CN115555027B - Preparation method and application of magnetic multivalent iron-manganese oxide catalyst - Google Patents
Preparation method and application of magnetic multivalent iron-manganese oxide catalyst Download PDFInfo
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- CN115555027B CN115555027B CN202211161195.9A CN202211161195A CN115555027B CN 115555027 B CN115555027 B CN 115555027B CN 202211161195 A CN202211161195 A CN 202211161195A CN 115555027 B CN115555027 B CN 115555027B
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- iron
- manganese
- magnetic
- multivalent
- manganese oxide
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- 239000003054 catalyst Substances 0.000 title claims abstract description 126
- WQHONKDTTOGZPR-UHFFFAOYSA-N [O-2].[O-2].[Mn+2].[Fe+2] Chemical compound [O-2].[O-2].[Mn+2].[Fe+2] WQHONKDTTOGZPR-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 47
- DALUDRGQOYMVLD-UHFFFAOYSA-N iron manganese Chemical compound [Mn].[Fe] DALUDRGQOYMVLD-UHFFFAOYSA-N 0.000 claims abstract description 48
- 229910052751 metal Inorganic materials 0.000 claims abstract description 41
- 239000002184 metal Substances 0.000 claims abstract description 39
- 239000012286 potassium permanganate Substances 0.000 claims abstract description 37
- 239000000725 suspension Substances 0.000 claims abstract description 37
- 229920001661 Chitosan Polymers 0.000 claims abstract description 34
- 239000002245 particle Substances 0.000 claims abstract description 23
- 239000003245 coal Substances 0.000 claims abstract description 22
- 239000000843 powder Substances 0.000 claims abstract description 17
- 239000002699 waste material Substances 0.000 claims abstract description 16
- 238000001354 calcination Methods 0.000 claims abstract description 15
- 150000003839 salts Chemical class 0.000 claims abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000006479 redox reaction Methods 0.000 claims abstract description 13
- 239000007787 solid Substances 0.000 claims abstract description 13
- 239000012153 distilled water Substances 0.000 claims abstract description 12
- 238000000465 moulding Methods 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 150000002696 manganese Chemical class 0.000 claims abstract description 7
- 238000004065 wastewater treatment Methods 0.000 claims abstract description 7
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 50
- 239000000243 solution Substances 0.000 claims description 37
- 238000003756 stirring Methods 0.000 claims description 33
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 30
- 238000000034 method Methods 0.000 claims description 29
- 239000002351 wastewater Substances 0.000 claims description 28
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 25
- 238000002156 mixing Methods 0.000 claims description 20
- 239000000203 mixture Substances 0.000 claims description 19
- 230000015556 catabolic process Effects 0.000 claims description 17
- 238000006731 degradation reaction Methods 0.000 claims description 17
- 238000001035 drying Methods 0.000 claims description 17
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 14
- 239000010881 fly ash Substances 0.000 claims description 14
- 239000010884 boiler slag Substances 0.000 claims description 13
- 238000000926 separation method Methods 0.000 claims description 13
- 239000011812 mixed powder Substances 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- 238000005469 granulation Methods 0.000 claims description 9
- 230000003179 granulation Effects 0.000 claims description 9
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 8
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 8
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 150000001450 anions Chemical class 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 2
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 2
- 239000012670 alkaline solution Substances 0.000 claims 2
- 150000002505 iron Chemical class 0.000 claims 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 38
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 239000002994 raw material Substances 0.000 abstract description 9
- 229910000616 Ferromanganese Inorganic materials 0.000 abstract description 8
- 230000002195 synergetic effect Effects 0.000 abstract description 8
- 125000000524 functional group Chemical group 0.000 abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 abstract description 7
- 229910001428 transition metal ion Inorganic materials 0.000 abstract description 7
- 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 description 18
- 229940099596 manganese sulfate Drugs 0.000 description 13
- 239000011702 manganese sulphate Substances 0.000 description 13
- 235000007079 manganese sulphate Nutrition 0.000 description 13
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 13
- 230000035484 reaction time Effects 0.000 description 12
- 239000002957 persistent organic pollutant Substances 0.000 description 11
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 10
- 238000006243 chemical reaction Methods 0.000 description 10
- 238000002474 experimental method Methods 0.000 description 9
- 238000009713 electroplating Methods 0.000 description 8
- 229910052742 iron Inorganic materials 0.000 description 8
- 229940071125 manganese acetate Drugs 0.000 description 8
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 8
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 8
- 230000003647 oxidation Effects 0.000 description 8
- 238000007254 oxidation reaction Methods 0.000 description 8
- 238000004939 coking Methods 0.000 description 7
- 238000004043 dyeing Methods 0.000 description 7
- 238000007639 printing Methods 0.000 description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 6
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 6
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 6
- 239000011565 manganese chloride Substances 0.000 description 6
- 235000002867 manganese chloride Nutrition 0.000 description 6
- 229940099607 manganese chloride Drugs 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000007789 sealing Methods 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 230000007613 environmental effect Effects 0.000 description 5
- 229910001437 manganese ion Inorganic materials 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- -1 iron ions Chemical class 0.000 description 4
- SURQXAFEQWPFPV-UHFFFAOYSA-L iron(2+) sulfate heptahydrate Chemical compound O.O.O.O.O.O.O.[Fe+2].[O-]S([O-])(=O)=O SURQXAFEQWPFPV-UHFFFAOYSA-L 0.000 description 4
- 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 description 4
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002734 clay mineral Substances 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- 229960002089 ferrous chloride Drugs 0.000 description 3
- 239000011790 ferrous sulphate Substances 0.000 description 3
- 235000003891 ferrous sulphate Nutrition 0.000 description 3
- 239000010842 industrial wastewater Substances 0.000 description 3
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 238000007885 magnetic separation Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000007935 neutral effect Effects 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 230000033116 oxidation-reduction process Effects 0.000 description 2
- 229960001841 potassium permanganate Drugs 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 150000003624 transition metals Chemical class 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 239000005995 Aluminium silicate Substances 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 150000004696 coordination complex Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- SOCTUWSJJQCPFX-UHFFFAOYSA-N dichromate(2-) Chemical compound [O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O SOCTUWSJJQCPFX-UHFFFAOYSA-N 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 1
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000010802 sludge Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 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
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B01J35/33—
-
- 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
-
- 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
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
Abstract
The invention relates to a preparation method and application of a magnetic multivalent iron-manganese oxide catalyst. The preparation method comprises the following steps: (1) Dropwise adding chitosan solution into the multi-source coal-based waste powder, and granulating and molding to obtain a carrier; (2) Adding divalent manganese salt, divalent ferric salt and trivalent ferric salt into distilled water, adding an alkali solution, and then dripping a potassium permanganate solution for oxidation-reduction reaction to obtain a multivalent iron-manganese metal suspension; (3) And (3) immersing the carrier in a multivalent iron-manganese metal suspension, and calcining the obtained solid particles to obtain the magnetic multivalent iron-manganese oxide catalyst. The invention takes the multi-source coal waste as the carrier raw material, combines the coordination and adsorption of the functional groups in the chitosan to the transition metal ions, and enhances the stability and catalytic effect of the catalyst; the catalytic efficiency of the catalyst is improved to the greatest extent by utilizing the self multivalent state characteristics of the ferro-manganese transition metal elements and the synergistic effect between the ferro-manganese bi-metal elements, and the application prospect in the field of organic wastewater treatment is wide.
Description
Technical Field
The invention relates to the technical field of catalyst material preparation and industrial wastewater treatment, in particular to a preparation method and application of an oxide catalyst.
Background
The industries of electroplating, coking, printing and dyeing, papermaking and the like can generate a large amount of wastewater, and the wastewater has complex components, strong toxicity, contains a large amount of organic pollutants which are difficult to degrade and has lasting environmental pollution. The method is used for effectively treating the environmental pollution of industrial organic wastewater, is not only an urgent task facing the current ecological environment protection in China, but also a strategic problem for realizing sustainable development of chemical industry and manufacturing industry.
Advanced oxidation methods (such as ozone oxidation, wet oxidation, fenton and Fenton-like oxidation, photocatalytic oxidation, electrolytic oxidation, plasma oxidation, and the like) have been attracting attention because of their advantages of strong oxidizing ability, high treatment efficiency, rapid reaction speed, easy control, and the like. The heterogeneous Fenton-like catalytic oxidation technology is a high-grade oxidation technology with extremely strong practicability and the most wide application, and the reaction principle is that a solid-phase catalyst is adopted to catalyze and decompose hydrogen peroxide or persulfate and the like to generate hydroxyl free radicals with extremely strong oxidability, so that organic pollutant molecules are thoroughly degraded into carbon dioxide and water. Wherein the catalyst is the core of the heterogeneous Fenton-like reaction, and the catalytic performance of the catalyst determines the efficiency of the whole reaction.
CN 106111156A discloses a Fenton-like magnetic catalyst of clay mineral supported metal oxide, which is prepared by adding clay mineral into ferric salt solution, adding alkali liquor to raise the pH value of the solution to 8-11, washing, drying to obtain precursor powder, immersing the precursor powder in solution containing other nonferrous metal salts, evaporating to dryness uniformly, and heat treating to obtain the high-efficiency Fenton-like magnetic catalyst based on clay mineral.
CN 108404929A discloses a magnetic nano ferro-manganese double metal oxide composite catalyst, which is prepared by dissolving ferrous sulfate heptahydrate and polyvinylpyrrolidone in deionized water, adding sodium hydroxide in oil bath magnetic stirring, drying to produce black precipitate to obtain ferroferric oxide, grinding the ferroferric oxide into powder, dissolving the powder and potassium permanganate in deionized water, adding dilute hydrochloric acid, transferring into a high-pressure reaction kettle, and heating to obtain the magnetic nano ferro-manganese double metal oxide composite catalyst.
CN 105688917A discloses a porous ceramsite Fenton catalyst, which is prepared by taking municipal sludge, clay, kaolin, fly ash, a silicon source, a copper-containing compound and an iron-containing compound as raw materials, uniformly mixing and extruding the components to obtain ceramsite blanks, drying, sintering and cooling.
In summary, in the prior art or because most catalysts use the synergistic effect between iron oxide and other metal oxides to drive interfacial electromigration to improve catalytic efficiency, the iron oxide still plays a dominant role in catalysis, so the improvement degree of catalytic efficiency is still limited, and the problem of low catalytic efficiency under neutral or weak alkaline conditions is unavoidable; or because the catalyst is in powder form, the catalyst is easy to agglomerate and run off in actual engineering and blocks the equipment pipeline; or the catalyst is difficult to separate and recycle and cannot be recycled, so that the problems of secondary pollution and the like are caused.
Along with the continuous promotion of energy conservation and emission reduction policies in China, the preparation method and the application of the multiphase Fenton-like catalyst which have high catalytic efficiency, wide applicable pH range and easy separation and recovery are provided while the environmental protection requirement of resource utilization is met, and the preparation method and the application are key problems to be solved in the current industrial wastewater treatment field.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide a magnetic multivalent iron-manganese oxide catalyst, a preparation method and application.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
the primary aim of the invention is to provide a preparation method of a magnetic multivalent iron-manganese oxide catalyst, which comprises the following steps: (1) preparation of a carrier; (2) preparing a multivalent iron-manganese metal suspension; (3) preparing a magnetic multivalent iron-manganese oxide catalyst; wherein,
(1) Preparation of the carrier: uniformly mixing the multi-source coal-based waste powder according to any proportion to obtain mixed powder; then placing the mixture into a granulator, and continuously dripping chitosan solution into the granulator to carry out granulation molding; drying to obtain a carrier; the multi-source coal-based waste is a combination of at least two of fly ash, coal gangue and boiler slag;
(2) Preparing a multivalent iron-manganese metal suspension: manganese (Mn) 2+ ) Salt, ferrous iron (Fe) 2+ ) Salts and ferric iron (Fe) 3+ ) Adding salt into distilled water, stirring, adding alkali solution, stirring rapidly, and slowly dripping potassium permanganate (KMnO 4 ) Carrying out oxidation-reduction reaction on the solution, and uniformly stirring to obtain multivalent iron-manganese metal suspension;
(3) Preparation of magnetic multivalent iron-manganese oxide catalyst: and (3) immersing the carrier prepared in the step (1) in the multivalent iron-manganese metal suspension prepared in the step (2), then carrying out solid-liquid separation, and calcining the obtained solid particles to obtain the magnetic multivalent iron-manganese oxide catalyst.
Specifically, in the step (1), the multi-source coal-based waste powder is taken as a carrier raw material and is uniformly mixed according to any proportion, so that an uneven rough porous surface is easy to form, the structure can increase the specific surface area and adsorption sites of the carrier, the surface of the multi-valence iron-manganese oxide is uniformly and dispersedly supported, and the loading rate of the multi-valence iron-manganese oxide is effectively improved.
Placing the mixed powder into a granulator, continuously dripping chitosan solution, fixing and forming a carrier by utilizing the bonding effect of chitosan, and enhancing the stability and catalytic effect of the catalyst by utilizing the strong coordination and adsorption capacity of functional groups such as rich hydroxyl, amino and the like in the chitosan structure on transition metal ions; in addition, chitosan has the advantages of biodegradability, low price, environmental friendliness and the like.
The spherical or spheroid-like structure with certain strength formed by granulating in the step (1) plays a role in bearing and supporting the magnetic multivalent iron-manganese oxide, and compared with the traditional powdery catalyst, the method can avoid agglomeration and loss, block equipment pipelines and improve the utilization rate of the catalyst.
The carrier obtained by the step (1) has the advantages of adjustability, structural diversity, multiple pores, large specific surface area and the like.
Adding the divalent manganese salt, the divalent ferric salt and the trivalent ferric salt into distilled water, stirring and mixing the materials to uniformly disperse the divalent manganese salt, the divalent ferric salt and the trivalent ferric salt; then adding alkali solution, stirring rapidly to form stable colloid solution, and promoting respective cyclic reaction rate by synergistic effect between ferrum and manganese bimetallic elements to improve catalytic efficiency.
Slowly dripping a potassium permanganate solution, uniformly stirring to strengthen the mass transfer process, and generating a plurality of intermediate-valence manganese ions by utilizing oxidation-reduction reaction of seven-valence manganese ions in potassium permanganate and divalent manganese ions in divalent manganese salt, so that the multivalent iron-manganese metal suspension simultaneously contains divalent iron ions, trivalent iron ions and a plurality of intermediate-valence manganese ions; this interaction between the multivalent transition metal ions is more prone to electron transfer, thereby effectively promoting the hydrogen peroxide to produce hydroxyl radicals to degrade organic contaminants.
Step (3) immersing the carrier in a multivalent iron-manganese metal suspension, and fully contacting and combining the carrier and the multivalent iron-manganese metal suspension to enable multivalent iron-manganese oxides to be uniformly attached to the surface of the carrier; meanwhile, hydroxyl and amino functional groups of chitosan in the carrier can coordinate with iron and manganese ions to generate a metal complex, and the coordination effect is utilized to enhance the activity of metal sites and promote the efficient and continuous progress of catalytic reaction.
And (3) calcining solid particles obtained by solid-liquid separation, firmly combining the multivalent iron-manganese oxide with a carrier, avoiding the multivalent iron-manganese oxide from falling off, and forming the iron ions into ferroferric oxide magnetic particles so that the catalyst has magnetic performance.
The magnetic multivalent iron-manganese oxide catalyst obtained by the step (3) has the advantages of stable structure, magnetic separation and recovery and high catalytic efficiency.
The invention provides a preparation method of a magnetic multivalent iron-manganese oxide catalyst, which can be preferably realized by the following scheme:
preferably, in the step (1), the addition amount of the chitosan is 10-13% or 13-15% of the mass of the carrier, and the mass concentration of the chitosan solution is 2-25 g/L or 25-50 g/L.
Preferably, in the step (2), mn 2+ ∶(Fe 2+ +Fe 3+ )∶KMnO 4 = (1-3): 1 (molar ratio), fe 2 + ∶Fe 3+ = (0.5-3): 1 (molar ratio), mn 2+ +KMnO 4 =0.5 to 1.5mol/L (molar concentration), alkali to (Mn 2+ +KMnO 4 ) = (10-20) to 1 (molar ratio).
Preferably, in the step (1), the drying temperature is 100-150 ℃ or 150-200 ℃ and the drying time is 2-4 hours or 4-6 hours; the particle size of the carrier is 1.5-3.0 mm or 3.0-5.0 mm, and the shape of the carrier is spherical or spheroid.
Preferably, in the step (2), the anions in the divalent manganese salt, the anions in the divalent ferric salt and the anions in the trivalent ferric salt are any one or a combination of at least two of sulfate, nitrate, acetate and chloride.
Preferably, in the step (2), the alkali solution is any one of sodium hydroxide solution, potassium hydroxide solution and ammonia solution, and the molar concentration of the alkali solution is 5-15 mol/L or 15-25 mol/L.
Preferably, in the step (3), the mass of the carrier and the magnetic multivalent iron-manganese oxide is (5-15) to 1.
Preferably, in the step (3), the carrier is immersed in the polyvalent iron-manganese metal suspension for 2-12 hours or 12-24 hours; the calcination temperature of the solid particles is 400-600 ℃ or 600-800 ℃, and the calcination time is 2-4 hours or 4-6 hours.
It is another object of the present invention to provide a magnetic multivalent iron manganese oxide catalyst prepared by the foregoing method.
Still another object of the present invention is to provide an application of the magnetic multivalent iron manganese oxide catalyst, specifically an application of degrading organic matters in organic wastewater treatment, which is realized by the following steps:
adding the magnetic multivalent iron-manganese oxide catalyst prepared by the method into the organic wastewater, adding hydrogen peroxide (hydrogen peroxide), and oscillating to finish degradation of the organic matters; wherein the pH of the organic wastewater is 3.0-9.0, or the pH is 3.0 or 5.0 or 7.0 or 9.0.
The invention effectively utilizes multi-source coal waste fly ash, coal gangue and boiler slag as carrier raw materials, combines the coordination and adsorption effects of functional groups in chitosan on transition metal ions to form a carrier with high specific surface area and multiple adsorption sites, further loads multivalent iron-manganese oxide on the surface of the carrier, and utilizes the multivalent characteristics of iron-manganese transition metal elements and the synergistic effect between iron-manganese bimetallic elements to prepare the magnetic multivalent iron-manganese oxide catalyst with high catalytic efficiency, wide applicable pH range, strong stability and easy separation and recovery.
The catalyst is applied to the treatment of organic wastewater, and the multivalent iron-manganese oxide and hydrogen peroxide are utilized to generate multiphase Fenton-like reaction to generate hydroxyl free radicals with strong oxidability to degrade organic pollutants. The oxidation-reduction cyclic reaction between the transition metal polyvalent states of the iron and the manganese in the catalyst is faster, the invalid decomposition of hydrogen peroxide can be avoided, and the synergistic effect of the mutual promotion of the cyclic reaction of the iron and the manganese double-metal elements is combined, so that the catalytic performance of the catalyst and the utilization rate of the hydrogen peroxide are improved to the greatest extent, and the efficient treatment of the organic wastewater is realized.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) The magnetic multivalent iron-manganese oxide catalyst prepared by the invention can rapidly and efficiently catalyze and degrade organic pollutants, and has the advantages of wide sources of raw materials, stable structure and simple and convenient operation.
(2) The magnetic multivalent iron-manganese oxide catalyst prepared by the invention has wide application pH range, can still maintain higher catalytic efficiency under neutral or weak alkaline conditions, can save acid-base medicament for regulating pH, reduces medicament cost, and is more suitable for practical engineering application.
(3) The magnetic multivalent iron-manganese oxide catalyst prepared by the invention can still maintain higher catalytic efficiency on low-dosage hydrogen peroxide, realize high-efficiency degradation of organic pollutants and effectively reduce the dosage of hydrogen peroxide in engineering application.
(4) The invention adopts the multi-source waste as the carrier raw material, combines the coordination and adsorption capacity of the functional groups in the chitosan to the transition metal ions, can enhance the stability and the catalytic effect of the catalyst, and can solve the practical problems of agglomeration and loss, equipment pipeline blockage and the like of the traditional powdery catalyst in engineering application by constructing the spherical or spheroidic structure, thereby having wide application prospect.
(5) The invention utilizes the synergistic effect between the ferro-manganese bimetallic elements to promote respective circulation reaction rates, combines the characteristic that the self-polyvalent state of the ferro-manganese transition metal elements is easy to generate electron migration, and promotes the oxidation-reduction circulation reaction together through double effects so as to furthest improve the catalytic efficiency of the catalyst.
(6) The invention effectively utilizes the multi-source coal waste fly ash, coal gangue and boiler slag, not only meets the environmental protection and energy saving requirements of resource utilization and realizes waste preparation by waste, but also forms a structure with adjustable and controllable high specific surface area and multiple pores, and effectively improves the load rate of the multivalent iron-manganese oxide; the transition metal iron-manganese oxide is used as the catalyst active material, so that the catalyst has the advantages of magnetic separation and recovery and high catalytic efficiency, and is particularly suitable for organic wastewater produced in electroplating, coking, printing and dyeing and papermaking industries.
Detailed Description
In order to make the techniques and advantages of the present invention more apparent, the present invention will be described in detail with reference to the following examples.
Example 1
The preparation method of the magnetic multivalent iron-manganese oxide catalyst provided by the embodiment comprises the following steps:
(1) Preparation of the carrier: uniformly mixing fly ash and gangue powder according to any proportion to obtain mixed powder; then placing the mixture into a granulator, continuously dripping 25g/L chitosan solution for granulation molding, wherein the adding amount of the chitosan is 13% of the mass of the carrier; drying at 150deg.C for 4 hr to obtain spherical carrier with particle diameter of 3.0 mm;
(2) Preparing a multivalent iron-manganese metal suspension: adding manganese sulfate, ferrous nitrate and ferric chloride into distilled water, stirring and mixing, then adding 15mol/L sodium hydroxide solution, rapidly stirring, slowly dripping potassium permanganate solution for oxidation-reduction reaction, and uniformly stirring, wherein the manganese sulfate is equal to (ferrous nitrate and ferric chloride) to potassium permanganate=2:2:1 (molar ratio), the ferrous nitrate is equal to ferric chloride=2:1 (molar ratio), the total molar concentration of the manganese sulfate and the potassium permanganate is 1.0mol/L, and the sodium hydroxide is equal to (manganese sulfate and potassium permanganate) =15:1 (molar ratio), so as to obtain a multivalent iron-manganese metal suspension;
(3) Preparation of magnetic multivalent iron-manganese oxide catalyst: and (3) immersing the carrier prepared in the step (1) in the multivalent iron-manganese metal suspension prepared in the step (2) for 12 hours, wherein the mass of the carrier and the magnetic multivalent iron-manganese oxide is 10:1, then carrying out solid-liquid separation, and calcining the obtained solid particles at 600 ℃ for 4 hours to obtain the magnetic multivalent iron-manganese oxide catalyst.
The magnetic multivalent iron-manganese oxide catalyst prepared in the embodiment is applied to catalytic degradation treatment of electroplating wastewater, and the influence of reaction time on catalytic degradation of organic matters is examined. The method comprises the following specific steps: 100mL of electroplating wastewater (COD is 362mg/L, pH with the value of 6.18) is added into a 250mL conical flask, 5.0g of the catalyst prepared by the method is added, then 0.5mL of hydrogen peroxide is added, the mixture is sealed by a sealing film, and then the mixture is placed into a constant temperature oscillator to oscillate under the conditions of 293K and 180 rpm; meanwhile, a comparative experiment without catalyst was performed. Sampling at the reaction time of 2min, 5min, 10min, 20min and 30min respectively, measuring COD in the sample at different reaction times, and calculating the COD removal rate. COD was measured according to the national environmental protection standard of the people's republic of China HJ828-2017 dichromate method. The COD and removal rate of the sample at different reaction times are shown in Table 1.
TABLE 1
As can be seen from table 1: the COD removal rate of the sample added with the catalyst reaches 87.8% in the reaction time of 2min, and the COD removal rate of the comparative sample without the catalyst is only 56.6% in the reaction time of 30min, so that the catalyst prepared by the method can rapidly and efficiently catalyze hydrogen peroxide to degrade organic pollutants.
Example 2
The preparation method of the magnetic multivalent iron-manganese oxide catalyst provided by the embodiment comprises the following steps:
(1) Preparation of the carrier: uniformly mixing fly ash and boiler slag powder according to any proportion to obtain mixed powder; then placing the mixture into a granulator, continuously dripping 2g/L chitosan solution for granulation molding, wherein the adding amount of the chitosan is 10% of the mass of the carrier; drying at 100deg.C for 6 hr to obtain spherical carrier with particle diameter of 1.5 mm;
(2) Preparing a multivalent iron-manganese metal suspension: adding manganese nitrate, ferrous sulfate and ferric acetate into distilled water, stirring and mixing, then adding 25mol/L potassium hydroxide solution, rapidly stirring, slowly dripping potassium permanganate solution for oxidation-reduction reaction, and uniformly stirring, wherein the ratio of manganese nitrate to (ferrous sulfate and ferric acetate) to potassium permanganate=1:1:1 (molar ratio), the ratio of ferrous sulfate to ferric acetate=0.5:1 (molar ratio), the total molar concentration of manganese nitrate and potassium permanganate is 0.5mol/L, and the ratio of potassium hydroxide to (manganese nitrate and potassium permanganate) =10:1 (molar ratio) to obtain a multivalent iron-manganese metal suspension;
(3) Preparation of magnetic multivalent iron-manganese oxide catalyst: and (3) immersing the carrier prepared in the step (1) in the multivalent iron-manganese metal suspension prepared in the step (2) for 2 hours, wherein the mass of the carrier and the magnetic multivalent iron-manganese oxide is 5:1, then carrying out solid-liquid separation, and calcining the obtained solid particles at 400 ℃ for 2 hours to obtain the magnetic multivalent iron-manganese oxide catalyst.
The magnetic multivalent iron-manganese oxide catalyst prepared in the embodiment is applied to catalytic degradation treatment of electroplating wastewater, and the influence of pH value on catalytic degradation of organic matters is examined. The method comprises the following specific steps: 100mL of electroplating wastewater (COD is 362mg/L, pH value is 6.18) is added into a 250mL conical flask, the pH value of the wastewater is respectively adjusted to 3.0, 5.0, 7.0 and 9.0 by adopting 10% hydrochloric acid and 0.1mol/L sodium hydroxide, 5.0g of the catalyst prepared by the method is added, 0.5mL of hydrogen peroxide is added, the mixture is sealed by a sealing film, and then the mixture is placed into a constant-temperature oscillator, and the mixture is oscillated for 5min under the conditions of 293K and 180 rpm. And measuring COD in the sample at different pH values, and calculating the COD removal rate. The COD and removal rates of the samples at different pH values are shown in Table 2.
TABLE 2
As can be seen from table 2: the COD removal rate of the sample added with the catalyst reaches more than 90% under the acidic condition, and the sample has higher catalytic efficiency for degrading organic pollutants; the catalyst prepared by the method has wide application pH range, can solve the problem of low catalytic efficiency of the catalyst under neutral or alkalescent conditions, saves acid-base medicament for regulating pH, reduces medicament cost and is more suitable for practical engineering application.
Example 3
The preparation method of the magnetic multivalent iron-manganese oxide catalyst provided by the embodiment comprises the following steps:
(1) Preparation of the carrier: uniformly mixing gangue and boiler slag powder according to any proportion to obtain mixed powder; then placing the mixture into a granulator, continuously dripping 50g/L chitosan solution for granulation molding, wherein the adding amount of the chitosan is 15% of the mass of the carrier; drying at 200deg.C for 2h to obtain spherical carrier with particle diameter of 5.0 mm;
(2) Preparing a multivalent iron-manganese metal suspension: adding manganese acetate, ferrous chloride and ferric nitrate into distilled water, stirring and mixing, then adding 5mol/L ammonia solution, rapidly stirring, slowly dripping potassium permanganate solution for oxidation-reduction reaction, and uniformly stirring, wherein manganese acetate is equal to (ferrous chloride and ferric nitrate) to potassium permanganate=3:3:1 (molar ratio), ferrous chloride is equal to ferric nitrate=3:1 (molar ratio), the total molar concentration of manganese acetate and potassium permanganate is 1.5mol/L, and ammonia is equal to (manganese acetate and potassium permanganate) =20:1 (molar ratio), so as to obtain a multivalent iron-manganese metal suspension;
(3) Preparation of magnetic multivalent iron-manganese oxide catalyst: and (3) immersing the carrier prepared in the step (1) in the multivalent iron-manganese metal suspension prepared in the step (2) for 24 hours, wherein the mass of the carrier and the magnetic multivalent iron-manganese oxide is 15:1, then carrying out solid-liquid separation, and calcining the obtained solid particles at 800 ℃ for 6 hours to obtain the magnetic multivalent iron-manganese oxide catalyst.
The magnetic multivalent iron-manganese oxide catalyst prepared in the embodiment is applied to catalytic degradation treatment of coking wastewater, and the influence of the addition amount of hydrogen peroxide on catalytic degradation of organic matters is examined. The method comprises the following specific steps: adding 100mL of coking wastewater (COD is 2300mg/L, pH with the value of 6.8-7.6) into a 250mL conical flask, adding 5.0g of the catalyst prepared by the method, respectively adding 0.1mL, 0.3mL and 0.5mL of hydrogen peroxide, sealing by using a sealing film, then placing into a constant-temperature oscillator, and oscillating for 5min under the conditions of 293K and 180 rpm; and (5) measuring COD in the sample under different hydrogen peroxide addition amounts, and calculating the COD removal rate. The COD and removal rate of the sample at different hydrogen peroxide addition amounts are shown in Table 3.
TABLE 3 Table 3
As can be seen from table 3: the COD removal rate of the sample added with the catalyst reaches more than 80% when the hydrogen peroxide addition amounts are 0.1mL, 0.3mL and 0.5mL respectively, the hydrogen peroxide utilization rate is higher, and organic matters can be fully and effectively degraded, so that the catalyst prepared by the method can still maintain higher catalytic efficiency on the hydrogen peroxide with low addition amount, realize the efficient degradation of organic pollutants in the coking wastewater, effectively reduce the hydrogen peroxide consumption in engineering application and reduce the medicament cost.
Example 4
The preparation method of the magnetic multivalent iron-manganese oxide catalyst provided by the embodiment comprises the following steps:
(1) Preparation of the carrier: uniformly mixing fly ash, coal gangue and boiler slag powder according to any proportion to obtain mixed powder; then placing the mixture into a granulator, continuously dripping 25g/L chitosan solution for granulation molding, wherein the adding amount of the chitosan is 13% of the mass of the carrier; drying at 150deg.C for 4 hr to obtain spherical carrier with particle diameter of 3.0 mm;
(2) Preparing a multivalent iron-manganese metal suspension: adding manganese chloride, ferrous acetate and ferric sulfate into distilled water, stirring and mixing, then adding 15mol/L sodium hydroxide solution, rapidly stirring, slowly dripping potassium permanganate solution for oxidation-reduction reaction, and uniformly stirring, wherein the total molar concentration of manganese chloride and potassium permanganate is 1.0mol/L, and the total molar concentration of sodium hydroxide and potassium permanganate is 15:1 (molar ratio), and the multivalent ferro-manganese metal suspension is obtained;
(3) Preparation of magnetic multivalent iron-manganese oxide catalyst: and (3) immersing the carrier prepared in the step (1) in the multivalent iron-manganese metal suspension prepared in the step (2) for 12 hours, wherein the mass of the carrier and the magnetic multivalent iron-manganese oxide is 10:1, then carrying out solid-liquid separation, and calcining the obtained solid particles at 600 ℃ for 2 hours to obtain the magnetic multivalent iron-manganese oxide catalyst.
The preparation method of the catalyst provided by the comparison experiment is the same as the preparation method described above except that the chitosan solution is not added in the step (1), and the step (2) and the step (3) are both the same as the preparation method described above. The step (1) comprises the following steps: uniformly mixing fly ash, coal gangue and boiler slag powder according to any proportion to obtain mixed powder; then placing the mixture into a granulator for granulating and molding; drying at 150deg.C for 4 hr to obtain spherical carrier with particle diameter of 3.0 mm.
The magnetic multivalent iron-manganese oxide catalyst prepared in the embodiment and the catalyst prepared in the comparison experiment are applied to catalytic degradation treatment of printing and dyeing wastewater, and influence of chitosan addition on catalytic degradation of organic matters in the catalyst preparation process is examined. The method comprises the following specific steps: 100mL of printing and dyeing wastewater (COD is 960mg/L, pH value is 6.0-8.0) is added into a 250mL conical flask, 5.0g of the magnetic multivalent iron-manganese oxide catalyst prepared by the method and the catalyst prepared by a comparative experiment are respectively added, 0.5mL of hydrogen peroxide is added, the mixture is sealed by a sealing film, and then the mixture is placed into a constant temperature oscillator for oscillation under the conditions of 293K and 180 rpm; sampling at the reaction time of 2min, 5min, 10min, 20min and 30min respectively, measuring COD in the samples under different catalysts, and calculating the COD removal rate. The COD and removal rates of the samples at the different catalysts are shown in Table 4.
TABLE 4 Table 4
As can be seen from table 4: the COD removal rate of the catalyst sample prepared by the method is more than 80% in different reaction time, and the catalytic effect is obvious; in contrast, the catalyst sample added with the comparative experiment was only 76.3% at 30min of reaction time; therefore, the invention can effectively enhance the catalytic effect of the catalyst by adding chitosan into the carrier, mainly utilizes the coordination and adsorption capacity of functional groups in the chitosan to transition metal ions, forms the carrier with high specific surface area and multiple adsorption sites, promotes the continuous progress of high-efficiency catalytic reaction, and realizes the high-efficiency degradation of organic pollutants in printing and dyeing wastewater.
Example 5
The preparation method of the magnetic multivalent iron-manganese oxide catalyst provided by the embodiment comprises the following steps:
(1) Preparation of the carrier: uniformly mixing fly ash, coal gangue and boiler slag powder according to any proportion to obtain mixed powder; then placing the mixture into a granulator, continuously dripping 2g/L chitosan solution for granulation molding, wherein the adding amount of the chitosan is 15% of the mass of the carrier; drying at 100deg.C for 2 hr to obtain spherical carrier with particle diameter of 1.5 mm;
(2) Preparing a multivalent iron-manganese metal suspension: adding manganese sulfate, ferrous acetate and ferric nitrate into distilled water, stirring and mixing, then adding 25mol/L potassium hydroxide solution, rapidly stirring, slowly dripping potassium permanganate solution for oxidation-reduction reaction, and uniformly stirring, wherein the ratio of manganese sulfate to (ferrous acetate and ferric nitrate) to potassium permanganate=3:1:1 (molar ratio), the ratio of ferrous acetate to ferric nitrate=0.5:1 (molar ratio), the total molar concentration of manganese sulfate to potassium permanganate is 0.5mol/L, and the ratio of potassium hydroxide to (manganese sulfate and potassium permanganate) =20:1 (molar ratio) to obtain a multivalent iron-manganese metal suspension;
(3) Preparation of magnetic multivalent iron-manganese oxide catalyst: and (3) immersing the carrier prepared in the step (1) in the multivalent iron-manganese metal suspension prepared in the step (2) for 2 hours, wherein the mass of the carrier and the magnetic multivalent iron-manganese oxide is 15:1, then carrying out solid-liquid separation, and calcining the obtained solid particles at 800 ℃ for 4 hours to obtain the magnetic multivalent iron-manganese oxide catalyst.
The preparation method of the catalyst provided by the comparative experiment is the same as the preparation method described above except that manganese sulfate is not added in step (2), and both in step (1) and step (3). The step (2) comprises the following steps: adding ferrous acetate and ferric nitrate into distilled water, stirring and mixing, then adding 25mol/L potassium hydroxide solution, stirring quickly, then slowly dripping potassium permanganate solution for oxidation-reduction reaction, and stirring uniformly, wherein (ferrous acetate and ferric nitrate) to potassium permanganate=1:1 (molar ratio), ferrous acetate to ferric nitrate=0.5:1 (molar ratio), the molar concentration of potassium permanganate is 0.5mol/L, and potassium hydroxide to potassium permanganate=20:1 (molar ratio), thus obtaining the ferro-manganese metal suspension.
The magnetic multivalent iron manganese oxide catalyst prepared in the embodiment and the catalyst prepared in the comparison experiment are applied to catalytic degradation treatment of papermaking wastewater, and influence of addition of divalent manganese salt on catalytic degradation of organic matters in the catalyst preparation process is examined. The method comprises the following specific steps: 100mL of papermaking wastewater (COD is 160mg/L, pH with the value of 7.2-7.8) is added into a 250mL conical flask, 5.0g of the magnetic multivalent iron-manganese oxide catalyst prepared by the method and the catalyst prepared by a comparative experiment are respectively added, then 0.5mL of hydrogen peroxide is added, the mixture is sealed by a sealing film, and then the mixture is placed into a constant temperature oscillator for oscillation under the conditions of 293K and 180 rpm; sampling at the reaction time of 2min, 5min, 10min, 20min and 30min respectively, measuring COD in the samples under different catalysts, and calculating the COD removal rate. The COD and removal rates of the samples at the different catalysts are shown in Table 5.
TABLE 5
As can be seen from table 5: the COD removal rate of the catalyst sample prepared by the method is more than 80% in different reaction time, and the catalytic effect is obvious; compared with the prior art, the catalyst sample added with the comparison experiment has the reaction time of only 76.3 percent in 30 minutes, so that the invention can effectively enhance the catalytic efficiency of the catalyst by loading the multivalent iron-manganese oxide on the surface of the carrier, and not only utilizes the synergistic effect between iron-manganese bimetallic materials, but also utilizes the characteristic that the multivalent metal materials are easy to undergo redox reaction electron migration, thereby maximally enhancing the catalytic efficiency and realizing the efficient degradation of organic pollutants in papermaking wastewater.
Example 6
The preparation method of the magnetic multivalent iron-manganese oxide catalyst provided by the embodiment comprises the following steps:
(1) Preparation of the carrier: uniformly mixing fly ash, coal gangue and boiler slag powder according to any proportion to obtain mixed powder; then placing the mixture into a granulator, continuously dripping 50g/L chitosan solution into the granulator for granulation molding, wherein the adding amount of the chitosan is 10% of the mass of the carrier; drying at 200deg.C for 6h to obtain spherical carrier with particle diameter of 5.0 mm;
(2) Preparing a multivalent iron-manganese metal suspension: adding manganese nitrate, manganese chloride, ferrous acetate and ferric sulfate into distilled water, stirring and mixing, then adding 5mol/L ammonia solution, stirring quickly, then slowly dripping potassium permanganate solution for oxidation-reduction reaction, and stirring uniformly, (manganese nitrate and manganese chloride): (ferrous acetate and ferric sulfate): (potassium permanganate): (molar ratio) is 1:2:1, ferrous acetate: ferric sulfate): (molar ratio) is 3:1, the total molar concentration of manganese nitrate, manganese chloride and potassium permanganate is 1.5mol/L, and ammonia: (manganese nitrate, manganese chloride and potassium permanganate) =5:1 (molar ratio), thus obtaining a multivalent iron-manganese metal suspension;
(3) Preparation of magnetic multivalent iron-manganese oxide catalyst: and (3) immersing the carrier prepared in the step (1) in the multivalent iron-manganese metal suspension prepared in the step (2) for 24 hours, wherein the mass of the carrier and the magnetic multivalent iron-manganese oxide is 5:1, then carrying out solid-liquid separation, and calcining the obtained solid particles at 400 ℃ for 6 hours to obtain the magnetic multivalent iron-manganese oxide catalyst.
The catalyst prepared by the method of the invention adopts a carrier structure formed by multi-source wastes, can effectively improve the loading rate and the utilization rate of the multivalent iron-manganese oxide, and can solve the practical problems of agglomeration and loss, equipment pipeline blockage and the like of the traditional powdery catalyst in engineering application by constructing and forming a spherical or spheroidic structure, thereby having wide application prospect.
Example 7
The preparation method of the magnetic multivalent iron-manganese oxide catalyst provided by the embodiment comprises the following steps:
(1) Preparation of the carrier: uniformly mixing fly ash, coal gangue and boiler slag powder according to any proportion to obtain mixed powder; then placing the mixture into a granulator, continuously dripping 25g/L chitosan solution for granulation molding, wherein the adding amount of the chitosan is 13% of the mass of the carrier; drying at 150deg.C for 4 hr to obtain spherical carrier with particle diameter of 3.0 mm;
(2) Preparing a multivalent iron-manganese metal suspension: adding manganese sulfate, manganese acetate, ferrous nitrate and ferric chloride into distilled water, stirring and mixing, then adding 15mol/L sodium hydroxide solution, stirring quickly, then slowly dripping potassium permanganate solution for oxidation-reduction reaction, and stirring uniformly, wherein the ratio of (manganese sulfate and manganese acetate) to (ferrous nitrate and ferric chloride) to potassium permanganate=2:1:1 (molar ratio), the ratio of ferrous nitrate to ferric chloride=2:1 (molar ratio), the total molar concentration of manganese sulfate, manganese acetate and potassium permanganate is 1.0mol/L, and the ratio of sodium hydroxide to (manganese sulfate, manganese acetate and potassium permanganate) =20:1 (molar ratio) to obtain a multivalent iron-manganese metal suspension;
(3) Preparation of magnetic multivalent iron-manganese oxide catalyst: and (3) immersing the carrier prepared in the step (1) in the multivalent iron-manganese metal suspension prepared in the step (2) for 12 hours, wherein the mass of the carrier and the magnetic multivalent iron-manganese oxide is 15:1, then carrying out solid-liquid separation, and calcining the obtained solid particles at 800 ℃ for 2 hours to obtain the magnetic multivalent iron-manganese oxide catalyst.
The invention effectively utilizes the multi-source coal waste fly ash, coal gangue and boiler slag as carrier raw materials, not only meets the environmental protection and energy saving requirements of resource utilization and realizes waste-by-waste production, but also forms a structure with adjustable and controllable structure, high specific surface area and multiple pores, and is beneficial to improving the load rate of the multivalent iron-manganese oxide; the transition metal iron and manganese are used as the catalyst active material, so that the catalyst has the advantages of magnetic separation and recovery and high catalytic efficiency, and is particularly suitable for organic wastewater produced in electroplating, coking, printing and dyeing and papermaking industries.
In summary, the invention effectively utilizes the multi-source coal waste fly ash, coal gangue or boiler slag as carrier raw materials, combines the coordination and adsorption capacity of functional groups in chitosan to transition metal ions to form a carrier with high specific surface area and multiple adsorption sites, further loads the multivalent iron-manganese oxide on the surface of the carrier, and utilizes the multivalent characteristics of iron-manganese transition metal elements and the synergistic effect between iron-manganese bimetallic elements to prepare the magnetic multivalent iron-manganese oxide catalyst with high catalytic efficiency, wide applicable pH range and strong stability. The catalyst has the advantages of wide raw material sources, simple operation, capability of efficiently catalyzing and degrading organic pollutants in industrial wastewater, easiness in separation and recovery, capability of reducing the hydrogen peroxide consumption, difficulty in agglomeration and loss, and wide application prospect in the field of organic wastewater treatment in electroplating, coking, printing and dyeing and papermaking industries.
Claims (10)
1. A method for preparing a magnetic multivalent iron-manganese oxide catalyst, comprising the following steps: (1) preparation of a carrier; (2) preparing a multivalent iron-manganese metal suspension; (3) preparing a magnetic multivalent iron-manganese oxide catalyst; wherein,
(1) Preparation of the carrier: uniformly mixing the multi-source coal-based waste powder according to any proportion to obtain mixed powder; then placing the mixture into a granulator, and continuously dripping chitosan solution into the granulator to carry out granulation molding; drying to obtain a carrier; the multi-source coal-based waste is a combination of at least two of fly ash, coal gangue and boiler slag;
(2) Preparing a multivalent iron-manganese metal suspension: mn of divalent manganese 2+ Salt, ferrous iron Fe 2+ Salts and ferric iron Fe 3+ Adding salt into distilled water, stirring, adding alkali solution, stirring rapidly, and slowly dripping potassium permanganate KMnO 4 Carrying out oxidation-reduction reaction on the solution, and uniformly stirring to obtain multivalent iron-manganese metal suspension;
(3) Preparation of magnetic multivalent iron-manganese oxide catalyst: immersing the carrier prepared in the step (1) in the multivalent iron-manganese metal suspension prepared in the step (2), and then carrying out solid-liquid separation, and calcining the obtained solid particles to obtain the magnetic multivalent iron-manganese oxide catalyst;
the step (2), mn 2+ ∶(Fe 2+ +Fe 3+ )∶KMnO 4 The mol ratio of (1-3) to 1,
Fe 2+ ∶Fe 3+ the mol ratio of (0.5-3) to 1,
Mn 2+ +KMnO 4 the total molar concentration is 0.5-1.5 mol/L,
alkali to (Mn) 2+ +KMnO 4 ) The mol ratio of (10-20) to 1.
2. The preparation method of the magnetic multivalent iron-manganese oxide catalyst according to claim 1, wherein in the step (1), the addition amount of chitosan is 10-15% of the mass of the carrier, and the mass concentration of the chitosan solution is 2-50 g/L.
3. The method for preparing a magnetic multivalent iron-manganese oxide catalyst according to claim 2, wherein the drying temperature is 100-200 ℃ and the drying time is 2-6 h in the step (1); the particle size of the carrier is 1.5-5.0 mm, and the shape of the carrier is spherical or spheroid.
4. The method for preparing a magnetic multivalent iron-manganese oxide catalyst according to any one of claims 1-3, wherein the anions in the divalent manganese salt, the anions in the divalent iron salt, and the anions in the trivalent iron salt are any one or a combination of at least two of sulfate, nitrate, acetate, and chloride ions.
5. The method for preparing a magnetic multivalent iron manganese oxide catalyst according to any one of claims 1 to 3, wherein the alkaline solution in step (2) is any one of sodium hydroxide solution, potassium hydroxide solution and ammonia solution, and the molar concentration of the alkaline solution is 5 to 25mol/L.
6. The method for preparing a magnetic multivalent iron-manganese oxide catalyst according to any one of claims 1-3, wherein the step (3) is carried out for 2-24 hours when the carrier is immersed in the multivalent iron-manganese metal suspension; the calcination temperature of the solid particles is 400-800 ℃, and the calcination time is 2-6 h.
7. A magnetic multivalent iron manganese oxide catalyst as claimed in any one of claims 1 to 6.
8. Use of the magnetic multivalent iron manganese oxide catalyst according to claim 7 in the treatment of organic wastewater.
9. Use of the magnetic multivalent iron manganese oxide catalyst according to claim 8 in organic wastewater treatment, having the steps of: adding a magnetic multivalent iron-manganese oxide catalyst into the organic wastewater, adding hydrogen peroxide, and oscillating to finish degradation of organic matters; wherein the pH of the organic wastewater is 3.0-9.0.
10. Use of the magnetic multivalent iron manganese oxide catalyst according to claim 8 in organic wastewater treatment, having the steps of: adding a magnetic multivalent iron-manganese oxide catalyst into the organic wastewater, adding hydrogen peroxide, and oscillating to finish degradation of organic matters; wherein the pH of the organic wastewater is 3.0 or 5.0 or 7.0 or 9.0.
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