CN108686673B - Ozone catalytic oxidation catalyst and preparation method thereof - Google Patents
Ozone catalytic oxidation catalyst and preparation method thereof Download PDFInfo
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- CN108686673B CN108686673B CN201810486622.8A CN201810486622A CN108686673B CN 108686673 B CN108686673 B CN 108686673B CN 201810486622 A CN201810486622 A CN 201810486622A CN 108686673 B CN108686673 B CN 108686673B
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- catalyst
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- activated carbon
- incinerator
- ash
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- 239000003054 catalyst Substances 0.000 title claims abstract description 123
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 15
- 230000003647 oxidation Effects 0.000 title claims abstract description 14
- 238000002360 preparation method Methods 0.000 title abstract description 28
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 85
- 230000004048 modification Effects 0.000 claims abstract description 25
- 238000012986 modification Methods 0.000 claims abstract description 25
- 239000002912 waste gas Substances 0.000 claims abstract description 23
- 239000000126 substance Substances 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 238000009832 plasma treatment Methods 0.000 claims abstract 7
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 55
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 55
- 238000005470 impregnation Methods 0.000 claims description 51
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 30
- 238000001035 drying Methods 0.000 claims description 28
- 239000011777 magnesium Substances 0.000 claims description 28
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 27
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 27
- 229910052742 iron Inorganic materials 0.000 claims description 27
- 229910052749 magnesium Inorganic materials 0.000 claims description 27
- 229910052759 nickel Inorganic materials 0.000 claims description 27
- 229910052726 zirconium Inorganic materials 0.000 claims description 27
- 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 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 238000002156 mixing Methods 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 16
- 239000003795 chemical substances by application Substances 0.000 claims description 10
- 230000035484 reaction time Effects 0.000 claims description 9
- 239000007787 solid Substances 0.000 claims description 9
- 239000011148 porous material Substances 0.000 claims description 8
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000003153 chemical reaction reagent Substances 0.000 claims description 5
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims description 5
- 230000033444 hydroxylation Effects 0.000 claims description 5
- 238000005805 hydroxylation reaction Methods 0.000 claims description 5
- REYJJPSVUYRZGE-UHFFFAOYSA-N Octadecylamine Chemical compound CCCCCCCCCCCCCCCCCCN REYJJPSVUYRZGE-UHFFFAOYSA-N 0.000 claims description 4
- 239000006227 byproduct Substances 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000002485 combustion reaction Methods 0.000 claims description 3
- 239000011572 manganese Substances 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 150000002505 iron Chemical class 0.000 claims description 2
- 159000000003 magnesium salts Chemical class 0.000 claims description 2
- 150000002696 manganese Chemical class 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 150000002815 nickel Chemical class 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- 150000003754 zirconium Chemical class 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims 2
- 230000000640 hydroxylating effect Effects 0.000 claims 2
- 229910052748 manganese Inorganic materials 0.000 claims 2
- 230000000694 effects Effects 0.000 abstract description 10
- 238000001179 sorption measurement Methods 0.000 abstract description 10
- 239000002699 waste material Substances 0.000 abstract description 7
- 238000006555 catalytic reaction Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 3
- 239000002184 metal Substances 0.000 abstract description 2
- 230000009965 odorless effect Effects 0.000 abstract description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 72
- 239000007864 aqueous solution Substances 0.000 description 61
- 239000007788 liquid Substances 0.000 description 40
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 35
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 229910001868 water Inorganic materials 0.000 description 28
- 235000019441 ethanol Nutrition 0.000 description 20
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical compound [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 description 20
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 20
- 229930195733 hydrocarbon Natural products 0.000 description 18
- 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
- 150000002430 hydrocarbons Chemical class 0.000 description 17
- 239000007789 gas Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 239000013598 vector Substances 0.000 description 11
- 238000001914 filtration Methods 0.000 description 10
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 10
- 239000000463 material Substances 0.000 description 10
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 10
- 238000004898 kneading Methods 0.000 description 8
- 239000011812 mixed powder Substances 0.000 description 8
- GETQZCLCWQTVFV-UHFFFAOYSA-N trimethylamine Chemical compound CN(C)C GETQZCLCWQTVFV-UHFFFAOYSA-N 0.000 description 8
- 238000005406 washing Methods 0.000 description 8
- 238000001354 calcination Methods 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 238000007605 air drying Methods 0.000 description 6
- 238000007385 chemical modification Methods 0.000 description 6
- 238000009210 therapy by ultrasound Methods 0.000 description 6
- 238000009489 vacuum treatment Methods 0.000 description 6
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 239000011541 reaction mixture Substances 0.000 description 5
- 239000004215 Carbon black (E152) Substances 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 4
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 4
- 238000010170 biological method Methods 0.000 description 4
- 229910000037 hydrogen sulfide Inorganic materials 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 4
- QMMFVYPAHWMCMS-UHFFFAOYSA-N Dimethyl sulfide Chemical compound CSC QMMFVYPAHWMCMS-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000002894 chemical waste Substances 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 238000002715 modification method Methods 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000002344 surface layer Substances 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 238000004065 wastewater treatment Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 239000003245 coal Substances 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000009616 inductively coupled plasma Methods 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 230000000704 physical effect Effects 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 239000010457 zeolite Substances 0.000 description 2
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 229920000049 Carbon (fiber) Polymers 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000004111 Potassium silicate Substances 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000004480 active ingredient Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 description 1
- 235000011114 ammonium hydroxide Nutrition 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000001555 benzenes Chemical class 0.000 description 1
- 235000011132 calcium sulphate Nutrition 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000013329 compounding Methods 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
- 238000006477 desulfuration reaction Methods 0.000 description 1
- 230000023556 desulfurization Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000009977 dual effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 159000000014 iron salts Chemical class 0.000 description 1
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 description 1
- 230000007794 irritation Effects 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 229940071125 manganese acetate Drugs 0.000 description 1
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- -1 methane hydrocarbons Chemical class 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 238000012430 stability testing Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
- PJVWKTKQMONHTI-UHFFFAOYSA-N warfarin Chemical compound OC=1C2=CC=CC=C2OC(=O)C=1C(CC(=O)C)C1=CC=CC=C1 PJVWKTKQMONHTI-UHFFFAOYSA-N 0.000 description 1
- 229960005080 warfarin Drugs 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8603—Removing sulfur compounds
- B01D53/8612—Hydrogen sulfide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8621—Removing nitrogen compounds
- B01D53/8634—Ammonia
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an ozone catalytic oxidation catalyst and a preparation method thereof. The carrier of the catalyst is a mixture of waste activated carbon and incinerator ash, and is preferably subjected to chemical surface modification and/or plasma treatment. The active metal component is loaded and is applied to the treatment of biochemical waste gas. The catalyst has good adsorption and catalysis effects on harmful substances in the waste gas, can be treated to be odorless and discharged, and cannot cause pollution.
Description
Technical Field
The invention relates to the technical field of ozone treatment, in particular to an ozone catalytic oxidation catalyst and a preparation method thereof.
Technical Field
The biological method for treating the wastewater is one of the main means of the current wastewater treatment, but the odor generated in the current biological method treatment process seriously harms the health and environment of human beings, the biochemical waste gas mainly comes from the volatilization of the wastewater, the main components of the biochemical waste gas are alkane organic matters, benzene series matters, ammonia, hydrogen sulfide and other substances, and the biochemical waste gas has the characteristics of large gas quantity, low concentration, large influence by seasons, low odor threshold value and strong irritation, and has great harm to the ecological environment and the health of personnel.
The common treatment means of biochemical waste gas include incineration method, absorption method, adsorption method, biological method and other methods, wherein the incineration cost is high, a large amount of fuel needs to be supplemented, and even the processes of desulfurization, denitration and the like need to be matched; the absorption method has low efficiency, is difficult to treat without odor, and the absorbed waste liquid can generate secondary pollution; the adsorption material is limited by the adsorption capacity of the adsorption material, and needs to be regenerated or replaced periodically; biological methods are weak in anti-interference capability and require the preparation of special strains to treat specific pollutants.
Ozone has extremely strong capability of decomposing pollutants, and has wide application in the fields of industrial wastewater treatment, refuse dump water seepage treatment and the like, but the ozone is only used for oxidizing and treating waste gas, the pollutants in the waste gas are difficult to be fully oxidized into pollution-free micromolecules, and in contrast, a high-grade oxidation mode is adopted, and the catalytic action of a catalyst is utilized to form a large amount of hydroxyl free radicals (& OH), so that organic matters in the waste gas are oxidized and decomposed into carbon dioxide and water, ammonia substances and the like are oxidized into nitrogen, sulfides such as methyl mercaptan and the like are oxidized into sulfate radicals, and the method has the advantages of high removal efficiency, no secondary pollution and the like.
The different catalysts have different treatment effects and costs. Therefore, the development of a high-efficiency catalyst is one of effective ways to improve the treatment effect.
The invention patent CN101406831A discloses a preparation method of a manganese dioxide supported catalyst, which is characterized in that one or more of active carbon, silica gel, zeolite or diatomite are taken as carriers, and the carriers are immersed in a manganese acetate solution, and the processes of evaporation, drying, roasting and the like are carried out to prepare the manganese dioxide supported catalyst.
The invention patent CN106475120A discloses a preparation method of an ozone catalyst, zeolite or activated carbon is respectively dipped and secondarily baked in aqueous solutions of sodium sulfate, aluminum sulfate, potassium sulfate, calcium sulfate and magnesium sulfate, and the surface layer and the inner film are combined more firmly due to the adoption of the secondary baking method.
The invention patent CN107456978A takes activated carbon as a carrier and copper, manganese, iron and ruthenium as active ingredients to prepare a catalyst loaded with a plurality of effective components.
However, the catalyst prepared by the prior art has the characteristics of unstable performance, low efficiency, short service life, easy change of surface properties and low repeated utilization rate, so that the catalyst is wasted and the cost is increased.
Disclosure of Invention
The invention aims to provide an ozone catalytic oxidation catalyst which has stable performance, long service life and high efficiency and can be recycled. The catalyst is applied to the treatment of biochemical waste gas, has high treatment efficiency, low cost, reusability and high stability, can treat the biochemical waste gas up to the standard, and does not produce secondary pollution.
The invention also provides a preparation method of the catalyst, and the process is simple.
In order to solve the technical problems, the invention provides the following technical scheme:
an ozone catalytic oxidation catalyst, the catalyst comprises a carrier and active components, the carrier comprises activated carbon and incinerator ash, and the active components comprise magnesium, nickel, manganese, zirconium and iron in oxide form; the catalyst comprises the following components by weight of the carrier:
1.0 to 5.0 wt% of magnesium, preferably 2.0 to 3.0 wt%;
1.0-6.5 wt% of nickel, preferably 2.0-3.5 wt%;
1.0-3.0 wt% of manganese, preferably 1.8-2.5 wt%;
1.5-2.5 wt% of zirconium, preferably 1.5-2.0 wt%;
1.0 to 6.5 wt%, preferably 2.0 to 5.0 wt% of iron.
The activated carbon is from activated carbon inactivated after treating waste gas, and the activated carbon can be, but is not limited to, coal carbon, shell carbon, wood carbon, activated carbon fiber and the like, and has a specific surface area of 600-3000 m-2Per g, preferably 800-3000m2(ii)/g; pore diameters of 0.2-3nm, preferably 0.5-2 nm; the fineness is 50-200 meshes, preferably 50-150 meshes.
The ash deposition of the incinerator is from byproducts generated after the combustion of the incinerator, the ash deposition can be but is not limited to products generated after the combustion of biochemical sludge, coal, chemical waste liquid and the like, and the specific surface area is 200-400m2Per g, preferably 250-400m2(ii)/g; the pore diameter is 3-12nm, preferably 3-5 nm.
A method of preparing the vector of the present invention, comprising the steps of: and uniformly mixing the activated carbon, the deposited ash of the incinerator and the peptizing agent, then making the mixture into strips, drying and roasting the strips to obtain the carrier.
The mass ratio of the active carbon to the accumulated ash of the incinerator is 1: 1-6, preferably 1: 1-5.
The peptizing agent is selected from one or more of citric acid, nitric acid and acetic acid.
The mass of the peptizing agent accounts for 20-40%, preferably 25-35% of the mass sum of the activated carbon and the ash deposited in the incinerator.
The catalyst is cylindrical, the diameter is 2-6mm, the length is 3-8mm, the preferred diameter is 2-4mm, and the preferred length is 2-7 mm.
The drying temperature is 70-110 ℃, the drying time is 2-8h, the preferred drying temperature is 80-110 ℃, and the drying time is 3-5 h.
The roasting temperature is 400-750 ℃, the roasting time is 1-4h, the roasting temperature is preferably 450-700 ℃, and the roasting time is 1.5-4 h.
The specific surface area of the carrier is 400-2200m2G, preferably 500-2200m2/g。
As a preferable technical scheme, the carrier is subjected to chemical surface modification, so that the number and concentration of functional groups on the surface of the carrier can be further increased, the adsorption effect is enhanced, the service life is prolonged, and the catalytic oxidation removal effect of ozone is improved.
The chemical surface modification method comprises the following steps: the carrier and the hydroxylation reagent are reacted firstly, and then dried to obtain the carrier with the chemically modified surface.
In the chemical surface modification method, the reaction temperature is 40-60 ℃, the reaction time is 10-30 min, the preferable reaction temperature is 50-60 ℃, and the reaction time is 15-30 min; the drying temperature is 60-100 ℃, preferably 80-100 ℃, and the drying time is 1-3h, preferably 2-3 h.
The hydroxylation reagent provided by the invention comprises but is not limited to ammonia water, ethylenediamine, ammonium nitrate, dodecylamine (DDA), Octadecylamine (OTDA) and the like, and preferably macromolecular modifiers such as DDA and/or OTDA and the like.
The mass ratio of the carrier to the hydroxylation reagent is 1: (0.5-12), preferably 1: (1-10).
As a preferable technical scheme, the carrier is subjected to plasma modification to obtain a plasma modified carrier, so that the number of surface hydroxyl groups is increased, and the catalytic activity is improved.
As a preferable technical scheme, the carrier with the modified chemical surface is subjected to plasma modification to obtain the carrier with the modified chemical surface and the plasma, so that the number of surface hydroxyl groups is further increased, and the catalytic activity is improved.
The plasma modification method comprises the following steps: treating the carrier or the chemically surface-modified carrier with plasma at a discharge voltage of 10-15kV, preferably 12-15kV, a discharge frequency of 30-110Hz, preferably 50-110Hz, a reaction time of 20-40min, preferably 25-35min, washing with pure water after the reaction, and drying.
A preparation method of an ozone catalytic oxidation catalyst comprises the following steps: adding a solution containing magnesium salt, nickel salt, manganese salt, zirconium salt and iron salt into the carrier or the chemically surface-modified carrier or the plasma-modified carrier or the chemically surface-modified and plasma-modified carrier according to the proportion, and performing equal-volume impregnation for 3-5h, preferably 3.5-5 h; then the obtained solid is baked step by step, firstly baked for 1-2h at the temperature of 150-; then cooling the solid to be below 100 ℃, and roasting the solid for 3 to 5 hours at the temperature of 420-480 ℃, preferably for 3.5 to 5 hours at the temperature of 430-460 ℃ to obtain the ozone catalytic oxidation catalyst. The surface layer and the inner layer are combined more firmly through secondary baking, and the service life of the catalyst is prolonged by more than 10%.
Preferably, the magnesium, nickel, manganese, zirconium and iron salts are respectively derived from one or more of nitrate, acetate and phosphate containing corresponding metal elements, preferably nitrate.
A method of treating exhaust gas comprising the steps of: the treatment of the exhaust gas with the catalyst prepared according to the present invention can be carried out in any reactor known in the art, preferably using a packed tower, the exhaust gas and ozoneIntroducing into a catalytic reaction tower together, wherein the reaction temperature is 10-45 ℃, and preferably 25-45 ℃; airspeed of 400--1Preferably 600--1；O3(mg/Nm3): non-methane Total hydrocarbons (mg/Nm)3) 0.12-0.35, preferably 0.18-0.3.
The ozone is from an ozone generator, oxygen is used as a gas source, and the concentration of the generated ozone is 6-10 wt%, preferably 7-10 wt%.
The exhaust gas according to the present invention preferably satisfies the following conditions: total non-methane hydrocarbons less than or equal to 1000mg/Nm3Preferably 0 to 800mg/Nm3(ii) a Ammonia gas is less than or equal to 200mg/Nm3Preferably 0 to 120mg/Nm3(ii) a Trimethylamine is less than or equal to 24mg/Nm3Preferably 0 to 15mg/Nm3(ii) a Methyl mercaptan is less than or equal to 2mg/Nm3Preferably 0 to 1mg/Nm3(ii) a Less than or equal to 5mg/Nm of dimethyl sulfide3Preferably 0 to 3mg/Nm3。
The catalyst of the present invention is used in treating biochemical bad smell to reach waste gas eliminating rate over 90% and no smell of waste gas.
The invention has the beneficial effects that:
(1) the waste activated carbon and the incinerator ash deposition carrier come from byproducts in the three-waste treatment process, are simple and easy to obtain, have low cost and realize the recycling of waste.
(2) The compounding of the activated carbon and the deposited ash of the incinerator realizes the distribution of different pore canals of the catalyst, and the use of the peptizing agent effectively expands the specific surface area of the carrier.
(3) The chemical modification of the carrier not only effectively increases the active groups on the surface of the carrier, realizes the synergistic effect of catalysis and adsorption on the carrier, improves the decomposition efficiency of the catalyst, and simultaneously adopts the ODTA and DDA modified catalyst to have certain enrichment effect on organic matters, thereby playing the dual roles of enrichment, adsorption and catalysis.
(4) The plasma modification of the carrier further increases the hydroxyl on the surface of the catalyst and improves the overall moisture resistance of the catalyst.
(5) The composition of various oxides such as magnesium, nickel, iron, manganese, zirconium and the like forms various centers for exciting ozone to be converted into hydroxyl radicals, and the porous channel structure, the multi-catalytic center and the synergistic effect with adsorption enable the catalyst to be fully contacted with ozone, so that the treatment efficiency is high.
(6) The secondary roasting technology ensures that the surface layer and the inner layer are combined more firmly, and prolongs the service life of the catalyst.
(7) The ozone catalyst used in the invention improves the adsorption effect on harmful substances in the waste gas, simultaneously, under the action of the catalyst, the ozone can be quickly converted into a large amount of OH, biochemical waste gas is treated to be nearly odorless, and simultaneously, the ozone catalyst can completely decompose the reacted ozone, so that secondary pollution is avoided.
Detailed Description
The technical solution and the effects of the present invention are further described by the following specific examples. The following examples are merely illustrative of the present invention and are not intended to limit the scope of the present invention. Simple modifications of the invention applying the inventive concept are within the scope of the invention as claimed.
The BET specific surface area and the pore diameter are measured by a specific surface area and porosity measuring instrument which is a Quadrasorb SI type specific surface area and porosity measuring instrument of the Congta company in America;
the element composition is measured by an inductively coupled plasma atomic emission spectrometer. The instrument is an ICP-OES type inductively coupled plasma atomic emission spectrometer 700Series of Agilent company in America;
measuring the reaction product by gas chromatography with an instrument GC7890 of Agilent company in America;
the plasma device is self-made and consists of a high-voltage pulse and discharge reactor;
an ozone generator, model CF-G-2, available from Qingdao national forest environmental protection science and technology, Inc.;
the catalytic oxidation tower was purchased from yozhou longtai ozone equipment manufacturing ltd;
activated carbon, waste from a warfarin chemical waste gas treatment system;
the ash accumulated in the incinerator comes from a Wanhua chemical incinerator and a byproduct after incineration of a waste energy furnace;
the biochemical waste gas is collected from a Wanhua chemical waste water treatment system, and comprises waste water accident pool, adjusting pool, anaerobic pool, aerobic pool, sludge dewatering room and other regional waste gas.
Example 1: preparation of the support
Preparation of A vector
Activated carbon A (specific surface area 3000 m)2Per g, aperture is 0.5nm), the crushing fineness is 50 meshes; 15g of pulverized activated carbon powder and incinerator ash A (specific surface area 400 m)2Per g, aperture 3nm)15g are mixed evenly; adding 9g of citric acid and 3g of water into the mixed powder, uniformly mixing, and kneading for 1 min; extruding the kneaded material into strips with the diameter of 2mm and the length of 5 mm; then drying at 100 ℃ for 3h, and roasting at 500 ℃ for 2h to obtain the finished product.
Preparation of vector B
Activated carbon A (specific surface area 3000 m)2Per g, aperture is 0.5nm), the crushing fineness is 50 meshes; 15g of pulverized activated carbon powder and incinerator ash B (specific surface area 250 m)2Per g, aperture 5nm)15g are mixed evenly; adding 9g of citric acid and 3g of water into the mixed powder, uniformly mixing, and kneading for 1 min; extruding the kneaded material into strips with the diameter of 2mm and the length of 5 mm; then drying at 100 deg.C for 3h, and calcining at 500 deg.C for 2 h. After the sample is cooled, 60ml of 5 wt% ODTA absolute ethanol solution is added, ultrasonic treatment is carried out for 20min under the reaction condition of 50 ℃, and then the sample is placed into a forced air drying oven to react for 3h under the condition of 100 ℃; after the reaction was completed, the reaction mixture was washed 2 times with absolute ethanol and then 2 times with pure water. Then placing the sample with the modified surface into 200mL of pure water, slowly pouring the sample into a plasma reactor, carrying out vacuum treatment on the reactor, and then starting a power supply to discharge, wherein the discharge voltage is 15kV, and the discharge frequency is 110 Hz. And taking out the carrier after reacting for 30min, washing with pure water, and drying to obtain the carrier after surface modification and plasma modification.
Preparation of C Carrier
Activated carbon B (specific surface area 820 m)2Per g, aperture is 2nm), the crushing fineness is 50 meshes; 5g of pulverized activated carbon powder and incinerator ash A (specific surface area 400 m)2Per g, aperture 3nm)25g are mixed evenly; adding 7.5g of citric acid and 4.5g of water into the mixed powder, uniformly mixing, and kneading for 1 min; extruding the kneaded material into strips with the diameter of 2mm and the length of 5 mm; then drying at 100 deg.C for 3h, and calcining at 500 deg.C for 2 h. After the sample is cooled, 60ml of 5 wt% ODTA absolute ethanol solution is added, ultrasonic treatment is carried out for 20min under the reaction condition of 50 ℃, and then the sample is placed into a forced air drying oven to react for 3h under the condition of 100 ℃; after the reaction was completed, the reaction mixture was washed 2 times with absolute ethanol and then 2 times with pure water. Then placing the sample with the modified surface into 200mL of pure water, slowly pouring the sample into a plasma reactor, carrying out vacuum treatment on the reactor, and then starting a power supply to discharge, wherein the discharge voltage is 15kV, and the discharge frequency is 110 Hz. And taking out the carrier after reacting for 30min, washing with pure water, and drying to obtain the carrier after surface modification and plasma modification.
Preparation of D vector
Activated carbon B (specific surface area 820 m)2Per g, aperture is 2nm), the crushing fineness is 50 meshes; 15g of pulverized activated carbon powder and incinerator ash B (specific surface area 250 m)2Per g, aperture 5nm)15g are mixed evenly; adding 7.5g of citric acid and 4.5g of water into the mixed powder, uniformly mixing, and kneading for 1 min; extruding the kneaded material into strips with the diameter of 2mm and the length of 5 mm; then drying at 100 deg.C for 3h, and calcining at 500 deg.C for 2 h. After the sample is cooled, 60ml of 5 wt% ODTA absolute ethanol solution is added, ultrasonic treatment is carried out for 20min under the reaction condition of 50 ℃, and then the sample is placed into a forced air drying oven to react for 3h under the condition of 100 ℃; after the reaction was completed, the reaction mixture was washed 2 times with absolute ethanol and then 2 times with pure water. Then placing the sample with the modified surface into 200mL of pure water, slowly pouring the sample into a plasma reactor, carrying out vacuum treatment on the reactor, and then starting a power supply to discharge, wherein the discharge voltage is 15kV, and the discharge frequency is 110 Hz. And taking out the carrier after reacting for 30min, washing with pure water, and drying to obtain the carrier after surface modification and plasma modification.
Preparation of E vector
Activated carbon B (specific surface area 820 m)2Per g, aperture is 2nm), the crushing fineness is 50 meshes; 5g of pulverized activated carbon powder and deposited ash of an incineratorB (specific surface area 400 m)2Per g, aperture 5nm)25g are mixed evenly; adding 9g of citric acid and 3g of water into the mixed powder, uniformly mixing, and kneading for 1 min; extruding the kneaded material into strips with the diameter of 2mm and the length of 5 mm; then drying at 100 deg.C for 3h, and calcining at 500 deg.C for 2 h. After the sample is cooled, 60ml of 5 wt% ODTA absolute ethanol solution is added, ultrasonic treatment is carried out for 20min under the reaction condition of 50 ℃, and then the sample is placed into a forced air drying oven to react for 3h under the condition of 100 ℃; after the reaction was completed, the reaction mixture was washed 2 times with absolute ethanol and then 2 times with pure water. Then placing the sample with the modified surface into 200mL of pure water, slowly pouring the sample into a plasma reactor, carrying out vacuum treatment on the reactor, and then starting a power supply to discharge, wherein the discharge voltage is 15kV, and the discharge frequency is 110 Hz. And taking out the carrier after reacting for 30min, washing with pure water, and drying to obtain the carrier after surface modification and plasma modification.
Preparation of F Carrier
Activated carbon A (specific surface area 3000 m)2Per g, aperture is 0.5nm), the crushing fineness is 50 meshes; 15g of pulverized activated carbon powder and incinerator ash A (specific surface area 250 m)2Per g, aperture 0.5nm)15g are mixed evenly; adding 7.5g of citric acid and 4.5g of water into the mixed powder, uniformly mixing, and kneading for 1 min; extruding the kneaded material into strips with the diameter of 2mm and the length of 5 mm; then drying at 100 deg.C for 3h, and calcining at 500 deg.C for 2 h. After the sample is cooled, adding 400ml of 5 wt% ODTA absolute ethanol solution, carrying out ultrasonic treatment for 20min under the reaction condition of 50 ℃, and then putting the sample into a forced air drying oven to react for 3h under the condition of 100 ℃; after the reaction is finished, washing the reaction product for 2 times by using absolute ethyl alcohol, and drying the reaction product at room temperature to obtain the surface modified carrier F.
Preparation of G vector
Activated carbon A (specific surface area 3000 m)2Per g, aperture is 0.5nm), the crushing fineness is 50 meshes; 15g of pulverized activated carbon powder and incinerator ash A (specific surface area 250 m)2Per g, aperture 0.5nm)15g are mixed evenly; adding 7.5g of citric acid and 4.5g of water into the mixed powder, uniformly mixing, and kneading for 1 min; extruding the kneaded material into strips with the diameter of 2mm and the length of 5 mm; then drying at 100 deg.C for 3h, and calcining at 500 deg.C for 2 h. To be treated as aboveAfter the product is cooled, putting the sample in 200mL of pure water, then slowly pouring the sample into a plasma reactor, carrying out vacuum treatment on the reactor, and then starting a power supply to discharge, wherein the discharge voltage is 15kV, and the discharge frequency is 110 Hz. And taking out the carrier after reacting for 30min, washing with pure water, and drying to obtain the plasma modified carrier G.
Preparation of H vector
Activated carbon A (specific surface area 3000 m)2Per g, aperture is 0.5nm), the crushing fineness is 50 meshes; 15g of pulverized activated carbon powder and incinerator ash A (specific surface area 250 m)2Per g, aperture 0.5nm)15g are mixed evenly; adding 7.5g of citric acid and 4.5g of water into the mixed powder, uniformly mixing, and kneading for 1 min; extruding the kneaded material into strips with the diameter of 2mm and the length of 5 mm; then drying at 100 deg.C for 3h, and calcining at 500 deg.C for 2 h. After the sample is cooled, adding 400ml of 5 wt% ODTA absolute ethanol solution, carrying out ultrasonic treatment for 20min under the reaction condition of 50 ℃, and then putting the sample into a forced air drying oven to react for 3h under the condition of 100 ℃; after the reaction was completed, the reaction mixture was washed 2 times with absolute ethanol and then 2 times with pure water. Then placing the sample with the modified surface into 200mL of pure water, slowly pouring the sample into a plasma reactor, carrying out vacuum treatment on the reactor, and then starting a power supply to discharge, wherein the discharge voltage is 15kV, and the discharge frequency is 110 Hz. And taking out the carrier after reacting for 30min, washing with pure water, and drying to obtain the carrier H subjected to surface modification and plasma modification.
The relevant physical properties of the vectors A to H are shown in Table 1.
Table 1: related physical Properties of the vector
| BET/(㎡/g) | Pore size/nm | |
| Carrier A | 2200 | 1.3 |
| Carrier B | 1850 | 1.5 |
| Carrier C | 820 | 3.2 |
| Carrier D | 780 | 3.5 |
| Carrier E | 560 | 4.2 |
| Vector F | 2100 | 1.3 |
| Vector G | 2120 | 1.3 |
| Carrier H | 2080 | 1.3 |
Example 2: preparation of catalyst # 0
200g of the A carrier is taken and put into a beaker, and simultaneously 40.0mL of magnesium nitrate aqueous solution containing 0.10g/mL of magnesium, 40.0mL of nickel nitrate aqueous solution containing 0.15g/mL of nickel, 40.0mL of manganese nitrate aqueous solution containing 0.10g/mL of manganese, 40.0mL of zirconium nitrate aqueous solution containing 0.1g/mL of zirconium and 40.0mL of ferric nitrate aqueous solution containing 0.10g/mL of iron are taken and added into ethanol aqueous solution with the ethanol concentration of 5 wt% to prepare impregnation liquid with the total volume of 500.0 mL. Uniformly mixing the impregnation liquid and the carrier in a beaker, keeping the temperature at 60 ℃ for impregnation for 5h, filtering the impregnation liquid, and putting the carrier adsorbed with the impregnation liquid into an oven for keeping the temperature at 180 ℃ for 2 h; then the catalyst is taken out, cooled to 100 ℃, and then roasted in a muffle furnace at 450 ℃ for 5 hours to obtain a 0# catalyst.
In the obtained 0# catalyst, the contents of the following components are calculated by taking the weight of the active carbon and the deposited ash of the incinerator as the reference: 2.0 wt% of magnesium, 3.0 wt% of nickel, 2 wt% of manganese, 2.0 wt% of zirconium and 2.0 wt% of iron.
Example 3: preparation of catalyst # 1
200g of the F carrier is put into a beaker, and 40.0mL of magnesium nitrate aqueous solution containing 0.10g/mL of magnesium, 40.0mL of nickel nitrate aqueous solution containing 0.15g/mL of nickel, 40.0mL of manganese nitrate aqueous solution containing 0.10g/mL of manganese, 40.0mL of zirconium nitrate aqueous solution containing 0.1g/mL of zirconium and 40.0mL of ferric nitrate aqueous solution containing 0.10g/mL of iron are added into ethanol aqueous solution with the ethanol concentration of 5 wt% to prepare impregnation liquid with the total volume of 500.0 mL. Uniformly mixing the impregnation liquid and the carrier in a beaker, keeping the temperature at 60 ℃ for impregnation for 5h, filtering the impregnation liquid, and putting the carrier adsorbed with the impregnation liquid into an oven for keeping the temperature at 180 ℃ for 2 h; then taking out the catalyst, cooling to 100 ℃, and then roasting in a muffle furnace at 450 ℃ for 5h to obtain the No. 1 catalyst.
In the obtained No. 1 catalyst, the contents of the following components are calculated by taking the weight of the plasma modified activated carbon and the incinerator ash as the reference: 2.0 wt% of magnesium, 3.0 wt% of nickel, 2 wt% of manganese, 2.0 wt% of zirconium and 2.0 wt% of iron.
Example 4: preparation of catalyst # 2
200G of the G carrier was placed in a beaker, and 40.0mL of a magnesium nitrate aqueous solution containing 0.10G/mL of magnesium, 40.0mL of a nickel nitrate aqueous solution containing 0.15G/mL of nickel, 40.0mL of a manganese nitrate aqueous solution containing 0.10G/mL of manganese, 40.0mL of a zirconium nitrate aqueous solution containing 0.1G/mL of zirconium, and 40.0mL of an iron nitrate aqueous solution containing 0.10G/mL of iron were added to an ethanol aqueous solution having an ethanol concentration of 5 wt%, to prepare a dipping solution having a total volume of 500.0 mL. And uniformly mixing the impregnation liquid and the carrier in a beaker, keeping the temperature at 60 ℃ for impregnation for 5h, filtering the impregnation liquid, and roasting the carrier adsorbed with the impregnation liquid in a drying oven at 450 ℃ for 5h to obtain the No. 2 catalyst.
In the obtained 2# catalyst, the contents of the following components are calculated by taking the weight of the activated carbon and the incinerator ash deposited after chemical modification and plasma modification as the reference: 2.0 wt% of magnesium, 3.0 wt% of nickel, 2 wt% of manganese, 2.0 wt% of zirconium and 2.0 wt% of iron.
Example 5: preparation of No. 3 catalyst
200g of H carrier is taken and put into a beaker, and simultaneously 40.0mL of magnesium nitrate aqueous solution containing 0.10g/mL of magnesium, 40.0mL of nickel nitrate aqueous solution containing 0.15g/mL of nickel, 40.0mL of manganese nitrate aqueous solution containing 0.10g/mL of manganese, 40.0mL of zirconium nitrate aqueous solution containing 0.1g/mL of zirconium and 40.0mL of ferric nitrate aqueous solution containing 0.10g/mL of iron are taken and added into ethanol aqueous solution with the ethanol concentration of 5 wt% to prepare impregnation liquid with the total volume of 500.0 mL. And uniformly mixing the impregnation liquid and the carrier in a beaker, keeping the temperature at 60 ℃ for impregnation for 5h, filtering the impregnation liquid, and roasting the carrier adsorbed with the impregnation liquid in a drying oven at 450 ℃ for 5h to obtain the 3# catalyst.
In the obtained 4# catalyst, the contents of the following components are calculated by taking the weight of the activated carbon and the incinerator ash deposited after chemical modification and plasma modification as the reference: 2.0 wt% of magnesium, 3.0 wt% of nickel, 2 wt% of manganese, 2.0 wt% of zirconium and 2.0 wt% of iron.
Example 6: preparation of catalyst # 4
200g of H carrier is taken and put into a beaker, and simultaneously 40.0mL of magnesium nitrate aqueous solution containing 0.10g/mL of magnesium, 40.0mL of nickel nitrate aqueous solution containing 0.15g/mL of nickel, 40.0mL of manganese nitrate aqueous solution containing 0.10g/mL of manganese, 40.0mL of zirconium nitrate aqueous solution containing 0.1g/mL of zirconium and 40.0mL of ferric nitrate aqueous solution containing 0.10g/mL of iron are taken and added into ethanol aqueous solution with the ethanol concentration of 5 wt% to prepare impregnation liquid with the total volume of 500.0 mL. Uniformly mixing the impregnation liquid and the carrier in a beaker, keeping the temperature at 60 ℃ for impregnation for 5h, filtering the impregnation liquid, and putting the carrier adsorbed with the impregnation liquid into an oven for keeping the temperature at 180 ℃ for 2 h; then the catalyst is taken out, cooled to 100 ℃, and then roasted in a muffle furnace at 450 ℃ for 5 hours to obtain the 4# catalyst.
In the obtained 4# catalyst, the contents of the following components are calculated by taking the weight of the activated carbon and the incinerator ash deposited after chemical modification and plasma modification as the reference: 2.0 wt% of magnesium, 3.0 wt% of nickel, 2 wt% of manganese, 2.0 wt% of zirconium and 2.0 wt% of iron.
Example 7: preparation of No. 5 catalyst
200g of the B carrier is taken and put into a beaker, and simultaneously 40.0mL of magnesium nitrate aqueous solution containing 0.15g/mL of magnesium, 40.0mL of nickel nitrate aqueous solution containing 0.15g/mL of nickel, 40.0mL of manganese nitrate aqueous solution containing 0.10g/mL of manganese, 40.0mL of zirconium nitrate aqueous solution containing 0.1g/mL of zirconium and 40.0mL of ferric nitrate aqueous solution containing 0.2g/mL of iron are taken and added into ethanol aqueous solution with the ethanol concentration of 5 wt% to prepare impregnation liquid with the total volume of 500.0 mL. Uniformly mixing the impregnation liquid and the carrier in a beaker, keeping the temperature at 60 ℃ for impregnation for 5h, filtering the impregnation liquid, and putting the carrier adsorbed with the impregnation liquid into an oven for keeping the temperature at 180 ℃ for 2 h; then the catalyst is taken out, cooled to 100 ℃, and then roasted for 5 hours in a muffle furnace at 450 ℃ to obtain the 5# catalyst.
In the obtained 5# catalyst, the contents of the following components are calculated by taking the weight of the active carbon and the deposited ash of the incinerator as the reference: 3.0 wt% of magnesium, 3.0 wt% of nickel, 2 wt% of manganese, 2.0 wt% of zirconium and 4.0 wt% of iron.
Example 8: preparation of No. 6 catalyst
200g of the C carrier is put into a beaker, and 40.0mL of magnesium nitrate aqueous solution containing 0.15g/mL of magnesium, 40.0mL of nickel nitrate aqueous solution containing 0.1g/mL of nickel, 50.0mL of manganese nitrate aqueous solution containing 0.10g/mL of manganese, 40.0mL of zirconium nitrate aqueous solution containing 0.1g/mL of zirconium and 40.0mL of ferric nitrate aqueous solution containing 0.2g/mL of iron are added into ethanol aqueous solution with the ethanol concentration of 5 wt% to prepare impregnation liquid with the total volume of 500.0 mL. Uniformly mixing the impregnation liquid and the carrier in a beaker, keeping the temperature at 60 ℃ for impregnation for 5h, filtering the impregnation liquid, and putting the carrier adsorbed with the impregnation liquid into an oven for keeping the temperature at 180 ℃ for 2 h; then the catalyst is taken out, cooled to 100 ℃, and then roasted in a muffle furnace at 450 ℃ for 5 hours to obtain the No. 6 catalyst.
In the obtained No. 6 catalyst, the contents of the following components are calculated by taking the weight of the active carbon and the deposited ash of the incinerator as the reference: 3.0 wt% of magnesium, 2.0 wt% of nickel, 2.5 wt% of manganese, 2.0 wt% of zirconium and 4.0 wt% of iron.
Example 9: preparation of No. 7 catalyst
200g of the D carrier is put into a beaker, and 40.0mL of magnesium nitrate aqueous solution containing 0.15g/mL of magnesium, 40.0mL of nickel nitrate aqueous solution containing 0.1g/mL of nickel, 50.0mL of manganese nitrate aqueous solution containing 0.10g/mL of manganese, 30.0mL of zirconium nitrate aqueous solution containing 0.1g/mL of zirconium and 40.0mL of ferric nitrate aqueous solution containing 0.2g/mL of iron are added into ethanol aqueous solution with the ethanol concentration of 5 wt% to prepare impregnation liquid with the total volume of 500.0 mL. Uniformly mixing the impregnation liquid and the carrier in a beaker, keeping the temperature at 60 ℃ for impregnation for 5h, filtering the impregnation liquid, and putting the carrier adsorbed with the impregnation liquid into an oven for keeping the temperature at 180 ℃ for 2 h; then the catalyst is taken out, cooled to 100 ℃, and then roasted in a muffle furnace at 450 ℃ for 5 hours to obtain the 7# catalyst.
In the obtained 7# catalyst, the contents of the following components are calculated by taking the weight of the activated carbon and the deposited ash of the incinerator as the reference: 3.0 wt% of magnesium, 2.0 wt% of nickel, 2.5 wt% of manganese, 1.5 wt% of zirconium and 4.0 wt% of iron.
Example 10: preparation of catalyst # 8
40.0mL of magnesium nitrate aqueous solution containing 0.15g/mL of magnesium, 40.0mL of nickel nitrate aqueous solution containing 0.1g/mL of nickel, 50.0mL of manganese nitrate aqueous solution containing 0.10g/mL of manganese, 30.0mL of zirconium nitrate aqueous solution containing 0.1g/mL of zirconium and 50.0mL of ferric nitrate aqueous solution containing 0.2g/mL of iron are added into ethanol aqueous solution with the ethanol concentration of 5 wt% to prepare impregnation liquid with the total volume of 500.0 mL. Uniformly mixing the impregnation liquid and the carrier in a beaker, keeping the temperature at 60 ℃ for impregnation for 5h, filtering the impregnation liquid, and putting the carrier adsorbed with the impregnation liquid into an oven for keeping the temperature at 180 ℃ for 2 h; then the catalyst is taken out, cooled to 100 ℃, and then roasted in a muffle furnace at 450 ℃ for 5 hours to obtain the 8# catalyst.
In the obtained 8# catalyst, the contents of the following components are calculated by taking the weight of the active carbon and the deposited ash of the incinerator as the reference: 3.0 wt% of magnesium, 2.0 wt% of nickel, 2.5 wt% of manganese, 1.5 wt% of zirconium and 5.0 wt% of iron.
Example 11: preparation of catalyst No. 9
18.0mL of magnesium nitrate aqueous solution containing 0.1g/mL of magnesium, 16.0mL of nickel nitrate aqueous solution containing 0.1g/mL of nickel, 24.0mL of manganese nitrate aqueous solution containing 0.10g/mL of manganese, 20.0mL of zirconium nitrate aqueous solution containing 0.1g/mL of zirconium and 20.0mL of ferric nitrate aqueous solution containing 0.2g/mL of iron were added to an ethanol aqueous solution having an ethanol concentration of 5 wt% to prepare a dipping solution having a total volume of 500.0 mL. Uniformly mixing the impregnation liquid and the carrier in a beaker, keeping the temperature at 60 ℃ for impregnation for 5h, filtering the impregnation liquid, and putting the carrier adsorbed with the impregnation liquid into an oven for keeping the temperature at 180 ℃ for 2 h; then the catalyst is taken out, cooled to 100 ℃, and then roasted in a muffle furnace at 450 ℃ for 5 hours to obtain the 9# catalyst.
In the obtained 9# catalyst, the contents of the following components are calculated by taking the weight of the activated carbon and the deposited ash of the incinerator as the reference: 0.9 wt% of magnesium, 0.8 wt% of nickel, 1.2 wt% of manganese, 1.0 wt% of zirconium and 2.0 wt% of iron.
Comparison of exhaust gas treatment Performance of different catalysts
In the following examples, biochemical waste gases shown in Table 2 were used as raw materials.
TABLE 2 Biochemical exhaust gas composition
Treating biochemical waste gas by using prepared catalysts with different forms, introducing the biochemical waste gas shown in table 2 and ozone into a catalytic reaction tower at the reaction temperature of 30 ℃ and the space velocity of 1000h-1、O3(mg/Nm3): non-methane Total hydrocarbons (mg/Nm)3) 0.2, namely the concentration of ozone in the mixed gas is 100mg/Nm3The results are as follows:
under the condition of not adding a catalyst, only ozone is used for oxidizing non-methane total hydrocarbon removal efficiency by 13%, trimethylamine by 5% and hydrogen sulfide by 7%;
the removal efficiency of the No. 0 catalyst for non-methane total hydrocarbons is 75.2 percent, the removal efficiency of trimethylamine is 81 percent, the removal efficiency of hydrogen sulfide is 92 percent, and the removal efficiency of the rest is not detected;
the removal efficiency of the 1# catalyst for the non-methane total hydrocarbons is 88.5 percent, and the rest is not detected;
the removal efficiency of the 2# catalyst for the non-methane total hydrocarbons is 85.2 percent, and the rest is not detected;
the removal efficiency of the 3# catalyst for the non-methane total hydrocarbons is 99 percent, and the rest is not detected;
the removal efficiency of the 4# catalyst for the non-methane total hydrocarbons is 99 percent, and the rest is not detected;
the removal efficiency of the 5# catalyst for the non-methane total hydrocarbons is 98.9 percent, and the rest is not detected;
the removal efficiency of the No. 6 catalyst for non-methane total hydrocarbons is 98 percent, and the rest is not detected;
the removal efficiency of the 7# catalyst for the non-methane total hydrocarbons is 98.1 percent, and the rest is not detected;
the removal efficiency of the 8# catalyst for the non-methane total hydrocarbons reaches 98 percent, and the rest is not detected;
the removal efficiency of the No. 9 catalyst for non-methane total hydrocarbons is 70%, the removal efficiency of trimethylamine is 75%, the removal efficiency of hydrogen sulfide is 92%, and the rest is not detected.
Through comparison, the 3-8# catalyst in the preferred range has the non-methane total hydrocarbon removal efficiency of over 98 percent, and can meet the requirement of odor treatment; through comparison of No. 3, No. 4 and No. 5 catalysts, the catalyst efficiency can be improved by chemical modification and plasma modification, the chemical modification effect is better than that of the plasma modification, the two modifications are carried out simultaneously, and the effect is optimal; when the active metal component is too low, the catalytic effect is remarkably reduced, as can be seen by comparing the catalyst # 8 with the catalyst # 9.
Stability test of catalyst # 3 and 4
Performing stability test on the 3# and 4# catalysts, introducing the biochemical waste gas shown in the table 2 and ozone into an ozone oxidation reaction tower together, wherein the reaction temperature is 30 ℃, and the space velocity is 1000h～1、O3(mg/Nm3): non-methane Total hydrocarbons (mg/Nm)3) 0.2, namely the concentration of ozone in the mixed gas is 100mg/Nm3After the continuous measurement for 500 hours, the catalytic efficiency of the 3# catalyst is 96.5% of the total hydrocarbon removal efficiency of non-methane, the rest of the catalyst is not detected, the non-methane total hydrocarbon removal efficiency of the 4# catalyst is still maintained at 99%, and the rest of the catalyst is not detected, and the catalyst after the reaction is measured, and the result is shown in table 3.
Results of stability testing of catalyst # s in tables 33 and 4
| Item | 3# catalyst | 4# catalyst |
| Pore size/nm | 1.3 | 1.31 |
| Mg content/wt% | 1.99 | 1.95 |
| Ni content/wt% | 3 | 2.98 |
| Mn content/wt% | 1.98 | 1.86 |
| Zr content/wt.% | 1.95 | 1.85 |
| Fe content/wt% | 1.97 | 1..82 |
Claims (16)
1. An ozone catalytic oxidation catalyst, the catalyst comprises a carrier and active components, the carrier comprises activated carbon and incinerator ash, and the active components comprise magnesium, nickel, manganese, zirconium and iron in oxide form; the catalyst comprises the following components by weight of the carrier:
1.0-5.0 wt% of magnesium;
1.0-6.5 wt% of nickel;
1.0-3.0 wt% of manganese;
1.5-2.5 wt% of zirconium;
1.0-6.5 wt% of iron;
the activated carbon is deactivated after the waste gas is treated, and the specific surface area is 600-3000m2Per g, the aperture is 0.2-3nm, and the fineness is 50-200 meshes; the accumulated ash of the incinerator comes from the byproducts generated after the combustion of the incinerator, and the specific surface area is 200-400m2The pore diameter is 3-12 nm;
the support is chemically surface modified, the chemical surface modification comprising the steps of: firstly, reacting a carrier with a hydroxylation reagent, and then drying to obtain a chemically surface-modified carrier; the hydroxylating agent comprises one or more of dodecylamine and octadecylamine; the mass ratio of the carrier to the hydroxylation reagent is 1: (0.5-12).
2. The catalyst of claim 1, wherein the composition of the catalyst comprises:
2.0-3.0 wt% of magnesium;
2.0-3.5 wt% of nickel;
1.8-2.5 wt% of manganese;
1.5-2.0 wt% of zirconium;
2.0-5.0 wt% of iron.
3. The catalyst as claimed in claim 1, wherein the specific surface area of the activated carbon is 800-3000m2Per g, the aperture is 0.5-2nm, and the fineness is 50-150 meshes; the specific surface area of the accumulated ash of the incinerator is 250-400m2G, the pore diameter is 3-5 nm.
4. The catalyst according to claim 1, wherein the mass ratio of the activated carbon to the incinerator ash is 1: (1-6).
5. The catalyst according to claim 1, wherein the mass ratio of the activated carbon to the incinerator ash is 1: (1-5).
6. The catalyst of claim 1, wherein the support is prepared by a method comprising: uniformly mixing the activated carbon, the deposited ash of the incinerator and the peptizing agent, then making the mixture into strips, drying and roasting the strips to obtain the carrier; the peptizing agent is selected from one or more of citric acid, nitric acid and acetic acid; the mass of the peptizing agent accounts for 20-40% of the mass sum of the activated carbon and the ash accumulated in the incinerator.
7. The catalyst according to claim 6, wherein the mass of the peptizing agent accounts for 25-35% of the mass sum of the activated carbon and the incinerator ash deposit.
8. The catalyst according to claim 1, wherein the reaction temperature of the chemical surface modification is 40-60 ℃ and the reaction time is 10-30 min.
9. The catalyst of claim 1, wherein the reaction temperature of the chemical surface modification is 50-60 ℃ and the reaction time is 15-30 min.
10. The catalyst according to claim 1, wherein the mass ratio of the carrier to the hydroxylating agent is 1: (1-10).
11. The catalyst according to claim 1, wherein the carrier is subjected to plasma treatment, the plasma treatment has a discharge voltage of 10-15kV, a discharge frequency of 30-110Hz, and a reaction time of 20-40 min.
12. The catalyst according to claim 11, wherein the plasma treatment has a discharge voltage of 12-15kV, a discharge frequency of 50-110Hz, and a reaction time of 25-35 min.
13. The catalyst according to claim 1, wherein the chemically surface-modified support is subjected to plasma treatment, the plasma treatment having a discharge voltage of 10-15kV, a discharge frequency of 30-110Hz, and a reaction time of 20-40 min.
14. The catalyst according to claim 13, wherein the plasma treatment has a discharge voltage of 12-15kV, a discharge frequency of 50-110Hz, and a reaction time of 25-35 min.
15. A process for preparing the catalyst of any one of claims 1-14, comprising the steps of: adding a solution containing magnesium salt, nickel salt, manganese salt, zirconium salt and iron salt into the carrier or the chemically surface-modified carrier or the plasma-modified carrier or the chemically surface-modified carrier and the plasma-modified carrier according to the proportion, and performing equal-volume impregnation for 3-5 h; roasting the obtained solid at the temperature of 150-240 ℃ for 1-2 h; then cooling the solid to be below 100 ℃, and roasting the solid for 3 to 5 hours at the temperature of 420-480 ℃ to obtain the ozone catalytic oxidation catalyst.
16. The method according to claim 15, wherein the impregnation time is 3.5-5 h; roasting the obtained solid at the temperature of 180-240 ℃ for 1.2-2 h; then cooling the solid to be below 100 ℃, and roasting the solid for 3.5 to 5 hours at the temperature of 430-460 ℃ to obtain the ozone catalytic oxidation catalyst.
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