 5mmoL/L2O2, will be anti-
Device is answered to be placed in water bath chader, rotating speed is 150rpm, and temperature is 25 DEG C；As a result show：Made with the catalyst that embodiment 5 is obtained
Heterogeneous class Fenton process for catalyst is processed in phenolic waste water, and after reaction 30min, the clearance of phenol reaches 99%, 90min
COD clearances reach 65% afterwards, and the utilization of hydrogen peroxide is higher, utilization rate up to 65% or so, and total iron ion of dissolution is less,
In waste water after reaction 90min, total iron content is 5.1mg.
Embodiment 6 (contrast)
Using heterogeneous class Fenton process Phenol-Containing Wastewater Treatment, with conical flask as reactor, initial phenol concentration is 50mg/L,
Fe is added simultaneously3O4The H of-Graphene fenton catalyst 1g/L and 5mmoL/L2O2, reactor is placed in water bath chader, is turned
Speed is 150rpm, and temperature is 25 DEG C；After reaction 30min, the clearance of phenol only has 42% to see accompanying drawing 3, with Fe0-Fe3O4- graphite
The catalytic effect of the heterogeneous class fenton catalyst of alkene differs greatly, and this shows the Fe that the method for the invention is prepared0-Fe3O4-
The heterogeneous class fenton catalyst of Graphene can improve Fe3+It is reduced to Fe2+Conversion rate, catalytic efficiency are significantly improved.
Claims (2)
1. the preparation method of the heterogeneous class fenton catalyst of a kind of magnetic iron-based with Graphene as carrier, it is characterised in that press
Row step is carried out：
A, 1.0-2.0 g graphene oxides are weighed, be added in the mixed liquor of ethylene glycol and diethylene glycol of 200 ml, ultrasound,
Add FeCl3 ·6H2O, sodium acetate and sodium acrylate, stir under room temperature so as to fully dissolve, obtain mixed liquor, wherein second
The volume ratio of glycol and diethylene glycol is 19:1；
B, the mixed liquor obtained in a is transferred in polytetrafluoro reactor, 200 DEG C of temperature, is incubated 10-15 h, then cooling chamber
Temperature, is 1 by the product volume ratio for obtaining:1 second alcohol and water is cleaned repeatedly, and the product after cleaning is distributed to 600 ml's
In the middle of deionized deoxygenated water, Fe is obtained3O4The aqueous dispersions of-Graphene；
C, weigh 1.5-2.0 g FeSO4·7H2O is dissolved in the deionized deoxygenated water of 50 ml；
D, the deionized deoxygenated water pH value of 50 ml in step c is adjusted to into 9 with the NaOH solution of 1 mol/L, is subsequently adding
1.36-2.0 g NaBH4Dissolving；
E, by FeSO4·7H2O solution is slowly dropped to the Fe obtained by step b3O4In the aqueous dispersions of-Graphene, stir under room temperature
Mix 1 h；
F, NaBH prepared by step d4Solution is slowly dropped in the mixed liquor obtained by step e, reacts 1 h, is received using Magnet
Collection product, is 1 by product volume ratio:1 ethanol:The mixture cleaning of water, is put into the 40 DEG C of dryings 24 of vacuum drying oven temperature
H, after grinding is sieved, that is, obtains Fe0-Fe3O4The heterogeneous class fenton catalyst of-Graphene.
2. the heterogeneous class fenton catalyst of the magnetic iron-based with Graphene as carrier that method according to claim 1 is obtained
The purposes in pollutant phenols in degrading waste water is prepared.
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