CN111569897A - Ozone catalyst and preparation method and application thereof - Google Patents
Ozone catalyst and preparation method and application thereof Download PDFInfo
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- CN111569897A CN111569897A CN202010397933.4A CN202010397933A CN111569897A CN 111569897 A CN111569897 A CN 111569897A CN 202010397933 A CN202010397933 A CN 202010397933A CN 111569897 A CN111569897 A CN 111569897A
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- base material
- raw coal
- catalyst
- coal powder
- ozone catalyst
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- 239000003054 catalyst Substances 0.000 title claims abstract description 101
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 64
- 239000000843 powder Substances 0.000 claims abstract description 55
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims abstract description 48
- 239000003245 coal Substances 0.000 claims abstract description 43
- 238000000227 grinding Methods 0.000 claims abstract description 41
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910001570 bauxite Inorganic materials 0.000 claims abstract description 30
- RHZUVFJBSILHOK-UHFFFAOYSA-N anthracen-1-ylmethanolate Chemical compound C1=CC=C2C=C3C(C[O-])=CC=CC3=CC2=C1 RHZUVFJBSILHOK-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000003830 anthracite Substances 0.000 claims abstract description 29
- 229910052742 iron Inorganic materials 0.000 claims abstract description 20
- 150000001879 copper Chemical class 0.000 claims abstract description 17
- 238000001035 drying Methods 0.000 claims abstract description 14
- 229940116318 copper carbonate Drugs 0.000 claims abstract description 11
- GEZOTWYUIKXWOA-UHFFFAOYSA-L copper;carbonate Chemical compound [Cu+2].[O-]C([O-])=O GEZOTWYUIKXWOA-UHFFFAOYSA-L 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 11
- 229910000365 copper sulfate Inorganic materials 0.000 claims abstract description 9
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims abstract description 9
- 229910021646 siderite Inorganic materials 0.000 claims abstract description 9
- 229910052595 hematite Inorganic materials 0.000 claims abstract description 8
- 239000011019 hematite Substances 0.000 claims abstract description 8
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000005995 Aluminium silicate Substances 0.000 claims abstract description 5
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 230000003213 activating effect Effects 0.000 claims abstract description 5
- 235000012211 aluminium silicate Nutrition 0.000 claims abstract description 5
- SVPXDRXYRYOSEX-UHFFFAOYSA-N bentoquatam Chemical compound O.O=[Si]=O.O=[Al]O[Al]=O SVPXDRXYRYOSEX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000002802 bituminous coal Substances 0.000 claims abstract description 5
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000000440 bentonite Substances 0.000 claims abstract description 4
- 229910000278 bentonite Inorganic materials 0.000 claims abstract description 4
- 238000004939 coking Methods 0.000 claims abstract description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 38
- 239000002245 particle Substances 0.000 claims description 31
- 238000007873 sieving Methods 0.000 claims description 28
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 20
- 239000002351 wastewater Substances 0.000 claims description 15
- 238000001816 cooling Methods 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 14
- 230000004913 activation Effects 0.000 claims description 11
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 11
- 238000003825 pressing Methods 0.000 claims description 10
- 239000010419 fine particle Substances 0.000 claims description 8
- 230000007935 neutral effect Effects 0.000 claims description 8
- 238000002791 soaking Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 5
- 239000011230 binding agent Substances 0.000 claims description 3
- 230000032683 aging Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- 239000008188 pellet Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 23
- 229910052751 metal Inorganic materials 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 238000007254 oxidation reaction Methods 0.000 description 22
- 230000003647 oxidation Effects 0.000 description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 20
- 239000000126 substance Substances 0.000 description 19
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- 238000006243 chemical reaction Methods 0.000 description 18
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- 230000008901 benefit Effects 0.000 description 4
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- 239000000356 contaminant Substances 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 239000011572 manganese Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 3
- 239000004480 active ingredient Substances 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 238000011049 filling Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910052748 manganese Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000000498 ball milling Methods 0.000 description 2
- 230000033558 biomineral tissue development Effects 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 150000002484 inorganic compounds Chemical class 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 150000002894 organic compounds Chemical class 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- -1 polycyclic aromatic compounds Chemical class 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- 239000005997 Calcium carbide Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- 229910002483 Cu Ka Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-M Thiocyanate anion Chemical compound [S-]C#N ZMZDMBWJUHKJPS-UHFFFAOYSA-M 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- XKMRRTOUMJRJIA-UHFFFAOYSA-N ammonia nh3 Chemical compound N.N XKMRRTOUMJRJIA-UHFFFAOYSA-N 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 150000002391 heterocyclic compounds Chemical class 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- ZMZDMBWJUHKJPS-UHFFFAOYSA-N hydrogen thiocyanate Natural products SC#N ZMZDMBWJUHKJPS-UHFFFAOYSA-N 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 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 1
- 229910000360 iron(III) sulfate Inorganic materials 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical group [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
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- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000002950 monocyclic group Chemical group 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000011197 physicochemical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920002401 polyacrylamide Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
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- 230000005855 radiation Effects 0.000 description 1
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- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 239000010456 wollastonite Substances 0.000 description 1
- 229910052882 wollastonite Inorganic materials 0.000 description 1
Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
-
- B01J35/60—
-
- B01J35/61—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/28—Treatment of water, waste water, or sewage by sorption
- C02F1/288—Treatment of water, waste water, or sewage by sorption using composite sorbents, e.g. coated, impregnated, multi-layered
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
Abstract
The invention relates to the technical field of environmental protection, in particular to an ozone catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: respectively activating the base material and the raw coal powder, then uniformly mixing the base material and the raw coal powder with iron ore, manganese dioxide and copper salt, and sequentially grinding, preparing mud, drying and roasting to obtain an ozone catalyst; wherein the mass ratio of the base material, the raw coal powder, the iron ore, the manganese dioxide and the copper salt is (3-5): (3-5): (3-4): (2-4): (6-8); the base material is one or more of bauxite, bentonite or kaolin; the raw coal powder is one or more of anthracite, bituminous coal or coking coal; the iron ore is any one or more of hematite, limonite or siderite; the copper salt is one or more of basic copper carbonate or copper sulfate. The metal elements in each catalytic unit of the catalyst can realize the release and supply of electrons by self, thereby improving the catalytic activity.
Description
Technical Field
The invention relates to the technical field of environmental protection, in particular to an ozone catalyst and a preparation method and application thereof.
Background
In recent years, the coal chemical industry has been rapidly developed, and the traditional coke, calcium carbide, synthetic ammonia and the like are changed into a novel coal chemical industry mainly comprising coal-to-liquid, coal-to-alcohol ether, coal-to-olefin and the like. Meanwhile, the water consumption in the coal chemical industry is increased year by year, and the yield of the organic wastewater difficult to degrade is increased. The coal chemical wastewater mainly comes from coal coking and coal gasification processes, and generally contains various inorganic and organic compounds due to the great difference of different water qualities of the processes. Wherein the inorganic compound is mainly ammonium salt, thiocyanide, sulfide, cyanide and the like; besides phenols, the organic compounds also contain toxic and harmful substances such as monocyclic and polycyclic aromatic compounds, heterocyclic compounds containing nitrogen, sulfur and oxygen, and the like, have high pollutant chroma, belong to high-concentration organic chemical wastewater which is difficult to be biochemically degraded, have high COD, chroma and ammonia nitrogen, and have poor biodegradability. The physicochemical and biological combined two-stage treatment is still difficult to reach the discharge standard, so the wastewater treatment is always a difficult problem in the field of domestic and foreign wastewater treatment.
At present, the main methods adopted for treating the coal chemical wastewater comprise: 1. chemical methods of materials, including coagulating sedimentation, adsorption method, photocatalytic oxidation, etc.; 2. oxidation methods including Fenton oxidation, ozone oxidation, electrochemical oxidation, photocatalytic oxidation, and the like; 3. membrane separation techniques. Among them, the physicochemical method is to convert the contaminants into solid precipitates or attach them to the surface of the adsorbent material, thereby achieving the purpose of separating the contaminants from the water, and thus it can be seen that in this method, the contaminants are only transformed into one form and the toxicity of the contaminants is not fundamentally eliminated. Besides the photocatalytic oxidation technology, the oxidation method has the disadvantages of high investment and operation cost, strict requirements on the quality of a reactor and poor economic benefit. The membrane separation technology has high one-time investment and high operation energy consumption, and in general, in order to discharge the effluent up to the standard, reverse osmosis technology is mostly added subsequently, so that a large amount of high-salt water is generated, and the treatment of the high-salt water is also a difficult problem in the water treatment industry at present.
Ozone has received much attention as a strong oxidant (oxidation-reduction potential of 2.08V) in the field of water treatment. However, the low mineralization rate of ozone alone means that it is more expensive to completely mineralize organic materials, and the intermediate products generated during the ozone reaction are more toxic and more difficult to remove. Compared with single ozone oxidation reaction, the catalytic ozone oxidation technology is taken as an advanced oxidation technology, the main mechanism is that hydroxyl free radicals with higher reaction rate and stronger oxidability are generated by catalytic ozone decomposition in the presence of a catalyst, and various products which are difficult to degrade in wastewater treatment can be degraded, so that the wastewater can be efficiently treated under the condition of low ozone adding amount. In addition, the ozone catalytic oxidation technology can meet the industrial application condition from process design to equipment configuration and is not influenced by natural conditions and technical bottlenecks; secondly, the degradation of the organic matters is relatively thorough, the generation amount of reaction byproducts is small, and the potential environmental risk is low.
However, because ozone has strong selectivity and almost has no oxidation effect on small molecular organic acids, a reaction system generated by hydroxyl radicals needs to be constructed, and the characteristics of strong oxidation property and poor selectivity of the hydroxyl radicals are utilized to carry out mineralization reaction on most organic matters, so that the COD content in the wastewater is reduced fundamentally. The ozone catalytic oxidation technology is to utilize the catalytic action of a catalyst to strengthen the generation of hydroxyl radicals in a reaction system, and the catalytic activity is a main index for evaluating the performance of the catalyst and is a key factor for promoting the generation of the hydroxyl radicals in the reaction system.
Therefore, the development of a high-efficiency catalytic material capable of rapidly promoting the ozone decomposition to generate hydroxyl radicals is a technical problem to be solved in the field.
Disclosure of Invention
The first purpose of the invention is to provide a preparation method of an ozone catalyst, and the catalyst prepared by the method solves the problem of loss of effective components;
the second purpose of the invention is to provide an ozone catalyst which has strong catalytic activity and stable physicochemical property;
the third purpose of the invention is to provide an application of an ozone catalyst, and the catalyst can effectively remove organic matters which are difficult to degrade in coal chemical industry wastewater.
The invention provides a preparation method of an ozone catalyst, which comprises the following steps:
respectively activating the base material and the raw coal powder, then uniformly mixing the base material and the raw coal powder with iron ore, manganese dioxide and copper salt, and sequentially grinding, preparing mud, drying and roasting to obtain an ozone catalyst;
wherein the mass ratio of the base material, the raw coal powder, the iron ore, the manganese dioxide and the copper salt is (3-5): (3-5): (3-4): (2-4): (6-8);
the base material is one or more of bauxite, bentonite or kaolin;
the raw coal powder is one or more of anthracite, bituminous coal or coking coal;
the iron ore is any one or more of hematite, limonite or siderite;
the copper salt is one or more of basic copper carbonate or copper sulfate.
The catalyst material commonly used in the prior art is in a form of loading on the surface of a base material, most effective elements are exposed outside the catalyst material, the catalyst material is easily influenced by hydraulic impact and oxidation of an oxidant, the loss of effective components is large, and the catalyst material is easily polluted by heavy metals in the reaction process. In order to solve the problem, the catalyst comprises a base material, a metal oxide and a metal simple substance, in the preparation process, the carbon element in the raw coal powder reduces the metal oxide into the metal simple substance, so that the prepared catalyst material belongs to an embedded coating type material, active ingredients are embedded into the base material to form a plurality of closed catalytic units, and the inside of each catalytic unit is subjected to electron transfer, so that the loss of the active elements is reduced, and the overflow amount of heavy metals in the reaction process is further reduced. In addition, in each catalytic unit, metal elements such as iron, manganese, copper and the like generate synergistic effect, can realize the release and supply of electrons by self, has stronger catalytic activity, effectively improves the generation amount of hydroxyl free radicals in a reaction system, has strong oxidation effect on various organic matters, increases the reaction rate, and fundamentally solves the problem of low ozone utilization rate in the ozone advanced oxidation technology.
Further, the method specifically comprises the following steps:
s1, respectively activating the base material and the raw coal powder by using phosphoric acid;
s2, uniformly mixing and grinding the base material and the raw coal powder after the activation treatment with iron ore, manganese dioxide and copper salt, and sieving the mixture through a 300-fold 500-mesh sieve after grinding;
s3, adding water into the mixed material obtained in the step S2 to prepare pug, and pressing the pug into particles;
s4, drying, roasting and sieving the particles in sequence to obtain the ozone catalyst.
The ozone catalyst prepared by the method has the advantages of large specific surface area, porous structure, element distribution and the like, and can overcome the defect of large loss of effective components.
Further, in step S1, during the activation treatment, firstly, the base material and the raw coal powder are ground and pulverized to 300-500 meshes respectively; then, respectively placing the base material and the raw coal powder in phosphoric acid with the concentration of 30-50%, soaking for 10-24h at 80-100 ℃, washing to be neutral by using water, and drying for 20-28h at 70-90 ℃.
The base material and the raw coal powder are respectively activated by phosphoric acid, so that impurities in the base material and the raw coal powder can be removed, and the surface of the base material can be activated to improve the curing effect between the effective components and the base material.
Further, in step S2, the iron ore, manganese dioxide and copper salt are ground and sieved with 300-500 mesh sieve before being mixed with the binder and the raw coal powder.
Before the ozone catalyst is prepared, raw materials of iron ore, manganese dioxide and copper salt are ground and crushed respectively, effective elements and base materials can be uniformly mixed to a certain extent, a plurality of catalytic units are formed in the whole material system, and each catalytic unit can realize the release and supply of electrons. And the prepared ozone catalyst has larger specific surface area and adsorption capacity, so that organic matters can be promoted to be oxidized on the surface of the catalyst under the coordination of adsorption, and residual trace organic matters can be deposited on the surface of the catalyst and then separated, thereby endowing ozone with higher catalytic activity.
Further, step S3 specifically includes: and (4) adding water into the mixed material obtained in the step (S2) to prepare pug, sealing and aging at room temperature for 2-3h, and pressing into particles with the particle size of 1-3 cm.
Further, in step S4, during the drying, the particles are placed at 80-100 ℃ for treatment for 8-12h to obtain blanks.
Further, in step S4, during the baking, the blank is placed in a nitrogen atmosphere, heated to 800-1000 ℃ at a heating rate of 400 ℃/h and kept at a constant temperature for 1-2h, and then cooled to room temperature at a cooling rate of 500 ℃ and 400-.
Further, in step S4, in the screening process, the roasted catalyst is screened by a 10-20 mesh sieve to remove fine particles, and the ozone catalyst is obtained.
An ozone catalyst prepared according to the above preparation method.
The ozone catalyst prepared by the method has the advantages of stable physical and chemical properties, strong catalytic activity, less loss of effective elements and long service life.
The application of the ozone catalyst in treating coal-fired wastewater.
The ozone catalyst prepared by the invention has strong catalytic activity, can quickly promote the cracking of ozone to generate hydroxyl radicals, and when the ozone catalyst is applied to the ozone oxidation technology for treating the coal chemical industry wastewater, the degradation of organic matters is thorough, the yield of reaction byproducts is small, and the potential risk is lower.
Compared with the prior art, the preparation method of the ozone catalyst has the following advantages:
1. the catalyst prepared by the preparation method is embedded and coated, a plurality of closed catalytic units can be formed, and due to the existence of van der Waals force, the active ingredients can form firm chemical bonds with the base material, so that the falling off caused by the impact of water force is effectively avoided, and the problem of the loss of the active ingredients is solved;
2. according to the catalyst prepared by the preparation method, in each catalytic unit, metal elements such as iron, copper and manganese act synergistically, release and supply of electrons can be realized, and the problems that the catalyst is invalid and effective components fall off due to oxidation of a single metal element are effectively avoided;
3. the catalyst prepared by the preparation method disclosed by the invention has high catalytic activity and large specific surface area, organic matters can be promoted to be oxidized on the surface of the catalyst under the cooperation of adsorption, and residual trace organic matters can be deposited on the surface of the catalyst and then separated;
4. the main raw materials of coal, iron ore, copper salt, manganese dioxide and base material used in the preparation process are common mineral raw materials with low price, and the whole preparation process does not need specific reaction equipment and has low production cost.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is an SEM photograph of an ozone catalyst of the present invention;
FIG. 2 is a graph showing the adsorption-desorption curves of N2 for the ozone catalyst of the present invention;
FIG. 3 is a pore size distribution diagram of the ozone catalyst of the present invention;
FIG. 4 is an XRD pattern of the ozone catalyst of the present invention;
FIG. 5 is an XPS plot of an ozone catalyst of the present invention;
FIG. 6 is a TEM photograph of the ozone catalyst of the present invention at 10000 times magnification;
FIG. 7 is a graph showing the detection of hydroxyl radicals in the ozone catalyst of the present invention;
FIG. 8 is a graph showing the measurement of superoxide radicals in the ozone catalyst of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the following embodiments, and it should be understood that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the description of the present invention, it is to be understood that the terms "center", "longitudinal", "lateral", "length", "width", "thickness", "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", "clockwise", "counterclockwise", and the like, indicate orientations and positional relationships based on those shown in the drawings, and are used only for convenience of description and simplicity of description, and do not indicate or imply that the device or element being referred to must have a particular orientation, be constructed and operated in a particular orientation, and thus, should not be considered as limiting the present invention.
Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, features defined as "first", "second", may explicitly or implicitly include one or more of the described features. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise. Furthermore, the terms "mounted," "connected," and "connected" are to be construed broadly and may, for example, be fixedly connected, detachably connected, or integrally connected; can be mechanically or electrically connected; they may be connected directly or indirectly through intervening media, or they may be interconnected between two elements. The specific meanings of the above terms in the present invention can be understood in specific cases to those skilled in the art.
Example 1
S11, grinding 100g of anthracite powder and 100g of bauxite by using a ball mill for not less than 30min, sieving by using a 300-mesh sieve after grinding, then soaking the ground bauxite and the anthracite powder by using 30% phosphoric acid at 100 ℃ for 20h for activation treatment, washing the bauxite and the anthracite powder to be neutral by using water, and drying the bauxite and the anthracite powder at 70 ℃ for 28 h;
s12, placing hematite, basic copper carbonate and manganese dioxide into a ball mill respectively, grinding for no less than 30min, sieving with a 300-mesh sieve after grinding, mixing activated bauxite and anthracite powder with 84g of hematite, 75g of manganese dioxide and 175g of basic copper carbonate after grinding and crushing, placing the mixture into the ball mill, grinding for no less than 30min, and sieving with the 300-mesh sieve after grinding;
s13, adding water into the mixed material obtained in the step S12 to prepare pug, wherein the added water is suitable for the pug to be agglomerated and not sticky, then pressing the pug into particles with the particle size of about 1cm, and placing the particles in an oven at 80 ℃ for treatment for 12 hours to prepare blanks;
s14, uniformly transferring the prepared blank into an atmosphere furnace, introducing nitrogen for protection, adjusting a temperature control system of the atmosphere furnace, heating to 800 ℃ at a heating rate of 320 ℃/h, keeping the temperature for 1h at constant temperature, cooling to room temperature at a cooling rate of 400 ℃, removing the catalyst material out of the atmosphere furnace, sieving with a 10-mesh sieve, and removing fine particles to obtain the ozone catalyst.
Example 2
S21, grinding 75g of bituminous coal powder and 75g of bentonite for not less than 30min by using a ball mill respectively, sieving by using a 400-mesh sieve after grinding, soaking the ground bauxite and anthracite powder in 40% phosphoric acid respectively at 80 ℃ for 24h for activation treatment, washing the bauxite and anthracite powder to be neutral by using water, and drying the bauxite and anthracite powder at 90 ℃ for 20 h;
s22, respectively placing limonite, copper sulfate and manganese dioxide in a ball mill to grind for no less than 30min, sieving by a 400-mesh sieve after grinding, uniformly mixing activated bentonite and bituminous coal powder with 75g of limonite, 50g of manganese dioxide and 150g of copper sulfate after grinding and crushing, placing in the ball mill to grind for no less than 30min, and sieving by the 400-mesh sieve after grinding;
s23, adding water into the mixed material obtained in the step S22 to prepare pug, wherein the added water is suitable for the pug to be agglomerated and not sticky, then pressing the pug into particles with the particle size of about 2cm, and placing the particles in an oven at 100 ℃ for treatment for 8 hours to prepare blanks;
s24, uniformly transferring the prepared blank into an atmosphere furnace, introducing nitrogen for protection, adjusting a temperature control system of the atmosphere furnace, heating to 1000 ℃ at a heating rate of 400 ℃/h, keeping the temperature for 1.5h at constant temperature, cooling to room temperature at a cooling rate of 500 ℃, removing the catalyst material out of the atmosphere furnace, sieving by a 10-mesh sieve, and removing fine particles to obtain the ozone catalyst.
Example 3
S31, grinding 125g of anthracite powder and 125g of bauxite by using a ball mill for not less than 30min, sieving by using a 500-mesh sieve, soaking the ground bauxite and the anthracite powder in 50% phosphoric acid at 90 ℃ for 15h for activation treatment, washing the bauxite and the anthracite powder to be neutral by using water, and drying the bauxite and the anthracite powder at 80 ℃ for 24 h;
s32, respectively placing siderite, basic copper carbonate and manganese dioxide in a ball mill to grind for no less than 30min, sieving by a 3500 sieve after grinding, uniformly mixing activated bauxite and anthracite powder with 100g siderite, 100g manganese dioxide and 200g copper salt after grinding and crushing, placing in the ball mill to grind for no less than 30min, and sieving by a 400-mesh sieve after grinding;
s33, adding water into the mixed material obtained in the step S32 to prepare pug, wherein the added water is suitable for the pug to be agglomerated and not sticky, then pressing the pug into particles with the particle size of about 1.5cm, and placing the particles in a 90 ℃ oven for treatment for 10 hours to prepare blanks;
s34, uniformly transferring the prepared blank into an atmosphere furnace, introducing nitrogen for protection, adjusting a temperature control system of the atmosphere furnace, heating to 900 ℃ at a heating rate of 350 ℃/h, keeping the temperature for 1h at constant temperature, cooling to room temperature at a cooling rate of 450 ℃, removing the catalyst material out of the atmosphere furnace, sieving with a 10-mesh sieve, and removing fine particles to obtain the ozone catalyst.
Example 4
S41, grinding 100g of anthracite powder and 100g of bauxite by using a ball mill for not less than 30min, sieving by using a 400-mesh sieve, soaking the ground bauxite and the anthracite powder by using 40% phosphoric acid at 80 ℃ for 10h for activation treatment, washing the bauxite and the anthracite powder to be neutral by using water, and drying the bauxite and the anthracite powder at 80 ℃ for 24 h;
s42, placing hematite, basic copper carbonate and manganese dioxide into a ball mill respectively, grinding for no less than 30min, sieving by a 400-mesh sieve after grinding, mixing activated bauxite and anthracite powder with 80g of iron ore, 75g of manganese dioxide and 125g of copper salt after grinding and crushing, placing the mixture into the ball mill, grinding for no less than 30min, and sieving by the 400-mesh sieve after grinding;
s43, adding water into the mixed material obtained in the step S42 to prepare pug, wherein the added water is suitable for the pug to be agglomerated and not sticky, then pressing the pug into particles with the particle size of about 1cm, and placing the particles in a 90 ℃ oven for treatment for 10 hours to prepare blanks;
s44, uniformly transferring the prepared blank into an atmosphere furnace, introducing nitrogen for protection, adjusting a temperature control system of the atmosphere furnace, heating to 1000 ℃ at a heating rate of 400 ℃/h, keeping the temperature for 1.5h at constant temperature, cooling to room temperature at a cooling rate of 450 ℃, removing the catalyst material out of the atmosphere furnace, sieving by a 10-mesh sieve, and removing fine particles to obtain the ozone catalyst.
Example 5
S51, grinding 100g of anthracite powder and 100g of bauxite by using a ball mill for not less than 30min, sieving by using a 400-mesh sieve, soaking the ground bauxite and the anthracite powder by using 40% phosphoric acid at 80 ℃ for 10h for activation treatment, washing the bauxite and the anthracite powder to be neutral by using water, and drying the bauxite and the anthracite powder at 80 ℃ for 24 h;
s52, grinding hematite, siderite, basic copper carbonate, copper sulfate and manganese dioxide in a ball mill for no less than 30min, sieving with a 400-mesh sieve after grinding, mixing bauxite and anthracite powder after activation treatment with 40g hematite, 40g siderite, 75g manganese dioxide, 100g basic copper carbonate and 25g copper sulfate after grinding and crushing, placing in a ball mill for grinding for no less than 30min, and sieving with a 400-mesh sieve after grinding;
s53, adding water into the mixed material obtained in the step S52 to prepare pug, wherein the added water is suitable for the pug to be agglomerated and not sticky, then pressing the pug into particles with the particle size of about 1cm, and placing the particles in a 90 ℃ oven for treatment for 10 hours to prepare blanks;
s54, uniformly transferring the prepared blank into an atmosphere furnace, introducing nitrogen for protection, adjusting a temperature control system of the atmosphere furnace, heating to 1000 ℃ at a heating rate of 400 ℃/h, keeping the temperature for 1.5h at constant temperature, cooling to room temperature at a cooling rate of 450 ℃, removing the catalyst material out of the atmosphere furnace, sieving by a 10-mesh sieve, and removing fine particles to obtain the ozone catalyst.
Example 6
S61, grinding 100g of anthracite powder, 50g of bauxite and 50g of kaolin by a ball mill for not less than 30min, sieving by a 400-mesh sieve, soaking the ground bauxite and anthracite powder in 40% phosphoric acid at 80 ℃ for 10h for activation treatment, washing with water to be neutral, and drying at 80 ℃ for 24 h;
s62, respectively placing siderite, basic copper carbonate, copper sulfate and manganese dioxide in a ball mill for grinding for no less than 30min, sieving by a 400-mesh sieve after grinding, uniformly mixing the activated bauxite, kaolin and anthracite powder with 80g siderite, 75g manganese dioxide, 100g basic copper carbonate and 25g copper sulfate which are ground and crushed, placing in the ball mill for grinding for no less than 30min, and sieving by the 400-mesh sieve after grinding;
s63, adding water into the mixed material obtained in the step S62 to prepare pug, wherein the added water is suitable for the pug to be agglomerated and not sticky, then pressing the pug into particles with the particle size of about 1cm, and placing the particles in a 90 ℃ oven for treatment for 10 hours to prepare blanks;
s64, uniformly transferring the prepared blank into an atmosphere furnace, introducing nitrogen for protection, adjusting a temperature control system of the atmosphere furnace, heating to 1000 ℃ at a heating rate of 400 ℃/h, keeping the temperature for 1.5h at constant temperature, cooling to room temperature at a cooling rate of 450 ℃, removing the catalyst material out of the atmosphere furnace, sieving by a 10-mesh sieve, and removing fine particles to obtain the ozone catalyst.
The structure of the ozone catalyst prepared in example 1 is characterized, and the characterization method and the result are as follows:
1. SEM photograph
And analyzing the particle size and the morphology structure of the composite catalyst material by using a Japanese Hitachi S-2400 field emission scanning electron microscope.
Fig. 1 is a scanning electron microscope image of the ozone catalyst material particles magnified 1000 times (a) and 3000 times (b), respectively, and the SEM image of fig. 1(a), which is a small magnification, shows that the synthesized porous ozone catalyst is composed of many irregular fine block-shaped powders, thereby making the surface of the ozone catalyst very rough. As shown in fig. 1(b), the finer structure of the surface of the synthesized ozone catalyst can be further observed by the SEM image with a larger magnification, and the fine block powder surface is very fluffy and stacked into a multi-stage structure, so that the catalyst is porous and has a larger specific surface area. .
2. Specific surface area and pore diameter
The specific surface area of the ozone catalyst material was measured by a nitrogen adsorption BET specific surface area meter model Gemini 2375V4.01 (Norcross, usa).
The nitrogen adsorption-desorption curve of fig. 2 shows a type IV isotherm with a hysteresis loop of H3, indicating that the ozone catalyst material has a strong force with nitrogen and the material shows porosity due to gas evolution during catalyst synthesis and the re-accumulation of plate-like particles to form slit pores. Therefore, the porous ozone catalyst synthesized by the invention has larger specific surface area (SBET is 220.8 m)2·g-1). As shown in FIG. 3, the Barrett-Joyner-Halenda (BJH) pore size distribution diagram of the ozone catalyst shows that the synthesized ozone catalystThe pore diameter of (2) is mainly distributed at 3.8 nm.
3. XRD spectrogram
The X-ray diffraction (XRD) pattern of the ozone catalyst material was obtained on a b/max-RB diffraction meter (Rigaku, Japan) using nickel filtered Cu Ka radiation with a scan range from 5 to 120 ℃ and a scan speed of 4/min.
As shown in fig. 4, the ozone catalyst synthesized by the present invention contains alumina, silica, etc., and is a mixture. The manganese oxide content during the synthesis is relatively low because manganese oxide forms iron-rich manganese wollastonite mainly with iron oxide and bauxite under ball milling and high temperature reaction, and the presence of this peak is also evident from the X-ray diffraction pattern (fig. 5). The copper oxide content is also relatively low during the synthesis, since it forms compounds (calcium copper iron oxide) mainly with other reactants under ball milling and high temperature reactions. In addition, XRD results also show that the ozone catalyst is a compound containing a zeolite structure, which provides a basis for larger specific surface area.
4. XPS spectra
The ozone catalyst material was subjected to full spectrum scanning using an X-ray spectrometer and its surface elements were analyzed.
The XPS spectrum of the ozone catalyst prepared by the invention is shown in figure 5. The peak positions are 531.3eV, 284.8eV and 103.2eV, which respectively correspond to three peaks of O1s, C1 s and Si 2 p; while the four peaks with binding energies at 74.2eV, 952.5eV, 711.4eV and 642.6eV, respectively, are attributed to the Al 2p, Cu 2p, Fe 2p and Mn 2p orbitals. The XPS spectrum shows that the synthesized ozone catalyst mainly contains non-metal elements such as Si and O (C peak is mainly derived from carbon substrate or air), and contains a small amount of metal elements such as Cu, Fe, Mn, Al and the like.
5. TEM photograph
The particle size and the micro-morphology structure of the ozone catalyst material are analyzed by using a FEI F20 field emission transmission electron microscope
As shown in fig. 6, the synthesized ozone catalyst is in a block shape and has a distinct porous structure. This is because, in the final high-temperature calcination step of the ozone catalyst, the carbon source escapes in the form of gas, so that the catalyst forms a porous structure. The TEM photograph further provides a direct basis for the catalyst to have porosity and a large specific surface area, consistent with SEM analysis results.
6. Hydroxyl radical and superoxide radical detection
As can be seen from fig. 7 and 8, the ozone catalyst prepared by the present invention can rapidly promote the ozone cracking to generate hydroxyl radicals and superoxide radicals, thereby improving the utilization rate of ozone.
In order to further research the catalytic activity of the prepared ozone catalyst, the invention selects coal chemical wastewater with TOC concentration of 400-500mg/L as a representative, and uses the ozone catalyst material prepared in the embodiments 1-6 to construct an ozone advanced oxidation system to remove organic matters in the water.
The processing steps are as follows: the method comprises the steps of using a reaction column with the diameter of 90mm multiplied by 300mm, the filling density of an ozone catalyst is 75%, the filling thickness is 200mm, the contact reaction time is 30min, the pH value of raw water is 7.8, the concentration of suspended solid (SS concentration) is 30mg/L, directly pumping coal chemical industry wastewater from the top of a reactor by using a micropump, uniformly inputting ozone into the reactor from the bottom through a gas distribution device, discharging water from the lower part after the reaction is finished, enabling the discharged water to enter a water collecting tank, adding 20ppm of polymeric ferric sulfate and 1ppm of polyacrylamide into the water tank, carrying out gradient stirring to keep the reaction for 20min, standing for 30min, adjusting the pH to 8-9, and standing for 30 min. And finally, detecting the content of organic matters in the effluent by using a TOC analyzer. Table 1 shows the effect of the ozone catalysts prepared in examples 1 to 6 on the treatment of wastewater from coal chemical industry.
TABLE 1 treatment Effect of ozone catalysts prepared in examples 1 to 6 on wastewater of coal chemical industry
As can be seen from Table 1, when the filling rate of the ozone catalyst is 75%, compared with the traditional advanced oxidation technology, the ozone catalyst prepared by the invention has higher degradation capability on specific organic matters in the coal chemical industry wastewater, the degradation efficiency is more than 98%, the ozone catalyst is far greater than the removal effect of common ozone advanced oxidation, the utilization rate of ozone is greatly improved, and the effluent can be directly discharged up to the standard.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the ozone catalyst is characterized by comprising the following steps of:
respectively activating the base material and the raw coal powder, then uniformly mixing the base material and the raw coal powder with iron ore, manganese dioxide and copper salt, and sequentially grinding, preparing mud, drying and roasting to obtain an ozone catalyst;
wherein the mass ratio of the base material, the raw coal powder, the iron ore, the manganese dioxide and the copper salt is (3-5): (3-5): (3-4): (2-4): (6-8);
the base material is one or more of bauxite, bentonite or kaolin;
the raw coal powder is one or more of anthracite, bituminous coal or coking coal;
the iron ore is any one or more of hematite, limonite or siderite;
the copper salt is one or more of basic copper carbonate or copper sulfate.
2. The preparation method according to claim 1, comprising the following steps:
s1, respectively activating the base material and the raw coal powder by using phosphoric acid;
s2, uniformly mixing and grinding the base material and the raw coal powder after the activation treatment with iron ore, manganese dioxide and copper salt, and sieving the mixture through a 300-fold 500-mesh sieve after grinding;
s3, adding water into the mixed material obtained in the step S2 to prepare pug, and pressing the pug into particles;
s4, drying, roasting and sieving the particles in sequence to obtain the ozone catalyst.
3. The method as claimed in claim 2, wherein in step S1, the activation treatment is performed by first grinding the binder and the raw coal powder to 300-500 mesh; then, respectively placing the base material and the raw coal powder in phosphoric acid with the concentration of 30-50%, soaking for 10-24h at 80-100 ℃, washing to be neutral by using water, and drying for 20-28h at 70-90 ℃.
4. The method as claimed in claim 2, wherein the iron ore, manganese dioxide and copper salt are ground and sieved with 300-500 mesh sieve before being mixed with the binder and the raw coal powder in step S2.
5. The method according to claim 2, wherein step S3 specifically includes: and (4) adding water into the mixed material obtained in the step (S2) to prepare pug, sealing and aging at room temperature for 2-3h, and pressing into particles with the particle size of 1-3 cm.
6. The method according to claim 2, wherein in the step S4, the pellets are treated at 80-100 ℃ for 8-12h to obtain a billet.
7. The method as claimed in claim 6, wherein in step S4, during the baking, the blank is placed in a nitrogen atmosphere, heated to 800-1000 ℃ at a heating rate of 400 ℃/h and kept at a constant temperature for 1-2h, and then cooled to room temperature at a cooling rate of 400-500 ℃.
8. The preparation method according to claim 7, wherein in the step S4, the calcined catalyst is sieved by a sieve with 10-20 meshes to remove fine particles, so that the ozone catalyst is obtained.
9. The ozone catalyst produced by the production method according to any one of claims 1 to 8.
10. Use of the ozone catalyst of claim 9 for treating coal-fired wastewater.
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